TWI684066B

TWI684066B - Photosensitive resin composition and method for manufacturing hardened relief pattern

Info

Publication number: TWI684066B
Application number: TW107130266A
Authority: TW
Inventors: 頼末友裕; 中村光孝; 井上泰平; 佐佐木隆弘
Original assignee: 日商旭化成股份有限公司
Priority date: 2016-04-14
Filing date: 2017-03-31
Publication date: 2020-02-01
Also published as: TWI717167B; TW202125103A; TW202016654A; JP2021182149A; TW201738655A; TWI753721B; JP2017198977A; TW201841060A; TWI638232B; JP2023169198A; JP6923334B2; JP2024032725A; JP7408599B2

Abstract

本發明提供一種能夠獲得於高溫保存(high temperature storage)試驗後於Cu層與硬化後之感光性樹脂層接觸之界面處不會產生空隙而密接性較高之樹脂層的感光性樹脂組合物、及使用該感光性樹脂組合物之硬化浮凸圖案之形成方法。本發明係一種感光性樹脂組合物及使用該感光性樹脂組合物之硬化浮凸圖案，該感光性樹脂組合物藉由將感光性樹脂與特定之塑化劑加以組合，能夠獲得於高溫保存(high temperature storage)試驗後於Cu層與樹脂層之界面處不會產生空隙而密接性較高之感光性樹脂。The present invention provides a photosensitive resin composition capable of obtaining a resin layer with high adhesion without generating voids at the interface between the Cu layer and the cured photosensitive resin layer after a high temperature storage test, And a method for forming a hard relief pattern using the photosensitive resin composition. The present invention is a photosensitive resin composition and a cured relief pattern using the photosensitive resin composition. The photosensitive resin composition can be obtained by high-temperature storage by combining the photosensitive resin with a specific plasticizer ( high temperature storage) Photosensitive resin with high adhesion without voids at the interface between the Cu layer and the resin layer.

Description

Photosensitive resin composition and method for manufacturing hardened relief pattern

本發明係關於一種用於形成例如電子零件之絕緣材料、及半導體裝置中之鈍化膜、緩衝塗膜、層間絕緣膜等之浮凸圖案的感光性樹脂組合物、及使用其之硬化浮凸圖案之形成方法。The present invention relates to a photosensitive resin composition for forming relief patterns of, for example, insulating materials for electronic parts, and passivation films, buffer coating films, interlayer insulating films in semiconductor devices, and hardened relief patterns using the same The formation method.

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、層間絕緣膜等係使用兼具優異之耐熱性、電氣特性及機械特性之聚醯亞胺樹脂、聚苯并㗁唑樹脂、酚樹脂等。該等樹脂之中，以感光性樹脂組合物之形式提供者藉由該組合物之塗佈、曝光、顯影、及利用固化而進行之熱醯亞胺化處理，可容易地形成耐熱性之浮凸圖案皮膜。此種感光性樹脂組合物與先前之非感光型材料相比具有能夠大幅縮減步驟之特徵。另外，半導體裝置(以下亦稱為「元件」)根據目的而藉由各種方法安裝於印刷基板。先前之元件一般而言係藉由利用細導線自元件之外部端子(焊墊)連接至引線框架之打線接合法製作。然而，於元件之高速化發展而動作頻率已達到GHz之今日，安裝中之各端子之配線長度之差異甚至會影響到元件之動作。因此，於高端用途之元件之安裝中，必須精確控制安裝配線之長度，若利用打線接合則難以滿足該要求。因此，提出有倒裝晶片安裝，即，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，將該晶片翻面(倒裝)而直接安裝於印刷基板(例如參照專利文獻1)。該倒裝晶片安裝由於可精確控制配線距離，故而用於處理高速信號之高端用途之元件，或由於安裝尺寸較小，故而用於行動電話等，其需求急遽擴大。於倒裝晶片安裝中使用聚醯亞胺、聚苯并㗁唑、酚樹脂等材料之情形時，待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而使表面粗化後，藉由濺鍍以1 μm以下之厚度形成成為鍍覆之籽晶層之金屬層後，以該金屬層為電極，藉由電解鍍覆而形成。此時，一般使用Ti作為成為籽晶層之金屬，使用Cu作為藉由電解鍍覆而形成之再配線層之金屬。針對此種金屬再配線層，要求再配線之金屬層與樹脂層之密接性於可靠性試驗後較高。作為此處進行之可靠性試驗，例如可列舉：於空氣中、125℃以上之高溫下保存100小時以上之高溫保存試驗；組裝配線並一面施加電壓，一面確認於空氣中、125℃左右之溫度下保存100小時以上之狀態下之動作的高溫動作試驗；於空氣中將-65～-40℃左右之低溫狀態與125～150℃左右之高溫狀態以週期加以反覆之溫度週期試驗；於溫度85℃以上且濕度85%以上之水蒸氣環境下保存之高溫高濕保存試驗；組裝配線並一面施加電壓一面進行相同之試驗的高溫高濕偏壓試驗；於空氣中或氮氣下複數次通過260℃之回流焊爐之回流焊試驗等。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層與樹脂層接觸之界面處產生空隙之問題。若於Cu層與樹脂層之界面處產生空隙，則兩者之密接性降低。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2001-338947號公報Previously, polyimide resins, polybenzoxazole resins, which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic parts, and passivation films, surface protective films, and interlayer insulating films for semiconductor devices. , Phenolic resin, etc. Among these resins, a supplier in the form of a photosensitive resin composition can easily form a heat-resistant float by coating, exposing, developing and thermally imidizing the composition by curing the composition. Convex pattern film. This photosensitive resin composition has the feature that it can greatly reduce the steps compared to the previous non-photosensitive material. In addition, semiconductor devices (hereinafter also referred to as "elements") are mounted on the printed circuit board by various methods according to purposes. The previous components are generally manufactured by wire bonding using thin wires to connect the external terminals (pads) of the components to the lead frame. However, with the rapid development of components and the operating frequency reaching GHz, the difference in the wiring length of each terminal during installation may even affect the operation of the component. Therefore, in the installation of high-end components, the length of the installation wiring must be accurately controlled. If wire bonding is used, it is difficult to meet this requirement. Therefore, flip chip mounting is proposed, that is, after forming a redistribution layer on the surface of a semiconductor wafer and forming bumps (electrodes) thereon, the wafer is flipped (flip) and directly mounted on a printed circuit board (for example Refer to Patent Document 1). The flip chip mounting can precisely control the wiring distance, so it is used for high-end components for processing high-speed signals, or because of the small installation size, it is used for mobile phones, etc., and its demand is rapidly expanding. When polyimide, polybenzoxazole, phenol resin and other materials are used in flip chip mounting, after the pattern of the resin layer is formed, a metal wiring layer forming step is performed. The metal wiring layer is usually plasma etched on the surface of the resin layer to roughen the surface, and then a metal layer that becomes a plated seed layer is formed by sputtering to a thickness of 1 μm or less, and the metal layer is used as an electrode. It is formed by electrolytic plating. At this time, Ti is generally used as the metal for the seed layer, and Cu is used as the metal for the rewiring layer formed by electrolytic plating. For such a metal rewiring layer, the adhesion between the metal layer and the resin layer of the rewiring is required to be higher after the reliability test. Examples of the reliability test performed here include a high-temperature storage test that is stored in air at a high temperature of 125°C or higher for 100 hours or more; the wiring is assembled and a voltage is applied to confirm the temperature in the air at about 125°C. High-temperature operation test of the operation under the condition of storage for more than 100 hours; temperature cycle test in which the low temperature state of about -65 ~ -40 ℃ and the high temperature state of about 125 ~ 150 ℃ are repeated in cycles in the air; at a temperature of 85 High-temperature and high-humidity storage test for storage in a water vapor environment with a temperature above ℃ and a humidity of more than 85%; high-temperature and high-humidity bias test for assembling the wiring and applying the voltage while performing the same test; passing 260°C in air or nitrogen multiple times Reflow soldering test of the reflow soldering furnace, etc. However, in the case of the high-temperature storage test in the reliability test described above, there is a problem that a void is generated at the interface where the Cu layer of the rewiring and the resin layer contact after the test. If voids are generated at the interface between the Cu layer and the resin layer, the adhesion between the two will decrease. [Prior Art Literature] [Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2001-338947

[發明所欲解決之問題] 本發明係鑒於此種先前實際情況研究所得者，其目的在於提供一種能夠獲得於高溫保存(high temperature storage)試驗後於Cu層與樹脂層接觸之界面處不會產生空隙而密接性較高之樹脂層的感光性樹脂組合物、使用該感光性樹脂組合物之硬化浮凸圖案之形成方法、及具有該硬化浮凸圖案而成之半導體裝置。 [解決問題之技術手段] 本發明者等人發現，藉由將特定之感光性樹脂與特定之塑化劑加以組合，而獲得一種能夠形成硬化膜之感光性樹脂組合物，由該硬化膜可獲得於高溫保存(high temperature storage)試驗後，於Cu層與樹脂層接觸之界面處不會產生空隙而密接性較高的樹脂層，從而完成本發明。即，本發明如下所述。 [1]一種感光性樹脂組合物，其包含： (A)選自由聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽、聚羥基醯胺、聚胺基醯胺、聚醯胺、聚醯胺醯亞胺、聚醯亞胺、聚苯并㗁唑、酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份， (B)塑化劑：以上述(A)樹脂100質量份為基準計0.1～50質量份，以及 (C)感光劑：以上述(A)樹脂100質量份為基準計1～50質量份。 [2]如[1]記載之感光性樹脂組合物，其中上述(A)樹脂為選自由包含下述通式(1)之聚醯亞胺前驅物、包含下述通式(4)之聚醯胺、包含下述通式(5)之聚㗁唑前驅物、包含下述通式(6)之聚醯亞胺、以及酚醛清漆、聚羥基苯乙烯及包含下述通式(7)之酚樹脂所組成之群中之至少一種。下述通式(1)為 [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、碳數1～30之飽和脂肪族基、芳香族基、或下述通式(2)： [化2]

(式中，R₃ 、R₄ 及R₅ 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、或碳數1～4之飽和脂肪族基、或下述通式(3)： [化3]

(式中，R₆ 、R₇ 及R₈ 分別獨立為氫原子或碳數1～3之有機基，並且m₂ 為2～10之整數)所表示之一價之銨離子}所表示之作為聚醯亞胺前驅物之聚醯胺酸、聚醯胺酸酯或聚醯胺酸鹽，下述通式(4)為具有 [化4]

{式中，X₂ 為碳數6～15之3價之有機基，Y₂ 為碳數6～35之2價之有機基，且可為同一結構或具有複數種結構，R₉ 為具有至少一個碳數3～20之自由基聚合性之不飽和鍵結基的有機基，並且n₂ 為1～1000之整數} 所表示之結構之聚醯胺，下述通式(5)為具有 [化5]

{式中，Y₃ 為具有碳原子之4價之有機基，Y₄ 、X₃ 及X₄ 分別獨立為具有2個以上之碳原子之2價之有機基，n₃ 為1～1000之整數，n₄ 為0～500之整數，n₃ /(n₃ ＋n₄ )＞0.5，並且包含X₃ 及Y₃ 之n₃ 個二羥基二醯胺單元以及包含X₄ 及Y₄ 之n₄ 個二醯胺單元之排列順序為任意} 所表示之結構之作為聚㗁唑前驅物之聚羥基醯胺，並且下述通式(6)為具有 [化6]

{式中，X₅ 為4～14價之有機基，Y₅ 為2～12價之有機基，R₁₀ 及R₁₁ 分別獨立地表示具有至少一個選自酚性羥基、磺酸基或硫醇基中之基的有機基，n₅ 為3～200之整數，並且m₃ 及m₄ 表示0～10之整數} 所表示之結構之聚醯亞胺，並且下述通式(7)為 [化7]

{式中，a為1～3之整數，b為0～3之整數，1≦(a＋b)≦4，R₁₂ 表示選自由碳數1～20之1價之有機基、鹵素原子、硝基及氰基所組成之群中之1價之取代基，於b為2或3之情形時，複數個R₁ 相互可相同或亦可不同，X表示選自由可具有不飽和鍵之碳數2～10之2價之脂肪族基、碳數3～20之2價之脂環式基、下述通式(8)： [化8]

(式中，p為1～10之整數)所表示之2價之伸烷氧基、及具有碳數6～12之芳香族環之2價之有機基所組成之群中之2價之有機基}所表示之酚樹脂。 [3]如[1]或[2]記載之感光性樹脂組合物，其中上述通式(7)中之X為選自由下述通式(9)： [化9]

{式中，R₁₃ 、R₁₄ 、R₁₅ 及R₁₆ 分別獨立為氫原子、碳數1～10之1價之脂肪族基、或氫原子之一部分或全部被取代為氟原子而成之碳數1～10之1價之脂肪族基，n₆ 為0～4之整數，且n₆ 為1～4之整數之情形時之R₁₇ 為鹵素原子、羥基、或碳數1～12之1價之有機基，至少1個R₆ 為羥基，n₆ 為2～4之整數之情形時之複數個R₁₇ 相互可相同或亦可不同}所表示之2價之基、及下述通式(10)： [化10]

{式中，R₁₈ 、R₁₉ 、R₂₀ 及R₂₁ 分別獨立表示氫原子、碳數1～10之1價之脂肪族基、或氫原子之一部分或全部被取代為氟原子而成之碳數1～10之1價之脂肪族基，W為單鍵、選自由可經氟原子取代之碳數1～10之脂肪族基、可經氟原子取代之碳數3～20之脂環式基、下述通式(8)： [化11]

(式中，p為1～10之整數)所表示之2價之伸烷氧基、及下述式(11)： [化12]

所表示之2價之基所組成之群中之2價之基}所表示之2價之基所組成之群中之2價之有機基。 [4]如[1]記載之感光性樹脂組合物，其中上述(B)塑化劑為選自由下述通式(7)： [化13]

{式中，X為包含碳數為1以上且15以下之飽和烴或不飽和烴或芳香族烴之結構，n為1～4之整數，於n為2以上之情形時，R分別可相同亦可不同，為碳數為2以上且15以下之飽和烴或不飽和烴或芳香族烴}所表示、下述通式(8)： [化14]

{式中，m為1～4之整數，於m為2以上之情形時，R分別可相同亦可不同，表示碳數為2以上且15以下之飽和烴或不飽和烴或芳香族烴}所表示、及下述通式(9)： [化15]

{式中，Y為包含碳數為1以上且10以下之飽和烴或不飽和烴或芳香族烴之結構，R分別可相同亦可不同，表示碳數為2以上且15以下之飽和烴或不飽和烴或芳香族烴}所組成之群中之至少一種。 [5]一種硬化浮凸圖案之製造方法，其包括：步驟(1)，其係藉由於基板上塗佈如[1]至[4]中任一項記載之感光性樹脂組合物而於上述基板上形成感光性樹脂層；步驟(2)，其係對上述感光性樹脂層進行曝光；步驟(3)，其係將上述曝光後之感光性樹脂層進行顯影而形成浮凸圖案；及步驟(4)，其係藉由對上述浮凸圖案進行加熱處理而形成硬化浮凸圖案。 [6]如[5]記載之方法，其中上述基板係由銅或銅合金形成。又，本發明者等人發現，藉由於感光性樹脂組合物中調配奈米粒子，可獲得能夠形成於高溫保存試驗後與Cu層接觸之界面處之空隙產生被抑制之硬化膜的感光性樹脂組合物。本發明亦可應用於以下之態樣。 [1]一種感光性樹脂組合物，其包含 (A)選自由聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽、聚羥基醯胺、聚胺基醯胺、聚醯胺、聚醯胺醯亞胺、聚醯亞胺、聚苯并㗁唑、以及酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份， (B-1)奈米粒子：以上述(A)樹脂100質量份為基準計0.01～10質量份，以及 (C)感光劑：以上述(A)樹脂100質量份為基準計1～50質量份。 [2]如[1]記載之感光性樹脂組合物，其中上述(A)樹脂為選自由包含下述通式(1)之聚醯亞胺前驅物、包含下述通式(4)之聚醯胺、包含下述通式(5)之聚㗁唑前驅物、包含下述通式(6)之聚醯亞胺、以及酚醛清漆、聚羥基苯乙烯及包含下述通式(7)之酚樹脂所組成之群中之至少一種。下述通式(1)為 [化16]

{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、碳數1～30之飽和脂肪族基、芳香族基、或下述通式(2)： [化17]

(式中，R₃ 、R₄ 及R₅ 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、或碳數1～4之飽和脂肪族基、或下述通式(3)： [化18]

(式中，R₆ 、R₇ 及R₈ 分別獨立為氫原子或碳數1～3之有機基，並且m₂ 為2～10之整數)所表示之一價之銨離子}所表示之作為聚醯亞胺前驅物之聚醯胺酸、聚醯胺酸酯或聚醯胺酸鹽，下述通式(4)為具有 [化19]

{式中，X₂ 為碳數6～15之3價之有機基，Y₂ 為碳數6～35之2價之有機基，且可為同一結構或具有複數種結構，R₉ 為具有至少一個碳數3～20之自由基聚合性之不飽和鍵結基的有機基，並且n₂ 為1～1000之整數} 所表示之結構之聚醯胺，下述通式(5)為具有 [化20]

{式中，Y₃ 為具有碳原子之4價之有機基，Y₄ 、X₃ 及X₄ 分別獨立為具有2個以上之碳原子之2價之有機基，n₃ 為1～1000之整數，n₄ 為0～500之整數，n₃ /(n₃ ＋n₄ )＞0.5，並且包含X₃ 及Y₃ 之n₃ 個二羥基二醯胺單元以及包含X₄ 及Y₄ 之n₄ 個二醯胺單元之排列順序為任意} 所表示之結構之作為聚㗁唑前驅物之聚羥基醯胺，下述通式(6)為具有 [化21]

{式中，X₅ 為4～14價之有機基，Y₅ 為2～12價之有機基，R₁₀ 及R₁₁ 分別獨立地表示具有至少一個選自酚性羥基、磺酸基或硫醇基中之基的有機基，n₅ 為3～200之整數，並且m₃ 及m₄ 表示0～10之整數} 所表示之結構之聚醯亞胺，並且下述通式(7)為 [化22]

{式中，a為1～3之整數，b為0～3之整數，1≦(a＋b)≦4，R₁₂ 表示選自由碳數1～20之1價之有機基、鹵素原子、硝基及氰基所組成之群中之1價之取代基，於b為2或3之情形時，複數個R₁ 相互可相同或亦可不同，X表示選自由可具有不飽和鍵之碳數2～10之2價之脂肪族基、碳數3～20之2價之脂環式基、下述通式(8)： [化23]

(式中，p為1～10之整數)所表示之2價之伸烷氧基、及具有碳數6～12之芳香族環之2價之有機基所組成之群中之2價之有機基}所表示之酚樹脂。 [3]如[1]或[2]記載之感光性樹脂組合物，其中上述感光性樹脂組合物包含具有上述通式(7)所表示之重複單元之酚樹脂，上述通式(7)中之X為選自由下述通式(9)： [化24]

{式中，R₁₃ 、R₁₄ 、R₁₅ 及R₁₆ 分別獨立為氫原子、碳數1～10之1價之脂肪族基、或氫原子之一部分或全部被取代為氟原子而成之碳數1～10之1價之脂肪族基，n₆ 為0～4之整數，且n₆ 為1～4之整數之情形時之R₁₇ 為鹵素原子、羥基、或碳數1～12之1價之有機基，至少1個R₁₇ 為羥基，n₆ 為2～4之整數之情形時之複數個R₁₇ 相互可相同或亦可不同}所表示之2價之基、及下述通式(10)： [化25]

{式中，R₁₈ 、R₁₉ 、R₂₀ 及R₂₁ 分別獨立表示氫原子、碳數1～10之1價之脂肪族基、或氫原子之一部分或全部被取代為氟原子而成之碳數1～10之1價之脂肪族基，W為單鍵、選自由可經氟原子取代之碳數1～10之脂肪族基、可經氟原子取代之碳數3～20之脂環式基、下述通式(8)： [化26]

(式中，p為1～10之整數)所表示之2價之伸烷氧基、及下述式(11)： [化27]

所表示之2價之基所組成之群中之2價之基}所表示之2價之基所組成之群中之2價之有機基。 [4]一種硬化浮凸圖案之製造方法，其包括：步驟(1)，其係藉由於基板上塗佈如[1]至[3]中任一項記載之感光性樹脂組合物而於上述基板上形成感光性樹脂層；步驟(2)，其係對上述感光性樹脂層進行曝光；步驟(3)，其係將上述曝光後之感光性樹脂層進行顯影而形成浮凸圖案；及步驟(4)，其係藉由對上述浮凸圖案進行加熱處理而形成硬化浮凸圖案。 [5]如[4]記載之方法，其中上述基板係由銅或銅合金形成。 [6]一種半導體裝置，其包含藉由如[4]或[5]記載之製造方法所獲得之硬化浮凸圖案。又，本發明者等人發現，藉由將感光性樹脂與特定之熱交聯劑加以組合，可獲得能夠形成於高溫保存試驗後與Cu層接觸之界面處之空隙產生被抑制之硬化膜的負型感光性樹脂組合物。本發明亦可應用於以下之態樣。 [1]一種負型感光性樹脂組合物，其包含 (A)選自由聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽所組成之群中之至少一種樹脂：100質量份， (B-2)熱交聯劑：以上述(A)樹脂100質量份為基準計0.01～50質量份，以及 (C)感光劑：以上述(A)樹脂100質量份為基準計1～50質量份。 [2]如[1]記載之感光性樹脂組合物，其中上述(A)樹脂為選自由包含下述通式(1)之聚醯亞胺前驅物、包含下述通式(4)之聚醯胺所組成之群中之至少一種。下述通式(1)為 [化28]

{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、碳數1～30之飽和脂肪族基、芳香族基、或下述通式(2)： [化29]

(式中，R₃ 、R₄ 及R₅ 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、或碳數1～4之飽和脂肪族基、或下述通式(3)： [化30]

(式中，R₆ 、R₇ 及R₈ 分別獨立為氫原子或碳數1～3之有機基，並且m₂ 為2～10之整數)所表示之一價之銨離子}所表示之作為聚醯亞胺前驅物之聚醯胺酸、聚醯胺酸酯或聚醯胺酸鹽，下述通式(4)為具有 [化31]

{式中，X₂ 為碳數6～15之3價之有機基，Y₂ 為碳數6～35之2價之有機基，且可為同一結構或具有複數種結構，R₉ 為具有至少一個碳數3～20之自由基聚合性之不飽和鍵結基的有機基，並且n₂ 為1～1000之整數} 所表示之結構之聚醯胺、或具有該結構之聚醯亞胺。 [3]如[1]記載之感光性樹脂組合物，其中上述(B-2)熱交聯劑為選自由(B-2-1)含有羥甲基或烷氧基烷基之至少一者之化合物、(B-2-2)含環氧乙烷環之化合物、(B-2-3)含異氰酸酯基之化合物、(B-2-4)含雙順丁烯二醯亞胺基之化合物、(B-2-5)含醛基之化合物、(B-2-6)含氧雜環丁烷環之化合物、(B-2-7)含苯并㗁𠯤環之化合物、(B-2-8)含㗁唑啉環之化合物、(B-2-9)含碳二醯亞胺基之化合物、(B-2-10)烯丙基化合物、(B-2-11)三𠯤硫醇化合物、及(B-2-12)金屬螯合化合物所組成之群中之至少一種。 [4]如[1]或[3]記載之感光性樹脂組合物，其中上述(B-2)熱交聯劑為(B-2-1)含有羥甲基或烷氧基烷基之至少一者之化合物。 [5]如[1]或[3]記載之感光性樹脂組合物，其中上述(B-2)熱交聯劑具有下述通式(TS1)： [化32]

{式中，Rs1為氫原子、選自由甲基、乙基、正丙基及異丙基所組成之群中之一價之基，Rs2為選自由羥基、碳原子數1～10之烷基、碳原子數1～10之烷氧基、碳原子數1～10之酯基、及胺基甲酸酯基所組成之群中之基，mm1為1～5之整數，mm2為0～4之整數。此處，1≦(mm1＋mm2)≦5，nn1為1～4之整數，V₁ 於nn1＝1時為CH₂ ORs1，於nn1＝2～4時為單鍵或2～4價之有機基。於CH₂ ORs1及R₁₀ 存在複數個之情形時，該等相互可相同亦可不同} 所表示之結構。 [6]一種硬化浮凸圖案之製造方法，其包括：步驟(1)，其係藉由於基板上塗佈如[1]至[5]中任一項記載之感光性樹脂組合物而於上述基板上形成感光性樹脂層；步驟(2)，其係對上述感光性樹脂層進行曝光；步驟(3)，其係將上述曝光後之感光性樹脂層進行顯影而形成浮凸圖案；及步驟(4)，其係藉由對上述浮凸圖案進行加熱處理而形成硬化浮凸圖案。 [7]如[6]記載之方法，其中上述基板係由銅或銅合金形成。又，本發明者等人發現，藉由將特定之感光性樹脂與特定之含氟疏水性化合物加以組合，而獲得一種能夠形成硬化膜之感光性樹脂組合物，由該硬化膜可獲得於高溫保存(high temperature storage)試驗後，於Cu層之與樹脂層接觸之界面處不會產生空隙而密接性較高的樹脂層。本發明亦可應用於以下之態樣。 [1]一種感光性樹脂組合物，其包含 (A)選自由聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽、聚羥基醯胺、聚胺基醯胺、聚醯胺、聚醯胺醯亞胺、聚醯亞胺、聚苯并㗁唑、酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份， (B-3)含氟疏水性化合物：以上述(A)樹脂100質量份為基準計0.01～50質量份，以及 (C)感光劑：以上述(A)樹脂100質量份為基準計1～50質量份。 [2]如[1]記載之感光性樹脂組合物，其中上述(A)樹脂為選自由包含下述通式(1)之聚醯亞胺前驅物、包含下述通式(4)之聚醯胺、包含下述通式(5)之聚㗁唑前驅物、包含下述通式(6)之聚醯亞胺、以及酚醛清漆、聚羥基苯乙烯及包含下述通式(7)之酚樹脂所組成之群中之至少一種。下述通式(1)為 [化33]

{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、碳數1～30之飽和脂肪族基、芳香族基、或下述通式(2)： [化34]

(式中，R₃ 、R₄ 及R₅ 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、或碳數1～4之飽和脂肪族基、或下述通式(3)： [化35]

(式中，R₆ 、R₇ 及R₈ 分別獨立為氫原子或碳數1～3之有機基，並且m₂ 為2～10之整數)所表示之一價之銨離子}所表示之作為聚醯亞胺前驅物之聚醯胺酸、聚醯胺酸酯或聚醯胺酸鹽，下述通式(4)為具有 [化36]

{式中，X₂ 為碳數6～15之3價之有機基，Y₂ 為碳數6～35之2價之有機基，且可為同一結構或具有複數種結構，R₉ 為具有至少一個碳數3～20之自由基聚合性之不飽和鍵結基的有機基，並且n₂ 為1～1000之整數} 所表示之結構之聚醯胺，下述通式(5)為具有 [化37]

{式中，Y₃ 為具有碳原子之4價之有機基，Y₄ 、X₃ 及X₄ 分別獨立為具有2個以上之碳原子之2價之有機基，n₃ 為1～1000之整數，n₄ 為0～500之整數，n₃ /(n₃ ＋n₄ )＞0.5，並且包含X₃ 及Y₃ 之n₃ 個二羥基二醯胺單元以及包含X₄ 及Y₄ 之n₄ 個二醯胺單元之排列順序為任意} 所表示之結構之作為聚㗁唑前驅物之聚羥基醯胺，下述通式(6)為具有 [化38]

{式中，X₅ 為4～14價之有機基，Y₅ 為2～12價之有機基，R₁₀ 及R₁₁ 分別獨立地表示具有至少一個選自酚性羥基、磺酸基或硫醇基中之基的有機基，n₅ 為3～200之整數，並且m₃ 及m₄ 表示0～10之整數} 所表示之結構之聚醯亞胺，並且下述通式(7)為 [化39]

{式中，a為1～3之整數，b為0～3之整數，1≦(a＋b)≦4，R₁₂ 表示選自由碳數1～20之1價之有機基、鹵素原子、硝基及氰基所組成之群中之1價之取代基，於b為2或3之情形時，複數個R₁ 相互可相同或亦可不同，X表示選自由可具有不飽和鍵之碳數2～10之2價之脂肪族基、碳數3～20之2價之脂環式基、下述通式(8)： [化40]

(式中，p為1～10之整數)所表示之2價之伸烷氧基、及具有碳數6～12之芳香族環之2價之有機基所組成之群中之2價之有機基}所表示之酚樹脂。 [3]如[1]或[2]記載之感光性樹脂組合物，其中上述通式(7)中之X為選自由下述通式(9)： [化41]

{式中，R₁₃ 、R₁₄ 、R₁₅ 及R₁₆ 分別獨立為氫原子、碳數1～10之1價之脂肪族基、或氫原子之一部分或全部被取代為氟原子而成之碳數1～10之1價之脂肪族基，n₆ 為0～4之整數，且n₆ 為1～4之整數之情形時之R₁₇ 為鹵素原子、羥基、或碳數1～12之1價之有機基，至少1個R₆ 為羥基，n₆ 為2～4之整數之情形時之複數個R₁₇ 相互可相同或亦可不同}所表示之2價之基、及下述通式(10)： [化42]

{式中，R₁₈ 、R₁₉ 、R₂₀ 及R₂₁ 分別獨立表示氫原子、碳數1～10之1價之脂肪族基、或氫原子之一部分或全部被取代為氟原子而成之碳數1～10之1價之脂肪族基，W為單鍵、選自由可經氟原子取代之碳數1～10之脂肪族基、可經氟原子取代之碳數3～20之脂環式基、下述通式(8)： [化43]

(式中，p為1～10之整數)所表示之2價之伸烷氧基、及下述式(11)： [化44]

所表示之2價之基所組成之群中之2價之基}所表示之2價之基所組成之群中之2價之有機基。 [4]如[1]至[3]中任一項記載之感光性樹脂組合物，其中上述(B-3)含氟疏水性化合物之分子中之氟原子之重量比率為30質量%以上且80質量%以下。 [5]如[1]至[4]中任一項記載之感光性樹脂組合物，其中上述(B-3)含氟疏水性化合物於分子內具有至少1個不飽和雙鍵。 [6]如[1]至[5]中任一項記載之感光性樹脂組合物，其中上述(B-3)含氟疏水性化合物為具有全氟基之丙烯酸酯或甲基丙烯酸酯化合物。 [7]一種硬化浮凸圖案之製造方法，其包括步驟(1)，其係藉由於基板上塗佈如[1]至[6]中任一項記載之感光性樹脂組合物而於上述基板上形成感光性樹脂層；步驟(2)，其係對上述感光性樹脂層進行曝光；步驟(3)，其係將上述曝光後之感光性樹脂層進行顯影而形成浮凸圖案；及步驟(4)，其係藉由對上述浮凸圖案進行加熱處理而形成硬化浮凸圖案。 [8]如[7]記載之方法，其中上述基板係由銅或銅合金形成。 [發明之效果] 根據本發明，可提供一種能夠獲得於高溫保存(high temperature storage)試驗後於Cu層與樹脂層之界面處不會產生空隙而密接性較高之感光性樹脂的感光性樹脂組合物、使用該感光性樹脂組合物之硬化浮凸圖案之形成方法、及具有該硬化浮凸圖案而成之半導體裝置。[Problems to be Solved by the Invention] The present invention has been obtained in view of such previous actual situation, and its purpose is to provide a method that can be obtained at the interface where the Cu layer and the resin layer are in contact after the high temperature storage test. A photosensitive resin composition having a resin layer with a high adhesiveness that generates voids, a method of forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern. [Technical Means for Solving the Problem] The present inventors have found that by combining a specific photosensitive resin with a specific plasticizer, a photosensitive resin composition capable of forming a cured film can be obtained from which After obtaining a high temperature storage test, a resin layer with a high adhesiveness does not generate a void at the interface between the Cu layer and the resin layer, thereby completing the present invention. That is, the present invention is as follows. [1] A photosensitive resin composition, comprising: (A) selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, At least one resin of the group consisting of polyimide amide imine, polyimide, polybenzoxazole, novolac, polyhydroxystyrene and phenol resin: (B) plasticizer: The above (A) 100 parts by mass of the resin is based on 0.1 to 50 parts by mass, and (C) the photosensitizer: 1 to 50 parts by mass based on the (A) 100 parts by mass of the resin. [2] The photosensitive resin composition according to [1], wherein the resin (A) is selected from a polyimide precursor containing the following general formula (1) and a polymer containing the following general formula (4) Acetamide, polyazole precursor containing the following general formula (5), polyimide containing the following general formula (6), and novolac, polyhydroxystyrene, and containing the following general formula (7) At least one of the group consisting of phenol resin. The following general formula (1) is [Chem 1]

{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 and a saturated carbon number of 1 to 30 An aliphatic group, an aromatic group, or the following general formula (2): [Chemical 2]

(In the formula, R ₃ , R ₄ and R ₅ 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) a monovalent organic group represented by 1 or a carbon number 1 Saturated aliphatic group of ～4, or the following general formula (3): [Chemical 3]

(In the formula, R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10) The monovalent ammonium ion represented by} The polyimide precursor, polyamic acid, polyamic acid ester or polyamino acid salt, the following general formula (4) is represented by [Chem. 4]

{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or have multiple structures, and R ₉ has at least An organic group having a radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n ₂ is an integer of 1 to 1000} Polyamide having a structure represented by the following general formula (5) having [ Change 5]

{In the formula, Y ₃ is a tetravalent organic group having carbon atoms, Y ₄ , X ₃ and X ₄ are each independently a divalent organic group having 2 or more carbon atoms, and n ₃ is an integer of 1 to 1000 , n ₄ is an integer of 0 to _{_{500., n 3 / (n 3 +}} n 4)> 0.5, and comprises X ₃ and Y ₃ of n ₃ dihydroxy two Amides unit and comprising X n ₄ and Y ₄ of ₄ The arrangement order of the diamide units is arbitrary} The polyhydroxyamide as the precursor of polyoxazole is represented by the structure represented by }, and the following general formula (6) has [Chem 6]

{In the formula, X ₅ is an organic group of 4 to 14 valences, Y ₅ is an organic group of 2 to 12 valences, R ₁₀ and R ₁₁ independently represent at least one selected from phenolic hydroxyl groups, sulfonic acid groups or thiols The organic group of the group in the group, n ₅ is an integer of 3 to 200, and m ₃ and m ₄ represent an integer of 0 to 10} Polyimide of the structure represented by the following general formula (7) is [ Change 7]

{In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, 1≦(a+b)≦4, R ₁₂ represents a monovalent organic group selected from carbon number 1-20, halogen atom, nitro group A monovalent substituent in the group consisting of and cyano, when b is 2 or 3, a plurality of R ₁ may be the same or different from each other, X represents a carbon number 2 selected from the group consisting of an unsaturated bond ～10 divalent aliphatic group, C 3-20 divalent alicyclic group, the following general formula (8): [化8]

(In the formula, p is an integer of 1-10) The divalent organic group represented by the divalent alkoxy group represented by the divalent organic group and the divalent organic group having an aromatic ring having 6 to 12 carbon atoms Phenolic resin represented by base}. [3] The photosensitive resin composition according to [1] or [2], wherein X in the general formula (7) is selected from the following general formula (9): [Chem 9]

{In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon in which a part or all of a hydrogen atom is substituted with a fluorine atom In the case of a monovalent aliphatic group of 1 to 10, n ₆ is an integer of 0 to 4, and n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or a carbon number of 1 to 12 Valent organic group, when at least one R ₆ is a hydroxyl group, and n ₆ is an integer of 2 to 4, the plural R ₁₇ may be the same as or different from each other} the divalent group represented by }, and the following general formula (10): [Chem 10]

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ independently represent a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon in which a part or all of a hydrogen atom is substituted with a fluorine atom The monovalent aliphatic group of 1 to 10, W is a single bond, is selected from the aliphatic group of 1 to 10 carbon atoms which may be substituted by fluorine atoms, and the alicyclic formula of 3 to 20 carbon atoms which may be substituted by fluorine atoms The following general formula (8): [Chem 11]

(In the formula, p is an integer of 1 to 10) The divalent alkoxy group represented by and the following formula (11): [Chem 12]

The divalent base in the group consisting of the represented divalent base} The divalent organic group in the group consisting of the represented divalent base}. [4] The photosensitive resin composition according to [1], wherein the plasticizer (B) is selected from the following general formula (7): [Chem 13]

{In the formula, X is a structure containing saturated or unsaturated hydrocarbons or aromatic hydrocarbons having a carbon number of 1 or more and 15 or less, n is an integer of 1 to 4, and when n is 2 or more, R may be the same It may also be different, and is represented by saturated or unsaturated hydrocarbons or aromatic hydrocarbons having a carbon number of 2 or more and 15 or less, and the following general formula (8):

{In the formula, m is an integer of 1 to 4, and when m is 2 or more, R may be the same or different, indicating a saturated or unsaturated hydrocarbon or aromatic hydrocarbon with a carbon number of 2 or more and 15 or less} Represented by the following general formula (9): [Chem. 15]

{In the formula, Y is a structure containing a saturated hydrocarbon or an unsaturated hydrocarbon or an aromatic hydrocarbon having a carbon number of 1 or more and 10 or less, and R may be the same or different, and represents a saturated hydrocarbon or a carbon number of 2 or more and 15 or less At least one of the group consisting of unsaturated hydrocarbons or aromatic hydrocarbons. [5] A method for manufacturing a hardened relief pattern, comprising: step (1), which is performed by applying the photosensitive resin composition as described in any one of [1] to [4] on the substrate Forming a photosensitive resin layer on the substrate; step (2), which exposes the photosensitive resin layer; step (3), which develops the exposed photosensitive resin layer to form a relief pattern; and steps (4) A heat-relief pattern is formed by subjecting the relief pattern to heat treatment. [6] The method according to [5], wherein the substrate is formed of copper or a copper alloy. Furthermore, the present inventors have found that by mixing nanoparticles in the photosensitive resin composition, it is possible to obtain a photosensitive resin capable of forming a cured film in which voids at the interface with the Cu layer after the high-temperature storage test are suppressed from being generated combination. The present invention can also be applied to the following aspects. [1] A photosensitive resin composition comprising (A) selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, poly At least one resin in the group consisting of amide imide, polyimide, polybenzoxazole, and novolac, polyhydroxystyrene, and phenol resin: 100 parts by mass, (B-1) nanoparticles : 0.01 to 10 parts by mass based on 100 parts by mass of the above (A) resin, and (C) photosensitizer: 1 to 50 parts by mass based on 100 parts by mass of the above (A) resin. [2] The photosensitive resin composition according to [1], wherein the resin (A) is selected from a polyimide precursor containing the following general formula (1) and a polymer containing the following general formula (4) Acetamide, polyazole precursor containing the following general formula (5), polyimide containing the following general formula (6), and novolac, polyhydroxystyrene, and containing the following general formula (7) At least one of the group consisting of phenol resin. The following general formula (1) is [Chem 16]

{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 and a saturated carbon number of 1 to 30 An aliphatic group, an aromatic group, or the following general formula (2): [Chem. 17]

(In the formula, R ₃ , R ₄ and R ₅ 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) a monovalent organic group represented by 1 or a carbon number 1 Saturated aliphatic group of ～4, or the following general formula (3): [Chem 18]

(In the formula, R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10) The monovalent ammonium ion represented by} Polyamide acid, polyamide acid ester or polyamide acid salt of polyimide precursor, the following general formula (4) has

{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or have multiple structures, and R ₉ has at least An organic group having a radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n ₂ is an integer of 1 to 1000} Polyamide having a structure represented by the following general formula (5) having [ Chemical 20]

{In the formula, Y ₃ is a tetravalent organic group having carbon atoms, Y ₄ , X ₃ and X ₄ are each independently a divalent organic group having 2 or more carbon atoms, and n ₃ is an integer of 1 to 1000 , n ₄ is an integer of 0 to _{_{500., n 3 / (n 3 +}} n 4)> 0.5, and comprises X ₃ and Y ₃ of n ₃ dihydroxy two Amides unit and comprising X n ₄ and Y ₄ of ₄ The arrangement order of the diacrylamide units is arbitrary} The polyhydroxyamide which is a precursor of polyoxazole with the structure represented by the following general formula (6) is represented by [Chem. 21]

{In the formula, X ₅ is an organic group of 4 to 14 valences, Y ₅ is an organic group of 2 to 12 valences, R ₁₀ and R ₁₁ independently represent at least one selected from phenolic hydroxyl groups, sulfonic acid groups or thiols The organic group of the group in the group, n ₅ is an integer of 3 to 200, and m ₃ and m ₄ represent an integer of 0 to 10} Polyimide of the structure represented by the following general formula (7) is [ Chemical 22]

{In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, 1≦(a+b)≦4, R ₁₂ represents a monovalent organic group selected from carbon number 1-20, halogen atom, nitro group A monovalent substituent in the group consisting of and cyano, when b is 2 or 3, a plurality of R ₁ may be the same or different from each other, X represents a carbon number 2 selected from the group consisting of an unsaturated bond ～10 divalent aliphatic group, C 3-20 divalent alicyclic group, the following general formula (8): [Chem 23]

(In the formula, p is an integer of 1-10) The divalent organic group represented by the divalent alkoxy group represented by the divalent organic group and the divalent organic group having an aromatic ring having 6 to 12 carbon atoms Phenolic resin represented by base}. [3] The photosensitive resin composition according to [1] or [2], wherein the photosensitive resin composition contains a phenol resin having a repeating unit represented by the above general formula (7), in the above general formula (7) X is selected from the following general formula (9): [Chem 24]

{In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon in which a part or all of a hydrogen atom is substituted with a fluorine atom In the case of a monovalent aliphatic group of 1 to 10, n ₆ is an integer of 0 to 4, and n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or a carbon number of 1 to 12 Valent organic group, when at least one R ₁₇ is a hydroxy group, and n ₆ is an integer of 2 to 4, the plural R ₁₇ groups may be the same or different from each other} the divalent group represented by }, and the following general formula (10): [Chem 25]

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ independently represent a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon in which a part or all of a hydrogen atom is substituted with a fluorine atom The monovalent aliphatic group of 1 to 10, W is a single bond, is selected from the aliphatic group of 1 to 10 carbon atoms which may be substituted by fluorine atoms, and the alicyclic formula of 3 to 20 carbon atoms which may be substituted by fluorine atoms Base, the following general formula (8): [Chem 26]

(In the formula, p is an integer of 1 to 10) The divalent alkoxy group represented by and the following formula (11): [Chem 27]

The divalent base in the group consisting of the represented divalent base} The divalent organic group in the group consisting of the represented divalent base}. [4] A method for manufacturing a hardened relief pattern, comprising: Step (1), which is performed by coating the photosensitive resin composition as described in any one of [1] to [3] on the substrate Forming a photosensitive resin layer on the substrate; step (2), which exposes the photosensitive resin layer; step (3), which develops the exposed photosensitive resin layer to form a relief pattern; and steps (4) A heat-relief pattern is formed by subjecting the relief pattern to heat treatment. [5] The method according to [4], wherein the substrate is formed of copper or a copper alloy. [6] A semiconductor device including the hardened relief pattern obtained by the manufacturing method described in [4] or [5]. Furthermore, the present inventors have found that by combining a photosensitive resin with a specific thermal cross-linking agent, it is possible to obtain a cured film that can be formed at the interface where it contacts the Cu layer after the high-temperature storage test is suppressed Negative photosensitive resin composition. The present invention can also be applied to the following aspects. [1] A negative photosensitive resin composition comprising (A) at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, and polyamic acid salt: 100 parts by mass, ( B-2) Thermal crosslinking agent: 0.01-50 parts by mass based on (A) 100 parts by mass of the resin, and (C) Sensitizer: 1-50 parts by mass based on (A) 100 parts by mass of the resin Copies. [2] The photosensitive resin composition according to [1], wherein the resin (A) is selected from a polyimide precursor containing the following general formula (1) and a polymer containing the following general formula (4) At least one of the groups formed by amides. The following general formula (1) is [Chem 28]

{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 and a saturated carbon number of 1 to 30 An aliphatic group, an aromatic group, or the following general formula (2): [Chem 29]

(In the formula, R ₃ , R ₄ and R ₅ 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) a monovalent organic group represented by 1 or a carbon number 1 ～4 saturated aliphatic group, or the following general formula (3): [Chem 30]

(In the formula, R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10) The monovalent ammonium ion represented by} The polyimide precursor, polyamic acid, polyamic acid ester or polyamic acid salt, the following general formula (4) has [Chem. 31]

{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or have multiple structures, and R ₉ has at least An organic group having a radically polymerizable unsaturated bond group with a carbon number of 3 to 20, and n ₂ is an integer of 1 to 1000} a polyamide having a structure represented by }, or a polyimide having the structure. [3] The photosensitive resin composition according to [1], wherein the (B-2) thermal crosslinking agent is at least one selected from (B-2-1) containing a hydroxymethyl group or an alkoxyalkyl group Compound, (B-2-2) compound containing ethylene oxide ring, (B-2-3) compound containing isocyanate group, (B-2-4) compound containing bis-cis-butadiene diimide group Compound, (B-2-5) compound containing aldehyde group, (B-2-6) compound containing oxetane ring, (B-2-7) compound containing benzo ring, (B -2-8) Compounds containing oxazoline rings, (B-2-9) compounds containing carbodiimide groups, (B-2-10) allyl compounds, (B-2-11) three 𠯤 At least one of the group consisting of thiol compound and (B-2-12) metal chelate compound. [4] The photosensitive resin composition according to [1] or [3], wherein the (B-2) thermal crosslinking agent is (B-2-1) at least one containing a hydroxymethyl group or an alkoxyalkyl group One of the compounds. [5] The photosensitive resin composition according to [1] or [3], wherein the (B-2) thermal crosslinking agent has the following general formula (TS1):

{In the formula, Rs1 is a hydrogen atom, a monovalent group selected from the group consisting of methyl, ethyl, n-propyl, and isopropyl, and Rs2 is selected from the group consisting of a hydroxyl group and an alkyl group having 1 to 10 carbon atoms. , A group consisting of an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a carbamate group, mm1 is an integer of 1 to 5, mm2 is 0 to 4 An integer. Here, 1≦(mm1+mm2)≦5, nn1 is an integer of 1 to 4, V ₁ is CH ₂ ORs1 when nn1=1, and a single bond or a 2-4 valent organic group when nn1=2 to 4. When there are a plurality of CH ₂ ORs1 and R ₁₀ , these structures may be the same as or different from each other}. [6] A method for manufacturing a hardened relief pattern, comprising: step (1), which is performed by applying the photosensitive resin composition as described in any one of [1] to [5] on the substrate Forming a photosensitive resin layer on the substrate; step (2), which exposes the photosensitive resin layer; step (3), which develops the exposed photosensitive resin layer to form a relief pattern; and steps (4) A heat-relief pattern is formed by subjecting the relief pattern to heat treatment. [7] The method according to [6], wherein the substrate is formed of copper or copper alloy. Moreover, the present inventors have found that by combining a specific photosensitive resin with a specific fluorine-containing hydrophobic compound, a photosensitive resin composition capable of forming a cured film can be obtained, from which the cured film can be obtained at a high temperature After the high temperature storage test, there is no void at the interface of the Cu layer in contact with the resin layer, and the resin layer has high adhesion. The present invention can also be applied to the following aspects. [1] A photosensitive resin composition comprising (A) selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, poly At least one resin from the group consisting of amide imide, polyimide, polybenzoxazole, novolac, polyhydroxystyrene and phenol resin: (B-3) fluorine-containing hydrophobic Compound: 0.01-50 parts by mass based on 100 parts by mass of the above (A) resin, and (C) Sensitizer: 1-50 parts by mass based on 100 parts by mass of the above (A) resin. [2] The photosensitive resin composition according to [1], wherein the resin (A) is selected from a polyimide precursor containing the following general formula (1) and a polymer containing the following general formula (4) Acetamide, polyazole precursor containing the following general formula (5), polyimide containing the following general formula (6), and novolac, polyhydroxystyrene, and containing the following general formula (7) At least one of the group consisting of phenol resin. The following general formula (1) is [Chem 33]

{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 and a saturated carbon number of 1 to 30 An aliphatic group, an aromatic group, or the following general formula (2): [Chem 34]

(In the formula, R ₃ , R ₄ and R ₅ 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) a monovalent organic group represented by 1 or a carbon number 1 Saturated aliphatic group of ～4, or the following general formula (3): [Chem 35]

{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or have multiple structures, and R ₉ has at least An organic group having a radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n ₂ is an integer of 1 to 1000} Polyamide having a structure represented by the following general formula (5) having [ Chemical 37]

{In the formula, Y ₃ is a tetravalent organic group having carbon atoms, Y ₄ , X ₃ and X ₄ are each independently a divalent organic group having 2 or more carbon atoms, and n ₃ is an integer of 1 to 1000 , n ₄ is an integer of 0 to _{_{500., n 3 / (n 3 +}} n 4)> 0.5, and comprises X ₃ and Y ₃ of n ₃ dihydroxy two Amides unit and comprising X n ₄ and Y ₄ of ₄ The arrangement order of the diacrylamide units is arbitrary} The polyhydroxyamide as a precursor of polyoxazole is a structure represented by the following general formula (6):

{In the formula, X ₅ is an organic group of 4 to 14 valences, Y ₅ is an organic group of 2 to 12 valences, R ₁₀ and R ₁₁ independently represent at least one selected from phenolic hydroxyl groups, sulfonic acid groups or thiols The organic group of the group in the group, n ₅ is an integer of 3 to 200, and m ₃ and m ₄ represent an integer of 0 to 10} Polyimide of the structure represented by the following general formula (7) is [ Chemical 39]

{In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, 1≦(a+b)≦4, R ₁₂ represents a monovalent organic group selected from carbon number 1-20, halogen atom, nitro group A monovalent substituent in the group consisting of and cyano, when b is 2 or 3, a plurality of R ₁ may be the same or different from each other, X represents a carbon number 2 selected from the group consisting of an unsaturated bond ～10 divalent aliphatic group, C 3-20 divalent alicyclic group, the following general formula (8): [Chem 40]

(In the formula, p is an integer of 1-10) The divalent organic group represented by the divalent alkoxy group represented by the divalent organic group and the divalent organic group having an aromatic ring having 6 to 12 carbon atoms Phenolic resin represented by base}. [3] The photosensitive resin composition as described in [1] or [2], wherein X in the above general formula (7) is selected from the following general formula (9):

{In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon in which a part or all of a hydrogen atom is substituted with a fluorine atom In the case of a monovalent aliphatic group of 1 to 10, n ₆ is an integer of 0 to 4, and n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or a carbon number of 1 to 12 Valent organic group, when at least one R ₆ is a hydroxyl group, and n ₆ is an integer of 2 to 4, the plural R ₁₇ may be the same as or different from each other} the divalent group represented by }, and the following general formula (10): [Chem 42]

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ independently represent a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon in which a part or all of a hydrogen atom is substituted with a fluorine atom The monovalent aliphatic group of 1 to 10, W is a single bond, is selected from the aliphatic group of 1 to 10 carbon atoms which may be substituted by fluorine atoms, and the alicyclic formula of 3 to 20 carbon atoms which may be substituted by fluorine atoms Base, the following general formula (8): [Chem. 43]

(In the formula, p is an integer of 1 to 10) The divalent alkoxy group represented by and the following formula (11): [Chem 44]

The divalent base in the group consisting of the represented divalent base} The divalent organic group in the group consisting of the represented divalent base}. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the weight ratio of fluorine atoms in the molecules of the above-mentioned (B-3) fluorine-containing hydrophobic compound is 30% by mass or more and 80% by mass or less. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the (B-3) fluorine-containing hydrophobic compound has at least one unsaturated double bond in the molecule. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the (B-3) fluorine-containing hydrophobic compound is an acrylate or methacrylate compound having a perfluoro group. [7] A method for manufacturing a hardened relief pattern, which includes step (1) by coating the photosensitive resin composition as described in any one of [1] to [6] on the substrate Forming a photosensitive resin layer thereon; step (2), which exposes the photosensitive resin layer; step (3), which develops the exposed photosensitive resin layer to form a relief pattern; and step ( 4) A heat-relief pattern is formed by subjecting the relief pattern to heat treatment. [8] The method according to [7], wherein the substrate is formed of copper or a copper alloy. [Effects of the Invention] According to the present invention, a photosensitive resin capable of obtaining a photosensitive resin having high adhesion without generating voids at the interface between the Cu layer and the resin layer after a high temperature storage test can be provided A composition, a method for forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern.

以下對用以實施本發明之形態(以下簡稱為「本實施形態」)進行詳細說明。再者，本實施形態為用以說明本發明之例示，而非意欲限定本發明。本發明可於其主旨之範圍內適當變化而實施。再者，本說明書中，於於通式中以同一符號表示之結構在分子中存在複數個之情形時，相互可相同或亦可不同。＜感光性樹脂組合物＞本實施形態係以如下成分作為必須成分，即，(A)選自由聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽、聚羥基醯胺、聚胺基醯胺、聚醯胺、聚醯胺醯亞胺、聚醯亞胺、聚苯并㗁唑、以及酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份、(B)塑化劑：以(A)樹脂100質量份為基準計0.1～50質量份、(C)感光劑：以(A)樹脂100質量份為基準計1～50質量份。＜感光性樹脂組合物＞又，另一實施形態係以如下成分作為必須成分，即，(A)選自由聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽、聚羥基醯胺、聚胺基醯胺、聚醯胺、聚醯胺醯亞胺、聚醯亞胺、聚苯并㗁唑、以及酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份、(B-1)奈米粒子：以(A)樹脂100質量份為基準計0.01～10質量份、(C)感光劑：以(A)樹脂100質量份為基準計1～50質量份。＜感光性樹脂組合物＞又，另一實施形態係負型感光性樹脂組合物，其以如下成分作為必須成分，即，(A)選自由聚醯胺酸、聚醯胺酸酯及聚醯胺酸鹽所組成之群中之至少一種樹脂：100質量份、(B-2)熱交聯劑：以(A)樹脂100質量份為基準計0.01～10質量份、(C)感光劑：以(A)樹脂100質量份為基準計1～50質量份。＜感光性樹脂組合物＞又，另一實施形態係以如下成分作為必須成分，即，(A)選自由聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽、聚羥基醯胺、聚胺基醯胺、聚醯胺、聚醯胺醯亞胺、聚醯亞胺、聚苯并㗁唑、以及酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂：100質量份、(B-3)含氟疏水性化合物：以上述(A)樹脂100質量份為基準計0.01～50質量份、(C)感光劑：以(A)樹脂100質量份為基準計1～50質量份。 (A)樹脂對本發明中所使用之(A)樹脂進行說明。本發明之(A)樹脂係以選自由聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽、聚羥基醯胺、聚胺基醯胺、聚醯胺、聚醯胺醯亞胺、聚醯亞胺、聚苯并㗁唑、以及酚醛清漆、聚羥基苯乙烯及酚樹脂所組成之群中之至少一種樹脂作為主成分。此處，所謂主成分意指含有占樹脂整體60質量%以上之該等樹脂，較佳為含有80質量%以上。又，視需要亦可含有其他樹脂。該等樹脂之重量平均分子量就熱處理後之耐熱性、機械特性之觀點而言，以基於凝膠滲透層析法之聚苯乙烯換算計，較佳為200以上，更佳為5,00以上。較佳為1,000以上，更佳為1,000以上。上限較佳為500,000以下，於製成感光性樹脂組合物之情形時，就於顯影液中之溶解性之觀點而言，更佳為20,000以下。本發明中，為了形成浮凸圖案，(A)樹脂較理想為感光性樹脂。感光性樹脂係與下述(C)感光劑一併使用而成為感光性樹脂組合物，於其後之顯影步驟中引起溶解或未溶解之現象的樹脂。作為感光性樹脂，於聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽、聚羥基醯胺、聚胺基醯胺、聚醯胺、聚醯胺醯亞胺、聚醯亞胺、聚苯并㗁唑、以及包含酚醛清漆、聚羥基苯乙烯之酚樹脂之中，就熱處理後之樹脂之耐熱性、機械特性優異之方面而言，可較佳地使用聚醯亞胺前驅物(聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽)、聚醯胺、聚羥基醯胺、聚醯亞胺及酚樹脂。又，該等感光性樹脂可根據所需用途而選擇與下述(C)感光劑一起製備負型或正型之任意感光性樹脂組合物等。 [(A)聚醯胺酸、聚醯胺酸酯、聚醯胺酸鹽] 本發明之感光性樹脂組合物中，就耐熱性及感光特性之觀點而言最佳之(A)樹脂之一例為上述通式(1)： [化45]

{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，R₁ 及R₂ 分別獨立為氫原子、碳數1～30之飽和脂肪族基、或上述通式(2)： [化46]

(式中，R₃ 、R₄ 及R₅ 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、或碳數1～4之飽和脂肪族基}所表示之1價之有機基、或下述通式(3)： [化47]

(式中，R₆ 、R₇ 及R₈ 分別獨立為氫原子或碳數1～3之有機基，並且m₂ 為2～10之整數)所表示之一價之銨離子}所表示之作為聚醯亞胺前驅物之聚醯胺酸、聚醯胺酸酯或聚醯胺酸鹽。聚醯亞胺前驅物藉由實施加熱(例如200℃以上)環化處理而轉化為聚醯亞胺。聚醯亞胺前驅物適用於負型感光性樹脂組合物用。上述通式(1)中，X₁ 所表示之4價之有機基就兼具耐熱性與感光特性之方面而言，較佳為碳數6～40之有機基，更佳為-COOR₁ 基及-COOR₂ 基與-CONH-基相互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，較佳為含有芳香族環之碳原子數6～40之有機基，更佳為列舉下述式(30)： [化48]

{式中，R25為選自氫原子、氟原子、C1～C10之烴基、C1～C10之含氟烴基之1價之基，l為選自0～2之整數，m為選自0～3之整數，n為選自0～4之整數} 所表示之結構，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。具有上述式所表示之結構之X₁ 基就兼具耐熱性與感光特性之方面而言尤佳。上述通式(1)中，Y₁ 所表示之2價之有機基就兼具耐熱性與感光特性之方面而言，較佳為碳數6～40之芳香族基，例如可列舉下述式(31)： [化49]

{式中，R25為選自氫原子、氟原子、C1～C10之烴基、C1～C10之含氟烴基之1價之基，n為選自0～4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(31)所表示之結構之Y₁ 基就兼具耐熱性與感光特性之方面而言尤佳。上述通式(2)中之R₃ 較佳為氫原子或甲基，R₄ 及R₅ 就感光特性之觀點而言，較佳為氫原子。又，m₁ 就感光特性之觀點而言，為2以上且10以下之整數，較佳為2以上且4以下之整數。於使用聚醯亞胺前驅物作為(A)樹脂之情形時，作為對感光性樹脂組合物賦予感光性之方式，可列舉酯鍵型與離子鍵型。前者係於聚醯亞胺前驅物之側鏈藉由酯鍵而導入具有光聚合性基、即烯烴性雙鍵之化合物的方法，後者係使聚醯亞胺前驅物之羧基與具有胺基之(甲基)丙烯酸系化合物之胺基經由離子鍵而鍵結從而賦予光聚合性基的方法。上述酯鍵型之聚醯亞胺前驅物係藉由如下方式獲得，即，首先，使包含上述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之碳數1～4之飽和脂肪族醇類進行反應，而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2價之有機基Y₁ 之二胺類進行醯胺縮聚合。 (酸/酯體之製備) 本發明中，作為適於製備酯鍵型之聚醯亞胺前驅物之包含4價之有機基X₁ 之四羧酸二酐，可列舉以具有上述通式(30)所表示之結構之四羧酸二酐為代表的例如均苯四甲酸二酐、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、聯苯基-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-苯二甲酸酐)丙烷、2,2-雙(3,4-苯二甲酸酐)-1,1,1,3,3,3-六氟丙烷等，較佳為列舉：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、聯苯基-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，但亦可將2種以上混合使用。本發明中，作為適於製備酯鍵型之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-丙烯醯胺基乙醇、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-甲基丙烯醯胺基乙醇、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。亦可於上述醇類中混合一部分作為碳數1～4之飽和脂肪族醇之例如甲醇、乙醇、正丙醇、異丙醇、正丁醇、第三丁醇等使用。使上述本發明中適宜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4～10小時使之溶解、混合，藉此進行酸酐之酯化反應，而可獲得所需之酸/酯體。 (聚醯亞胺前驅物之製備) 對上述酸/酯體(典型而言為下述溶劑中之溶液)，於冰浴冷卻下投入適宜之脫水縮合劑、例如二環碳二醯亞胺、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加以混合而將酸/酯體製成聚酸酐後，於其中滴加投入另外使本發明中適宜使用之包含2價之有機基Y₁ 之二胺類溶解或分散於溶劑所得者，進行醯胺縮聚合，藉此可獲得目標聚醯亞胺前驅物。或者使用亞硫醯氯等而使上述酸/酯體中之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，藉此可獲得目標聚醯亞胺前驅物。作為本發明中適宜使用之包含2價之有機基Y₁ 之二胺類，可列舉以具有上述通式(31)所表示之結構之二胺為代表的例如對苯二胺、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被甲基、乙基、羥基甲基、羥基乙基、鹵素等取代者，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、2,2'-二甲基聯苯胺、2,2'-雙(三氟甲基)-4,4'-二胺基聯苯、2,2'-雙(氟)-4,4'-二胺基聯苯、4,4'-二胺基八氟聯苯等；較佳為列舉：對苯二胺、間苯二胺、4,4'-二胺基二苯醚、2,2'-二甲基聯苯胺、2,2'-雙(三氟甲基)-4,4'-二胺基聯苯、2,2'-雙(氟)-4,4'-二胺基聯苯、4,4'-二胺基八氟聯苯等、以及該等之混合物等，但並不限定於此。又，為了提高藉由於基板上塗佈本發明之感光性樹脂組合物而於基板上形成之樹脂層與各種基板的密接性，於製備聚醯亞胺前驅物時，亦可與1,3-雙(3-胺基丙基)四甲基二矽氧烷、1,3-雙(3-胺基丙基)四苯基二矽氧烷等二胺基矽氧烷類進行共聚。醯胺縮聚合反應結束後，視需要將共存於該反應液中之脫水縮合劑之吸水副產物過濾分離後，於所獲得之聚合物成分中投入水、脂肪族低級醇、或其混合液等不良溶劑而使聚合物成分析出，進而反覆進行再溶解、再沈澱析出操作等，藉此精製聚合物，並進行真空乾燥而單離目標聚醯亞胺前驅物。為了提高精製度，亦可使該聚合物之溶液通過填充有利用適宜之有機溶劑而膨潤之陰離子及/或陽離子交換樹脂的管柱而去除離子性雜質。另一方面，上述離子鍵型之聚醯亞胺前驅物典型而言係使四羧酸二酐與二胺反應而獲得。於該情形時，上述通式(1)中之R₁ 及R₂ 中之至少一者為羥基。作為四羧酸二酐，較佳為包含上述式(30)之結構之四羧酸之酸酐，作為二胺，較佳為包含上述式(31)之結構之二胺。藉由對所獲得之聚醯胺前驅物添加下述具有胺基之(甲基)丙烯酸系化合物，而利用羧基與胺基之離子鍵結而賦予光聚合性基。作為具有胺基之(甲基)丙烯酸系化合物，例如較佳為丙烯酸二甲胺基乙酯、甲基丙烯酸二甲胺基乙酯、丙烯酸二乙胺基乙酯、甲基丙烯酸二乙胺基乙酯、丙烯酸二甲胺基丙酯、甲基丙烯酸二甲胺基丙酯、丙烯酸二乙胺基丙酯、甲基丙烯酸二乙胺基丙酯、丙烯酸二甲胺基丁酯、甲基丙烯酸二甲胺基丁酯、丙烯酸二乙胺基丁酯、甲基丙烯酸二乙胺基丁酯、等丙烯酸二烷基胺基烷基酯或甲基丙烯酸二烷基胺基烷基酯，其中，就感光特性之觀點而言，較佳為胺基上之烷基之碳數為1～10、烷基鏈之碳數為1～10的丙烯酸二烷基胺基烷基酯或甲基丙烯酸二烷基胺基烷基酯。關於該等具有胺基之(甲基)丙烯酸系化合物之調配量，相對於(A)樹脂100質量份而為1～20質量份，就光感度特性之觀點而言，較佳為2～15質量份。相對於(A)樹脂100質量份，藉由調配作為(C)感光劑之具有胺基之(甲基)丙烯酸系化合物1質量份以上而光感度優異，藉由調配20質量份以下而厚膜硬化性優異。關於上述酯鍵型及上述離子鍵型之聚醯亞胺前驅物之分子量，於以基於凝膠滲透層析法之聚苯乙烯換算重量平均分子量之形式測定之情形時，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，且浮凸圖案之解像性能良好。作為凝膠滲透層析法之展開溶劑，推薦使用四氫呋喃及N-甲基-2-吡咯啶酮。又，重量平均分子量係根據使用標準單分散聚苯乙烯所製作之校準曲線而求出。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中選擇。 [(A)聚醯胺] 本發明之感光性樹脂組合物中之較佳之(A)樹脂之另一例為具有下述通式(4)： [化50]

{式中，X₂ 為碳數6～15之3價之有機基，Y₂ 為碳數6～35之2價之有機基，且可為同一結構或具有複數種結構，R₉ 為具有至少一個碳數3～20之自由基聚合性之不飽和鍵結基的有機基，並且n₂ 為1～1000之整數} 所表示之結構之聚醯胺。該聚醯胺適用於負型感光性樹脂組合物用。上述通式(4)中，作為R₉ 所表示之基，就兼具感光特性與耐化學品性之方面而言，較佳為下述通式(32) [化51]

{式中，R₃₂ 為具有至少一個碳數2～19之自由基聚合性之不飽和鍵結基的有機基} 所表示之基。上述通式(4)中，作為X₂ 所表示之3價之有機基，較佳為碳數6～15之3價之有機基，例如較佳為選自下述式(33)： [化52]

所表示之基中之芳香族基，進而更佳為自胺基取代間苯二甲酸結構中去除羧基及胺基所得之芳香族基。上述通式(4)中，作為Y₂ 所表示之2價之有機基，較佳為碳數6～35之有機基，進而更佳為具有1～4個可經取代之芳香族環或脂肪族環之環狀有機基、或者不具有環狀結構之脂肪族基或矽氧烷基。作為Y₂ 所表示之2價之有機基，可列舉下述通式(I)及下述通式(34)、(35)： [化53]

[化54]

{式中，R₃₃ 及R₃₄ 分別獨立為選自由羥基、甲基(-CH₃ )、乙基(-C₂ H₅ )、丙基(-C₃ H₇ )或丁基(-C₄ H₉ )所組成之群中之一種基，並且該丙基及丁基包括各種異構物} [化55]

{式中，m₇ 為0～8之整數，m₈ 及m₉ 分別獨立為0～3之整數，m₁₀ 及m₁₁ 分別獨立為0～10之整數，並且R₃₅ 及R₃₆ 為甲基(-CH₃ )、乙基(-C₂ H₅ )、丙基(-C₃ H₇ )、丁基(-C₄ H₉ )或該等之異構物}。關於不具有環狀結構之脂肪族基或矽氧烷基，作為其較佳者，可列舉下述通式(36)： [化56]

{式中，m₁₂ 為2～12之整數，m₁₃ 為1～3之整數，m₁₄ 為1～20之整數，並且R₃₇ 、R₃₈ 、R₃₉ 及R₄₀ 分別獨立為碳數1～3之烷基或可經取代之苯基}。本發明之聚醯胺樹脂例如可藉由如下方式合成。 (苯二甲酸化合物封端體之合成) 第一步，使具有3價之芳香族基X₂ 之化合物、例如選自由經胺基取代之鄰苯二甲酸、經胺基取代之間苯二甲酸及經胺基取代之對苯二甲酸所組成之群中之至少1種以上之化合物(以下稱為「苯二甲酸化合物」)1莫耳、和會與胺基反應之化合物1莫耳進行反應，而合成該苯二甲酸化合物之胺基經下述包含自由基聚合性之不飽和鍵之基修飾、封端的化合物(以下稱為「苯二甲酸化合物封端體」)。該等可單獨使用，亦可混合使用。若成為苯二甲酸化合物經上述包含自由基聚合性之不飽和鍵之基封端的結構，則可對聚醯胺樹脂賦予負型之感光性(光硬化性)。作為包含自由基聚合性之不飽和鍵之基，較佳為具有碳數3～20之自由基聚合性之不飽和鍵結基的有機基，尤佳為包含甲基丙烯醯基或丙烯醯基之基。上述苯二甲酸化合物封端體可藉由使苯二甲酸化合物之胺基、與具有至少一個碳數3～20之自由基聚合性之不飽和鍵結基的醯氯、異氰酸酯或環氧化合物等進行反應而獲得。作為適宜之醯氯，可列舉：(甲基)丙烯醯氯、2-[(甲基)丙烯醯氧基]乙醯氯、3-[(甲基)丙烯醯氧基]丙醯氯、氯甲酸2-[(甲基)丙烯醯氧基]乙酯、氯甲酸3-[(甲基)丙烯醯氧基丙基]酯等。作為適宜之異氰酸酯，可列舉：異氰酸2-(甲基)丙烯醯氧基乙酯、異氰酸1,1-雙[(甲基)丙烯醯氧基甲基]乙酯、異氰酸2-[2-(甲基)丙烯醯氧基乙氧基]乙酯等。作為適宜之環氧化合物，可列舉(甲基)丙烯酸縮水甘油酯等。該等可單獨使用，亦可混合使用，但尤佳為使用甲基丙烯醯氯及/或異氰酸2-(甲基丙烯醯氧基)乙酯。進而，作為該等苯二甲酸化合物封端體，苯二甲酸化合物為5-胺基間苯二甲酸者可獲得不僅感光特性優異且加熱硬化後之膜特性亦優異之聚醯胺，因此較佳。上述封端反應可藉由於吡啶等鹼性觸媒或二月桂酸二正丁基錫等錫系觸媒之存在下，將苯二甲酸化合物與封端劑視需要於如下所述之溶劑中攪拌溶解、混合而進行。醯氯等根據封端劑之種類而會於封端反應之過程中生成副產物氯化氫。於該情形時，為了防止對以後之步驟造成污染，較佳為適當進行精製，即，暫且使之於水中再沈澱並水洗乾燥、或使之通過填充有離子交換樹脂之管柱而去除減少離子成分等。 (聚醯胺之合成) 使上述苯二甲酸化合物封端體與具有2價之有機基Y₂ 之二胺化合物於吡啶或三乙胺等鹼性觸媒之存在下，於如下所述之溶劑中混合而使之進行醯胺縮聚合，藉此可獲得本發明之聚醯胺。作為醯胺縮聚合方法，可列舉：使用脫水縮合劑而使苯二甲酸化合物封端體成為對稱聚酸酐後與二胺化合物混合之方法、或藉由已知方法使苯二甲酸化合物封端體實現醯氯化後與二胺化合物混合之方法、使二羧酸成分與活性酯化劑於脫水縮合劑之存在下反應而實現活性酯化後與二胺化合物混合之方法等。作為脫水縮合劑，例如作為較佳者，可列舉：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。作為氯化劑，可列舉亞硫醯氯等。作為活性酯化劑，可列舉：N-羥基丁二醯亞胺或1-羥基苯并三唑、N-羥基-5-降𦯉烯-2,3-二羧醯亞胺、2-羥基亞胺基-2-氰基乙酸乙酯、2-羥基亞胺基-2-氰基乙醯胺等。作為具有有機基Y₂ 之二胺化合物，較佳為選自由芳香族二胺化合物、芳香族雙胺基苯酚化合物、脂環式二胺化合物、直鏈脂肪族二胺化合物、矽氧烷二胺化合物所組成之群中之至少一種二胺化合物，視需要亦可併用複數種。作為芳香族二胺化合物，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、以及該等之苯環上之氫原子之一部被選自由甲基、乙基、羥基甲基、羥基乙基及鹵素原子所組成之群中之1種以上之基取代的二胺化合物。作為該苯環上之氫原子被取代的二胺化合物之例，可列舉：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'-二胺基聯苯基等。作為芳香族雙胺基苯酚化合物，可列舉：3,3'-二羥基聯苯胺、3,3'-二胺基-4,4'-二羥基聯苯、3,3'-二羥基-4,4'-二胺基二苯基碸、雙-(3-胺基-4-羥基苯基)甲烷、2,2-雙-(3-胺基-4-羥基苯基)丙烷、2,2-雙-(3-胺基-4-羥基苯基)六氟丙烷、2,2-雙-(3-羥基-4-胺基苯基)六氟丙烷、雙-(3-羥基-4-胺基苯基)甲烷、2,2-雙-(3-羥基-4-胺基苯基)丙烷、3,3'-二羥基-4,4'-二胺基二苯甲酮、3,3'-二羥基-4,4'-二胺基二苯醚、4,4'-二羥基-3,3'-二胺基二苯醚、2,5-二羥基-1,4-二胺基苯、4,6-二胺基間苯二酚、1,1-雙(3-胺基-4-羥基苯基)環己烷、4,4-(α-甲基亞苄基)-雙(2-胺基苯酚)等。作為脂環式二胺化合物，可列舉：1,3-二胺基環戊烷、1,3-二胺基環己烷、1,3-二胺基-1-甲基環己烷、3,5-二胺基-1,1-二甲基環己烷、1,5-二胺基-1,3-二甲基環己烷、1,3-二胺基-1-甲基-4-異丙基環己烷、1,2-二胺基-4-甲基環己烷、1,4-二胺基環己烷、1,4-二胺基-2,5-二乙基環己烷、1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷、2-(3-胺基環戊基)-2-丙基胺、薄荷烷二胺、異佛爾酮二胺、降𦯉烷二胺、1-環庚烯-3,7-二胺、4,4'-亞甲基雙(環己基胺)、4,4'-亞甲基雙(2-甲基環己基胺)、1,4-雙(3-胺基丙基)哌𠯤、3,9-雙(3-胺基丙基)-2,4,8,10-四氧雜螺-[5,5]-十一烷等。作為直鏈脂肪族二胺化合物，可列舉：1,2-二胺基乙烷、1,4-二胺基丁烷、1,6-二胺基己烷、1,8-二胺基辛烷、1,10-二胺基癸烷、1,12-二胺基十二烷等烴型二胺、或2-(2-胺基乙氧基)乙基胺、2,2'-(乙二氧基)二乙基胺、雙[2-(2-胺基乙氧基)乙基]醚等伸烷氧型二胺等。作為矽氧烷二胺化合物，可列舉二甲基(聚)矽氧烷二胺，例如信越化學工業製造之商標名PAM-E、KF-8010、X-22-161A等。醯胺縮聚合反應結束後，視需要將反應液中所析出之源自脫水縮合劑之析出物等過濾分離。繼而，於反應液中投入水或脂肪族低級醇或其混合液等聚醯胺之不良溶劑而使聚醯胺析出。進而，使所析出之聚醯胺再次溶解於溶劑，反覆實施再沈澱析出操作，藉此進行精製，並進行真空乾燥，而單離目標聚醯胺。再者，為了進一步提高精製度，可使該聚醯胺之溶液通過填充有離子交換樹脂之管柱而去除離子性雜質。聚醯胺之基於凝膠滲透層析法(以下稱為「GPC」)之聚苯乙烯換算重量平均分子量較佳為7,000～70,000，進而更佳為10,000～50,000。若聚苯乙烯換算重量平均分子量為7,000以上，則確保硬化浮凸圖案之基本物性。又，若聚苯乙烯換算重量平均分子量為70,000以下，則確保形成浮凸圖案時之顯影溶解性。作為GPC之溶離液，推薦使用四氫呋喃或N-甲基-2-吡咯啶酮。又，重量平均分子量值係根據使用標準單分散聚苯乙烯所製作之校準曲線而求出。作為標準單分散聚苯乙烯，推薦自昭和電工製造之有機溶劑系標準試樣STANDARD SM-105中選擇。 [(A)聚羥基醯胺] 本發明之感光性樹脂組合物中之較佳之(A)樹脂之另一例為具有下述通式(5)： [化57]

{式中，Y₃ 為具有碳原子之4價之有機基，較佳為具有2個以上之碳原子之4價之有機基，Y₄ 、X₃ 及X₄ 分別獨立為具有2個以上之碳原子之2價之有機基，n₃ 為1～1000之整數，n₄ 為0～500之整數，n₃ /(n₃ ＋n₄ )＞0.5，並且包含X₃ 及Y₃ 之n₃ 個二羥基二醯胺單元以及包含X₄ 及Y₄ 之n₄ 個二醯胺單元之排列順序為任意}所表示之結構之聚羥基醯胺(聚㗁唑前驅物(以下有時將上述通式(5)所表示之聚羥基醯胺簡稱為「聚㗁唑前驅物」))。聚㗁唑前驅物為具有上述通式(5)中之n₃ 個二羥基二醯胺單元(以下有時簡稱為二羥基二醯胺單元)之聚合物，亦可具有上述通式(5)中之n₄ 個二醯胺單元(以下有時簡稱為二醯胺單元)。 X₃ 之碳原子數基於獲得感光特性之目的而較佳為2個以上且40個以下，X₄ 之碳原子數基於獲得感光特性之目的而較佳為2個以上且40個以下，Y₃ 之碳原子數基於獲得感光特性之目的而較佳為2個以上且40個以下，並且Y₄ 之碳原子數基於獲得感光特性之目的而較佳為2個以上且40個以下。該二羥基二醯胺單元可藉由使具有Y₃ (NH₂ )₂ (OH)₂ 之結構之二胺基二羥基化合物(較佳為雙胺基苯酚)與具有X₃ (COOH)₂ 之結構之二羧酸進行合成而形成。以下，以上述二胺基二羥基化合物為雙胺基苯酚之情形為例而說明典型態樣。該雙胺基苯酚之2組胺基與羥基分別相互位於鄰位，該二羥基二醯胺單元於約250～400℃之加熱下閉環而轉化為耐熱性之聚㗁唑結構。通式(5)中之n₃ 基於獲得感光特性之目的而為1以上，且基於獲得感光特性之目的而為1000以下。n₃ 較佳為2～1000之範圍，更佳為3～50之範圍，最佳為3～20之範圍。視需要亦可於聚㗁唑前驅物上縮合n₄ 個上述二醯胺單元。該二醯胺單元可藉由使具有Y₄ (NH₂ )₂ 之結構之二胺與具有X₄ (COOH)₂ 之結構之二羧酸進行合成而形成。通式(5)中之n₄ 為0～500之範圍，藉由n₄ 為500以下而獲得良好之感光特性。n₄ 更佳為0～10之範圍。若二醯胺單元相對於二羥基二醯胺單元之比率過高，則於用作顯影液之鹼性水溶液中之溶解性降低，因此通式(5)中之n₃ /(n₃ ＋n₄ )之值超過0.5，更佳為0.7以上，最佳為0.8以上。關於作為具有Y₃ (NH₂ )₂ (OH)₂ 之結構之二胺基二羥基化合物的雙胺基苯酚，例如可列舉：3,3'-二羥基聯苯胺、3,3'-二胺基-4,4'-二羥基聯苯、4,4'-二胺基-3,3'-二羥基聯苯、3,3'-二胺基-4,4'-二羥基二苯基碸、4,4'-二胺基-3,3'-二羥基二苯基碸、雙-(3-胺基-4-羥基苯基)甲烷、2,2-雙-(3-胺基-4-羥基苯基)丙烷、2,2-雙-(3-胺基-4-羥基苯基)六氟丙烷、2,2-雙-(4-胺基-3-羥基苯基)六氟丙烷、雙-(4-胺基-3-羥基苯基)甲烷、2,2-雙-(4-胺基-3-羥基苯基)丙烷、4,4'-二胺基-3,3'-二羥基二苯甲酮、3,3'-二胺基-4,4'-二羥基二苯甲酮、4,4'-二胺基-3,3'-二羥基二苯醚、3,3'-二胺基-4,4'-二羥基二苯醚、1,4-二胺基-2,5-二羥基苯、1,3-二胺基-2,4-二羥基苯、1,3-二胺基-4,6-二羥基苯等。該等雙胺基苯酚可單獨使用或將2種以上組合使用。作為該雙胺基苯酚中之Y₃ 基，就感光特性之方面而言，較佳為下述式(37)： [化58]

{式中，Rs1與Rs2分別獨立地表示氫原子、甲基、乙基、丙基、環戊基、環己基、苯基、三氟甲基}所表示者。又，作為具有Y₄ (NH₂ )₂ 之結構之二胺，可列舉芳香族二胺、矽二胺等。其中，作為芳香族二胺，例如可列舉：間苯二胺、對苯二胺、2,4-甲苯二胺、3,3'-二胺基二苯醚、3,4'-二胺基二苯醚、4,4'-二胺基二苯醚、3,3'-二胺基二苯基碸、4,4'-二胺基二苯基碸、3,4'-二胺基二苯基碸、3,3'-二胺基二苯基甲烷、4,4'-二胺基二苯基甲烷、3,4'-二胺基二苯基甲烷、4,4'-二胺基二苯硫醚、3,3'-二胺基二苯基酮、4,4'-二胺基二苯基酮、3,4'-二胺基二苯基酮、2,2'-雙(4-胺基苯基)丙烷、2,2'-雙(4-胺基苯基)六氟丙烷、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、4-甲基-2,4-雙(4-胺基苯基)-1-戊烯、 4-甲基-2,4-雙(4-胺基苯基)-2-戊烯、1,4-雙(α,α-二甲基-4-胺基苄基)苯、亞胺基二對苯二胺、1,5-二胺基萘、2,6-二胺基萘、4-甲基-2,4-雙(4-胺基苯基)戊烷、5(或6)-胺基-1-(4-胺基苯基)-1,3,3-三甲基茚滿、雙(對胺基苯基)氧化膦、4,4'-二胺基偶氮苯、4,4'-二胺基二苯基脲、4,4'-雙(4-胺基苯氧基)聯苯、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、2,2-雙[4-(3-胺基苯氧基)苯基]二苯甲酮、4,4'-雙(4-胺基苯氧基)二苯基碸、4,4'-雙[4-(α,α-二甲基-4-胺基苄基)苯氧基]二苯甲酮、4,4'-雙[4-(α,α-二甲基-4-胺基苄基)苯氧基]二苯基碸、4,4'-二胺基聯苯、 4,4'-二胺基二苯甲酮、苯基茚滿二胺、3,3'-二甲氧基-4,4'-二胺基聯苯、3,3'-二甲基-4,4'-二胺基聯苯、鄰甲苯胺碸、2,2-雙(4-胺基苯氧基苯基)丙烷、雙(4-胺基苯氧基苯基)碸、雙(4-胺基苯氧基苯基)硫醚、1,4-(4-胺基苯氧基苯基)苯、1,3-(4-胺基苯氧基苯基)苯、9,9-雙(4-胺基苯基)茀、4,4'-二-(3-胺基苯氧基)二苯基碸、4,4'-二胺基苯甲醯苯胺等、以及該等芳香族二胺之芳香核之氫原子被選自由氯原子、氟原子、溴原子、甲基、甲氧基、氰基及苯基所組成之群中之至少一種基或原子取代的化合物。又，作為上述二胺，為了提高與基材之接著性而可選擇矽二胺。作為矽二胺之例，可列舉：雙(4-胺基苯基)二甲基矽烷、雙(4-胺基苯基)四甲基矽氧烷、雙(4-胺基苯基)四甲基二矽氧烷、雙(γ-胺基丙基)四甲基二矽氧烷、1,4-雙(γ-胺基丙基二甲基矽烷基)苯、雙(4-胺基丁基)四甲基二矽氧烷、雙(γ-胺基丙基)四苯基二矽氧烷等。又，作為具有X₃ (COOH)₂ 或X₄ (COOH)₂ 之結構之較佳之二羧酸，可列舉X₃ 及X₄ 分別為具有直鏈、支鏈或環狀結構之脂肪族基或芳香族基者。其中，較佳為可含有芳香族環或脂肪族環之碳原子數2個以上且40個以下之有機基，X₃ 及X₄ 分別可較佳地自下述式(38)： [化59]

{式中，R₄₁ 表示選自由-CH₂ -、-O-、-S-、-SO₂ -、-CO-、-NHCO-及-C(CF₃ )₂ -所組成之群中之2價之基} 所表示之芳香族基中進行選擇，該等於感光特性之方面較佳。聚㗁唑前驅物亦可為末端基經特定之有機基封端者。於使用經封端基封端之聚㗁唑前驅物之情形時，有望使本發明之感光性樹脂組合物之加熱硬化後之塗膜之機械物性(尤其伸長率)及硬化浮凸圖案形狀變得良好。作為此種封端基之較佳例，可列舉下述式(39)： [化60]

所表示者。聚㗁唑前驅物之基於凝膠滲透層析法之聚苯乙烯換算重量平均分子量較佳為3,000～70,000，更佳為6,000～50,000。該重量平均分子量就硬化浮凸圖案之物性之觀點而言，較佳為3,000以上。又，就解像性之觀點而言，較佳為70,000以下。作為凝膠滲透層析法之展開溶劑，推薦使用四氫呋喃、N-甲基-2-吡咯啶酮。又，分子量係根據使用標準單分散聚苯乙烯所製作之校準曲線而求出。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中選擇。 [(A)聚醯亞胺] 本發明之感光性樹脂組合物中之較佳之(A)樹脂之另一例為具有上述通式(6)： [化61]

{式中，X₅ 表示4～14價之有機基，Y₅ 表示2～12價之有機基，R₁₀ 及R₁₁ 表示具有至少一個選自酚性羥基、磺酸基或硫醇基中之基的有機基，且可相同或亦可不同，n₅ 為3～200之整數，並且m₃ 及m₄ 為0～10之整數} 所表示之結構之聚醯亞胺。此處，通式(6)所表示之樹脂於表現充分之膜特性時無需藉由熱處理步驟而產生化學變化，因此適合於更低溫下進行處理，就該方面而言尤佳。上述通式(6)所表示之結構單元中之X₅ 較佳為碳數4～40之4價～14價之有機基，就兼具耐熱性與感光特性之方面而言，進而較佳為含有芳香族環或脂肪族環之碳原子數5～40之有機基。上述通式(6)所表示之聚醯亞胺可使四羧酸、對應之四羧酸二酐、四羧酸二酯二氯化物等與二胺、對應之二異氰酸酯化合物、三甲基矽烷基化二胺進行反應而獲得。聚醯亞胺一般而言可藉由使作為由四羧酸二酐與二胺反應獲得之聚醯亞胺前驅物之一者的聚醯胺酸經過利用加熱或酸或鹼等進行之化學處理而發生脫水閉環而獲得。作為適宜之四羧酸二酐，可列舉：均苯四甲酸二酐、3,3',4,4'-聯苯基四羧酸二酐、2,3,3',4'-聯苯基四羧酸二酐、2,2',3,3'-聯苯基四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二無水物、2,2-雙(2,3-二羧基苯基)丙烷二無水物、1,1-雙(3,4-二羧基苯基)乙烷二無水物、1,1-雙(2,3-二羧基苯基)乙烷二無水物、雙(3,4-二羧基苯基)甲烷二無水物、雙(2,3-二羧基苯基)甲烷二無水物、雙(3,4-二羧基苯基)碸二無水物、雙(3,4-二羧基苯基)醚二無水物、1,2,5,6-萘四羧酸二酐、9,9-雙(3,4-二羧基苯基)茀酸二酐、 9,9-雙{4-(3,4-二羧基苯氧基)苯基}茀酸二酐、2,3,6,7-萘四羧酸二酐、2,3,5,6-吡啶四羧酸二酐、3,4,9,10-苝四羧酸二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二無水物等芳香族四羧酸二酐、或丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐等脂肪族四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐及下述通式(40)： [化62]

{式中，R₄₂ 表示選自氧原子、C(CF₃ )₂ 、C(CH₃ )₂ 或SO₂ 中之基，並且R₄₃ 及R₄₄ 可相同或亦可不同，且表示選自氫原子、羥基或硫醇基中之基}所表示之化合物。該等之中，較佳為3,3',4,4'-聯苯基四羧酸二酐、2,3,3',4'-聯苯基四羧酸二酐、2,2',3,3'-聯苯基四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二無水物、2,2-雙(2,3-二羧基苯基)丙烷二無水物、1,1-雙(3,4-二羧基苯基)乙烷二無水物、1,1-雙(2,3-二羧基苯基)乙烷二無水物、雙(3,4-二羧基苯基)甲烷二無水物、雙(2,3-二羧基苯基)甲烷二無水物、雙(3,4-二羧基苯基)碸二無水物、雙(3,4-二羧基苯基)醚二無水物、2,2-雙(3,4-二羧基苯基)六氟丙烷二無水物、3,3',4,4'-二苯基碸四羧酸二酐、9,9-雙(3,4-二羧基苯基)茀酸二酐、9,9-雙{4-(3,4-二羧基苯氧基)苯基}茀酸二酐及下述通式(41) [化63]

{式中，R₄₅ 表示選自氧原子、C(CF₃ )₂ 、C(CH₃ )₂ 或SO₂ 中之基，並且R₄₆ 及R₄₇ 可相同或亦可不同，且表示選自氫原子、羥基或硫醇基中之基}所表示之結構之酸二酐。該等可單獨使用或2種以上組合使用。上述通式(6)之Y₅ 表示二胺之結構成分，作為該二胺，表示含有芳香族環或脂肪族環之2～12價之有機基，其中較佳為碳原子數5～40之有機基。作為二胺之具體例，可列舉：3,4'-二胺基二苯醚、4,4'-二胺基二苯醚、3,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基甲烷、3,4'-二胺基二苯基碸、4,4'-二胺基二苯基碸、3,4'-二胺基二苯硫醚、4,4'-二胺基二苯硫醚、1,4-雙(4-胺基苯氧基)苯、苯炔、間苯二胺、對苯二胺、1,5-萘二胺、2,6-萘二胺、雙(4-胺基苯氧基苯基)碸、雙(3-胺基苯氧基苯基)碸、雙(4-胺基苯氧基)聯苯、雙{4-(4-胺基苯氧基)苯基}醚、1,4-雙(4-胺基苯氧基)苯、2,2'-二甲基-4,4'-二胺基聯苯、2,2'-二乙基-4,4'-二胺基聯苯、3,3'-二甲基-4,4'-二胺基聯苯、 3,3'-二乙基-4,4'-二胺基聯苯、2,2',3,3'-四甲基-4,4'-二胺基聯苯、3,3',4,4'-四甲基-4,4'-二胺基聯苯、2,2'-二(三氟甲基)-4,4'-二胺基聯苯、9,9-雙(4-胺基苯基)茀或該等之芳香族環經烷基或鹵素原子取代的化合物、或者脂肪族之環己基二胺、亞甲基雙環己基胺、及下述通式(42)： [化64]

{式中，R₄₈ 表示選自氧原子、C(CF₃ )₂ 、C(CH₃ )₂ 或SO₂ 中之基，並且R₄₉ ～R₅₂ 可相同或亦可不同，且表示選自氫原子、羥基或硫醇基中之基}所表示之結構之二胺等。該等之中，較佳為3,4'-二胺基二苯醚、4,4'-二胺基二苯醚、3,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基甲烷、3,4'-二胺基二苯基碸、4,4'-二胺基二苯基碸、3,4'-二胺基二苯硫醚、4,4'-二胺基二苯硫醚、間苯二胺、P-苯二胺、1,4-雙(4-胺基苯氧基)苯、9,9-雙(4-胺基苯基)茀、及下述通式(43)： [化65]

{式中，R₅₃ 表示選自氧原子、C(CF₃ )₂ 、C(CH₃ )₂ 或SO₂ 中之基，並且R₅₄ ～R₅₇ 可相同或亦可不同，且表示選自氫原子、羥基或硫醇基中之基} 所表示之結構之二胺。該等之中，尤佳為3,4'-二胺基二苯醚、4,4'-二胺基二苯醚、3,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基甲烷、3,4'-二胺基二苯基碸、4,4'-二胺基二苯基碸、1,4-雙(4-胺基苯氧基)苯、及下述通式(44)： [化66]

{式中，R₅₈ 表示選自氧原子、C(CF₃ )₂ 、C(CH₃ )₂ 或SO₂ 中之基，並且R₅₉ 及R₆₀ 可相同或亦可不同，且表示選自氫原子、羥基或硫醇基中之基} 所表示之結構之二胺。該等可單獨使用或2種以上組合使用。通式(6)之R₁₀ 及R₁₁ 表示酚性羥基、磺酸基、或硫醇基。本發明中，作為R₁₀ 及R₁₁ ，可使酚性羥基、磺酸基及/或硫醇基混合存在。藉由控制R₁₀ 及R₁₁ 之鹼可溶性基之量，於鹼性水溶液中之溶解速度發生變化，因此可藉由該調整而獲得具有適度之溶解速度之感光性樹脂組合物。進而，為了提高與基板之接著性，亦可於不會降低耐熱性之範圍內與作為X₅ 、Y₅ 之具有矽氧烷結構之脂肪族基進行共聚。具體而言，可列舉與1～10莫耳%之作為二胺成分之雙(3-胺基丙基)四甲基二矽氧烷、雙(對胺基苯基)八甲基五矽氧烷等進行共聚者等。上述聚醯亞胺可利用如下等方法獲得聚醯亞胺前驅物後，利用採用已知之醯亞胺化反應法使該聚醯亞胺前驅物完全醯亞胺化之方法、或中途停止醯亞胺化反應而導入一部分醯亞胺結構(於該情形時為聚醯胺醯亞胺)之方法、或藉由將完全醯亞胺化之聚合物與該聚醯亞胺前驅物進行摻合而導入一部分醯亞胺結構之方法進行合成，上述獲得聚醯亞胺前驅物之方法如下：例如使四羧酸二酐與二胺化合物(一部分經作為單胺之末端封端劑取代)於低溫下反應；使四羧酸二酐(一部分經作為酸酐或單醯氯化合物或單活性酯化合物之末端封端劑取代)與二胺化合物於低溫下反應；由四羧酸二酐與醇而獲得二酯，其後與二胺(一部分經作為單胺之末端封端劑取代)於縮合劑之存在下反應；由四羧酸二酐與醇而獲得二酯，其後將剩餘之二羧酸進行醯氯化，使之與二胺(一部分經作為單胺之末端封端劑取代)反應。上述聚醯亞胺較佳為以相對於構成感光性樹脂組合物之樹脂整體而醯亞胺化率為15%以上之方式具有聚醯亞胺。進而較佳為20%以上。此處所謂醯亞胺化率係指構成感光性樹脂組合物之樹脂整體中所存在之醯亞胺化之比率。若醯亞胺化率低於15%，則熱硬化時之收縮量變大，不適於厚膜製作。醯亞胺化率可藉由以下方法而容易地算出。首先，測定聚合物之紅外線吸收光譜，確認存在源自聚醯亞胺之醯亞胺結構之吸收波峰(1780 cm-1附近、1377 cm-1附近)。繼而，於350℃下對該聚合物進行1小時之熱處理，測定熱處理後之紅外線吸收光譜，將1377 cm-1附近之波峰強度與熱處理前之強度進行比較，藉此算出熱處理前聚合物中之醯亞胺化率。關於上述聚醯亞胺之分子量，於以基於凝膠滲透層析法之聚苯乙烯換算重量平均分子量測定之情形時，較佳為3,000～200,000，更佳為5,000～50,000。於重量平均分子量為3,000以上之情形時機械物性良好，於50,000以下之情形時於顯影液中之分散性良好，且浮凸圖案之解像性能良好。作為凝膠滲透層析法之展開溶劑，推薦使用四氫呋喃及N-甲基-2-吡咯啶酮。又，分子量係根據使用標準單分散聚苯乙烯所製作之校準曲線而求出。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中選擇。進而，於本發明中，亦可較佳地使用酚樹脂。 [(A)酚樹脂] 本實施形態中之所謂酚樹脂意指具有包含酚性羥基之重複單元之樹脂。(A)酚樹脂於熱硬化時不發生如聚醯亞胺前驅物進行環化(醯亞胺化)之結構變化，因此具有能夠於低溫(例如250℃以下)下硬化之優點。本實施形態中，(A)酚樹脂之重量平均分子量較佳為700～100,000，更佳為1,500～80,000，進而較佳為2,000～50,000。重量平均分子量就硬化膜之回流焊處理適用性之觀點而言，較佳為700以上，另一方面，就感光性樹脂組合物之鹼溶解性之觀點而言，較佳為100,000以下。本文中之重量平均分子量之測定可藉由凝膠滲透層析法(GPC)進行，根據使用標準聚苯乙烯所製作之校準曲線而算出。 (A)酚樹脂就於鹼性水溶液中之溶解性、形成抗蝕圖案時之感度與解像性、及硬化膜之殘留應力之觀點而言，較佳為選自酚醛清漆、聚羥基苯乙烯、具有下述通式(7)： [化67]

{式中，a為1～3之整數，b為0～3之整數，1≦(a＋b)≦4，R₂₆ 表示選自由碳數1～20之1價之有機基、鹵素原子、硝基及氰基所組成之群中之1價之取代基，於b為2或3之情形時，複數個R₁₂ 相互可相同或亦可不同，X表示選自由可具有不飽和鍵之碳數2～10之2價之脂肪族基、碳數3～20之2價之脂環式基、下述通式(8)： [化68]

(式中，p為1～10之整數)所表示之2價之伸烷氧基、及具有碳數6～12之芳香族環之2價之有機基所組成之群中之2價之有機基} 所表示之重複單元之酚樹脂、及經具有碳數4～100之不飽和烴基之化合物改性的酚樹脂中之至少一種酚樹脂。 (酚醛清漆) 本文中，所謂酚醛清漆意指藉由使酚類與甲醛於觸媒存在下進行縮合而獲得之聚合物全體。一般而言，酚醛清漆可使1莫耳之酚類與相對於該酚類而未達1莫耳之甲醛進行縮合而獲得。作為上述酚類，例如可列舉：苯酚、鄰甲酚、間甲酚、對甲酚、鄰乙基苯酚、間乙基苯酚、對乙基苯酚、鄰丁基苯酚、間丁基苯酚、對丁基苯酚、2,3-二甲苯酚、2,4-二甲苯酚、2,5-二甲苯酚、2,6-二甲苯酚、3,4-二甲苯酚、3,5-二甲苯酚、2,3,5-三甲基苯酚、3,4,5-三甲基苯酚、兒茶酚、間苯二酚、連苯三酚、α-萘酚、β-萘酚等。作為具體之酚醛清漆，例如可列舉：苯酚/甲醛縮合酚醛清漆樹脂、甲酚/甲醛縮合酚醛清漆樹脂、苯酚-萘酚/甲醛縮合酚醛清漆樹脂等。酚醛清漆之重量平均分子量較佳為700～100,000，更佳為1,500～80,000，進而較佳為2,000～50,000。重量平均分子量就硬化膜之回流焊處理適用性之觀點而言，較佳為700以上，另一方面，就感光性樹脂組合物之鹼溶解性之觀點而言，較佳為100,000以下。 (聚羥基苯乙烯) 本文中，所謂聚羥基苯乙烯意指含有羥基苯乙烯作為聚合單元之聚合物全體。作為聚羥基苯乙烯之較佳例，可列舉聚對乙烯基苯酚。聚對乙烯基苯酚意指含有對乙烯基苯酚作為聚合單元之聚合物全體。因此，只要不違反本發明之目的，則可使用羥基苯乙烯(例如對乙烯基苯酚)以外之聚合單元來構成聚羥基苯乙烯(例如聚對乙烯基苯酚)。聚羥基苯乙烯中，以全部聚合單元之莫耳數基準計之羥基苯乙烯單元之莫耳數之比率較佳為10莫耳%～99莫耳%，更佳為20～97莫耳%，進而較佳為30～95莫耳%。於上述比率為10莫耳%以上之情形時，於感光性樹脂組合物之鹼溶解性之觀點而言有利，於99莫耳%以下之情形時，於使含有下述共聚成分之組合物硬化而成之硬化膜之回流焊適用性之觀點而言有利。羥基苯乙烯(例如對乙烯基苯酚)以外之聚合單元可為能夠與羥基苯乙烯(例如對乙烯基苯酚)進行共聚之任意之聚合單元。作為形成羥基苯乙烯(例如對乙烯基苯酚)以外之聚合單元的共聚成分，並無限定，可列舉：例如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸羥基乙酯、甲基丙烯酸丁酯、丙烯酸辛酯、甲基丙烯酸2-乙氧基乙酯、丙烯酸第三丁酯、1,5-戊二醇二丙烯酸酯、丙烯酸N,N-二乙基胺基乙酯、乙二醇二丙烯酸酯、1,3-丙二醇二丙烯酸酯、癸二醇二丙烯酸酯、癸二醇二甲基丙烯酸酯、1,4-環己二醇二丙烯酸酯、2,2-二羥甲基丙烷二丙烯酸酯、甘油二丙烯酸酯、三丙二醇二丙烯酸酯、甘油三丙烯酸酯、2,2-二(對羥基苯基)丙烷二甲基丙烯酸酯、三乙二醇二丙烯酸酯、聚氧乙基-2-2-二(對羥基苯基)丙烷二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、聚氧丙基三羥甲基丙烷三丙烯酸酯、乙二醇二甲基丙烯酸酯、丁二醇二甲基丙烯酸酯、1,3-丙二醇二甲基丙烯酸酯、丁二醇二甲基丙烯酸酯、1,3-丙二醇二甲基丙烯酸酯、1,2,4-丁三醇三甲基丙烯酸酯、2,2,4-三甲基-1,3-戊二醇二甲基丙烯酸酯、季戊四醇三甲基丙烯酸酯、1,2-二甲基丙烯酸1-苯基乙二酯、季戊四醇四甲基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、1,5-戊二醇二甲基丙烯酸酯及1,4-苯二醇二甲基丙烯酸酯之類的丙烯酸之酯；苯乙烯以及例如2-甲基苯乙烯及乙烯基甲苯之類的經取代之苯乙烯；例如丙烯酸乙烯酯及甲基丙烯酸乙烯酯之類的乙烯酯單體；以及鄰乙烯基苯酚、間乙烯基苯酚等。又，作為上述說明之酚醛清漆及聚羥基苯乙烯，分別可單獨使用1種或將2種以上組合使用。聚羥基苯乙烯之重量平均分子量較佳為700～100,000，更佳為1,500～80,000，進而較佳為2,000～50,000。重量平均分子量就硬化膜之回流焊處理適用性之觀點而言，較佳為700以上，另一方面，就感光性樹脂組合物之鹼溶解性之觀點而言，較佳為100,000以下。 (通式(7)所表示之酚樹脂) 本實施形態中，(A)酚樹脂亦較佳為包含具有下述通式(7)： [化69]

{式中，a為1～3之整數，b為0～3之整數，1≦(a＋b)≦4，R₁₂ 表示選自由碳數1～20之1價之有機基、鹵素原子、硝基及氰基所組成之群中之1價之取代基，於b為2或3之情形時，複數個R₁₂ 相互可相同或亦可不同，X表示選自由可具有不飽和鍵之碳數2～10之2價之脂肪族基、碳數3～20之2價之脂環式基、下述通式(8)： [化70]

(式中，p為1～10之整數)所表示之2價之伸烷氧基、及具有碳數6～12之芳香族環之2價之有機基所組成之群中之2價之有機基}所表示之重複單元之酚樹脂。具有上述重複單元之酚樹脂與例如先前使用之聚醯亞胺樹脂及聚苯并㗁唑樹脂相比能夠於低溫下硬化，且能夠形成具有良好之伸長率之硬化膜，於該方面而言特別有利。酚樹脂分子中所存在之上述重複單元可為1種或2種以上之組合。上述通式(7)中，R₁₂ 就合成通式(7)之樹脂時之反應性之觀點而言為選自由碳數1～20之1價之有機基、鹵素原子、硝基及氰基所組成之群中之1價之取代基。R₁₂ 就鹼溶解性之觀點而言，較佳為選自由鹵素原子、硝基、氰基、可具有不飽和鍵之碳數1～10之脂肪族基、碳數6～20之芳香族基、及下述通式(45)： [化71]

{式中，R₆₁ 、R₆₂ 及R₆₃ 分別獨立表示氫原子、可具有不飽和鍵之碳數1～10之脂肪族基、碳數3～20之脂環式基、或碳數6～20之芳香族基，並且R₆₄ 表示可具有不飽和鍵之碳數1～10之2價之脂肪族基、碳數3～20之2價之脂環式基、或碳數6～20之2價之芳香族基}所表示之四種基所組成之群中之1價之取代基。本實施形態中，上述通式(7)中，a為1～3之整數，但就鹼溶解性及伸長率之觀點而言，較佳為2。又，於a為2之情形時，羥基彼此之取代位置可為鄰位、間位及對位之任意位置。並且，於a為3之情形時，羥基彼此之取代位置可為1,2,3-位、1,2,4-位及1,3,5-位等任意位置。本實施形態中，上述通式(7)中，於a為1之情形時，為了提高鹼溶解性，可對具有通式(7)所表示之重複單元之酚樹脂(以下亦稱為(a1)樹脂)進而混合選自酚醛清漆及聚羥基苯乙烯中之酚樹脂(以下亦稱為(a2)樹脂)。 (a1)樹脂與(a2)樹脂之混合比以質量比計較佳為(a1)/(a2)＝10/90～90/10之範圍。該混合比就於鹼性水溶液中之溶解性、及硬化膜之伸長率之觀點而言，較佳為(a1)/(a2)＝10/90～90/10，更佳為(a1)/(a2)＝20/80～80/20，進而較佳為(a1)/(a2)＝30/70～70/30。關於作為上述(a2)樹脂之酚醛清漆及聚羥基苯乙烯，可使用與上述(酚醛清漆)及(聚羥基苯乙烯)項中所示者相同之樹脂。本實施形態中，上述通式(7)中，b為0～3之整數，但就鹼溶解性及伸長率之觀點而言，較佳為0或1。又，於b為2或3之情形時，複數個R₁₂ 相互可相同或亦可不同。進而，本實施形態中，上述通式(7)中，a及b滿足1≦(a＋b)≦4之關係。本實施形態中，上述通式(7)中，X就硬化浮凸圖案形狀、及硬化膜之伸長率之觀點而言為選自由可具有不飽和鍵之碳數2～10之2價之脂肪族基、碳數3～20之2價之脂環式基、上述通式(8)所表示之伸烷氧基、及具有碳數6～12之芳香族環之2價之有機基所組成之群中之2價之有機基。該等2價之有機基之中，就硬化後之膜之強韌性之觀點而言，X較佳為選自由下述通式(9)： [化72]

{式中，R₁₃ 、R₁₄ 、R₁₅ 及R₁₆ 分別獨立為氫原子、碳數1～10之1價之脂肪族基、或氫原子之一部分或全部被取代為氟原子而成之碳數1～10之1價之脂肪族基，n₆ 為0～4之整數，且n₆ 為1～4之整數之情形時之R₁₇ 為鹵素原子、羥基、或碳數1～12之1價之有機基，至少1個R₁₇ 為羥基，n₆ 為2～4之整數之情形時之複數個R₁₇ 相互可相同或亦可不同}所表示之2價之基、及下述通式(10)： [化73]

{式中，R₁₈ 、R₁₉ 、R₂₀ 及R₂₁ 分別獨立表示氫原子、碳數1～10之1價之脂肪族基、或氫原子之一部分或全部被取代為氟原子而成之碳數1～10之1價之脂肪族基，W為單鍵、選自由可經氟原子取代之碳數1～10之脂肪族基、可經氟原子取代之碳數3～20之脂環式基、下述通式(8)： [化74]

(式中，p為1～10之整數)所表示之2價之伸烷氧基、及下述式(11)： [化75]

所表示之2價之基所組成之群中之2價之有機基}所表示之2價之基所組成之群中之2價之有機基。上述具有碳數6～12之芳香族環之2價之有機基X之碳數較佳為8～75，更佳為8～40。再者，上述具有碳數6～12之芳香族環之2價之有機基X之結構一般而言不同於上述通式(7)中之芳香環上鍵結有OH基及任意之R₁₂ 基之結構。進而，上述通式(10)所表示之2價之有機基就樹脂組合物之圖案形成性、及硬化後之硬化膜之伸長率良好之觀點而言，更佳為下述式(12)： [化76]

所表示之2價之有機基，進而尤佳為下述式(13)： [化77]

所表示之2價之有機基。通式(7)所表示之結構中，X尤佳為上述式(12)或(13)所表示之結構，X之以式(12)或(13)表示之結構所代表之部位之比率就伸長率之觀點而言，較佳為20質量%以上，更佳為30質量%以上。上述比率就組合物之鹼溶解性之觀點而言，較佳為80質量%以下，更佳為70質量%以下。又，具有上述通式(7)所表示之結構之酚樹脂之中，就組合物之鹼溶解性、及硬化膜之伸長率之觀點而言，尤佳為於同一樹脂骨架內具有下述通式(14)所表示之結構及下述通式(15)所表示之結構該兩者的結構。 [化78]

{式中，R₂₁ 為選自由烴基及烷氧基所組成之群中之碳數1～10之1價之基，n₇ 為2或3，n₈ 為0～2之整數，m₅ 為1～500之整數，2≦(n₇ ＋n₈ )≦4，於n₈ 為2之情形時，複數個R₂₁ 相互可相同或亦可不同} [化79]

{式中，R₂₂ 及R₂₃ 分別獨立為選自由烴基及烷氧基所組成之群中之碳數1～10之1價之基，n₉ 為1～3之整數，n₁₀ 為0～2之整數，n₁₁ 為0～3之整數，m₆ 為1～500之整數，2≦(n₉ ＋n₁₀ )≦4，於n₁₀ 為2之情形時，複數個R₂₂ 相互可相同或亦可不同，於n₁₁ 為2或3之情形時，複數個R₂₃ 相互可相同或亦可不同} 上述通式(14)之m₅ 及上述通式(15)之m₆ 表示酚樹脂之主鏈中之各自之重複單元之總數。即，(A)酚樹脂中，例如上述通式(14)所表示之結構中之括弧內之重複單元與上述通式(15)所表示之結構中之括弧內之重複單元可以無規、嵌段或該等之組合之形式排列。m₅ 及m₆ 分別獨立為1～500之整數，下限值較佳為2，更佳為3，上限值較佳為450，更佳為400，進而較佳為350。m₅ 及m₆ 就硬化後之膜之強韌性之觀點而言，較佳為分別獨立為2以上，就於鹼性水溶液中之溶解性之觀點而言，較佳為450以下。m₅ 與m₆ 之合計就硬化後之膜之強韌性之觀點而言，較佳為2以上，更佳為4以上，進而較佳為6以上，就於鹼性水溶液中之溶解性之觀點而言，較佳為200以下，更佳為175以下，進而較佳為150以下。於同一樹脂骨架內具有上述通式(14)所表示之結構及上述通式(15)所表示之結構該兩者的(A)酚樹脂中，上述通式(14)所表示之結構之莫耳比率越高，則硬化後之膜物性越良好，耐熱性亦越優異，另一方面，上述通式(15)所表示之結構之莫耳比率越高，則鹼溶解性越良好，硬化後之圖案形狀越優異。因此，上述通式(14)所表示之結構相對於上述通式(15)所表示之結構的比率m₅ /m₆ 就硬化後之膜物性之觀點而言，較佳為20/80以上，更佳為40/60以上，尤佳為50/50以上，就鹼溶解性及硬化浮凸圖案形狀之觀點而言，較佳為90/10以下，更佳為80/20以下，進而較佳為70/30以下。具有通式(7)所表示之重複單元之酚樹脂典型而言包含酚化合物與共聚成分(具體而言為選自由具有醛基之化合物(亦包括如三㗁烷般分解生成醛化合物之化合物)、具有酮基之化合物、分子內具有2個羥甲基之化合物、分子內具有2個烷氧基甲基之化合物、及分子內具有2個鹵烷基之化合物所組成之群中之1種以上之化合物)，更典型而言可藉由使包含該等之單體成分進行聚合反應而合成。例如可使如下所述之苯酚及/或苯酚衍生物(以下亦統稱為「酚化合物」)與醛化合物、酮化合物、羥甲基化合物、烷氧基甲基化合物、二烯化合物或鹵烷基化合物等共聚成分進行聚合而獲得(A)酚樹脂。於該情形時，上述通式(7)中，芳香環上鍵結有OH基及任意之R₁₂ 基之結構所表示之部分源自上述酚化合物，X所表示之部分源自上述共聚成分。就反應控制、以及所獲得之(A)酚樹脂及感光性樹脂組合物之穩定性之觀點而言，酚化合物與上述共聚成分之添加莫耳比(酚化合物)：(共聚成分)較佳為5：1～1.01：1，更佳為2.5：1～1.1：1。具有通式(7)所表示之重複單元之酚樹脂之重量平均分子量較佳為700～100,000，更佳為1,500～80,000，進而較佳為2,000～50,000。重量平均分子量就硬化膜之回流焊處理適用性之觀點而言，較佳為700以上，另一方面，就感光性樹脂組合物之鹼溶解性之觀點而言，較佳為100,000以下。作為可用於獲得具有通式(7)所表示之重複單元之酚樹脂的酚化合物，例如可列舉：甲酚、乙基苯酚、丙基苯酚、丁基苯酚、戊基苯酚、環己基苯酚、羥基聯苯、苄基苯酚、硝基苄基苯酚、氰基苄基苯酚、金剛烷苯酚、硝基苯酚、氟苯酚、氯苯酚、溴苯酚、三氟甲基苯酚、N-(羥基苯基)-5-降𦯉烯-2,3-二羧基醯亞胺、N-(羥基苯基)-5-甲基-5-降𦯉烯-2,3-二羧基醯亞胺、三氟甲基苯酚、羥基苯甲酸、羥基苯甲酸甲酯、羥基苯甲酸乙酯、羥基苯甲酸苄酯、羥基苯甲醯胺、羥基苯甲醛、羥基苯乙酮、羥基二苯甲酮、羥基苯甲腈、間苯二酚、二甲苯酚、兒茶酚、甲基兒茶酚、乙基兒茶酚、己基兒茶酚、苄基兒茶酚、硝基苄基兒茶酚、甲基間苯二酚、乙基間苯二酚、己基間苯二酚、苄基間苯二酚、硝基苄基間苯二酚、氫醌、咖啡酸、二羥基苯甲酸、二羥基苯甲酸甲酯、二羥基苯甲酸乙酯、二羥基苯甲酸丁酯、二羥基苯甲酸丙酯、二羥基苯甲酸苄酯、二羥基苯甲醯胺、二羥基苯甲醛、二羥基苯乙酮、二羥基二苯甲酮、二羥基苯甲腈、N-(二羥基苯基)-5-降𦯉烯-2,3-二羧基醯亞胺、N-(二羥基苯基)-5-甲基-5-降𦯉烯-2,3-二羧基醯亞胺、硝基兒茶酚、氟兒茶酚、氯兒茶酚、溴兒茶酚、三氟甲基兒茶酚、硝基間苯二酚、氟間苯二酚、氯間苯二酚、溴間苯二酚、三氟甲基間苯二酚、連苯三酚、間苯三酚、1,2,4-三羥基苯、三羥基苯甲酸、三羥基苯甲酸甲酯、三羥基苯甲酸乙酯、三羥基苯甲酸丁酯、三羥基苯甲酸丙酯、三羥基苯甲酸苄酯、三羥基苯甲醯胺、三羥基苯甲醛、三羥基苯乙酮、三羥基二苯甲酮、三羥基苯甲腈等。作為上述醛化合物，例如可列舉：乙醛、丙醛、三甲基乙醛、丁醛、戊醛、己醛、三㗁烷、乙二醛、環己醛、二苯基乙醛、乙基丁醛、苯甲醛、乙醛酸、5-降𦯉烯-2-羧基醛、丙二醛、丁二醛、戊二醛、柳醛、萘甲醛、對苯二甲醛等。作為上述酮化合物，例如可列舉：丙酮、甲基乙基酮、二乙基酮、二丙基酮、二環己基酮、二苄基酮、環戊酮、環己酮、雙環己酮、環己烷二酮、3-丁炔-2-酮、2-降𦯉酮、金剛酮、2,2-雙(4-氧雜環己基)丙烷等。作為上述羥甲基化合物，例如可列舉：2,6-雙(羥基甲基)對甲酚、2,6-雙(羥基甲基)-4-乙基苯酚、2,6-雙(羥基甲基)-4-丙基苯酚、2,6-雙(羥基甲基)-4-正丁基苯酚、2,6-雙(羥基甲基)-4-第三丁基苯酚、2,6-雙(羥基甲基)-4-甲氧基苯酚、2,6-雙(羥基甲基)-4-乙氧基苯酚、2,6-雙(羥基甲基)-4-丙氧基苯酚、2,6-雙(羥基甲基)-4-正丁氧基苯酚、2,6-雙(羥基甲基)-4-第三丁氧基苯酚、1,3-雙(羥基甲基)脲、核糖醇、阿拉伯糖醇、阿洛醇、2,2-雙(羥基甲基)丁酸、2-苄氧基-1,3-丙二醇、2,2-二甲基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、單乙酸甘油酯、2-甲基-2-硝基-1,3-丙二醇、5-降𦯉烯-2,2-二甲醇、5-降𦯉烯-2,3-二甲醇、季戊四醇、2-苯基-1,3-丙二醇、三羥甲基乙烷、三羥甲基丙烷、3,6-雙(羥基甲基)均四甲苯、2-硝基對苯二甲醇、1,10-二羥基癸烷、1,12-二羥基十二烷、1,4-雙(羥基甲基)環己烷、1,4-雙(羥基甲基)環己烯、1,6-雙(羥基甲基)金剛烷、1,4-苯二甲醇、1,3-苯二甲醇、2,6-雙(羥基甲基)-1,4-二甲氧基苯、2,3-雙(羥基甲基)萘、2,6-雙(羥基甲基)萘、1,8-雙(羥基甲基)蒽、2,2'-雙(羥基甲基)二苯醚、4,4'-雙(羥基甲基)二苯醚、4,4'-雙(羥基甲基)二苯硫醚、4,4'-雙(羥基甲基)二苯甲酮、4-羥基甲基苯甲酸-4'-羥基甲基苯酯、4-羥基甲基苯甲酸-4'-羥基甲基苯胺、4,4'-雙(羥基甲基)苯基脲、4,4'-雙(羥基甲基)苯基胺基甲酸酯、1,8-雙(羥基甲基)蒽、4,4'-雙(羥基甲基)聯苯、2,2'-二甲基-4,4'-雙(羥基甲基)聯苯、2,2-雙(4-羥基甲基苯基)丙烷、乙二醇、二乙二醇、三乙二醇、四乙二醇、丙二醇、二丙二醇、三丙二醇、四丙二醇等。作為上述烷氧基甲基化合物，例如可列舉：2,6-雙(甲氧基甲基)對甲酚、2,6-雙(甲氧基甲基)-4-乙基苯酚、2,6-雙(甲氧基甲基)-4-丙基苯酚、2,6-雙(甲氧基甲基)-4-正丁基苯酚、2,6-雙(甲氧基甲基)-4-第三丁基苯酚、2,6-雙(甲氧基甲基)-4-甲氧基苯酚、2,6-雙(甲氧基甲基)-4-乙氧基苯酚、2,6-雙(甲氧基甲基)-4-丙氧基苯酚、2,6-雙(甲氧基甲基)-4-正丁氧基苯酚、2,6-雙(甲氧基甲基)-4-第三丁氧基苯酚、1,3-雙(甲氧基甲基)脲、2,2-雙(甲氧基甲基)丁酸、2,2-雙(甲氧基甲基)-5-降𦯉烯、2,3-雙(甲氧基甲基)-5-降𦯉烯、1,4-雙(甲氧基甲基)環己烷、1,4-雙(甲氧基甲基)環己烯、1,6-雙(甲氧基甲基)金剛烷、1,4-雙(甲氧基甲基)苯、1,3-雙(甲氧基甲基)苯、2,6-雙(甲氧基甲基)-1,4-二甲氧基苯、2,3-雙(甲氧基甲基)萘、2,6-雙(甲氧基甲基)萘、1,8-雙(甲氧基甲基)蒽、2,2'-雙(甲氧基甲基)二苯醚、4,4'-雙(甲氧基甲基)二苯醚、4,4'-雙(甲氧基甲基)二苯硫醚、4,4'-雙(甲氧基甲基)二苯甲酮、4-甲氧基甲基苯甲酸-4'-甲氧基甲基苯基、4-甲氧基甲基苯甲酸-4'-甲氧基甲基苯胺、4,4'-雙(甲氧基甲基)苯基脲、4,4'-雙(甲氧基甲基)苯基胺基甲酸酯、1,8-雙(甲氧基甲基)蒽、4,4'-雙(甲氧基甲基)聯苯、2,2'-二甲基-4,4'-雙(甲氧基甲基)聯苯、2,2-雙(4-甲氧基甲基苯基)丙烷、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、丙二醇二甲醚、二丙二醇二甲醚、三丙二醇二甲醚、四丙二醇二甲醚等。作為上述二烯化合物，例如可列舉：丁二烯、戊二烯、己二烯、庚二烯、辛二烯、3-甲基-1,3-丁二烯、1,3-丁二醇-二甲基丙烯酸酯、2,4-己二烯-1-醇、甲基環己二烯、環戊二烯、環己二烯、環庚二烯、環辛二烯、二環戊二烯、1-羥基二環戊二烯、1-甲基環戊二烯、甲基二環戊二烯、二烯丙醚、二烯丙基硫醚、己二酸二烯丙酯、2,5-降𦯉二烯、四氫茚、5-亞乙基-2-降𦯉烯、5-乙烯基-2-降𦯉烯、三聚氰酸三烯丙酯、異三聚氰酸二烯丙酯、異三聚氰酸三烯丙酯、異三聚氰酸二烯丙基丙酯等。作為上述鹵烷基化合物，例如可列舉：二氯二甲苯、雙氯甲基二甲氧基苯、雙氯甲基均四甲苯、雙氯甲基聯苯、雙氯甲基-聯苯基羧酸、雙氯甲基-聯苯基二羧酸、雙氯甲基-甲基聯苯、雙氯甲基-二甲基聯苯、雙氯甲基蒽、乙二醇雙(氯乙基)醚、二乙二醇雙(氯乙基)醚、三乙二醇雙(氯乙基)醚、四乙二醇雙(氯乙基)醚等。使上述酚化合物與共聚成分藉由脫水、脫鹵化氫、或脫醇而縮合，或一面使不飽和鍵斷鍵一面進行聚合，藉此可獲得(A)酚樹脂，聚合時亦可使用觸媒。作為酸性之觸媒，例如可列舉：鹽酸、硫酸、硝酸、磷酸、亞磷酸、甲磺酸、對甲苯磺酸、二甲基硫酸、二乙基硫酸、乙酸、草酸、1-羥基亞乙基-1,1'-二膦酸、乙酸鋅、三氟化硼、三氟化硼-苯酚錯合物、三氟化硼-醚錯合物等。另一方面，作為鹼性之觸媒，例如可列舉：氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化鈣、氫氧化鋇、碳酸鈉、三乙胺、吡啶、4-N,N-二甲基胺基吡啶、哌啶、哌𠯤、1,4-二氮雜雙環[2.2.2]辛烷、1,8-二氮雜雙環[5.4.0]-7-十一烯、1,5-二氮雜雙環[4.3.0]-5-壬烯、氨、六亞甲基四胺等。關於用以獲得具有通式(7)所表示之重複結構之酚樹脂的觸媒之量，相對於共聚成分(即酚化合物以外之成分)之合計莫耳數、較佳為醛化合物、酮化合物、羥甲基化合物、烷氧基甲基化合物、二烯化合物及鹵烷基化合物之合計莫耳數100莫耳%，較佳為0.01莫耳%～100莫耳%之範圍。 (A)酚樹脂之合成反應中，反應溫度通常較佳為40℃～250℃，更佳為100℃～200℃之範圍，並且反應時間較佳為約1小時～10小時。視需要可使用能夠使該樹脂充分溶解之溶劑。再者，具有通式(7)所表示之重複結構之酚樹脂亦可為於無損本發明之效果之範圍內進而聚合有不成為上述通式(7)之結構之原料的酚化合物者。所謂無損本發明之效果之範圍係例如成為(A)酚樹脂之原料的酚化合物總莫耳數之30%以下。 (經具有碳數4～100之不飽和烴基之化合物改性的酚樹脂) 經具有碳數4～100之不飽和烴基之化合物改性的酚樹脂為苯酚或其衍生物與具有碳數4～100之不飽和烴基之化合物(以下有時簡稱為「含不飽和烴基之化合物」)之反應產物(以下亦稱為「不飽和烴基改性苯酚衍生物」)和醛類的縮聚合產物，或為酚樹脂和含不飽和烴基之化合物的反應產物。苯酚衍生物可使用與上述作為具有通式(7)所表示之重複單元之酚樹脂之原料所記述之苯酚衍生物相同者。關於含不飽和烴基之化合物之不飽和烴基，就硬化膜之殘留應力及回流焊處理適用性之觀點而言，較佳為包含2個以上之不飽和基。又，就製成樹脂組合物時之相溶性及硬化膜之殘留應力之觀點而言，不飽和烴基較佳為碳數4～100，更佳為碳數8～80，進而較佳為碳數10～60。作為含不飽和烴基之化合物，例如可列舉：碳數4～100之不飽和烴、具有羧基之聚丁二烯、環氧化聚丁二烯、亞麻醇、油醇、不飽和脂肪酸及不飽和脂肪酸酯。作為適宜之不飽和脂肪酸，可列舉：丁烯酸、肉豆蔻油酸、棕櫚油酸、油酸、反油酸、異油酸、鱈油酸、芥子酸、二十四烯酸、亞麻油酸、α-次亞麻油酸、桐酸、十八碳四烯酸、花生四烯酸、二十碳五烯酸、鯡魚酸及二十二碳六烯酸。該等之中，尤其就硬化膜之伸長率、及硬化膜之可撓性之觀點而言，尤佳為作為不飽和脂肪酸酯之植物油。植物油通常包含甘油與不飽和脂肪酸之酯，存在碘值為100以下之不乾性油、超過100且未達130之半乾性油或130以上之乾性油。作為不乾性油，例如可列舉：橄欖油、牽牛花籽油、何首烏油、茶梅油、山茶油、蓖麻油及花生油。作為半乾性油，例如可列舉：玉米油、棉籽油及芝麻油。作為乾性油，例如可列舉：桐油、亞麻仁油、大豆油、胡桃油、紅花油、葵花籽油、荏子油及芥子油。又，亦可使用由該等植物油加工而成之加工植物油。上述植物油之中，就於苯酚或其衍生物或者酚樹脂與植物油之反應中防止隨反應過度進行而產生之凝膠化、提高良率之觀點而言，較佳為使用不乾性油。另一方面，就抗蝕圖案之密接性、機械特性及耐熱衝擊性提高之觀點而言，較佳為使用乾性油。乾性油之中，就可更有效且確實地發揮本發明之效果之方面而言，較佳為桐油、亞麻仁油、大豆油、胡桃油及紅花油，更佳為桐油及亞麻仁油。該等植物油可單獨使用1種或將2種以上組合使用。苯酚或其衍生物與含不飽和烴基之化合物的反應較佳為於50～130℃下進行。關於苯酚或其衍生物與含不飽和烴基之化合物的反應比率，就降低硬化膜之殘留應力之觀點而言，相對於苯酚或其衍生物100質量份，含不飽和烴基之化合物較佳為1～100質量份，更佳為5～50質量份。若含不飽和烴基之化合物未達1質量份，則存在硬化膜之可撓性降低之傾向，若超過100質量份，則存在硬化膜之耐熱性降低之傾向。於上述反應中，視需要亦可使用對甲苯磺酸、三氟甲磺酸等作為觸媒。使利用上述反應而生成之不飽和烴基改性苯酚衍生物與醛類進行縮聚合，藉此生成經含不飽和烴基之化合物改性的酚樹脂。醛類例如自甲醛、乙醛、糠醛、苯甲醛、羥基苯甲醛、甲氧基苯甲醛、羥基苯基乙醛、甲氧基苯基乙醛、巴豆醛、氯乙醛、氯苯基乙醛、丙酮、甘油醛、乙醛酸、乙醛酸甲酯、乙醛酸苯酯、乙醛酸羥基苯酯、甲醯基乙酸、甲醯基乙酸甲酯、2-甲醯基丙酸、2-甲醯基丙酸甲酯、丙酮酸、乙醯丙酸、4-乙醯丁酸、丙酮二羧酸及3,3'-4,4'-二苯甲酮四羧酸中選擇。又，亦可使用多聚甲醛、三㗁烷等甲醛前驅物。該等醛類可單獨使用1種或將2種以上組合使用。上述醛類與上述不飽和烴基改性苯酚衍生物之反應為縮聚合反應，可採用先前公知之酚樹脂之合成條件。反應較佳為於酸或鹼等觸媒之存在下進行，就樹脂之聚合度(分子量)之觀點而言，更佳為使用酸觸媒。作為酸觸媒，例如可列舉：鹽酸、硫酸、甲酸、乙酸、對甲苯磺酸及草酸。該等酸觸媒可單獨使用1種或將2種以上組合使用。上述反應通常較佳為於反應溫度100～120℃下進行。又，反應時間根據所使用之觸媒之種類或量而不同，通常為1～50小時。反應結束後，藉由將反應產物於200℃以下之溫度下減壓脫水而獲得經含不飽和烴基之化合物改性的酚樹脂。再者，反應時可使用甲苯、二甲苯、甲醇等溶劑。經含不飽和烴基之化合物改性的酚樹脂亦可藉由使間二甲苯之類的苯酚以外之化合物及醛類一起與上述不飽和烴基改性苯酚衍生物進行縮聚合而獲得。於該情形時，苯酚以外之化合物相對於由苯酚衍生物與含不飽和烴基之化合物反應而獲得之化合物的添加莫耳比較佳為未達0.5。經含不飽和烴基之化合物改性的酚樹脂亦可藉由使酚樹脂與含不飽和烴基之化合物進行反應而獲得。該情形時所使用之酚樹脂為酚化合物(即苯酚及/或苯酚衍生物)與醛類之縮聚合產物。於該情形時，作為苯酚衍生物及醛類，可使用與上述苯酚衍生物及醛類相同者，可於如上所述之先前公知之條件下合成酚樹脂。作為由適宜用於形成經含不飽和烴基之化合物改性的酚樹脂之酚化合物與醛類所獲得之酚樹脂之具體例，可列舉：苯酚/甲醛酚醛清漆樹脂、甲酚/甲醛酚醛清漆樹脂、苯二甲酚/甲醛酚醛清漆樹脂、間苯二酚/甲醛酚醛清漆樹脂及苯酚-萘酚/甲醛酚醛清漆樹脂。與酚樹脂反應之含不飽和烴基之化合物可使用和上述參與製造與醛類反應之不飽和烴基改性苯酚衍生物的含不飽和烴基之化合物相同者。酚樹脂與含不飽和烴基之化合物的反應通常較佳為於50～130℃下進行。又，關於酚樹脂與含不飽和烴基之化合物的反應比率，就提高硬化膜(抗蝕圖案)之可撓性之觀點而言，相對於酚樹脂100質量份，含不飽和烴基之化合物較佳為1～100質量份，更佳為2～70質量份，進而較佳為5～50質量份。若含不飽和烴基之化合物未達1質量份，則存在硬化膜之可撓性降低之傾向，若超過100質量份，則存在反應中產生凝膠化之可能性變高之傾向、及硬化膜之耐熱性降低之傾向。於酚樹脂與含不飽和烴基之化合物反應時視需要亦可使用對甲苯磺酸、三氟甲磺酸等作為觸媒。再者，反應時可使用例如甲苯、二甲苯、甲醇、四氫呋喃等溶劑，於下文進行詳細說明。亦可使用藉由使利用如上方法所生成之經含不飽和烴基之化合物改性的酚樹脂中所殘留之酚性羥基進而與多元酸酐進行反應而實現酸改性的酚樹脂。藉由利用多元酸酐進行酸改性而導入羧基，於鹼性水溶液(用作顯影液者)中之溶解性進一步提高。多元酸酐只要具有含複數個羧基之多元酸之羧基經脫水縮合而形成之酸酐基，則並無特別限定。作為多元酸酐，例如可列舉：鄰苯二甲酸酐、琥珀酸酐、辛烯基琥珀酸酐、十五烯基琥珀酸酐、順丁烯二酸酐、伊康酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、耐地酸酐、3,6-內亞甲基四氫鄰苯二甲酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、四溴鄰苯二甲酸酐及偏苯三甲酸酐等二元酸酐，聯苯基四羧酸二酐、萘四羧酸二酐、二苯醚四羧酸二酐、丁烷四羧酸二酐、環戊烷四羧酸二酐、均苯四甲酸二酐及二苯甲酮四羧酸二酐等芳香族四元酸二酐。該等可單獨使用1種或將2種以上組合使用。該等之中，多元酸酐較佳為二元酸酐，更佳為選自由四氫鄰苯二甲酸酐、琥珀酸酐及六氫鄰苯二甲酸酐所組成之群中之1種以上。於該情形時，具有可形成形狀更良好之抗蝕圖案之優點。酚性羥基與多元酸酐之反應可於50～130℃下進行。於該反應中，相對於酚性羥基1莫耳，較佳為使0.10～0.80莫耳之多元酸酐進行反應，更佳為使0.15～0.60莫耳進行反應，進而較佳為使0.20～0.40莫耳進行反應。若多元酸酐未達0.10莫耳，則存在顯影性降低之傾向，若超過0.80莫耳，則存在未曝光部之耐鹼性降低之傾向。再者，就使反應快速進行之觀點而言，上述反應時視需要可含有觸媒。作為觸媒，可列舉：三乙胺等三級胺、三乙基苄基氯化銨等四級銨鹽、2-乙基-4-甲基咪唑等咪唑化合物、三苯基膦等磷化合物。進而經多元酸酐改性之酚樹脂之酸值較佳為30～200 mgKOH/g，更佳為40～170 mgKOH/g，進而較佳為50～150 mgKOH/g。若酸值未達30 mgKOH/g，則與酸值處於上述範圍之情形相比存在鹼性顯影所需時間較長之傾向，若超過200 mgKOH/g，則與酸值處於上述範圍之情形相比存在未曝光部之耐顯影液性降低之傾向。關於經含不飽和烴基之化合物改性的酚樹脂之分子量，考慮到於鹼性水溶液中之溶解性、或感光特性與硬化膜物性之均衡性，以重量平均分子量計較佳為1000～100000，更佳為2000～100000。作為本實施形態之(A)酚樹脂，亦較佳為選自具有上述通式(7)所表示之重複單元之酚樹脂及上述經具有碳數4～100之不飽和烴基之化合物改性的酚樹脂中之至少一種酚樹脂(以下亦稱為(a3)樹脂)、與選自酚醛清漆及聚羥基苯乙烯中之酚樹脂(以下亦稱為(a4)樹脂)的混合物。(a3)樹脂與(a4)樹脂之混合比以質量比計為(a3)/(a4)＝5/95～95/5之範圍。該混合比就於鹼性水溶液中之溶解性、形成抗蝕圖案時之感度與解像性、及硬化膜之殘留應力、回流焊處理適用性之觀點而言，較佳為(a3)/(a4)＝5/95～95/5，更佳為(a3)/(a4)＝10/90～90/10，進而較佳為(a3)/(a4)＝15/85～85/15。關於作為上述(a4)樹脂之酚醛清漆及聚羥基苯乙烯，可使用與上述(酚醛清漆)及(聚羥基苯乙烯)項中所示者相同之樹脂。 (B)塑化劑以下對本實施形態中之(B)塑化劑進行詳細說明。(B)塑化劑係於對使用本實施形態之感光性樹脂組合物所形成之浮凸圖案進行加熱硬化時提高(A)樹脂之流動性、提高(A)樹脂之聚合物之堆積性的化合物。藉由堆積性提高，而可抑制於高溫保存試驗中產生空隙，可抑制於Cu層與樹脂層之界面處密接性降低。(B)塑化劑只要為符合上述條件者，則並無特別限定。關於作為(B)塑化劑發揮功能之化合物，可尤佳地使用下述通式(7)： [化80]

{式中，X為包含碳數為1以上且15以下之飽和烴或不飽和烴或芳香族烴之結構，n為1～4之整數，於n為2以上之情形時，R分別可相同亦可不同，為碳數為2以上且15以下之飽和烴或不飽和烴或芳香族烴)所表示之化合物。其中，作為本發明之塑化劑，較佳為選自由下述通式(8)： [化81]

{式中，m為1～4之整數，於m為2以上之情形時，R分別可相同亦可不同，表示碳數為2以上且15以下之飽和烴或不飽和烴或芳香族烴}所表示、或下述通式(9)： [化82]

{式中，Y為包含碳數為1以上且10以下之飽和烴或不飽和烴或芳香族烴之結構，R分別可相同亦可不同，表示碳數為2以上且15以下之飽和烴或不飽和烴或芳香族烴}所組成之群中之至少一種。作為上述通式(7)所表示之塑化劑，可列舉：苯甲酸酯、鄰苯二甲酸酯、間苯二甲酸酯、對苯二甲酸酯、偏苯三甲酸酯、均苯四甲酸酯及脂肪族酸四氫糠酯等。作為苯甲酸酯之具體之化合物例，可列舉：苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸丁酯、苯甲酸戊酯、苯甲酸庚酯、苯甲酸正辛酯、苯甲酸壬酯、苯甲酸異壬酯、苯甲酸異癸酯、苯甲酸2-乙基己酯、苯甲酸異癸酯、苯甲酸丁基苄酯、苯甲酸環丙酯、苯甲酸環丁酯、苯甲酸環戊酯、苯甲酸環己酯、苯甲酸環庚酯、苯甲酸烯丙酯、苯甲酸丁基苄酯、苯甲酸苯酯。其中，尤其適宜使用苯甲酸2-乙基己酯、苯甲酸環己酯、苯甲酸苯酯。作為鄰苯二甲酸酯之具體之化合物例，可列舉：鄰苯二甲酸二甲酯、鄰苯二甲酸二乙酯、鄰苯二甲酸二丙酯、鄰苯二甲酸二丁酯、鄰苯二甲酸二戊酯、鄰苯二甲酸二庚酯、鄰苯二甲酸二正辛酯、鄰苯二甲酸二壬酯、鄰苯二甲酸二異壬酯、鄰苯二甲酸二異癸酯、鄰苯二甲酸雙(2-乙基己基)酯、鄰苯二甲酸二異癸酯、鄰苯二甲酸丁基苄酯、鄰苯二甲酸二環丙酯、鄰苯二甲酸二環丁酯、鄰苯二甲酸二環戊酯、鄰苯二甲酸二環己酯、鄰苯二甲酸二環庚酯、鄰苯二甲酸二烯丙酯、鄰苯二甲酸雙丁基苄酯、鄰苯二甲酸二苯酯。其中，尤其適宜使用鄰苯二甲酸雙(2-乙基己基)酯、鄰苯二甲酸二環己酯、鄰苯二甲酸二苯酯。作為間苯二甲酸酯之具體之化合物例，可列舉：間苯二甲酸二甲酯、間苯二甲酸二乙酯、間苯二甲酸二丙酯、間苯二甲酸二丁酯、間苯二甲酸二戊酯、間苯二甲酸二庚酯、間苯二甲酸二正辛酯、間苯二甲酸二壬酯、間苯二甲酸二異壬酯、間苯二甲酸二異癸酯、間苯二甲酸雙(2-乙基己基)酯、間苯二甲酸二異癸酯、間苯二甲酸丁基苄酯、間苯二甲酸二環丙酯、間苯二甲酸二環丁酯、間苯二甲酸二環戊酯、間苯二甲酸二環己酯、間苯二甲酸二環庚酯、間苯二甲酸二烯丙酯、間苯二甲酸雙丁基苄酯、間苯二甲酸二苯酯。其中，尤其適宜使用間苯二甲酸雙(2-乙基己基)酯、間苯二甲酸二環己酯、間苯二甲酸二苯酯。作為對苯二甲酸酯之具體之化合物例，可列舉：對苯二甲酸二甲酯、對苯二甲酸二乙酯、對苯二甲酸二丙酯、對苯二甲酸二丁酯、對苯二甲酸二戊酯、對苯二甲酸二庚酯、對苯二甲酸二正辛酯、對苯二甲酸二壬酯、對苯二甲酸二異壬酯、對苯二甲酸二異癸酯、對苯二甲酸雙(2-乙基己基)酯、對苯二甲酸二異癸酯、對苯二甲酸丁基苄酯、對苯二甲酸二環丙酯、對苯二甲酸二環丁酯、對苯二甲酸二環戊酯、對苯二甲酸二環己酯、對苯二甲酸二環庚酯、對苯二甲酸二烯丙酯、對苯二甲酸雙丁基苄酯、對苯二甲酸二苯酯。其中，尤其適宜使用對苯二甲酸雙(2-乙基己基)酯、對苯二甲酸二環己酯、對苯二甲酸二苯酯。作為偏苯三甲酸酯之具體之化合物例，可列舉：偏苯三甲酸三甲酯、偏苯三甲酸三乙酯、偏苯三甲酸三丙酯、偏苯三甲酸三丁酯、偏苯三甲酸三戊酯、偏苯三甲酸三庚酯、偏苯三甲酸三正辛酯、偏苯三甲酸三壬酯、偏苯三甲酸三異壬酯、偏苯三甲酸三異癸酯、偏苯三甲酸三(2-乙基己基)酯、偏苯三甲酸三異癸酯、偏苯三甲酸三丁基苄酯、偏苯三甲酸三環丙酯、偏苯三甲酸三環丁酯、偏苯三甲酸三環戊酯、偏苯三甲酸三環己酯、偏苯三甲酸三環庚酯、偏苯三甲酸三烯丙酯、偏苯三甲酸三丁基苄酯、偏苯三甲酸三苯酯。其中，尤其適宜使用偏苯三甲酸三(2-乙基己基)酯、偏苯三甲酸三環己酯、偏苯三甲酸三苯酯。作為均苯四甲酸酯之具體之化合物例，可列舉：均苯四甲酸四甲酯、均苯四甲酸四乙酯、均苯四甲酸四丙酯、均苯四甲酸四丁酯、均苯四甲酸四戊酯、均苯四甲酸四庚酯、均苯四甲酸四正辛酯、均苯四甲酸四壬酯、均苯四甲酸四異壬酯、均苯四甲酸四異癸酯、均苯四甲酸四(2-乙基己基)酯、均苯四甲酸四異癸酯、均苯四甲酸四丁基苄酯、均苯四甲酸四環丙酯、均苯四甲酸四環丁酯、均苯四甲酸四環戊酯、均苯四甲酸四環己酯、均苯四甲酸四環庚酯、均苯四甲酸四烯丙酯、均苯四甲酸四丁基苄酯、均苯四甲酸四苯酯。其中，尤其適宜使用均苯四甲酸四(2-乙基己基)酯、均苯四甲酸四環己酯、均苯四甲酸四苯酯。作為上述通式(8)所表示之塑化劑，適宜使用丙二酸酯、琥珀酸酯、戊二酸酯、己二酸酯、庚二酸酯、辛二酸酯、壬二酸酯、癸二酸酯等。作為丙二酸酯之具體之化合物例，可列舉：丙二酸二甲酯、丙二酸二乙酯、丙二酸二丙酯、丙二酸二丁酯、丙二酸二戊酯、丙二酸二庚酯、丙二酸二正辛酯、丙二酸二壬酯、丙二酸二異壬酯、丙二酸二異癸酯、丙二酸雙(2-乙基己基)酯、丙二酸二異癸酯、丙二酸丁基苄酯、丙二酸二環丙酯、丙二酸二環丁酯、丙二酸二環戊酯、丙二酸二環己酯、丙二酸二環庚酯、丙二酸二烯丙酯、丙二酸雙丁基苄酯、丙二酸二苯酯。其中，尤其適宜使用丙二酸雙(2-乙基己基)酯、丙二酸二環己酯、丙二酸二苯酯。作為琥珀酸酯之具體之化合物例，可列舉：琥珀酸二甲酯、琥珀酸二乙酯、琥珀酸二丙酯、琥珀酸二丁酯、琥珀酸二戊酯、琥珀酸二庚酯、琥珀酸二正辛酯、琥珀酸二壬酯、琥珀酸二異壬酯、琥珀酸二異癸酯、琥珀酸雙(2-乙基己基)酯、琥珀酸二異癸酯、琥珀酸丁基苄酯、琥珀酸二環丙酯、琥珀酸二環丁酯、琥珀酸二環戊酯、琥珀酸二環己酯、琥珀酸二環庚酯、琥珀酸二烯丙酯、琥珀酸雙丁基苄酯、琥珀酸二苯酯。其中，尤其適宜使用琥珀酸雙(2-乙基己基)酯、琥珀酸二環己酯、琥珀酸二苯酯。作為戊二酸酯之具體之化合物例，可列舉：戊二酸二甲酯、戊二酸二乙酯、戊二酸二丙酯、戊二酸二丁酯、戊二酸二戊酯、戊二酸二庚酯、戊二酸二正辛酯、戊二酸二壬酯、戊二酸二異壬酯、戊二酸二異癸酯、戊二酸雙(2-乙基己基)酯、戊二酸二異癸酯、戊二酸丁基苄酯、戊二酸二環丙酯、戊二酸二環丁酯、戊二酸二環戊酯、戊二酸二環己酯、戊二酸二環庚酯、戊二酸二烯丙酯、戊二酸雙丁基苄酯、戊二酸二苯酯。其中，尤其適宜使用戊二酸雙(2-乙基己基)酯、戊二酸二環己酯、戊二酸二苯酯。作為己二酸酯之具體之化合物例，可列舉：己二酸二甲酯、己二酸二乙酯、己二酸二丙酯、己二酸二丁酯、己二酸二戊酯、己二酸二庚酯、己二酸二正辛酯、己二酸二壬酯、己二酸二異壬酯、己二酸二異癸酯、己二酸雙(2-乙基己基)酯、己二酸二異癸酯、己二酸丁基苄酯、己二酸二環丙酯、己二酸二環丁酯、己二酸二環戊酯、己二酸二環己酯、己二酸二環庚酯、己二酸二烯丙酯、己二酸雙丁基苄酯、己二酸二苯酯。其中，尤其適宜使用己二酸雙(2-乙基己基)酯、己二酸二環己酯、己二酸二苯酯。作為庚二酸酯之具體之化合物例，可列舉：庚二酸二甲酯、庚二酸二乙酯、庚二酸二丙酯、庚二酸二丁酯、庚二酸二戊酯、庚二酸二庚酯、庚二酸二正辛酯、庚二酸二壬酯、庚二酸二異壬酯、庚二酸二異癸酯、庚二酸雙(2-乙基己基)酯、庚二酸二異癸酯、庚二酸丁基苄酯、庚二酸二環丙酯、庚二酸二環丁酯、庚二酸二環戊酯、庚二酸二環己酯、庚二酸二環庚酯、庚二酸二烯丙酯、庚二酸雙丁基苄酯、庚二酸二苯酯。其中，尤其適宜使用庚二酸雙(2-乙基己基)酯、庚二酸二環己酯、庚二酸二苯酯。作為辛二酸酯之具體之化合物例，可列舉：辛二酸二甲酯、辛二酸二乙酯、辛二酸二丙酯、辛二酸二丁酯、辛二酸二戊酯、辛二酸二庚酯、辛二酸二正辛酯、辛二酸二壬酯、辛二酸二異壬酯、辛二酸二異癸酯、辛二酸雙(2-乙基己基)酯、辛二酸二異癸酯、辛二酸丁基苄酯、辛二酸二環丙酯、辛二酸二環丁酯、辛二酸二環戊酯、辛二酸二環己酯、辛二酸二環庚酯、辛二酸二烯丙酯、辛二酸雙丁基苄酯、辛二酸二苯酯。其中，尤其適宜使用辛二酸雙(2-乙基己基)酯、辛二酸二環己酯、辛二酸二苯酯。作為壬二酸酯之具體之化合物例，可列舉：壬二酸二甲酯、壬二酸二乙酯、壬二酸二丙酯、壬二酸二丁酯、壬二酸二戊酯、壬二酸二庚酯、壬二酸二正辛酯、壬二酸二壬酯、壬二酸二異壬酯、壬二酸二異癸酯、壬二酸雙(2-乙基己基)酯、壬二酸二異癸酯、壬二酸丁基苄酯、壬二酸二環丙酯、壬二酸二環丁酯、壬二酸二環戊酯、壬二酸二環己酯、壬二酸二環庚酯、壬二酸二烯丙酯、壬二酸雙丁基苄酯、壬二酸二苯酯。其中，尤其適宜使用壬二酸雙(2-乙基己基)酯、壬二酸二環己酯、壬二酸二苯酯。作為癸二酸酯之具體之化合物例，可列舉：癸二酸二甲酯、癸二酸二乙酯、癸二酸二丙酯、癸二酸二丁酯、癸二酸二戊酯、癸二酸二庚酯、癸二酸二正辛酯、癸二酸二壬酯、癸二酸二異壬酯、癸二酸二異癸酯、癸二酸雙(2-乙基己基)酯、癸二酸二異癸酯、癸二酸丁基苄酯、癸二酸二環丙酯、癸二酸二環丁酯、癸二酸二環戊酯、癸二酸二環己酯、癸二酸二環庚酯、癸二酸二烯丙酯、癸二酸雙丁基苄酯、癸二酸二苯酯。其中，尤其適宜使用癸二酸雙(2-乙基己基)酯、癸二酸二環己酯、癸二酸二苯酯。作為脂肪族酸四氫糠酯之具體之化合物例，可列舉：甲酸四氫糠酯、乙酸四氫糠酯、丙酸四氫糠酯、丁酸四氫糠酯、異丁酸四氫糠酯、戊酸四氫糠酯、異戊酸四氫糠酯、己酸四氫糠酯等。其中，尤其適宜使用丙酸四氫糠酯、丁酸四氫糠酯、異丁酸四氫糠酯。關於塑化劑(B)之含量，相對於樹脂(A)100質量份，較佳為0.1～50質量份，更佳為1～40質量份，進而較佳為1～30質量份。若含量多於該範圍，則玻璃轉移溫度降低，因此欠佳，若含量少於該範圍，則無法獲得充分之塑化性，與銅表面之間容易產生空隙。本實施形態中之塑化劑(B)之作用在於：於對使用本實施形態之感光性樹脂組合物所形成之浮凸圖案進行加熱硬化時，提高(A)樹脂之流動性，提高(A)樹脂之聚合物之堆積性。藉此獲得強固之硬化膜，可抑制於高溫保存試驗中產生空隙，可抑制於Cu層與樹脂層之界面處密接性降低。本實施形態之感光性樹脂組合物可含有(B-1)奈米粒子、(B-2)熱交聯劑及(B-3)含氟疏水性化合物中之任一者代替上述(B)塑化劑或與之併用。藉由將感光性樹脂、與特定之(B-1)奈米粒子、(B-2)熱交聯劑、或(B-3)含氟疏水性化合物加以組合，可提供一種感光性樹脂組合物、及使用該感光性樹脂組合物之硬化浮凸圖案之形成方法，由上述感光性樹脂組合物能夠獲得於高溫保存(high temperature storage)試驗後，於Cu層與樹脂層之界面處不會產生空隙而密接性較高的感光性樹脂。 (B-1)奈米粒子 (B-1)奈米粒子於室溫下呈固體狀，就透光性之觀點而言為平均一次粒徑1 μm以下、較佳為300 nm以下之粒子。一次粒徑可藉由SEM觀察或雷射繞射而求出。又，就HTS時之Cu耐遷移性之觀點而言，較佳為縱橫比5以上之板狀、鱗片狀、針狀或纖維狀之粒子，就與(A)樹脂之相溶性之觀點而言，較佳為利用矽烷偶合劑等進行有表面處理。進而，就耐水性之觀點而言，該等奈米粒子較佳為包含氧化物、複合氧化物、摻雜型氧化物、含氧酸、含氧酸鹽、氮化物、碳化物或硫化物。作為本發明中可使用之(B-1)奈米粒子，例如可列舉：SiO₂ 、Al₂ O₃ 、TiO₂ 、ZrO₂ 、HfO₂ 、V₂ O₅ 、WO₃ 、In₂ O₃ 、SnO₂ 、Sb₂ O₃ 、Nb₂ O₅ 、MoO₃ 、Fe₂ O₃ 、CuO、ZnO、CaO、MgO、艾羅技(Aerosil)、矽鋁、雲母、蒙脫石、滑石、黏土、水鋁礦、高嶺土、(聚)磷酸鋯、鈦酸鋇、碳酸鈣、(聚)鎢酸鋯、PZT(Lead Zirconium Titanate，鋯鈦酸鉛)、玻璃、硼酸鋁、氮化鋁、氮化鈦、氮化矽、氮化硼、或該等之混合物等。藉由添加奈米粒子，可降低感光性樹脂之熱膨脹係數。藉由熱膨脹係數降低而抑制於高溫保存試驗時樹脂產生熱膨脹，抑制發生銅遷移。此時，作為奈米粒子，縱橫比較高之形狀者可憑藉更少量之添加而降低熱膨脹係數，因此較佳。又，縱橫比較高之形狀者存在銅表面上之空隙數變少、顯影性或耐化學品性變得良好之傾向，從而更佳。就銅表面上之空隙數、顯影性或耐化學品性之觀點而言，奈米粒子之縱橫比較佳為大於1，縱橫比較佳為2以上，更佳為3以上，更佳為4以上。又，縱橫比更佳為5以上，更佳為8以上，更佳為10以上，更佳為12以上，更佳為15以上，尤佳為20以上。縱橫比係表示奈米粒子之長軸之長度/短軸之長度的值。於奈米粒子為標準球體之情形時，縱橫比成為1。於奈米粒子並非標準球體或標準橢圓體之情形時，以能夠將奈米粒子完全包於內部之大小之球體中之最小之球體之直徑作為奈米粒子之長軸，以能夠完全含於奈米粒子內部之大小之球體中之最大之球體之直徑作為奈米粒子之短軸。關於(B-1)奈米粒子之調配量，相對於(A)樹脂100質量份為0.1～50質量份，較佳為0.05～10質量份。就耐遷移性之觀點而言，較理想為0.1質量份以上，就溶解性之觀點而言，較理想為未達50質量份。 (B-2)熱交聯劑對本發明中使用之(B-2)熱交聯劑進行說明。(B-2)熱交聯劑係指於對使用本實施形態之感光性樹脂組合物所形成之浮凸圖案進行加熱硬化時，能夠與(A)樹脂交聯、或交聯劑本身形成交聯網狀結構的化合物。(B)熱交聯劑只要為符合上述條件者，則並無特別限定，較佳為下述(B-2-1)～(B-2-12)所示之任一者。 (B-2-1)含羥甲基及/或烷氧基甲基之化合物所謂含羥甲基及/或烷氧基甲基之化合物係分子內含有下述通式(TS2)： [化83]

{式中，Rs3為1價之有機基或氫原子}所表示之有機基之化合物。具體而言，可列舉具有下述通式(TS1)： [化84]

{式中，Rs1為氫原子、選自由甲基、乙基、正丙基及異丙基所組成之群中之一價之基，Rs2為選自由羥基、碳原子數1～10之烷基、碳原子數1～10之烷氧基、碳原子數1～10之酯基、及胺基甲酸酯基所組成之群中之基，mm1為1～5之整數，mm2為0～4之整數。此處，1≦(mm1＋mm2)≦5，nn1為1～4之整數，V₁ 於nn1＝1時為CH₂ ORs1，於nn1＝2～4時為單鍵或2～4價之有機基。於CH₂ ORs1及R₁₀ 存在複數個之情形時，該等相互可相同亦可不同}、以及通式(TS3)及(TS4)： [化85]

{式中，Rs3及Rs4分別獨立為氫原子、及選自由碳原子數1～10之烴基所組成之群中之1價之有機基} [化86]

{式中，Rs5分別獨立為氫原子、及選自由碳原子數1～10之烴基所組成之群中之1價之有機基}所表示之結構之N-羥甲基化合物及N-烷氧基甲基化合物等，但並不限定於該等。作為較佳之具體例，可列舉：Cymel(註冊商標)300、301、303、370、325、327、701、266、267、238、1141、272、202、1156、1158、1123、1170、1174、UFR 65、300、Micoat 102、105(以上為Mitsui Cytec公司製造)、NIKALAC(註冊商標)MX-270、-280、-290、NIKALAC MS-11、NIKALAC MW-30、-100、-300、-390、-750(以上為SANWA CHEMICAL公司製造)、DML-OCHP、DML-MBPC、DML-BPC、DML-PEP、DML-34X、DML-PSBP、DML-PTBP、DML-PCHP、DML-POP、DML-PFP、DML-MBOC、BisCMP-F、DML-BisOC-Z、DML-BisOCHP-Z、DML-BisOC-P、DMOM-PTBT、TMOM-BP、TMOM-BPA、TML-BPAFMF、TM-BIP-A、HMOM-TP-HAP(以上為本州化學工業公司製造)、苯二甲醇、雙(羥基甲基)甲酚、雙(羥基甲基)二甲氧基苯、雙(羥基甲基)二苯醚、雙(羥基甲基)二苯甲酮、羥基甲基苯甲酸羥基甲基苯酯、雙(羥基甲基)聯苯、二甲基雙(羥基甲基)聯苯、雙(甲氧基甲基)苯、雙(甲氧基甲基)甲酚、雙(甲氧基甲基)二甲氧基苯、雙(甲氧基甲基)二苯醚、雙(甲氧基甲基)二苯甲酮、甲氧基甲基苯甲酸甲氧基甲基苯酯、雙(甲氧基甲基)聯苯、二甲基雙(甲氧基甲基)聯苯、酚醛清漆之羥甲基化體等。其中，更佳為具有上述通式(12)所表示之結構者，具體而言，可列舉：DML-OCHP、DML-MBPC、DML-BPC、DML-PEP、DML-34X、DML-PSBP、DML-PTBP、DML-PCHP、DML-POP、DML-PFP、DML-MBOC、BisCMP-F、DML-BisOC-Z、DML-BisOCHP-Z、DML-BisOC-P、DMOM-PTBT、TMOM-BP、TMOM-BPA、TML-BPAFMF、TM-BIP-A、HMOM-TP-HAP(以上為本州化學工業公司製造)、苯二甲醇、雙(羥基甲基)甲酚、雙(羥基甲基)二甲氧基苯、雙(羥基甲基)二苯醚、雙(羥基甲基)二苯甲酮、羥基甲基苯甲酸羥基甲基苯酯、雙(羥基甲基)聯苯、二甲基雙(羥基甲基)聯苯、雙(甲氧基甲基)苯、雙(甲氧基甲基)甲酚、雙(甲氧基甲基)二甲氧基苯、雙(甲氧基甲基)二苯醚、雙(甲氧基甲基)二苯甲酮、甲氧基甲基苯甲酸甲氧基甲基苯酯、雙(甲氧基甲基)聯苯、二甲基雙(甲氧基甲基)聯苯基及酚醛清漆之羥甲基化體。該等之中，尤佳為TMOM-BP、TMOM-BPA、TML-BPAFMF、TM-BIP-A、HMOM-TP-HAP。 (B-2-2)環氧乙烷化合物作為環氧乙烷(環氧)化合物，只要為分子內含有環氧基之化合物，則並無特別限制，具體而言，可列舉：苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚型環氧樹脂、三苯酚型環氧樹脂、四苯酚型環氧樹脂、苯酚-苯二甲基型環氧樹脂、萘酚-苯二甲基型環氧樹脂、苯酚-萘酚型環氧樹脂、苯酚-二環戊二烯型環氧樹脂、脂環式環氧樹脂、鏈狀脂肪族環氧樹脂、二乙二醇二縮水甘油醚、山梨醇聚縮水甘油醚、丙二醇二縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、1,1,2,2-四(對羥基苯基)乙烷四縮水甘油醚、甘油三縮水甘油醚、鄰第二丁基苯基縮水甘油醚、1,6-雙(2,3-環氧丙氧基)萘、二甘油聚縮水甘油醚、聚乙二醇縮水甘油醚、YDB-340、YDB-412、YDF-2001、YDF-2004(商品名，新日鐵化學股份有限公司製造)、GAN、GOT、NC-3000-H、EPPN-501H、EPPN-502H、EOCN-1020、NC-6000、NC-7000L、EPPN-201L、XD-1000、EOCN-4600(商品名，日本化藥股份有限公司製造)、Epikote(註冊商標)1001、Epikote 1007、Epikote 1009、Epikote 5050、Epikote 5051、Epikote 1031S、Epikote 180S65、Epikote 157H70、YX-315-75(商品名，Japan Epoxy Resins股份有限公司製造)、EHPE3150、PLACCEL G402、PUE101、PUE105(商品名，Diacel Chemical Industries股份有限公司製造)、EPICLON(註冊商標)830、850、1050、N-680、N-690、N-695、N-770、HP-7200、HP-820、EXA-850CRP、860、EXA-4701、EXA-4850-1000(商品名，DIC公司製造)、DENACOL(註冊商標)EX-201、EX-212L、EX-214L、EX-216L、EX-251、EX-203、EX-313、EX-314、EX-321、EX-411、EX-511、EX-512、EX-612、EX-614、EX-614B、EX-711、EX-731、EX-810、EX-850L、EX-911、EM-150(商品名，Nagase chemteX公司製造)、Epolight(註冊商標)70P、40E、100E、100MF、200E、400E、200P、400P、1500NP、80MF、4000、3002(商品名，共榮社化學製造)、jER(註冊商標)828、834、1001、1002、1003、1004、1005、1007、1010、1100L、630、ESCN-220L、220F、220H、220HH、180H65、1032H60、YX4000H、152、157S70、1031(三菱化學製造)、Adeka Resin(註冊商標)EP-4000s、EP-4003s(Adeka製造)等。該等之中，就HTS試驗後之可靠性之觀點而言，尤佳為異三聚氰酸三縮水甘油酯、EPICLON 830、850、1050、N-680、N-690、N-695、N-770、HP-7200、HP-820、EXA-4850-1000、DENACOL EX-201、EX-313、EX-314、EX-321、EX-411、EX-511、EX-512、EX-612、EX-614、EX-614B、EX-731、EX-810、EX-911、及EM-150之環氧化合物。 (B-2-3)含異氰酸酯基之化合物作為含異氰酸酯基之化合物，只要為分子內含有異氰酸酯基之化合物，則並無特別限制，就HTS試驗後之可靠性之觀點而言，較佳為4,4'-二苯基甲烷二異氰酸酯、甲苯二異氰酸酯、1,3-苯二亞甲基二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、異佛爾酮二異氰酸酯、六亞甲基二異氰酸酯、Takenate(註冊商標)500、600、Cosmonate(註冊商標)NBDI、ND(商品名，三井化學公司製造)Duranate(註冊商標)17B-60PX、TPA-B80E、MF-B60X、MF-K60X、E402-B80T(商品名，Asahi Kasei Chemicals公司製造)等。 (B-2-4)雙順丁烯二醯亞胺化合物作為雙順丁烯二醯亞胺化合物，只要為分子內含有順丁烯二醯亞胺基之化合物，則並無特別限制，就HTS試驗後之可靠性之觀點而言，較佳為4,4'-二苯基甲烷雙順丁烯二醯亞胺、苯基甲烷順丁烯二醯亞胺、間伸苯基雙順丁烯二醯亞胺、雙酚A二苯醚雙順丁烯二醯亞胺、3,3'-二甲基-5,5'-二乙基-4,4'-二苯基甲烷雙順丁烯二醯亞胺、4-甲基-1,3-伸苯基雙順丁烯二醯亞胺、1,6'-雙順丁烯二醯亞胺-(2,2,4-三甲基)己烷、4,4'-二苯醚雙順丁烯二醯亞胺、4,4'-二苯基碸雙順丁烯二醯亞胺、1,3-雙(3-順丁烯二醯亞胺苯氧基)苯、1,3-雙(4-順丁烯二醯亞胺苯氧基)苯、BMI-1000、BMI-1100、BMI-2000、BMI-2300、BMI-3000、BMI-4000、BMI-5100、BMI-7000、BMI-TMH、BMI-6000、BMI-8000(商品名，大和化成工業股份有限公司製造)等。 (B-2-5)含醛基之化合物作為含醛基之化合物，只要為分子內含有醛基之化合物，則並無特別限制，就HTS試驗後之可靠性之觀點而言，較佳為甲醛、苯甲醛、乙醛、丙醛、苯基乙醛、α-苯基丙醛、β-苯基丙醛、鄰羥基苯甲醛、間羥基苯甲醛、對羥基苯甲醛、鄰甲基苯甲醛、間甲基苯甲醛、對甲基苯甲醛、糠醛、乙二醛、戊二醛、對苯二甲醛、間苯二甲醛、六亞甲基四胺、三㗁烷、丙二醛、丁二醛等。 (B-2-6)含氧雜環丁烷環之化合物所謂含氧雜環丁烷環之化合物係含有下述式： [化87]

所表示之2價之基之化合物。作為含氧雜環丁烷環之化合物，只要分子內含有氧雜環丁基，則並無特別限制，可列舉：1,4-雙{[(3-乙基-3-氧雜環丁基)甲氧基]甲基}苯、雙[1-乙基(3-氧雜環丁基)]甲醚、4,4'-雙[(3-乙基-3-氧雜環丁基)甲氧基甲基]聯苯、4,4'-雙(3-乙基-3-氧雜環丁基甲氧基)聯苯、乙二醇雙(3-乙基-3-氧雜環丁基甲基)醚、二乙二醇雙(3-乙基-3-氧雜環丁基甲基)醚、雙(3-乙基-3-氧雜環丁基甲基)二酚酸酯、三羥甲基丙烷三(3-乙基-3-氧雜環丁基甲基)醚、季戊四醇四(3-乙基-3-氧雜環丁基甲基)醚、3-乙基-3{[(3-乙基氧雜環丁烷-基)甲氧基]甲基}氧雜環丁烷、東亞合成股份有限公司製造之3-乙基-3-羥基甲基氧雜環丁烷(OXT-101)、2-乙基己基氧雜環丁烷(OXT-212)、苯二甲基雙氧雜環丁烷(OXT-121)、3-乙基-3-{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷(OXT-221)、OX-SQ-H、OXT-191、PNOX-1009、RSOX、以下之： [化88]

、宇部興產股份有限公司之Etanacol EHO、OXBP、OXMA、OXIPA、HBOX、OXTP等。其中，就於顯影液中之溶解性及所獲得之硬化膜之伸長率之觀點而言，較佳為OXBP、OXIPA、OXT-121及OXT-221。 (B-2-7)含苯并㗁𠯤環之化合物作為含苯并㗁𠯤環之化合物，只要為分子內含有苯并㗁𠯤環之化合物，則並無特別限制，就HTS試驗後之可靠性之觀點而言，較佳為日本專利特開2006-335671號公報所揭示之化合物、以及雙酚F型苯并㗁𠯤BF-BXZ、雙酚A型苯并㗁𠯤BA-BXZ、雙酚S型苯并㗁𠯤BS-BXZ(商品名，小西化學工業製造)等。 (B-2-8)含㗁唑啉環之化合物作為含㗁唑啉環之化合物，只要為分子內含有㗁唑啉環之化合物，則並無特別限制，可列舉：2-㗁唑啉、2-胺基-2-㗁唑啉、2,2'-雙(2-㗁唑啉)、1,3-雙(4,5-二氫-2-㗁唑基)苯、1,4-雙(4,5-二氫-2-㗁唑基)苯、1,3,5-三(4,5-二氫-2-㗁唑基)苯、2,2'-(2,6-吡啶二基)雙(4-異丙基-2-㗁唑啉)、2,2'-(2,6-吡啶二基)雙(4-苯基-2-㗁唑啉)、2-苯基(2-㗁唑啉)、4,4-二甲基-2-㗁唑啉、2,2'-亞異丙基雙(4-苯基-2-㗁唑啉)、2-乙基-2-㗁唑啉、2,2'-亞異丙基雙(4-第三丁基-2-㗁唑啉)、2-異丙基-2-㗁唑啉、4-甲氧基甲基-2-甲基-5-苯基-2-㗁唑啉、2-甲基-2-㗁唑啉、2,4,4-三甲基-2-㗁唑啉、日本觸媒公司製造之Epocros系列K-1010E、K-2010E、K-1020E、K-2020E、K-1030E、K-2030E、WS-500、WS-700、RPS-1005、RAS-1005等。就HTS試驗後之可靠性之觀點而言，較佳為例如2,2'-雙(2-㗁唑啉)、1,3-雙(4,5-二氫-2-㗁唑基)苯、1,4-雙(4,5-二氫-2-㗁唑基)苯、1,3,5-三(4,5-二氫-2-㗁唑基)苯、2-苯基(2-㗁唑啉)、Epocros WS-500等。又，含㗁唑啉環之化合物更佳為下述通式(TS5)： [化89]

{式中，Rs6為碳數1～10之有機基，nn2為0～4之整數} 所表示之化合物，最佳為1,3-雙(4,5-二氫-2-㗁唑基)苯及1,3,5-三(4,5-二氫-2-㗁唑基)苯。 (B-2-9)含碳二醯亞胺基之化合物作為含碳二醯亞胺基之化合物，只要為分子內含有碳二醯亞胺基之化合物，則並無特別限定，就HTS試驗後之可靠性之觀點而言，較佳為雙(2,6-二異丙基苯基)碳二醯亞胺、Carbodilite SV-02、V-01、V-02、V-03、V-04、V-05、V-07、V-09、E-01、E-02、LA-1(商品名，Nisshinbo Chemical公司製造)等。 (B-2-10)烯丙基化合物作為烯丙基化合物，只要分子內含有烯丙基，則並無特別限制，可列舉：三羥甲基丙烷三甲基丙烯酸酯、1,3,5-苯三羧酸三烯丙酯、偏苯三甲酸三烯丙酯、均苯四甲酸四烯丙酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、三羥甲基丙烷三丙烯酸酯、二三羥甲基丙烷四丙烯酸酯、NK Ester 1G、2G、3G、4G、9G、14G、NPG、BPE-100、BPE-200、BPE-500、BPE-1400、A-200、A-400、A-600、TMPT、A-TMM-3(商品名，新中村化學工業公司製造)、BANI-M、BANI-X(商品名，丸善石油化學股份有限公司製造)等。該等之中，就HTS試驗後之可靠性之觀點而言，尤佳為乙酸乙烯酯、三羥甲基丙烷三甲基丙烯酸酯、1,3,5-苯三羧酸三烯丙酯、偏苯三甲酸三烯丙酯、均苯四甲酸四烯丙酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、三羥甲基丙烷三丙烯酸酯、二三羥甲基丙烷四丙烯酸酯、BANIM及BANI-X。 (B-2-11)三𠯤硫醇化合物作為三𠯤硫醇化合物，只要分子內含有三聚硫氰酸基，則並無特別限制，就HTS試驗後之可靠性之觀點而言，較佳為2,4,6-三硫醇-1,3,5-三𠯤、2-二甲基胺基-4,6-二硫醇-1,3,5-三𠯤、2-二丁基胺基-4,6-二硫醇-1,3,5-三𠯤、2-苯基胺基-4,6-二硫醇-1,3,5-三𠯤等。 (B-2-12)金屬螯合化合物作為金屬螯合化合物，可列舉：鋁螯合化合物、鈦螯合化合物、鋯螯合化合物、鉻螯合化合物、鎂螯合化合物、鎳螯合化合物等，就HTS試驗後之可靠性之觀點而言，較佳為乙醯丙酮鋁(III)鹽、乙醯丙酮鈦(IV)鹽、乙醯丙酮鉻(III)鹽、乙醯丙酮鎂(II)鹽、乙醯丙酮鎳(II)鹽、乙醯丙酮鋯(IV)鹽、三氟乙醯丙酮鋁(III)鹽、三氟乙醯丙酮鈦(IV)鹽、三氟乙醯丙酮鉻(III)鹽、三氟乙醯丙酮鎂(II)鹽、三氟乙醯丙酮鎳(II)鹽、三氟乙醯丙酮鋯(IV)鹽、二異丙氧基雙(乙醯丙酮酸)鈦、四乙醯丙酮酸鈦、二-2-乙基己氧基雙(2-乙基-3-羥基己醇)鈦、二異丙氧基雙(乙基乙醯乙酸)鈦等。該等化合物之中，就HTS試驗後之可靠性之觀點而言，較佳為乙醯丙酮鋁(III)鹽、乙醯丙酮鈦(IV)鹽、乙醯丙酮鋯(IV)鹽、乙醯丙酮鎳(II)鹽、三氟乙醯丙酮鋁(III)鹽、三氟乙醯丙酮鈦(IV)鹽、三氟乙醯丙酮鎳(II)鹽、三氟乙醯丙酮鋯(IV)鹽、二異丙氧基雙(乙醯丙酮酸)鈦、四乙醯丙酮酸鈦、二-2-乙基己氧基雙(2-乙基-3-羥基己醇)鈦、及二異丙氧基雙(乙基乙醯乙酸)鈦，就於矽晶圓上之密接性之觀點而言，較佳為乙醯丙酮鋁(III)鹽、乙醯丙酮鈦(IV)鹽、乙醯丙酮鋯(IV)鹽、三氟乙醯丙酮鋁(III)鹽、三氟乙醯丙酮鈦(IV)鹽、三氟乙醯丙酮鋯(IV)鹽、及二異丙氧基雙(乙醯丙酮酸)鈦。該等(B-2-1)～(B-2-12)記載之交聯劑之中，就HTS試驗後之可靠性之觀點而言，較佳為(B-2-1)含羥甲基及/或烷氧基甲基之化合物、(B-2-2)環氧乙烷化合物、(B-2-3)含異氰酸酯基之化合物、(B-2-4)含雙順丁烯二醯亞胺基之化合物、(B-2-5)含醛基之化合物、(B-2-6)含氧雜環丁烷環之化合物、(B-2-7)含苯并㗁𠯤環之化合物、(B-2-8)含㗁唑啉環之化合物、(B-2-10)烯丙基化合物，更佳為(B-2-1)含羥甲基及/或烷氧基甲基之化合物、(B-2-3)含異氰酸酯基之化合物、(B-2-4)含雙順丁烯二醯亞胺基之化合物、(B-2-6)含氧雜環丁烷環之化合物、(B-2-7)含苯并㗁𠯤環之化合物、(B-2-10)烯丙基化合物，最佳為(B-2-1)含羥甲基及/或烷氧基甲基之化合物。該等交聯劑(B-2)可單獨使用1種或將2種以上組合使用。以上之(B-2)交聯劑之中，本發明較佳為使用(B-2-1)含羥甲基及/或烷氧基甲基之化合物，更佳為使用下述通式(12)： [化90]

{式中，Rs1為氫原子、選自由甲基、乙基、正丙基及異丙基所組成之群中之一價之基，Rs2為選自由羥基、碳原子數1～10之烷基、碳原子數1～10之烷氧基、碳原子數1～10之酯基、及胺基甲酸酯基所組成之群中之基，mm1為1～5之整數，mm2為0～4之整數。此處，1≦(mm1＋mm2)≦5，nn1為1～4之整數，V₁ 於nn1＝1時為CH₂ ORs1，於nn1＝2～4時為單鍵或2～4價之有機基。於CH₂ ORs1及R₁₀ 存在複數個之情形時，該等相互可相同亦可不同}所表示之羥甲基化合物及烷氧基甲基化合物。藉由添加交聯劑，可提高相同固化溫度下之樹脂之玻璃轉移溫度。藉由樹脂之玻璃轉移溫度提高而抑制銅向樹脂中遷移。關於交聯劑(B-2)之調配量，相對於樹脂(A)100質量份，較佳為0.1～50質量份，更佳為1～30質量份，進而較佳為5～20質量份。 (B-3)含氟疏水性化合物以下對本實施形態中之(B-3)含氟疏水性化合物進行詳細說明。(B)含氟疏水性化合物只要為分子中含有氟原子且具有疏水性之化合物，則並無特別限定。可較佳地用作本實施形態之(B-3)含氟疏水性化合物的化合物為醯基氟(acid fluoride)、氟化丙烯酸酯、氟化甲基丙烯酸酯、氟化醇、氟化烷烴、氟化酯及氟化醚等。＜醯基氟＞關於作為(B-3)含氟疏水性化合物之醯基氟之具體之化合物例，可較佳地使用全氟戊醯氟、全氟己醯氟、全氟庚醯氟、全氟辛醯氟、全氟琥珀醯氟、六氟戊二醯氟、八氟己二醯氟、全氟甲氧基丙醯氟、全氟丁氧基乙氧基乙醯氟、全氟聚醚二丙烯醯氟(n＝1)、全氟聚醚二丙烯醯氟(n＝2)、全氟己酸、全氟庚酸、全氟辛酸、全氟壬酸、全氟癸酸、全氟十一酸、全氟十二酸、全氟十四酸、全氟十六酸、全氟-3,5,5-三甲基己酸、全氟-3,7-二甲基辛酸、全氟琥珀酸、全氟戊二酸、全氟己二酸、全氟辛二酸、全氟壬二酸、全氟癸二酸、全氟十二烷二酸、全氟-3,6-二氧雜庚酸、全氟-3,6,9-三氧雜癸酸、全氟-3,6-二氧雜癸酸、全氟-3,6,9-三氧雜十三酸、全氟-3,6-二氧雜辛烷-1,8-二酸、全氟-3,6,9-三氧雜十一烷-1,11-二酸等。＜氟化丙烯酸酯＞關於作為(B-3)含氟疏水性化合物之氟化丙烯酸酯之具體之化合物例，可較佳地使用丙烯酸1H,1H-全氟正丁酯、丙烯酸1H,1H-全氟正辛酯、丙烯酸1H,1H-全氟正癸酯、1H,1H,6H,6H-全氟-1,6-己二醇二丙烯酸酯、1H,1H,8H,8H-全氟四乙二醇二丙烯酸酯、1H,1H,6H,6H-全氟三乙二醇二丙烯酸酯、1H,1H,4H,4H-全氟二乙二醇二丙烯酸酯、1H,1H,10H,10H-五乙二醇二丙烯酸酯、1H,1H,18H,18H-九乙二醇二丙烯酸酯、全氟-1,6-己二醇二丙烯酸酯、全氟四乙二醇二丙烯酸酯、全氟三乙二醇二丙烯酸酯、全氟二乙二醇二丙烯酸酯、五乙二醇二丙烯酸酯、九乙二醇二丙烯酸酯等。其中，可尤佳地使用1H,1H,6H,6H-全氟-1,6-己二醇二丙烯酸酯及1H,1H,8H,8H-全氟四乙二醇二丙烯酸酯，可分別作為Exfluor公司製造之製品名C6DIACRY及製品名DA-F4EO而獲得。＜氟化甲基丙烯酸酯＞關於作為(B-3)含氟疏水性化合物之氟化甲基丙烯酸酯之具體之化合物例，可較佳地使用甲基丙烯酸1H,1H-全氟正丁酯、甲基丙烯酸1H,1H-全氟正辛酯、甲基丙烯酸1H,1H-全氟正癸酯、1H,1H,6H,6H-全氟-1,6-己二醇二甲基丙烯酸酯、1H,1H,8H,8H-全氟四乙二醇二甲基丙烯酸酯、1H,1H,6H,6H-全氟三乙二醇二甲基丙烯酸酯、1H,1H,4H,4H-全氟二乙二醇二甲基丙烯酸酯、1H,1H,10H,10H-五乙二醇二甲基丙烯酸酯、1H,1H,18H,18H-九乙二醇二甲基丙烯酸酯、全氟-1,6-己二醇二甲基丙烯酸酯、全氟四乙二醇二甲基丙烯酸酯、全氟三乙二醇二甲基丙烯酸酯、全氟二乙二醇二甲基丙烯酸酯、五乙二醇二甲基丙烯酸酯、九乙二醇二甲基丙烯酸酯等。＜氟化醇＞關於作為(B-3)含氟疏水性化合物之氟化醇之具體之化合物例，可較佳地使用1H,1H-全氟-1-己醇、1H,1H-全氟-1-庚醇、1H,1H-全氟-1-辛醇、1H,1H-全氟-1-壬醇、1H,1H-全氟-1-癸醇、1H,1H-全氟-1-十一醇、1H,1H-全氟-1-十二醇、1H,1H-全氟-1-十四醇、1H,1H-全氟-1-十六醇、全氟-3,5,5-三甲基己烷-1-醇、全氟-3,7-二甲基辛烷-1-醇、1H,1H,4H,4H-全氟-1,4-丁二醇、1H,1H,5H,5H-全氟-1,5-戊二醇、1H,1H,5H,5H-全氟-1,5-戊二醇、1H,1H,6H,6H-全氟-1,6-己二醇、1H,1H,8H,8H-全氟-1,8-辛二醇、1H,1H,9H,9H-全氟-1,9-壬二醇、1H,1H,10H,10H-全氟-1,10-癸二醇、1H,1H,12H,12H-全氟-1,12-十二烷二醇、全氟-第三丁醇、氟化二乙二醇單甲醚、氟化三乙二醇單甲醚、氟化二乙二醇單丁醚、氟化三乙二醇單丁醚、氟化三乙二醇、氟化四乙二醇等。＜氟化烷烴＞關於作為(B-3)含氟疏水性化合物之氟化烷烴之具體之化合物例，可較佳地使用全氟庚烷、全氟辛烷、全氟壬烷、全氟十三烷、全氟十五烷、1H-全氟戊烷、1H-全氟己烷、1H-全氟庚烷、1H-全氟辛烷、1H-全氟壬烷、1H-全氟癸烷、1H-全氟十一烷、1H-全氟十三烷、1H-全氟十五烷、1H-全氟-2,4,4-三甲基戊烷、1H-全氟-2,6-二甲基庚烷、1H,4H-全氟丁烷、1H,6H-全氟己烷、1H,7H-全氟庚烷、1H,8H-全氟辛烷、1H,10H-全氟癸烷等。＜氟化酯＞關於作為(B-3)含氟疏水性化合物之氟化酯之具體之化合物例，可較佳地使用全氟戊酸甲酯、全氟己酸甲酯、全氟庚酸甲酯、全氟辛酸甲酯、全氟壬酸甲酯、全氟癸酸甲酯、全氟十一酸甲酯、全氟十二酸甲酯、全氟十四酸甲酯、全氟十六酸甲酯、全氟琥珀酸二甲酯、全氟戊二酸二甲酯、全氟己二酸二甲酯、全氟辛二酸二甲酯、全氟壬二酸二甲酯、全氟癸二酸二甲酯、全氟-1,12-癸二酸二甲酯、全氟-3,6-二氧雜庚酸甲酯、全氟-3,6,9-三氧雜癸酸甲酯、全氟-3,6-二氧雜癸酸甲酯、全氟-3,6,9-三氧雜十三酸甲酯、全氟-3,6-二氧雜辛烷-1,8-二酸二甲酯、全氟-3,6,9-三氧雜十一烷-1,11-二酸二甲酯等。＜氟化醚＞關於作為(B-3)含氟疏水性化合物之氟化醚之具體之化合物例，可較佳地使用全氟(二乙二醇二甲醚)、全氟(三乙二醇二甲醚)、全氟(三乙二醇二甲醚)等。 (B-3)含氟疏水性化合物之分子中之氟原子之重量比率較佳為30質量%以上且80質量%以下。若氟之重量比率少於該範圍，則無法獲得充分之疏水性。又，若氟多於該範圍，則與溶劑之相溶性降低，不易獲得表面平坦性均勻之塗佈膜，因此欠佳。氟重量含有比率之範圍更佳為35質量%以上且75質量%以內。本實施形態中之(B-3)含氟疏水性化合物較佳為於分子內具有至少1個以上之不飽和雙鍵。若具有不飽和雙鍵，則於曝光步驟中，於(B-3)含氟疏水性化合物彼此之分子間、及與(A)樹脂之分子間進行交聯反應。藉此，於加熱處理時(B-3)含氟疏水性化合物不易揮發，可表現出充分之疏水性效果。不飽和雙鍵之較佳例為丙烯酸酯及甲基丙烯酸酯等。關於(B-3)含氟疏水性化合物之含量，相對於樹脂(A)100質量份，較佳為0.01～50質量份，更佳為0.02～30質量份，進而較佳為0.05～20質量份。若含量多於該範圍，則與溶劑之相溶性降低，難以獲得表面平坦性均勻之塗佈膜，因此欠佳，若含量少於該範圍，則無法獲得充分之疏水性效果，與銅表面之間容易產生空隙。 (C)感光劑對本發明所使用之(C)感光劑進行說明。(C)感光劑根據本發明之感光性樹脂組合物為例如主要使用聚醯亞胺前驅物及/或聚醯胺作為(A)樹脂之負型，或為例如主要使用聚㗁唑前驅物、可溶性聚醯亞胺、酚醛清漆、聚羥基苯乙烯及酚樹脂之至少一種作為(A)樹脂之正型等而不同。關於(C)感光劑於感光性樹脂組合物中之調配量，相對於(A)感光性樹脂100質量份為1～50質量份。上述調配量就光感度或圖案化性之觀點而言為1質量份以上，就感光性樹脂組合物之硬化性或硬化後之感光性樹脂層之物性之觀點而言為50質量份以下。 [(C)負型感光劑：聚合起始劑、光酸產生劑] 首先，對期望為負型之情形進行說明。於該情形時，使用光聚合起始劑及/或光酸產生劑作為(C)感光劑，作為光聚合起始劑，較佳為光自由基聚合起始劑，較佳為列舉：二苯甲酮、鄰苯甲醯苯甲酸甲酯、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-氧硫𠮿

、2-甲基9-氧硫𠮿

、2-異丙基9-氧硫𠮿

、二乙基9-氧硫𠮿

等9-氧硫𠮿

衍生物，苯偶醯、苯偶醯二甲基縮酮、苯偶醯-β-甲氧基乙基縮醛等苯偶醯衍生物，安息香、安息香甲醚等安息香衍生物，1-苯基-1,2-丁烷二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙烷二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙烷二酮-2-(鄰乙氧基羰基)肟、1-苯基-1,2-丙烷二酮-2-(鄰苯甲醯基)肟、1,3-二苯基丙烷三酮-2-(鄰乙氧基羰基)肟、1-苯基-3-乙氧基丙烷三酮-2-(鄰苯甲醯基)肟等肟類，N-苯基甘胺酸等N-芳基甘胺酸類，苯甲醯基過氯化物等過氧化物類，芳香族聯咪唑類，二茂鈦類，α-(正辛磺醯氧基亞胺基)-4-甲氧基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，尤其就光感度之方面而言，更佳為肟類。於在負型之感光性樹脂組合物中使用光酸產生劑作為(C)感光劑之情形時，於紫外線之類之活性光線之照射下呈現酸性，且具有藉由該作用而使下述交聯劑與作為(A)成分之樹脂進行交聯、或使交聯劑彼此進行聚合之作用。作為該光酸產生劑之例，可使用二芳基鋶鹽、三芳基鋶鹽、二烷基苯甲醯甲基鋶鹽、二芳基錪鹽、芳基重氮鎓鹽、芳香族四羧酸酯、芳香族磺酸酯、硝基苄基酯、肟磺酸酯、芳香族N-氧基醯亞胺磺酸酯、芳香族磺醯胺、含鹵烷基之烴系化合物、含鹵烷基之雜環狀化合物、萘醌二疊氮-4-磺酸酯等。此種化合物視需要可併用2種以上、或與其他增感劑組合使用。上述光酸產生劑之中，尤其就光感度之方面而言，更佳為芳香族肟磺酸酯、芳香族N-氧基醯亞胺磺酸酯。關於負型之情形時之該等感光劑之調配量，相對於(A)樹脂100質量份為1～50質量份，就光感度特性之觀點而言，較佳為2～15質量份。藉由調配相對於(A)樹脂100質量份為1質量份以上之(C)感光劑，光感度優異，藉由調配50質量份以下，厚膜硬化性優異。進而，如上所述，於通式(1)所表示之(A)樹脂為離子鍵型之情形時，為了經由離子鍵對(A)樹脂之側鏈賦予光聚合性基而使用具有胺基之(甲基)丙烯酸系化合物。於該情形時，具有胺基之(甲基)丙烯酸系化合物係用作(C)感光劑，如上所述，例如較佳為丙烯酸二甲胺基乙酯、甲基丙烯酸二甲胺基乙酯、丙烯酸二乙胺基乙酯、甲基丙烯酸二乙胺基乙酯、丙烯酸二甲胺基丙酯、甲基丙烯酸二甲胺基丙酯、丙烯酸二乙胺基丙酯、甲基丙烯酸二乙胺基丙酯、丙烯酸二甲胺基丁酯、甲基丙烯酸二甲胺基丁酯、丙烯酸二乙胺基丁酯、甲基丙烯酸二乙胺基丁酯等丙烯酸二烷基胺基烷基酯或甲基丙烯酸二烷基胺基烷基酯，其中，就感光特性之觀點而言，較佳為胺基上之烷基之碳數為1～10、烷基鏈之碳數為1～10之丙烯酸二烷基胺基烷基酯或甲基丙烯酸二烷基胺基烷基酯。關於該等具有胺基之(甲基)丙烯酸系化合物之調配量，相對於(A)樹脂100質量份為1～20質量份，就光感度特性之觀點而言，較佳為2～15質量份。藉由調配相對於(A)樹脂100質量份為1質量份以上之具有胺基之(甲基)丙烯酸系化合物作為(C)感光劑，光感度優異，藉由調配20質量份以下，厚膜硬化性優異。其次，對期望為正型之情形進行說明。於該情形時，使用光酸產生劑作為(C)感光劑，具體而言，可使用重氮醌化合物、鎓鹽、含鹵素之化合物等，就溶劑溶解性及保存穩定性之觀點而言，較佳為具有重氮醌結構之化合物。 [(C)正型感光劑：具有醌二疊氮基之化合物] 作為(C)具有醌二疊氮基之化合物(以下亦稱為「(C)醌二疊氮化合物」)，可例示具有1,2-苯醌二疊氮結構之化合物、及具有1,2-萘醌二疊氮結構之化合物，乃美國專利第2,772,972號說明書、美國專利第2,797,213號說明書、及美國專利第3,669,658號說明書等中之公知物質。該(C)醌二疊氮化合物較佳為選自由以下詳細說明之具有特定結構之聚羥基化合物之1,2-萘醌二疊氮-4-磺酸酯、及該聚羥基化合物之1,2-萘醌二疊氮-5-磺酸酯所組成之群中之至少一種化合物(以下亦稱為「NQD化合物」)。該NQD化合物係藉由如下方式獲得：依據常規方法，利用氯磺酸或亞硫醯氯將萘醌二疊氮磺酸化合物進行磺醯氯化，使所獲得之萘醌二疊氮磺醯氯與聚羥基化合物進行縮合反應。例如可藉由如下方式獲得：使聚羥基化合物與特定量之1,2-萘醌二疊氮-5-磺醯氯或1,2-萘醌二疊氮-4-磺醯氯於二㗁烷、丙酮或四氫呋喃等溶劑中，於三乙胺等鹼性觸媒之存在下反應而進行酯化，將所獲得之產物水洗並加以乾燥。本實施形態中，就形成抗蝕圖案時之感度與解像性之觀點而言，(C)具有醌二疊氮基之化合物較佳為下述通式(70)～(74)所表示之羥基化合物之1,2-萘醌二疊氮-4-磺酸酯及/或1,2-萘醌二疊氮-5-磺酸酯。通式(70)由 [化91]

{式中，X₁₁ 及X₁₂ 分別獨立表示氫原子或碳數1～60(較佳為碳數1～30)之1價之有機基，X₁₃ 及X₁₄ 分別獨立表示氫原子或碳數1～60(較佳為碳數1～30)之1價之有機基，r1、r2、r3及r4分別獨立為0～5之整數，r3及r4之至少一者為1～5之整數，(r1＋r3)≦5，並且(r2＋r4)≦5}所表示。通式(71)由 [化92]

{式中，Z表示碳數1～20之4價之有機基，X₁₅ 、X₁₆ 、X₁₇ 及X₁₈ 分別獨立表示碳數1～30之1價之有機基，r6為0或1之整數，r5、r7、r8及r9分別獨立為0～3之整數，r10、r11、r12及r13分別獨立為0～2之整數，並且r10、r11、r12及r13不會均為0}所表示。且通式(72)由 [化93]

{式中，r14表示1～5之整數，r15表示3～8之整數，(r14×r15)個之L分別獨立表示碳數1～20之1價之有機基，(r15)個之T¹ 及(r15)個之T² 分別獨立表示氫原子或碳數1～20之1價之有機基}所表示。且通式(73)由 [化94]

{式中，A表示脂肪族之包含三級或四級碳之2價之有機基，並且M表示2價之有機基，較佳為表示選自下述化學式： [化95]

所表示之3種基中之2價之基}所表示。進而，通式(74)由 [化96]

{式中，r17、r18、r19及r20分別獨立為0～2之整數，r17、r18、r19及r20之至少一者為1或2，X₂₀ ～X₂₉ 分別獨立表示氫原子、鹵素原子、選自由烷基、烯基、烷氧基、烯丙基及醯基所組成之群中之1價之基，並且Y₁₀ 、Y₁₁ 及Y₁₂ 分別獨立表示單鍵、選自由-O-、-S-、-SO-、-SO₂ -、-CO-、-CO₂ -、亞環戊基、亞環己基、伸苯基、及碳數1～20之2價之有機基所組成之群中之2價之基}所表示。於另一實施形態中，上述通式(74)中，Y₁₀ ～Y₁₂ 較佳為分別獨立地自下述通式： [化97]

[化98]

[化99]

{式中，X₃₀ 及X₃₁ 分別獨立表示氫原子、選自由烷基、烯基、芳基、及取代芳基所組成之群中之至少一種1價之基，X₃₂ 、X₃₃ 、X₃₄ 及X₃₅ 分別獨立表示氫原子或烷基，r21為1～5之整數，並且X₃₆ 、X₃₇ 、X₃₈ 及X₃₉ 分別獨立表示氫原子或烷基} 所表示之三種2價之有機基中選擇。作為上述通式(70)所表示之化合物，可列舉下述式(75)～(79)所表示之羥基化合物。此處，通式(75)為 [化100]

{式中，r16分別獨立為0～2之整數，並且X₄₀ 分別獨立表示氫原子或碳數1～20之1價之有機基，於X₄₀ 存在複數個之情形時，複數個X₄₀ 相互可相同或亦可不同，並且X₄₀ 較佳為下述通式： [化101]

(式中，r18為0～2之整數，X₄₁ 表示氫原子、選自由烷基及環烷基所組成之群中之1價之有機基，並且於r18為2之情形時，2個X₄₁ 相互可相同亦可不同) 所表示之1價之有機基}，通式(76)由 [化102]

{式中，X₄₂ 表示氫原子、選自由碳數1～20之烷基、碳數1～20之烷氧基及碳數1～20之環烷基所組成之群中之1價之有機基}所表示。又，通式(77)為 [化103]

{式中，r19分別獨立為0～2之整數，X₄₃ 分別獨立表示氫原子或下述通式： [化104]

(式中，r20為0～2之整數，X₄₅ 選自由氫原子、烷基及環烷基所組成之群中，並且於r20為2之情形時，2個X₄₅ 相互可相同亦可不同)所表示之1價之有機基，並且X₄₄ 選自由氫原子、碳數1～20之烷基、及碳數1～20之環烷基所組成之群中}，式(78)及(79)為如下結構。 [化105]

[化106]

作為上述通式(70)所表示之化合物，就製成NQD化物時之感度較高、且於感光性樹脂組合物中之析出性較低之方面而言，較佳為下述式(80)～(82)所表示之羥基化合物。式(80)～(82)之結構如下所示。 [化107]

[化108]

[化109]

作為上述通式(76)所表示之化合物，就製成NQD化物時之感度較高、且於感光性樹脂組合物中之析出性較低之方面而言，較佳為下述式(83)： [化110]

所表示之羥基化合物。作為上述通式(77)所表示之化合物，就製成NQD化物時之感度較高、且於感光性樹脂組合物中之析出性較低之方面而言，較佳為下述式(84)～(86)所表示之羥基化合物。式(84)～(86)之結構如下所示。 [化111]

[化112]

[化113]

上述通式(71)中，Z只要為碳數1～20之4價之有機基即可，並無特別限定，就感度之觀點而言，較佳為具有下述式： [化114]

所表示之結構之4價之基。上述通式(71)所表示之化合物之中，就製成NQD化物時之感度較高、且於感光性樹脂組合物中之析出性較低之方面而言，較佳為下述式(87)～(90)所表示之羥基化合物。式(87)～(90)之結構如下所示。 [化115]

[化116]

[化117]

[化118]

作為上述通式(72)所表示之化合物，就製成NQD化物時之感度較高、且於感光性樹脂組合物中之析出性較低之方面而言，較佳為下述式(91)： [化119]

{式中，r40分別獨立為0～9之整數}所表示之羥基化合物。作為上述通式(73)所表示之化合物，就製成NQD化物時之感度較高、且於感光性樹脂組合物中之析出性較低之方面而言，較佳為下述式(92)及(93)所表示之羥基化合物。式(92)及(93)之結構如下所示。 [化120]

[化121]

作為上述通式(74)所表示之化合物，就感度較高、且於感光性樹脂組合物中之析出性較低之方面而言，具體而言較佳為下述式(94)： [化122]

所表示之聚羥基化合物之NQD化物。於(C)具有醌二疊氮基之化合物具有1,2-萘醌二疊氮磺醯基之情形時，該基可為1,2-萘醌二疊氮-5-磺醯基或1,2-萘醌二疊氮-4-磺醯基之任意者。1,2-萘醌二疊氮-4-磺醯基能夠吸收水銀燈之i射線區域，因此適於利用i射線進行曝光。另一方面，1,2-萘醌二疊氮-5-磺醯基甚至能夠吸收水銀燈之g射線區域，因此適於利用g射線進行曝光。本實施形態中，較佳為根據進行曝光之波長而選擇1,2-萘醌二疊氮-4-磺酸酯化合物及1,2-萘醌二疊氮-5-磺酸酯化合物之一者或兩者。又，亦可使用於同一分子中具有1,2-萘醌二疊氮-4-磺醯基及1,2-萘醌二疊氮-5-磺醯基之1,2-萘醌二疊氮磺酸酯化合物，亦可將1,2-萘醌二疊氮-4-磺酸酯化合物與1,2-萘醌二疊氮-5-磺酸酯化合物混合使用。 (C)具有醌二疊氮基之化合物中，就顯影對比度之觀點而言，羥基化合物之萘醌二疊氮磺醯基酯之平均酯化率較佳為10%～100%，進而較佳為20%～100%。就感度及伸長率等硬化膜物性之觀點而言，作為NQD化合物之較佳例，例如可列舉下述通式群所表示者。 [化123]

可列舉{式中，Q為氫原子、或下述式群： [化124]

中之任一者所表示之萘醌二疊氮磺酸酯基，但Q不會全體同時為氫原子}所表示者。於該情形時，作為NQD化合物，可使用於同一分子中具有4-萘醌二疊氮磺醯基及5-萘醌二疊氮磺醯基之萘醌二疊氮磺醯基酯化合物，亦可將4-萘醌二疊氮磺醯基酯化合物與5-萘醌二疊氮磺醯基酯化合物混合使用。上述段落[0243]所記載之萘醌二疊氮磺酸酯基之中，尤佳為下述通式(95)： [化125]

所表示者。作為上述鎓鹽，可列舉：錪鹽、鋶鹽、鏻鹽、銨鹽及重氮鎓鹽等，較佳為選自由二芳基錪鹽、三芳基鋶鹽及三烷基鋶鹽所組成之群中之鎓鹽。作為上述含鹵素之化合物，可列舉含鹵烷基之烴化合物等，較佳為三氯甲基三𠯤。關於正型之情形時之該等光酸產生劑之調配量，相對於(A)樹脂100質量份而為1～50質量份，較佳為5～30質量份。若作為(C)感光劑之光酸產生劑之調配量為1質量份以上，則感光性樹脂組合物之圖案化性良好，若為50質量份以下，則感光性樹脂組合物之硬化後之膜之拉伸伸長率良好，且曝光部之顯影殘留物(浮渣)較少。上述NQD化合物可單獨使用，亦可將2種以上混合使用。本實施形態中，關於感光性樹脂組合物中之(C)具有醌二疊氮基之化合物之調配量，相對於(A)樹脂100質量份而為0.1質量份～70質量份，較佳為1質量份～40質量份，更佳為3質量份～30質量份，進而較佳為5質量份～30質量份。若該調配量為0.1質量份以上，則獲得良好之感度，另一方面，若為70質量份以下，則硬化膜之機械物性良好。本發明之感光性樹脂組合物亦可進而含有上述(A)～(C)成分以外之成分。該成分之較佳者根據作為(A)樹脂例如使用聚醯亞胺前驅物及聚醯胺等之負型、或使用聚㗁唑前驅物、可溶性聚醯亞胺及酚樹脂等之正型等而不同。本實施形態中之作為負型樹脂組合物之上述聚醯亞胺前驅物樹脂組合物及聚醯胺樹脂組合物、或者作為正型感光性樹脂組合物之聚㗁唑樹脂組合物、可溶性聚醯亞胺樹脂組合物及酚樹脂組合物中可包含用以使該等樹脂溶解之溶劑。＜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、四氫呋喃甲醇、乙二醇二甲醚、二乙二醇二甲醚、四氫呋喃、𠰌啉、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、苯乙二醇及四氫呋喃甲醇。此種溶劑之中，尤佳為可使生成聚合物完全溶解者，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。作為適用於上述酚樹脂之溶劑，可列舉：雙(2-甲氧基乙基)醚、甲基溶纖劑、乙基溶纖劑、丙二醇單甲醚、丙二醇單甲醚乙酸酯、二乙二醇二甲醚、二丙二醇二甲醚、環己酮、環戊酮、甲苯、二甲苯、γ-丁內酯、N-甲基-2-吡咯啶酮等，但並不限定於該等。本發明之感光性樹脂組合物中，關於溶劑之使用量，相對於(A)樹脂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。本發明之感光性樹脂組合物亦可進而含有上述(A)～(C)成分以外之成分。例如於使用本發明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，為了抑制銅上產生變色，可任意地調配唑類化合物及嘌呤衍生物等含氮雜環化合物。作為唑類化合物，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-(2-二甲基胺基乙基)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。尤佳為列舉：甲苯并三唑、5-甲基-1H-苯并三唑及4-甲基-1H-苯并三唑。又，該等唑類化合物可使用1種或以2種以上之混合物之形式使用。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。關於感光性樹脂組合物含有上述唑類化合物或嘌呤衍生物之情形時之調配量，相對於(A)樹脂100質量份，較佳為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。若唑類化合物相對於(A)樹脂100質量份之調配量為0.1質量份以上，則於銅或銅合金之上形成本發明之感光性樹脂組合物之情形時，抑制銅或銅合金表面產生變色，另一方面，若為20質量份以下，則光感度優異。又，為了抑制銅表面上產生變色而可任意地調配受阻酚化合物。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-氫醌、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)、四[3-(3,5-二第三丁基-4-羥基苯基)丙酸]季戊四醇酯、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)-1,3,5-三𠯤-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)-1,3,5-三𠯤-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)-1,3,5-三𠯤-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]-1,3,5-三𠯤-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]-1,3,5-三𠯤-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)-1,3,5-三𠯤-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)-1,3,5-三𠯤-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)-1,3,5-三𠯤-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)-1,3,5-三𠯤-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)-1,3,5-三𠯤-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)-1,3,5-三𠯤-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)-1,3,5-三𠯤-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)-1,3,5-三𠯤-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)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮等，但並不限定於此。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)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮等。關於受阻酚化合物之調配量，相對於(A)樹脂100質量份，較佳為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。若受阻酚化合物相對於(A)樹脂100質量份之調配量為0.1質量份以上，則例如於銅或銅合金之上形成本發明之感光性樹脂組合物之情形時，防止銅或銅合金產生變色或受到腐蝕，另一方面，若為20質量份以下，則光感度優異。本發明之感光性樹脂組合物亦可含有交聯劑。交聯劑可為於對使用本發明之感光性樹脂組合物所形成之浮凸圖案進行加熱硬化時，能夠使(A)樹脂交聯、或交聯劑本身能夠形成交聯網狀結構的交聯劑。交聯劑可進一步強化由感光性樹脂組合物所形成之硬化膜之耐熱性及耐化學品性。作為交聯劑，例如可列舉：作為含有羥甲基及/或烷氧基甲基之化合物的Cymel(註冊商標)300、301、303、370、325、327、701、266、267、238、1141、272、202、1156、1158、1123、1170、1174，UFR 65、300，Micoat 102、105(以上為Mitsui Cytec公司製造)；NIKALAC(註冊商標)MX-270、-280、-290，NIKALAC MS-11，NIKALAC MW-30、-100、-300、-390、-750(以上為SANWA CHEMICAL公司製造)；DML-OCHP、DML-MBPC、DML-BPC、DML-PEP、DML-34X、DML-PSBP、DML-PTBP、DML-PCHP、DML-POP、DML-PFP、DML-MBOC、BisCMP-F、DML-BisOC-Z、DML-BisOCHP-Z、DML-BisOC-P、DMOM-PTBT、TMOM-BP、TMOM-BPA、TML-BPAF-MF(以上為本州化學工業公司製造)；苯二甲醇、雙(羥基甲基)甲酚、雙(羥基甲基)二甲氧基苯、雙(羥基甲基)二苯醚、雙(羥基甲基)二苯甲酮、羥基甲基苯甲酸羥基甲基苯酯、雙(羥基甲基)聯苯、二甲基雙(羥基甲基)聯苯、雙(甲氧基甲基)苯、雙(甲氧基甲基)甲酚、雙(甲氧基甲基)二甲氧基苯、雙(甲氧基甲基)二苯醚、雙(甲氧基甲基)二苯甲酮、甲氧基甲基苯甲酸甲氧基甲基苯酯、雙(甲氧基甲基)聯苯、二甲基雙(甲氧基甲基)聯苯等。又，可列舉：作為環氧乙烷化合物之苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚型環氧樹脂、三苯酚型環氧樹脂、四苯酚型環氧樹脂、苯酚-苯二甲基型環氧樹脂、萘酚-苯二甲基型環氧樹脂、苯酚-萘酚型環氧樹脂、苯酚-二環戊二烯型環氧樹脂、脂環式環氧樹脂、脂肪族環氧樹脂、二乙二醇二縮水甘油醚、山梨醇聚縮水甘油醚、丙二醇二縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、1,1,2,2-四(對羥基苯基)乙烷四縮水甘油醚、甘油三縮水甘油醚、鄰第二丁基苯基縮水甘油醚、1,6-雙(2,3-環氧丙氧基)萘、二甘油聚縮水甘油醚、聚乙二醇縮水甘油醚、YDB-340、YDB-412、YDF-2001、YDF-2004(以上為商品名，新日鐵化學股份有限公司製造)、NC-3000-H、EPPN-501H、EOCN-1020、NC-7000L、EPPN-201L、XD-1000、EOCN-4600(以上為商品名，日本化藥股份有限公司製造)、Epikote(註冊商標)1001、Epikote 1007、Epikote 1009、Epikote 5050、Epikote 5051、Epikote 1031S、Epikote 180S65、Epikote 157H70、YX-315-75(以上為商品名，Japan Epoxy Resins股份有限公司製造)、EHPE3150、PLACCEL G402、PUE101、PUE105(以上為商品名，Diacel Chemical Industries股份有限公司製造)、EPICLON(註冊商標)830、850、1050、N-680、N-690、N-695、N-770、HP-7200、HP-820、EXA-4850-1000(以上為商品名，DIC公司製造)、DENACOL(註冊商標)EX-201、EX-251、EX-203、EX-313、EX-314、EX-321、EX-411、EX-511、EX-512、EX-612、EX-614、EX-614B、EX-711、EX-731、EX-810、EX-911、EM-150(以上為商品名，Nagase chemteX公司製造)、Epolight(註冊商標)70P、Epolight 100MF(以上為商品名，共榮社化學製造)等。又，可列舉：作為含異氰酸酯基之化合物之4,4'-二苯基甲烷二異氰酸酯、甲苯二異氰酸酯、1,3-苯二亞甲基二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、異佛爾酮二異氰酸酯、六亞甲基二異氰酸酯、Takenate(註冊商標)500、600、Cosmonate(註冊商標)NBDI、ND(以上為商品名，三井化學公司製造)、Duranate(註冊商標)17B-60PX、TPA-B80E、MF-B60X、MF-K60X、E402-B80T(以上為商品名，Asahi Kasei Chemicals公司製造)等。又，可列舉：作為雙順丁烯二醯亞胺化合物之4,4'-二苯基甲烷雙順丁烯二醯亞胺、苯基甲烷順丁烯二醯亞胺、間伸苯基雙順丁烯二醯亞胺、雙酚A二苯醚雙順丁烯二醯亞胺、3,3'-二甲基-5,5'-二乙基-4,4'-二苯基甲烷雙順丁烯二醯亞胺、4-甲基-1,3-伸苯基雙順丁烯二醯亞胺、1,6'-雙順丁烯二醯亞胺-(2,2,4-三甲基)己烷、4,4'-二苯醚雙順丁烯二醯亞胺、4,4'-二苯基碸雙順丁烯二醯亞胺、1,3-雙(3-順丁烯二醯亞胺苯氧基)苯、1,3-雙(4-順丁烯二醯亞胺苯氧基)苯、BMI-1000、BMI-1100、BMI-2000、BMI-2300、BMI-3000、BMI-4000、BMI-5100、BMI-7000、BMI-TMH、BMI-6000、BMI-8000(以上為商品名，大和化成工業股份有限公司製造)等，但只要為如上所述般進行熱交聯之化合物，則並不限定於該等。關於使用交聯劑之情形時之調配量，相對於(A)樹脂100質量份，較佳為0.5～20質量份，更佳為2～10質量份。於該調配量為0.5質量份以上之情形時，表現出良好之耐熱性及耐化學品性，另一方面，於為20質量份以下之情形時，保存穩定性優異。本發明之感光性樹脂組合物亦可包含有機鈦化合物。藉由包含有機鈦化合物，而即便於約250℃之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。又，尤其藉由使感光性樹脂組合物中含有(B)化合物與有機鈦化合物該兩者，而具有固化後之樹脂層不僅基板接著性優異且耐化學品性亦優異之效果。又，尤其藉由使感光性樹脂組合物中含有(B-1)奈米粒子與有機鈦化合物該兩者，而具有固化後之樹脂層不僅基板接著性優異且耐化學品性亦優異之效果。又，尤其藉由使感光性樹脂組合物中含有(B-2)熱交聯劑與有機鈦化合物該兩者，而具有固化後之樹脂層不僅基板接著性優異且耐化學品性亦優異之效果。又，尤其藉由使感光性樹脂組合物中含有(B-3)化合物與有機鈦化合物該兩者，而具有固化後之樹脂層不僅基板接著性優異且耐化學品性亦優異之效果。作為可使用之有機鈦化合物，可列舉鈦原子上經由共價鍵或離子鍵而鍵結了有機化學物質者。將有機鈦化合物之具體例示於以下之I)～VII)： I)鈦螯合物化合物：其中，就負型感光性樹脂組合物之保存穩定性及獲得良好圖案之方面而言，更佳為具有2個以上之烷氧基之鈦螯合物，具體例如下：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(乙基乙醯乙酸)二異丙醇鈦等。 II)四烷氧基鈦化合物：例如四(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(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)四乙醯丙酮酸鈦化合物：例如四乙醯丙酮酸鈦等。 VII)鈦酸酯偶合劑：例如三(十二烷基苯磺醯基)鈦酸異丙酯等。其中，就表現出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)鈦螯合物化合物、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一種化合物。尤佳為雙(乙基乙醯乙酸)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。關於調配有機鈦化合物之情形時之調配量，相對於(A)樹脂100質量份，較佳為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，表現出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。進而，為了提高使用本發明之感光性樹脂組合物所形成之膜與基材之接著性，可任意地調配接著助劑。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]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)丙基琥珀酸酐等矽烷偶合劑，及三(乙基乙醯乙酸)鋁、三(乙醯丙酮酸)鋁、乙醯乙酸乙基鋁二異丙酯等鋁系接著助劑等。該等接著助劑之中，就接著力之方面而言，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，關於接著助劑之調配量，相對於(A)樹脂100質量份，較佳為0.5～25質量份之範圍。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-(m-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、胺基甲酸(3-三乙氧基矽烷基丙基)第三丁酯、(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、雙(戊二酸)鈦-O,O'-雙(氧基乙基)-胺基丙基三乙氧基矽烷、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，亦可將複數種組合使用。作為矽烷偶合劑，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、及下述結構所表示之矽烷偶合劑。 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關於使用矽烷偶合劑之情形時之調配量，相對於(A)樹脂100質量份，較佳為0.01～20質量份。本發明之感光性樹脂組合物亦可進而含有上述成分以外之成分。該成分之較佳者根據作為(A)樹脂例如使用聚醯亞胺前驅物及聚醯胺等之負型或使用聚㗁唑前驅物、可溶性聚醯亞胺及酚樹脂等之正型等而不同。於使用聚醯亞胺前驅物或聚醯胺等作為(A)樹脂之負型之情形時，為了提高光感度而可任意地調配增感劑。作為該增感劑，例如可列舉：米其勒酮、4,4'-雙(二乙基胺基)二苯甲酮、2,5-雙(4'-二乙基胺基亞苄基)環戊烷、2,6-雙(4'-二乙基胺基亞苄基)環己酮、2,6-雙(4'-二乙基胺基亞苄基)-4-甲基環己酮、4,4'-雙(二甲基胺基)查爾酮、4,4'-雙(二乙基胺基)查爾酮、對二甲基胺基亞桂皮基茚滿酮、對二甲基胺基亞苄基茚滿酮、2-(對二甲基胺基苯基伸聯苯基)苯并噻唑、2-(對二甲基胺基苯基伸乙烯基)苯并噻唑、2-(對二甲基胺基苯基伸乙烯基)異萘并噻唑、1,3-雙(4'-二甲基胺基亞苄基)丙酮、1,3-雙(4'-二乙基胺基亞苄基)丙酮、3,3'-羰基-雙(7-二乙基胺基香豆素)、3-乙醯基-7-二甲基胺基香豆素、3-乙氧基羰基-7-二甲基胺基香豆素、3-苄氧基羰基-7-二甲基胺基香豆素、3-甲氧基羰基-7-二乙基胺基香豆素、3-乙氧基羰基-7-二乙基胺基香豆素、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-𠰌啉基二苯甲酮、二甲基胺基苯甲酸異戊酯、二乙基胺基苯甲酸異戊酯、2-巰基苯并咪唑、1-苯基-5-巰基四唑、2-巰基苯并噻唑、2-(對二甲基胺基苯乙烯基)苯并㗁唑、2-(對二甲基胺基苯乙烯基)苯并噻唑、2-(對二甲基胺基苯乙烯基)萘并(1,2-d)噻唑、2-(對二甲基胺基苯甲醯基)苯乙烯等。該等可單獨使用或以例如2～5者之組合之形式使用。關於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，相對於(A)樹脂100質量份，較佳為0.1～25質量份。又，為了提高浮凸圖案之解像性，可任意地調配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而進行自由基聚合反應之(甲基)丙烯酸系化合物，並不特別限定於以下所列者，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、丙烯酸異𦯉酯及甲基丙烯酸異𦯉酯、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。於感光性樹脂組合物含有用以提高浮凸圖案之解像性的上述具有光聚合性之不飽和鍵之單體之情形時，關於具有光聚合性之不飽和鍵之單體之調配量，相對於(A)樹脂100質量份，較佳為1～50質量份。又，於使用聚醯亞胺前驅物或聚醯胺等作為(A)樹脂之負型之情形時，尤其是為了提高以包含溶劑之溶液之狀態保存時之感光性樹脂組合物之黏度及光感度之穩定性，可任意地調配熱聚合抑制劑。作為熱聚合抑制劑，可使用氫醌、N-亞硝基二苯基胺、對第三丁基兒茶酚、啡噻𠯤、N-苯基萘基胺、乙二胺四乙酸、1,2-環己二胺四乙酸、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。關於感光性樹脂組合物中調配熱聚合抑制劑之情形時之調配量，相對於(A)樹脂100質量份，較佳為0.005～12質量份之範圍。另一方面，本發明之感光樹脂組合物中，於使用聚㗁唑前驅物、可溶性聚醯亞胺或酚樹脂等作為(A)樹脂之正型之情形時，視需要可適當添加先前作為感光性樹脂組合物之添加劑而使用之染料、界面活性劑、以及熱酸產生劑、溶解促進劑、用以提高與基材之密接性之接著助劑等。若更具體地說明上述添加劑，則作為染料，例如可列舉：甲基紫、結晶紫、孔雀綠等。又，作為界面活性劑，例如可列舉包含聚丙二醇或聚氧乙烯月桂醚等聚二醇類或其衍生物之非離子系界面活性劑，例如Fluorad(商品名，住友3M公司製造)、MEGAFAC(商品名，Dainippon Ink & Chemical Industry公司製造)或Lumiflon(商品名，旭硝子公司製造)等氟系界面活性劑，例如KP341(商品名，信越化學工業公司製造)、DBE(商品名，Chisso公司製造)、Glanol(商品名，共榮社化學公司製造)等有機矽氧烷界面活性劑。作為接著助劑，例如可列舉：烷基咪唑啉、丁酸、烷基酸、聚羥基苯乙烯、聚乙烯基甲醚、第三丁基酚醛清漆、環氧矽烷、環氧聚合物等、及各種矽烷偶合劑。關於上述染料及界面活性劑之調配量，相對於(A)樹脂100質量份，較佳為0.1～30質量份。又，就即便於降低硬化溫度之情形時亦表現出良好之硬化物之熱物性及機械物性之觀點而言，可任意地調配熱酸產生劑。就即便於降低硬化溫度之情形時亦表現出良好之硬化物之熱物性及機械物性之觀點而言，較佳為調配熱酸產生劑。作為熱酸產生劑，可列舉：具有利用熱而產生酸之功能之鎓鹽等由強酸與鹼所形成之鹽、或醯亞胺磺酸酯。作為鎓鹽，例如可列舉：芳基重氮鎓鹽、二苯基錪鹽等二芳基錪鹽；二(第三丁基苯基)錪鹽等二(烷基芳基)錪鹽；三甲基鋶鹽之類的三烷基鋶鹽；二甲基苯基鋶鹽等二烷基單芳基鋶鹽；二苯基甲基鋶鹽等二芳基單烷基錪鹽；三芳基鋶鹽等。該等之中，較佳為對甲苯磺酸之二(第三丁基苯基)錪鹽、三氟甲磺酸之二(第三丁基苯基)錪鹽、三氟甲磺酸之三甲基鋶鹽、三氟甲磺酸之二甲基苯基鋶鹽、三氟甲磺酸之二苯基甲基鋶鹽、九氟丁磺酸之二(第三丁基苯基)錪鹽、樟腦磺酸之二苯基錪鹽、乙磺酸之二苯基錪鹽、苯磺酸之二甲基苯基鋶鹽、甲苯磺酸之二苯基甲基鋶鹽等。又，作為由強酸與鹼所形成之鹽，除上述鎓鹽以外，亦可使用由如下強酸與鹼所形成之鹽，例如吡啶鎓鹽。作為強酸，可列舉：對甲苯磺酸、苯磺酸之類的芳基磺酸，樟腦磺酸、三氟甲磺酸、九氟丁磺酸之類的全氟烷基磺酸，甲磺酸、乙磺酸、丁磺酸之類的烷基磺酸等。作為鹼，可列舉：吡啶、2,4,6-三甲基吡啶之類的烷基吡啶、2-氯-N-甲基吡啶之類的N-烷基吡啶、鹵化-N-烷基吡啶等。作為醯亞胺磺酸酯，例如可使用萘甲醯亞胺磺酸酯、鄰苯二甲醯亞胺磺酸酯等，只要為於熱作用下產生酸之化合物，則並無限定。關於使用熱酸產生劑之情形時之調配量，相對於(A)樹脂100質量份，較佳為0.1～30質量份，更佳為0.5～10質量份，進而較佳為1～5質量份。於正型之感光性樹脂組合物之情形時，為了促進於感光後無用之樹脂之去除，可使用溶解促進劑。較佳為例如具有羥基或羧基之化合物。作為具有羥基之化合物之例，可列舉：用於上述萘醌二疊氮化合物之壓載劑、以及對異丙苯基苯酚、雙酚類、間苯二酚類、及MtrisPC、MtetraPC等直鏈狀酚化合物、TrisP-HAP、TrisP-PHBA、TrisP-PA等非直鏈狀酚化合物(均為本州化學工業公司製造)、二苯基甲烷之2～5個苯酚取代體、3,3-二苯基丙烷之1～5個苯酚取代體、使2,2-雙-(3-胺基-4-羥基苯基)六氟丙烷與5-降𦯉烯-2,3-二羧酸酐以莫耳比1：2進行反應而獲得之化合物、使雙-(3-胺基-4-羥基苯基)碸與1,2-環己基二羧酸酐以莫耳比1：2進行反應而獲得之化合物、N-羥基琥珀醯亞胺、N-羥基苯二甲醯亞胺、N-羥基5-降𦯉烯-2,3-二羧醯亞胺等。作為具有羧基之化合物之例，可列舉：3-苯基乳酸、4-羥基苯基乳酸、4-羥基苦杏仁酸、3,4-二羥基苦杏仁酸、4-羥基-3-甲氧基苦杏仁酸、2-甲氧基-2-(1-萘基)丙酸、苦杏仁酸、2-苯乳酸、α-甲氧基苯基乙酸、O-乙醯基苦杏仁酸、伊康酸等。關於使用溶解促進劑之情形時之調配量，相對於(A)樹脂100質量份，較佳為0.1～30質量份。＜硬化浮凸圖案之製造方法及半導體裝置＞又，本發明提供一種硬化浮凸圖案之製造方法，其包括：步驟(1)，其係藉由於基板上塗佈上述本發明之感光性樹脂組合物而於該基板上形成樹脂層；步驟(2)，其係對該樹脂層進行曝光；步驟(3)，其係將該曝光後之樹脂層進行顯影而形成浮凸圖案；及步驟(4)，其係藉由對該浮凸圖案進行加熱處理而形成硬化浮凸圖案。以下說明各步驟之典型態樣。 (1)藉由於基板上塗佈感光性樹脂組合物而於該基板上形成樹脂層之步驟於本步驟中，於基材上塗佈本發明之感光性樹脂組合物，視需要其後加以乾燥而形成樹脂層。作為塗佈方法，可採用先前用於感光性樹脂組合物塗佈之方法，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、利用噴霧塗佈機進行噴霧塗佈之方法等。作為使用本發明之感光性樹脂組合物形成浮凸圖案之方法，不僅可藉由於基板上塗佈該感光性樹脂組合物而於該基板上形成樹脂層，亦可藉由將該感光性樹脂組合物製成膜之形態後於基板上積層感光性樹脂組合物之層而形成樹脂層。又，於支持基材上形成本發明之感光性樹脂組合物之膜，於使用該膜時，可於積層後去除支持基材，亦可於積層前去除支持基材。視需要可使包含感光性樹脂組合物之塗膜乾燥。作為乾燥方法，可採用風乾、利用烘箱或加熱板進行之加熱乾燥、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℃下、1分鐘～1小時之條件下進行乾燥。藉由如上方式而可於基板上形成樹脂層。 (2)對樹脂層進行曝光之步驟於本步驟中，使用接觸式曝光機、鏡面投影曝光機、步進機等曝光裝置，隔著具有圖案之光罩(photomask)或掩膜(reticle)、或者直接地藉由紫外線光源等對上述所形成之樹脂層進行曝光。其後，為了提高光感度等，視需要亦可實施任意之溫度及時間之組合之條件下之曝光後烘烤(PEB)及/或顯影前烘烤。烘烤條件之範圍較佳為溫度：40～120℃、時間：10秒～240秒，但只要無損本發明之感光性樹脂組合物之各特性，則不限於該範圍。 (3)將曝光後之樹脂層進行顯影而形成浮凸圖案之步驟於本步驟中，將曝光後之感光性樹脂層之曝光部或未曝光部顯影去除。於使用負型之感光性樹脂組合物之情形(例如使用聚醯亞胺前驅物或聚醯胺作為(A)樹脂之情形)時，將未曝光部顯影去除，於使用正型之感光性樹脂組合物之情形(例如使用聚㗁唑前驅物或可溶性聚醯亞胺作為(A)樹脂之情形)時，將曝光部顯影去除。作為顯影方法，可自先前已知之光阻之顯影方法、例如旋轉噴霧法、覆液法、伴有超音波處理之浸漬法等中選擇任意方法而使用。又，於顯影後，為了調整浮凸圖案之形狀等，視需要亦可實施任意之溫度及時間之組合之條件下之顯影後烘烤。作為顯影時使用之顯影液，較佳為針對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。例如於不溶於鹼性水溶液之感光性樹脂組合物之情形時，作為良溶劑，較佳為N-甲基吡咯啶酮、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，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。於將良溶劑與不良溶劑混合使用之情形時，較佳為根據感光性樹脂組合物中之聚合物之溶解性而調整不良溶劑相對於良溶劑之比率。又，亦可將2種以上之各溶劑、例如複數種溶劑組合使用。另一方面，於溶於鹼性水溶液之感光性樹脂組合物之情形時，顯影時使用之顯影液係將鹼性水溶液可溶性聚合物溶解去除者，典型而言為溶解有鹼性化合物之鹼性水溶液。顯影液中所溶解之鹼性化合物可為無機鹼性化合物或有機鹼性化合物中之任意者。作為該無機鹼性化合物，例如可列舉：氫氧化鋰、氫氧化鈉、氫氧化鉀、磷酸氫二銨、磷酸氫二鉀、磷酸氫二鈉、矽酸鋰、矽酸鈉、矽酸鉀、碳酸鋰、碳酸鈉、碳酸鉀、硼酸鋰、硼酸鈉、硼酸鉀、及氨等。又，作為該有機鹼性化合物，例如可列舉：氫氧化四甲基銨、氫氧化四乙基銨、氫氧化三甲基羥基乙基銨、甲胺、二甲胺、三甲胺、單乙胺、二乙胺、三乙胺、正丙胺、二正丙胺、異丙胺、二異丙胺、甲基二乙基胺、二甲基乙醇胺、乙醇胺、及三乙醇胺等。進而，視需要可於上述鹼性水溶液中適量添加甲醇、乙醇、丙醇或乙二醇等水溶性有機溶劑、界面活性劑、保存穩定劑、及樹脂之溶解抑止劑等。藉由如上方式可形成浮凸圖案。 (4)藉由對浮凸圖案進行加熱處理而形成硬化浮凸圖案之步驟於本步驟中，藉由對經上述顯影而獲得之浮凸圖案進行加熱而轉變為硬化浮凸圖案。作為加熱硬化之方法，可選擇使用加熱板者、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。加熱可於例如180℃～400℃下、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。＜半導體裝置＞本發明亦提供一種包含藉由上述本發明之硬化浮凸圖案之製造方法所獲得之硬化浮凸圖案的半導體裝置。本發明亦提供一種包含作為半導體元件之基材、與於上述基材上藉由上述硬化浮凸圖案製造方法所形成之樹脂之硬化浮凸圖案的半導體裝置。又，本發明亦適用於使用半導體元件作為基材，包括上述硬化浮凸圖案之製造方法作為步驟之一部分的半導體裝置之製造方法。本發明之半導體裝置可藉由將利用上述硬化浮凸圖案製造方法所形成之硬化浮凸圖案形成為表面保護膜、層間絕緣膜、再配線用絕緣膜、倒裝晶片裝置用保護膜、或具有凸塊結構之半導體裝置之保護膜等，並與已知之半導體裝置之製造方法進行組合而製造。本發明之感光性樹脂組合物除如上所述般適用於半導體裝置以外，亦可用於多層電路之層間絕緣、撓性貼銅板之保護塗層、阻焊膜、及液晶配向膜等用途。 [實施例] 以下，藉由實施例而具體地說明本發明，但本發明並不限定於此。於實施例、比較例及製造例中，依據以下方法測定及評價感光性樹脂組合物之物性。 (1)重量平均分子量藉由凝膠滲透層析法(標準聚苯乙烯換算)測定各樹脂之重量平均分子量(Mw)。測定所使用之管柱為昭和電工股份有限公司製造之商標名「Shodex 805M/806M串聯」，標準單分散聚苯乙烯選擇昭和電工股份有限公司製造之商標名「Shodex STANDARD SM-105」，展開溶劑為N-甲基-2-吡咯啶酮，檢測器使用昭和電工股份有限公司製造之商標名「Shodex RI-930」。 (2)Cu上之硬化浮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(Fujimi Electronic Industry股份有限公司製造，厚度625±25 μm)上依序濺鍍厚200 nm之Ti、厚400 nm之Cu。繼而，使用塗佈顯影儀(Coater Developer)(D-Spin60A型，SOKUDO公司製造)，於該晶圓上旋轉塗佈藉由下述方法所製備之感光性樹脂組合物，加以乾燥，藉此形成厚10 μm之塗膜(於第2實施例中形成厚6～10 μm之塗膜)。使用附測試圖案之光罩，利用平行光光罩對準曝光機(PLA-501FA型，Canon公司製造)，對該塗膜照射300 mJ/cm² 之能量。繼而，於負型之情形時使用環戊酮作為顯影液，於正型之情形時使用2.38%TMAH(tetramethylammonium hydroxide，四甲基氫氧化銨)作為顯影液，利用塗佈顯影儀(D-Spin60A型，SOKUDO公司製造)對該塗膜進行噴霧顯影，於負型之情形時使用丙二醇甲醚乙酸酯進行沖洗，於正型之情形時使用純水進行沖洗，藉此獲得Cu上之浮凸圖案。使用升溫程式型固化爐(VF-2000型，Koyo Lindberg公司製造)，於氮氣環境下，於各實施例所記載之溫度下對Cu上形成有該浮凸圖案之晶圓進行2小時之加熱處理，藉此於Cu上獲得包含厚約6～7 μm之樹脂之硬化浮凸圖案。 (3)Cu上之硬化浮凸圖案之高溫保存(high temperature storage)試驗與其後之評價使用升溫程式型固化爐(VF-2000型，Koyo Lindberg公司製造)，於空氣中，於150℃下對Cu上形成有該硬化浮凸圖案之晶圓加熱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)，藉由電漿蝕刻而去除Cu上全部之樹脂層。電漿蝕刻條件如下所述。輸出：133 W 氣體種類、流量：O₂ ：40 ml/min＋CF₄ ：1 ml/min 氣體壓力：50 Pa 模式：強力模式(hard mode) 蝕刻時間：1800秒利用FE-SEM(field emission-scanning electron microscope，場發射掃描式電子顯微鏡)(S-4800型，Hitachi High-Technologies公司製造)觀察樹脂層全部經去除之Cu表面，使用圖像解析軟體(A像君，旭化成公司製造)，算出空隙於Cu層之表面所占之面積比率。＜第1實施例＞作為第1實施例，進行以下之實驗。＜製造例1＞((A)作為聚醯亞胺前驅物之聚合物(A)-1之合成) 於容積2 L之可分離式燒瓶中放入4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g，添加甲基丙烯酸2-羥基乙酯(HEMA)131.2 g與γ-丁內酯400 ml並於室溫下攪拌，一面攪拌一面添加吡啶81.5 g而獲得反應混合物。於由反應產生之放熱結束後，靜置冷卻至室溫，放置16小時。繼而，於冰浴冷卻下，一面攪拌一面歷時40分鐘向反應混合物中添加使二環己基碳二醯亞胺(DCC)206.3 g溶解於γ-丁內酯180 ml所得之溶液，繼而，一面攪拌一面歷時60分鐘添加使4,4'-二胺基二苯醚(DADPE)93.0 g懸浮於γ-丁內酯350 ml所得者。進而於室溫下攪拌2小時後，添加乙醇30 ml並攪拌1小時，繼而，添加γ-丁內酯400 ml。藉由過濾而去除反應混合物中所生成之沈澱物，獲得反應液。將所獲得之反應液添加至3 L之乙醇中，而生成包含粗聚合物之沈澱物。過濾分離所生成之粗聚合物，使之溶解於四氫呋喃1.5 L而獲得粗聚合物溶液。將所獲得之粗聚合物溶液滴加至28 L之水中而使聚合物沈澱，過濾分離所獲得之沈澱物後，進行真空乾燥而獲得粉末狀之聚合物(聚合物(A)-1)。藉由凝膠滲透層析法(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。再者，各製造例中獲得之樹脂之重量平均分子量係採用凝膠滲透層析法(GPC)，於以下之條件下進行測定，求出以標準聚苯乙烯換算計之重量平均分子量。泵：JASCO PU-980 檢測器：JASCO RI-930 管柱烘箱：JASCO CO-965 40℃ 管柱：2根Shodex KD-806M串聯流動相：0.1 mol/L LiBr/NMP(N-methylpyrrolidone，N-甲基吡咯啶酮) 流速：1 ml/min. ＜製造例2＞((A)作為聚醯亞胺前驅物之聚合物(A)-2之合成) 使用3,3',4,4'-聯苯基四羧酸二酐(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，藉由與上述製造例1所記載之方法相同之方式進行反應，而獲得聚合物(A)-2。藉由凝膠滲透層析法(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。＜製造例3＞((A)作為聚醯亞胺前驅物之聚合物(A)-3之合成) 使用2,2'-雙三氟甲基-4,4'-二胺基聯苯(TFMB)147.8 g代替製造例1之4,4'-二胺基二苯醚(DADPE)93.0 g，除此以外，藉由與上述製造例1所記載之方法相同之方式進行反應，而獲得聚合物(A)-3。藉由凝膠滲透層析法(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21,000。＜製造例4＞((A)作為聚醯胺之聚合物(A)-4之合成) (苯二甲酸化合物封端體AIPA-MO之合成) 於容積5 L之可分離式燒瓶中投入5-胺基間苯二甲酸{以下簡記為AIPA}543.5 g、N-甲基-2-吡咯啶酮1700 g，進行混合攪拌，藉由水浴加熱至50℃。利用滴液漏斗於其中滴加投入使異氰酸2-甲基丙烯醯氧基乙酯512.0 g(3.3 mol)經γ-丁內酯500 g稀釋所得者，直接於50℃下攪拌2小時左右。藉由低分子量凝膠滲透層析法{以下記為低分子量GPC}確認反應結束(5-胺基間苯二甲酸消失)後，將該反應液投入至15 L之離子交換水中，進行攪拌，加以靜置，待出現反應產物之結晶化沈澱後將其過濾分離，經適當水洗後，於40℃下真空乾燥48小時，藉此獲得由5-胺基間苯二甲酸之胺基與異氰酸2-甲基丙烯醯氧基乙酯之異氰酸酯基作用所得之AIPA-MO。所獲得之AIPA-MO之低分子量GPC純度約為100%。 (聚合物(A)-4之合成) 於容積2 L之可分離式燒瓶中投入所獲得之AIPA-MO 100.89 g(0.3 mol)、吡啶71.2 g(0.9 mol)、GBL(丁內酯，γ-butyrolactone)400 g，進行混合，藉由冰浴冷卻至5℃。於冰浴冷卻下，歷時20分鐘左右於其中滴加使二環己基碳二醯亞胺(DCC)125.0 g(0.606 mol)經GBL 125 g溶解稀釋所得者，繼而，歷時20分鐘左右滴加使4,4'-雙(4-胺基苯氧基)聯苯{以下記為BAPB}103.16 g(0.28 mol)經NMP 168 g溶解所得者，藉由冰浴維持3小時未達5℃，繼而移除冰浴，於室溫下攪拌5小時。藉由過濾而去除反應混合物中所生成之沈澱物，獲得反應液。於所獲得之反應液中滴加水840 g與異丙醇560 g之混合液，分離所析出之聚合物，使之再溶解於NMP 650 g。將所獲得之粗聚合物溶液滴加至5 L之水中使聚合物沈澱，過濾分離所獲得之沈澱物後，進行真空乾燥而獲得粉末狀之聚合物(聚合物(A)-4)。藉由凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物(A)-4之分子量，結果重量平均分子量(Mw)為34,700。＜製造例5＞((A)作為聚㗁唑前驅物之聚合物(A)-5之合成) 於容積3 L之可分離式燒瓶中將2,2-雙(3-胺基-4-羥基苯基)-六氟丙烷183.1 g、N,N-二甲基乙醯胺(DMAc)640.9 g、吡啶63.3 g於室溫(25℃)下進行混合攪拌，製成均勻溶液。利用滴液漏斗於其中滴加使4,4'-二苯醚二甲醯氯118.0 g經二乙二醇二甲醚(DMDG)354 g溶解所得者。此時，將可分離式燒瓶於15～20℃之水浴中冷卻。滴液所需之時間為40分鐘，反應液溫最高為30℃。滴液結束後經過3小時後，向反應液中添加1,2-環己基二羧酸酐30.8 g(0.2 mol)，於室溫下攪拌放置15小時，使聚合物鏈之占總數99%之胺末端基經羧基環己基醯胺基封端。此時之反應率可藉由利用高效液相層析法(HPLC)追蹤所投入之1,2-環己基二羧酸酐之殘量而容易地算出。其後，將上述反應液於高速攪拌下滴加至2 L之水中而使聚合物分散析出，將其回收，經適當水洗，脫水後實施真空乾燥，而獲得藉由凝膠滲透層析(GPC)法所測得之重量平均分子量9,000(聚苯乙烯換算)之粗聚苯并㗁唑前驅物。使上述獲得之粗聚苯并㗁唑前驅物再溶解於γ-丁內酯(GBL)後，對其利用陽離子交換樹脂及陰離子交換樹脂進行處理，將藉此獲得之溶液投入至離子交換水中後，過濾分離所析出之聚合物，進行水洗並真空乾燥，藉此獲得經精製之聚苯并㗁唑前驅物(聚合物(A)-5)。＜製造例6＞((A)作為聚醯亞胺之聚合物(A)-6之合成) 對裝有Teflon(註冊商標)製錨型攪拌器之玻璃製可分離式四口燒瓶安裝附迪安-斯塔克分離器之冷卻管。一面通入氮氣，一面將上述燒瓶浸於矽油浴中進行攪拌。添加2,2-雙(3-胺基-4-羥基苯基)丙烷(Clariant Japan公司製造)(以下記為BAP)72.28 g(280 mmol)、5-(2,5-二側氧四氫-3-呋喃基)-3-甲基-環己烯-1,2二羧酸酐(東京化成工業股份有限公司製造)(以下記為MCTC)70.29 g(266 mmol)、γ-丁內酯254.6 g、甲苯60 g，於室溫下以100 rpm攪拌4小時後，添加5-降𦯉烯-2,3-二羧酸酐(東京化成工業股份有限公司製造)4.6 g(28 mmol)，一面通入氮氣一面於矽浴溫度50℃下以100 rpm加熱攪拌8小時。其後，加熱至矽浴溫度180℃，以100 rpm加熱攪拌2小時。去除於反應中所餾出之甲苯、水。醯亞胺化反應結束後恢復至室溫。其後將上述反應液於高速攪拌下滴加至3 L之水中而使聚合物分散析出，將其回收，經適當水洗，脫水後實施真空乾燥，而獲得藉由凝膠滲透層析(GPC)法所測得之重量平均分子量23,000(聚苯乙烯換算)之粗聚醯亞胺(聚合物(A)-6)。＜製造例7＞((A)作為酚樹脂之聚合物(A)-8之合成) 對容積1.0 L之附迪安-斯塔克裝置之可分離式燒瓶進行氮氣置換，其後，於該可分離式燒瓶中將間苯二酚81.3 g(0.738 mol)、BMMB 84.8 g(0.35 mol)、對甲苯磺酸3.81 g(0.02 mol)、丙二醇單甲醚(以下亦稱為PGME)116 g於50℃下進行混合攪拌，而使固形物溶解。藉由油浴將混合溶液加熱至120℃，確認自反應液生成了甲醇。直接於120℃下將反應液攪拌3小時。繼而，於另一容器中將2,6-雙(羥基甲基)對甲酚24.9 g(0.150 mol)、PGME 249 g進行混合攪拌，使之均勻溶解，將所獲得之溶液使用滴液漏斗歷時1小時滴加至該可分離式燒瓶內，滴液後進而攪拌2小時。反應結束後，進行與製造例7相同之處理，而以產率77%獲得包含間苯二酚/BMMB/2,6-雙(羥基甲基)對甲酚之共聚物(聚合物H)。該聚合物H之藉由GPC法之標準聚苯乙烯換算所求出之重量平均分子量為9,900。＜實施例1＞使用聚合物(A)-1、(A)-2，藉由以下之方法製備負型感光性樹脂組合物，並進行感光性樹脂組合物之評價。將作為聚醯亞胺前驅物之聚合物(A)-1 50 g與(A)-2 50 g(相當於(A)樹脂)與鄰苯二甲酸二環己酯(東京化成工業股份有限公司製造，相當於(B)-1)4 g、1-苯基-1,2-丙烷二酮-2-(O-乙氧基羰基)-肟(表1中記為「PDO」)(相當於(C)感光劑)4 g、四乙二醇二甲基丙烯酸酯8 g、N-[3-(三乙氧基矽烷基)丙基]苯二甲醯胺酸1.5 g一併溶解於包含N-甲基-2-吡咯啶酮(以下記為NMP)80 g與乳酸乙酯20 g之混合溶劑。藉由進而添加少量之上述混合溶劑而將所獲得之溶液之黏度調整為約35泊(poise)，製成負型感光性樹脂組合物。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.1%之結果。＜實施例2＞上述實施例1中，將(B)成分變為鄰苯二甲酸二苯酯(東京化成工業股份有限公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.9%之結果。＜實施例3＞上述實施例1中，將(B)成分變為鄰苯二甲酸二-2-乙基己酯(東京化成工業股份有限公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.2%之結果。＜實施例4＞上述實施例1中，將(B)成分變為偏苯三甲酸二環己酯(東京化成工業股份有限公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.3%之結果。＜實施例5＞上述實施例1中，將(B)成分變為均苯四甲酸二環己酯(東京化成工業股份有限公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.2%之結果。＜實施例6＞上述實施例1中，將(B)成分變為己二酸二環己酯(東京化成工業股份有限公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.9%之結果。＜實施例7＞上述實施例1中，將(B)成分變為癸二酸二環己酯(東京化成工業股份有限公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.8%之結果。＜實施例8＞上述實施例1中，將(B)成分變為丁酸四氫糠酯(東京化成工業股份有限公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.8%之結果。＜實施例9＞上述實施例1中，將(B)-1成分之添加量變為2 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得7.6%之結果。＜實施例10＞上述實施例1中，將(B)-1成分之添加量變為8 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.8%之結果。＜實施例11＞上述實施例1中，將(B)-1成分之添加量變為16 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得10.5%之結果。＜實施例12＞上述實施例1中，將固化溫度自230℃變為350℃，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.5%之結果。＜實施例13＞上述實施例1中，作為(A)樹脂，將聚合物(A)-1 50 g與聚合物(A)-2 50 g變為聚合物(A)-1 100 g，將(C)成分自PDO變為1,2-辛烷二酮-1-{4-(苯硫基)-2-(O-苯甲醯基肟)}(Irgacure OXE01(BASF公司製造，商品名))2.5 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.3%之結果。＜實施例14＞上述實施例12中，將溶劑變為γ-丁內酯85 g與二甲基亞碸15 g，除此以外，藉由與實施例12相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.5%之結果。＜實施例15＞上述實施例1中，作為(A)樹脂，將聚合物(A)-1 50 g與聚合物(A)-2 50 g變為聚合物(A)-3 100 g，並將固化溫度自230℃變為350℃，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.8%之結果。＜實施例16＞上述實施例1中，作為(A)樹脂，將聚合物(A)-1 50 g與聚合物(A)-2 50 g變為聚合物(A)-4 100 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.9%之結果。＜實施例17＞使用聚合物(A)-5，藉由以下之方法製備正型感光性樹脂組合物，並對所製備之感光性樹脂組合物進行評價。將作為聚㗁唑前驅物之聚合物(A)-5 100 g(相當於(A)樹脂)與下述式(96)： [化127]

所表示之77%之酚性羥基經萘醌二疊氮-4-磺酸酯化之感光性重氮醌化合物(東洋合成公司製造，相當於(C)成分)(C1)15 g溶解於γ-丁內酯(作為溶劑)100 g。藉由進而添加少量之γ-丁內酯而將所獲得之溶液之黏度調整為約20泊(poise)，製成正型感光性樹脂組合物。針對該組合物，藉由上述方法進行350℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.1%之結果。＜實施例18＞上述實施例17中，作為(A)樹脂，將聚合物(A)-5 100 g變為聚合物(A)-6 100 g，除此以外，藉由與實施例17相同之方式製備正型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行250℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得6.2%之結果。＜實施例19＞上述實施例17中，作為(A)樹脂，將聚合物(A)-6 100 g變為聚合物(A)-7(酚醛清漆樹脂，聚苯乙烯換算重量平均分子量(Mw)＝10,600(旭有機材公司製造，製品名EP-4080G)100 g，除此以外，藉由與實施例17相同之方式製備正型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行250℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.2%之結果。＜實施例20＞上述實施例17中，作為(A)樹脂，將聚合物(A)-6 100 g變為聚合物(A)-7(酚醛清漆樹脂，聚苯乙烯換算重量平均分子量(Mw)＝10,600(旭有機材公司製造，製品名EP-4080G)100 g，將(B)成分變為丁酸四氫糠酯(東京化成工業股份有限公司製造)，除此以外，藉由與實施例17相同之方式製備正型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行250℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.6%之結果。＜實施例21＞上述實施例17中，作為(A)樹脂，將聚合物(A)-6 100 g變為聚合物(A)-8 100 g，除此以外，藉由與實施例17相同之方式製備正型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行250℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.6%之結果。＜實施例22＞上述實施例17中，作為(A)樹脂，將聚合物(A)-6 100 g變為聚合物(A)-8 100 g，將(B)成分變為丁酸四氫糠酯(東京化成工業股份有限公司製造)，除此以外，藉由與實施例17相同之方式製備正型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行250℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.3%之結果。＜比較例1＞於實施例1之組成中，不添加(B)-1成分，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物，並進行與實施例1相同之評價。由於不含本發明之(B)塑化劑，故評價結果為15.2%。＜比較例2＞於實施例16之組成中，不添加(B)-1成分，除此以外，藉由與實施例15相同之方式製備負型感光性樹脂組合物，並進行與實施例15相同之評價。由於不含本發明之(B)塑化劑，故評價結果為14.3%。＜比較例3＞於實施例14之組成中，不添加(B)-1成分，除此以外，藉由與實施例13相同之方式製備負型感光性樹脂組合物，並進行與實施例13相同之評價。由於不含本發明之(B)塑化劑，故評價結果為15.7%。＜比較例4＞於實施例18之組成中，不添加(B)-1成分，除此以外，藉由與實施例17相同之方式製備正型感光性樹脂組合物，並進行與實施例17相同之評價。由於不含本發明之(B)塑化劑，故評價結果為16.3%。＜比較例5＞於實施例1之組成中，將(B)-1成分之添加量變為0.05 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物，並進行與實施例1相同之評價。評價結果為13.1%。＜比較例6＞於實施例1之組成中，將(B)-1成分之添加量變為60 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物，並進行與實施例1相同之評價。評價結果為15.2%。將該等實施例1～22、比較例1～6之結果彙總示於表1。 [表1]

＜第2實施例＞作為第2實施例，進行以下之實驗。＜製造例1＞((A)作為聚醯亞胺前驅物之聚合物A之合成) 於容積2 L之可分離式燒瓶中放入4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g，添加甲基丙烯酸2-羥基乙酯(HEMA)131.2 g與γ-丁內酯400 ml並於室溫下攪拌，一面攪拌一面添加吡啶81.5 g而獲得反應混合物。於由反應產生之放熱結束後，靜置冷卻至室溫，放置16小時。繼而，於冰浴冷卻下，一面攪拌一面歷時40分鐘向反應混合物中添加使二環己基碳二醯亞胺(DCC)206.3 g溶解於γ-丁內酯180 ml所得之溶液，繼而，一面攪拌一面歷時60分鐘添加使4,4'-二胺基二苯醚(DADPE)93.0 g懸浮於γ-丁內酯350 ml所得者。進而於室溫下攪拌2小時後，添加乙醇30 ml並攪拌1小時，繼而，添加γ-丁內酯400 ml。藉由過濾而去除反應混合物中所生成之沈澱物，獲得反應液。將所獲得之反應液添加至3 L之乙醇中，而生成包含粗聚合物之沈澱物。過濾分離所生成之粗聚合物，使之溶解於四氫呋喃1.5 L而獲得粗聚合物溶液。將所獲得之粗聚合物溶液滴加至28 L之水中而使聚合物沈澱，過濾分離所獲得之沈澱物後，進行真空乾燥而獲得粉末狀之聚合物(聚合物A)。藉由凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物A之分子量，結果重量平均分子量(Mw)為20,000。再者，各製造例中獲得之樹脂之重量平均分子量係採用凝膠滲透層析法(GPC)，於以下之條件下進行測定，求出以標準聚苯乙烯換算計之重量平均分子量。泵：JASCO PU-980 檢測器：JASCO RI-930 管柱烘箱：JASCO CO-965 40℃ 管柱：2根Shodex KD-806M串聯流動相：0.1 mol/L LiBr/NMP 流速：1 ml/min. ＜製造例2＞((A)作為聚醯亞胺前驅物之聚合物B之合成) 使用3,3',4,4'-聯苯基四羧酸二酐(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，藉由與上述製造例1所記載之方法相同之方式進行反應，而獲得聚合物B。藉由凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物B之分子量，結果重量平均分子量(Mw)為22,000。＜製造例3＞((A)作為聚醯亞胺前驅物之聚合物C之合成) 使用2,2'-雙三氟甲基-4,4'-二胺基聯苯(TFMB)147.8 g代替製造例1之4,4'-二胺基二苯醚(DADPE)93.0 g，除此以外，藉由與上述製造例1所記載之方法相同之方式進行反應，而獲得聚合物C。藉由凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物C之分子量，結果重量平均分子量(Mw)為21,000。＜製造例4＞((A)作為聚醯胺之聚合物D之合成) (苯二甲酸化合物封端體AIPA-MO之合成) 於容積5 L之可分離式燒瓶中投入5-胺基間苯二甲酸{以下簡記為AIPA}543.5 g、N-甲基-2-吡咯啶酮1700 g，進行混合攪拌，藉由水浴加熱至50℃。利用滴液漏斗於其中滴加投入使異氰酸2-甲基丙烯醯氧基乙酯512.0 g(3.3 mol)經γ-丁內酯500 g稀釋所得者，直接於50℃下攪拌2小時左右。藉由低分子量凝膠滲透層析法{以下記為低分子量GPC}確認反應結束(5-胺基間苯二甲酸消失)後，將該反應液投入至15 L之離子交換水中，進行攪拌，加以靜置，待出現反應產物之結晶化沈澱後將其過濾分離，經適當水洗後，於40℃下真空乾燥48小時，藉此獲得由5-胺基間苯二甲酸之胺基與異氰酸2-甲基丙烯醯氧基乙酯之異氰酸酯基作用所得之AIPA-MO。所獲得之AIPA-MO之低分子量GPC純度約為100%。 (聚合物D之合成) 於容積2 L之可分離式燒瓶中投入所獲得之AIPA-MO 100.89 g(0.3 mol)、吡啶71.2 g(0.9 mol)、GBL 400 g，進行混合，藉由冰浴冷卻至5℃。於冰浴冷卻下，歷時20分鐘左右於其中滴加使二環己基碳二醯亞胺(DCC)125.0 g(0.606 mol)經GBL 125 g溶解稀釋所得者，繼而，歷時20分鐘左右滴加使4,4'-雙(4-胺基苯氧基)聯苯{以下記為BAPB}103.16 g(0.28 mol)經NMP 168 g溶解所得者，藉由冰浴維持3小時未達5℃，繼而移除冰浴，於室溫下攪拌5小時。藉由過濾而去除反應混合物中所生成之沈澱物，獲得反應液。於所獲得之反應液中滴加水840 g與異丙醇560 g之混合液，分離所析出之聚合物，使之再溶解於NMP 650 g。將所獲得之粗聚合物溶液滴加至5 L之水中使聚合物沈澱，過濾分離所獲得之沈澱物後，進行真空乾燥而獲得粉末狀之聚合物(聚合物E)。藉由凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物D之分子量，結果重量平均分子量(Mw)為34,700。＜製造例5＞((A)作為聚㗁唑前驅物之聚合物E之合成) 於容積3 L之可分離式燒瓶中將2,2-雙(3-胺基-4-羥基苯基)-六氟丙烷183.1 g、N,N-二甲基乙醯胺(DMAc)640.9 g、吡啶63.3 g於室溫(25℃)下進行混合攪拌，製成均勻溶液。利用滴液漏斗於其中滴加使4,4'-二苯醚二甲醯氯118.0 g經二乙二醇二甲醚(DMDG)354 g溶解所得者。此時，將可分離式燒瓶於15～20℃之水浴中冷卻。滴液所需之時間為40分鐘，反應液溫最高為30℃。滴液結束後經過3小時後，向反應液中添加1,2-環己基二羧酸酐30.8 g(0.2 mol)，於室溫下攪拌放置15小時，使聚合物鏈之占總數99%之胺末端基經羧基環己基醯胺基封端。此時之反應率可藉由利用高效液相層析法(HPLC)追蹤所投入之1,2-環己基二羧酸酐之殘量而容易地算出。其後，將上述反應液於高速攪拌下滴加至2 L之水中而使聚合物分散析出，將其回收，經適當水洗，脫水後實施真空乾燥，而獲得藉由凝膠滲透層析(GPC)法所測得之重量平均分子量9,000(聚苯乙烯換算)之粗聚苯并㗁唑前驅物。使上述獲得之粗聚苯并㗁唑前驅物再溶解於γ-丁內酯(GBL)後，對其利用陽離子交換樹脂及陰離子交換樹脂進行處理，將藉此獲得之溶液投入至離子交換水中後，過濾分離所析出之聚合物，進行水洗並真空乾燥，藉此獲得經精製之聚苯并㗁唑前驅物(聚合物E)。＜製造例6＞((A)作為聚醯亞胺之聚合物F之合成) 對裝有Teflon(註冊商標)製錨型攪拌器之玻璃製可分離式四口燒瓶安裝附迪安-斯塔克分離器之冷卻管。一面通入氮氣，一面將上述燒瓶浸於矽油浴中進行攪拌。添加2,2-雙(3-胺基-4-羥基苯基)丙烷(Clariant Japan公司製造)(以下記為BAP)72.28 g(280 mmol)、5-(2,5-二側氧四氫-3-呋喃基)-3-甲基-環己烯-1,2二羧酸酐(東京化成工業股份有限公司製造)(以下記為MCTC)70.29 g(266 mmol)、γ-丁內酯254.6 g、甲苯60 g，於室溫下以100 rpm攪拌4小時後，添加5-降𦯉烯-2,3-二羧酸酐(東京化成工業股份有限公司製造)4.6 g(28 mmol)，一面通入氮氣一面於矽浴溫度50℃下以100 rpm加熱攪拌8小時。其後，加熱至矽浴溫度180℃，以100 rpm加熱攪拌2小時。去除於反應中所餾出之甲苯、水。醯亞胺化反應結束後恢復至室溫。其後將上述反應液於高速攪拌下滴加至3 L之水中而使聚合物分散析出，將其回收，經適當水洗，脫水後實施真空乾燥，而獲得藉由凝膠滲透層析(GPC)法所測得之重量平均分子量23,000(聚苯乙烯換算)之粗聚醯亞胺(聚合物F)。＜製造例7＞((A)作為酚樹脂之聚合物G之合成) 於容積0.5 L之附迪安-斯塔克裝置之可分離式燒瓶中將3,5-二羥基苯甲酸甲酯128.3 g(0.76 mol)、4,4'-雙(甲氧基甲基)聯苯(以下亦稱為「BMMB」)121.2 g(0.5 mol)、二乙基硫酸3.9 g(0.025 mol)、二乙二醇二甲醚140 g於70℃下進行混合攪拌，而使固形物溶解。藉由油浴將混合溶液加熱至140℃，確認自反應液生成了甲醇。直接於140℃下攪拌反應液2小時。繼而，將反應容器於大氣中冷卻，向其中另外添加100 g之四氫呋喃并攪拌。將上述反應稀釋液於高速攪拌下滴加至4 L之水中而使樹脂分散析出，將其回收，經適當水洗，脫水後實施真空乾燥，而以產率70%獲得包含3,5-二羥基苯甲酸甲酯/BMMB之共聚物(聚合物G)。該聚合物G之藉由GPC法之標準聚苯乙烯換算所求出之重量平均分子量為21,000。＜製造例8＞((A)作為酚樹脂之聚合物H之合成) 對容積1.0 L之附迪安-斯塔克裝置之可分離式燒瓶進行氮氣置換，其後，於該可分離式燒瓶中將間苯二酚81.3 g(0.738 mol)、BMMB 84.8 g(0.35 mol)、對甲苯磺酸3.81 g(0.02 mol)、丙二醇單甲醚(以下亦稱為PGME)116 g於50℃下進行混合攪拌，而使固形物溶解。藉由油浴將混合溶液加熱至120℃，確認自反應液生成了甲醇。直接於120℃下將反應液攪拌3小時。繼而，於另一容器中將2,6-雙(羥基甲基)對甲酚24.9 g(0.150 mol)、PGME 249 g進行混合攪拌，使之均勻溶解，將所獲得之溶液使用滴液漏斗歷時1小時滴加至該可分離式燒瓶內，滴液後進而攪拌2小時。反應結束後，進行與製造例7相同之處理，而以產率77%獲得包含間苯二酚/BMMB/2,6-雙(羥基甲基)對甲酚之共聚物(聚合物H)。該聚合物H之藉由GPC法之標準聚苯乙烯換算所求出之重量平均分子量為9,900。＜實施例1＞使用聚合物A、B，藉由以下之方法製備負型感光性樹脂組合物，並對所製備之感光性樹脂組合物進行評價。將作為聚醯亞胺前驅物之聚合物A 50 g與B 50 g(相當於(A)樹脂)與磷酸鋯(長軸100 nm、短軸5 nm之板狀粒子，相當於縱橫比20之(B-1)奈米粒子)5 g、1-苯基-1,2-丙烷二酮-2-(O-乙氧基羰基)-肟(表1中記為「PDO」)(相當於(C)感光劑)4 g、四乙二醇二甲基丙烯酸酯8 g、N-[3-(三乙氧基矽烷基)丙基]苯二甲醯胺酸1.5 g一併溶解於包含N-甲基-2-吡咯啶酮(以下記為NMP)80 g與乳酸乙酯20 g之混合溶劑。藉由進而添加少量之上述混合溶劑而將所獲得之溶液之黏度調整為約35泊(poise)，製成負型感光性樹脂組合物。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.5%之結果。＜實施例2＞上述實施例1中，作為(B-1)成分，將磷酸鋯之添加量變為1 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得6.6%之結果。＜實施例3＞上述實施例1中，作為(B-1)成分，使用蒙脫石(長軸100 nm、短軸10 nm，縱橫比10之板狀粒子)代替磷酸鋯，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.8%之結果。＜實施例4＞上述實施例1中，作為(B-1)成分，使用艾羅技(粒徑12 nm之球狀粒子，縱橫比1)1 g代替磷酸鋯5 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.4%之結果。＜實施例5＞藉由與上述實施例1相同之方式製備負型感光性樹脂組合物溶液，針對該組合物，藉由上述方法進行350℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.5%之結果。＜實施例6＞上述實施例1中，作為(A)樹脂，將聚合物A 50 g與聚合物B 50 g變為聚合物A 100 g，作為(C)成分，將PDO 4 g變為1,2-辛烷二酮-1-{4-(苯硫基)-2-(O-苯甲醯基肟)}(Irgacure OXE01(BASF公司製造，商品名))2.5 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.3%之結果。＜實施例7＞上述實施例1中，作為(A)樹脂，將聚合物A 50 g與聚合物B 50 g變為聚合物A 100 g，作為(C)成分，將PDO 4 g變為1,2-辛烷二酮-1-{4-(苯硫基)-2-(O-苯甲醯基肟)}(Irgacure OXE01(BASF公司製造，商品名))2.5 g，進而將溶劑變為γ-丁內酯85 g與二甲基亞碸15 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.3%之結果。＜實施例8＞上述實施例1中，作為(A)樹脂，將聚合物A 50 g與聚合物B 50 g變為聚合物C 100 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行350℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.8%之結果。＜實施例9＞上述實施例1中，作為(A)樹脂，將聚合物A 50 g與聚合物B 50 g變為聚合物D 100 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行250℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.6%之結果。＜實施例10＞使用聚合物E，藉由以下之方法製備正型感光性樹脂組合物，並對所製備之感光性樹脂組合物進行評價。將作為聚㗁唑前驅物之聚合物E 100 g(相當於(A)樹脂)與下述式(96)： [化128]

所表示之77%之酚性羥基經萘醌二疊氮-4-磺酸酯化之感光性重氮醌化合物(東洋合成公司製造，相當於(C)感光劑)(C1)15 g、磷酸鋯(長徑100 nm、厚度5 nm之板狀粒子，相當於(B)奈米粒子)5 g、3-第三丁氧基羰基胺基丙基三乙氧基矽烷6 g一併溶解於γ-丁內酯(作為溶劑)100 g。藉由進而添加少量之γ-丁內酯而將所獲得之溶液之黏度調整為約20泊(poise)，製成正型感光性樹脂組合物。針對該組合物，藉由上述方法進行350℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.7%之結果。＜實施例11＞上述實施例10中，作為(A)樹脂，將聚合物E 100 g變為聚合物F 100 g，除此以外，藉由與實施例10相同之方式製備正型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行250℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.7%之結果。＜實施例12＞上述實施例10中，作為(A)樹脂，將聚合物E 100 g變為聚合物G 100 g，除此以外，藉由與實施例10相同之方式製備正型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行220℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.4%之結果。＜實施例13＞上述實施例10中，作為(A)樹脂，將聚合物E 100 g變為聚合物H 100 g，除此以外，藉由與實施例10相同之方式製備正型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行220℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.5%之結果。＜比較例1＞於實施例1之組成中，不添加磷酸鋯，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物，並進行與實施例1相同之評價。由於不含本發明之(B)化合物，故評價結果為14.3%。＜比較例2＞於實施例8之組成中，不添加磷酸鋯，除此以外，藉由與實施例8相同之方式製備負型感光性樹脂組合物，並進行與實施例10相同之評價。由於不含本發明之(B)化合物，故評價結果為14.9%。＜比較例3＞於實施例10之組成中，不添加磷酸鋯，除此以外，藉由與實施例10相同之方式製備正型感光性樹脂組合物，並進行與實施例10相同之評價。由於不含本發明之(B)化合物，故評價結果為14.6%。將該等結果彙總示於表2。 [表2]

＜第3實施例＞作為第3實施例，進行以下之實驗。＜製造例1＞((A)作為聚醯亞胺前驅物之聚合物A之合成) 於容積2 L之可分離式燒瓶中放入4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g，添加甲基丙烯酸2-羥基乙酯(HEMA)131.2 g與γ-丁內酯400 ml並於室溫下攪拌，一面攪拌一面添加吡啶81.5 g而獲得反應混合物。於由反應產生之放熱結束後，靜置冷卻至室溫，放置16小時。繼而，於冰浴冷卻下，一面攪拌一面歷時40分鐘向反應混合物中添加使二環己基碳二醯亞胺(DCC)206.3 g溶解於γ-丁內酯180 ml所得之溶液，繼而，一面攪拌一面歷時60分鐘添加使4,4'-二胺基二苯醚(DADPE)93.0 g懸浮於γ-丁內酯350 ml所得者。進而於室溫下攪拌2小時後，添加乙醇30 ml並攪拌1小時，繼而，添加γ-丁內酯400 ml。藉由過濾而去除反應混合物中所生成之沈澱物，獲得反應液。將所獲得之反應液添加至3 L之乙醇中，而生成包含粗聚合物之沈澱物。過濾分離所生成之粗聚合物，使之溶解於四氫呋喃1.5 L而獲得粗聚合物溶液。將所獲得之粗聚合物溶液滴加至28 L之水中而使聚合物沈澱，過濾分離所獲得之沈澱物後，進行真空乾燥而獲得粉末狀之聚合物(聚合物A)。藉由凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物A之分子量，結果重量平均分子量(Mw)為20,000。再者，各製造例中獲得之樹脂之重量平均分子量係採用凝膠滲透層析法(GPC)，於以下之條件下進行測定，求出以標準聚苯乙烯換算計之重量平均分子量。泵：JASCO PU-980 檢測器：JASCO RI-930 管柱烘箱：JASCO CO-965 40℃ 管柱：2根Shodex KD-806M串聯流動相：0.1 mol/L LiBr/NMP 流速：1 ml/min. ＜製造例2＞((A)作為聚醯亞胺前驅物之聚合物B之合成) 使用3,3',4,4'-聯苯基四羧酸二酐(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，藉由與上述製造例1所記載之方法相同之方式進行反應，而獲得聚合物B。藉由凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物B之分子量，結果重量平均分子量(Mw)為22,000。＜製造例3＞((A)作為聚醯亞胺前驅物之聚合物C之合成) 使用2,2'-雙三氟甲基-4,4'-二胺基聯苯(TFMB)147.8 g代替製造例1之4,4'-二胺基二苯醚(DADPE)93.0 g，除此以外，藉由與上述製造例1所記載之方法相同之方式進行反應，而獲得聚合物C。藉由凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物C之分子量，結果重量平均分子量(Mw)為21,000。＜製造例4＞((A)作為聚醯胺之聚合物D之合成) (苯二甲酸化合物封端體AIPA-MO之合成) 於容積5 L之可分離式燒瓶中投入5-胺基間苯二甲酸{以下簡記為AIPA}543.5 g、N-甲基-2-吡咯啶酮1700 g，進行混合攪拌，藉由水浴加熱至50℃。利用滴液漏斗於其中滴加投入使異氰酸2-甲基丙烯醯氧基乙酯512.0 g(3.3 mol)經γ-丁內酯500 g稀釋所得者，直接於50℃下攪拌2小時左右。藉由低分子量凝膠滲透層析法{以下記為低分子量GPC}確認反應結束(5-胺基間苯二甲酸消失)後，將該反應液投入至15 L之離子交換水中，進行攪拌，加以靜置，待出現反應產物之結晶化沈澱後將其過濾分離，經適當水洗後，於40℃下真空乾燥48小時，藉此獲得由5-胺基間苯二甲酸之胺基與異氰酸2-甲基丙烯醯氧基乙酯之異氰酸酯基作用所得之AIPA-MO。所獲得之AIPA-MO之低分子量GPC純度約為100%。 (聚合物D之合成) 於容積2 L之可分離式燒瓶中投入所獲得之AIPA-MO 100.89 g(0.3 mol)、吡啶71.2 g(0.9 mol)、GBL 400 g，進行混合，藉由冰浴冷卻至5℃。於冰浴冷卻下，歷時20分鐘左右於其中滴加使二環己基碳二醯亞胺(DCC)125.0 g(0.606 mol)經GBL 125 g溶解稀釋所得者，繼而，歷時20分鐘左右滴加使4,4'-雙(4-胺基苯氧基)聯苯{以下記為BAPB}103.16 g(0.28 mol)經NMP 168 g溶解所得者，藉由冰浴維持3小時未達5℃，繼而移除冰浴，於室溫下攪拌5小時。藉由過濾而去除反應混合物中所生成之沈澱物，獲得反應液。於所獲得之反應液中滴加水840 g與異丙醇560 g之混合液，分離所析出之聚合物，使之再溶解於NMP 650 g。將所獲得之粗聚合物溶液滴加至5 L之水中使聚合物沈澱，過濾分離所獲得之沈澱物後，進行真空乾燥而獲得粉末狀之聚合物(聚合物E)。藉由凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物D之分子量，結果重量平均分子量(Mw)為34,700。＜實施例1＞使用聚合物A、B，藉由以下之方法製備負型感光性樹脂組合物，並對所製備之感光性樹脂組合物進行評價。將作為聚醯亞胺前驅物之聚合物A 50 g與B 50 g(相當於(A)樹脂)與TMOM-BP(商品名，本州化學，相當於(B-2)熱交聯劑)10 g、1-苯基-1,2-丙烷二酮-2-(O-乙氧基羰基)-肟(表1中記為「PDO」)(相當於(C)感光劑)4 g、四乙二醇二甲基丙烯酸酯8 g、N-[3-(三乙氧基矽烷基)丙基]苯二甲醯胺酸1.5 g一併溶解於包含N-甲基-2-吡咯啶酮(以下記為NMP)80 g與乳酸乙酯20 g之混合溶劑。藉由進而添加少量之上述混合溶劑而將所獲得之溶液之黏度調整為約35泊(poise)，製成負型感光性樹脂組合物。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.7%之結果。＜實施例2＞上述實施例1中，作為(B-2)成分，將TMOM-BP之添加量變為20 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得3.8%之結果。＜實施例3＞上述實施例1中，作為(B-2)成分，將TMOM-BP之添加量變為5 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得9.3%之結果。＜實施例4＞上述實施例1中，作為(B-2)成分，使用TM-BIP-A(商品名，本州化學)代替TMOM-BP，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.2%之結果。＜實施例5＞上述實施例1中，作為(B-2)成分，使用HMOM-TP-HAP(商品名，本州化學)代替TMOM-BP，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.8%之結果。＜實施例6＞上述實施例1中，作為(B-2)成分，使用NIKALAC MW-390(商品名，SANWA CHEMICAL)代替TMOM-BP，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得10.3%之結果。＜實施例7＞上述實施例1中，作為(A)樹脂，將聚合物A 50 g與聚合物B 50 g變為聚合物A 100 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.3%之結果。＜實施例8＞上述實施例1中，作為(A)樹脂，將聚合物A 50 g與聚合物B 50 g變為聚合物A 100 g，作為(C)成分，將PDO 4 g變為1,2-辛烷二酮-1-{4-(苯硫基)-2-(O-苯甲醯基肟)}(Irgacure OXE01(BASF公司製造，商品名))2.0 g，進而將溶劑變為γ-丁內酯80 g與二甲基亞碸20 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.8%之結果。＜實施例9＞上述實施例1中，作為(A)樹脂，將聚合物A 50 g與聚合物B 50 g變為聚合物C 100 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行350℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.0%之結果。＜實施例10＞上述實施例1中，作為(A)樹脂，將聚合物A 50 g與聚合物B 50 g變為聚合物D 100 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行250℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得6.9%之結果。＜比較例1＞於實施例1之組成中，不添加TMOM-BP，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物，並進行與實施例1相同之評價。由於不含本發明之(B)化合物，故評價結果為14.3%。＜比較例2＞於實施例10之組成中，不添加TMOM-BP，除此以外，藉由與實施例10相同之方式製備負型感光性樹脂組合物，並進行與實施例11相同之評價。由於不含本發明之(B)化合物，故評價結果為15.5%。將該等實施例1～10、比較例1～2之結果彙總示於表3。 [表3]

＜第4實施例＞作為第4實施例，進行以下之實驗。＜製造例1＞((A)作為聚醯亞胺前驅物之聚合物(A)-1之合成) 於容積2 L之可分離式燒瓶中放入4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g，添加甲基丙烯酸2-羥基乙酯(HEMA)131.2 g與γ-丁內酯400 ml並於室溫下攪拌，一面攪拌一面添加吡啶81.5 g而獲得反應混合物。於由反應產生之放熱結束後，靜置冷卻至室溫，放置16小時。繼而，於冰浴冷卻下，一面攪拌一面歷時40分鐘向反應混合物中添加使二環己基碳二醯亞胺(DCC)206.3 g溶解於γ-丁內酯180 ml所得之溶液，繼而，一面攪拌一面歷時60分鐘添加使4,4'-二胺基二苯醚(DADPE)93.0 g懸浮於γ-丁內酯350 ml所得者。進而於室溫下攪拌2小時後，添加乙醇30 ml並攪拌1小時，繼而，添加γ-丁內酯400 ml。藉由過濾而去除反應混合物中所生成之沈澱物，獲得反應液。將所獲得之反應液添加至3 L之乙醇中，而生成包含粗聚合物之沈澱物。過濾分離所生成之粗聚合物，使之溶解於四氫呋喃1.5 L而獲得粗聚合物溶液。將所獲得之粗聚合物溶液滴加至28 L之水中而使聚合物沈澱，過濾分離所獲得之沈澱物後，進行真空乾燥而獲得粉末狀之聚合物(聚合物(A)-1)。藉由凝膠滲透層析法(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。再者，各製造例中獲得之樹脂之重量平均分子量係採用凝膠滲透層析法(GPC)，於以下之條件下進行測定，求出以標準聚苯乙烯換算計之重量平均分子量。泵：JASCO PU-980 檢測器：JASCO RI-930 管柱烘箱：JASCO CO-965 40℃ 管柱：2根Shodex KD-806M串聯流動相：0.1 mol/L LiBr/NMP 流速：1 ml/min. ＜製造例2＞((A)作為聚醯亞胺前驅物之聚合物(A)-2之合成) 使用3,3',4,4'-聯苯基四羧酸二酐(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，藉由與上述製造例1所記載之方法相同之方式進行反應，而獲得聚合物(A)-2。藉由凝膠滲透層析法(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。＜製造例3＞((A)作為聚醯亞胺前驅物之聚合物(A)-3之合成) 使用2,2'-雙三氟甲基-4,4'-二胺基聯苯(TFMB)147.8 g代替製造例1之4,4'-二胺基二苯醚(DADPE)93.0 g，除此以外，藉由與上述製造例1所記載之方法相同之方式進行反應，而獲得聚合物(A)-3。藉由凝膠滲透層析法(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21,000。＜製造例4＞((A)作為聚醯胺之聚合物(A)-4之合成) (苯二甲酸化合物封端體AIPA-MO之合成) 於容積5 L之可分離式燒瓶中投入5-胺基間苯二甲酸{以下簡記為AIPA}543.5 g、N-甲基-2-吡咯啶酮1700 g，進行混合攪拌，藉由水浴加熱至50℃。利用滴液漏斗於其中滴加投入使異氰酸2-甲基丙烯醯氧基乙酯512.0 g(3.3 mol)經γ-丁內酯500 g稀釋所得者，直接於50℃下攪拌2小時左右。藉由低分子量凝膠滲透層析法{以下記為低分子量GPC}確認反應結束(5-胺基間苯二甲酸消失)後，將該反應液投入至15 L之離子交換水中，進行攪拌，加以靜置，待出現反應產物之結晶化沈澱後將其過濾分離，經適當水洗後，於40℃下真空乾燥48小時，藉此獲得由5-胺基間苯二甲酸之胺基與異氰酸2-甲基丙烯醯氧基乙酯之異氰酸酯基作用所得之AIPA-MO。所獲得之AIPA-MO之低分子量GPC純度約為100%。 (聚合物(A)-4之合成) 於容積2 L之可分離式燒瓶中投入所獲得之AIPA-MO 100.89 g(0.3 mol)、吡啶71.2 g(0.9 mol)、GBL 400 g，進行混合，藉由冰浴冷卻至5℃。於冰浴冷卻下，歷時20分鐘左右於其中滴加使二環己基碳二醯亞胺(DCC)125.0 g(0.606 mol)經GBL 125 g溶解稀釋所得者，繼而，歷時20分鐘左右滴加使4,4'-雙(4-胺基苯氧基)聯苯{以下記為BAPB}103.16 g(0.28 mol)經NMP 168 g溶解所得者，藉由冰浴維持3小時未達5℃，繼而移除冰浴，於室溫下攪拌5小時。藉由過濾而去除反應混合物中所生成之沈澱物，獲得反應液。於所獲得之反應液中滴加水840 g與異丙醇560 g之混合液，分離所析出之聚合物，使之再溶解於NMP 650 g。將所獲得之粗聚合物溶液滴加至5 L之水中使聚合物沈澱，過濾分離所獲得之沈澱物後，進行真空乾燥而獲得粉末狀之聚合物(聚合物(A)-4)。藉由凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物(A)-4之分子量，結果重量平均分子量(Mw)為34,700。＜製造例5＞((A)作為聚㗁唑前驅物之聚合物(A)-5之合成) 於容積3 L之可分離式燒瓶中將2,2-雙(3-胺基-4-羥基苯基)-六氟丙烷183.1 g、N,N-二甲基乙醯胺(DMAc)640.9 g、吡啶63.3 g於室溫(25℃)下進行混合攪拌，製成均勻溶液。利用滴液漏斗於其中滴加使4,4'-二苯醚二甲醯氯118.0 g經二乙二醇二甲醚(DMDG)354 g溶解所得者。此時，將可分離式燒瓶於15～20℃之水浴中冷卻。滴液所需之時間為40分鐘，反應液溫最高為30℃。滴液結束後經過3小時後，向反應液中添加1,2-環己基二羧酸酐30.8 g(0.2 mol)，於室溫下攪拌放置15小時，使聚合物鏈之占總數99%之胺末端基經羧基環己基醯胺基封端。此時之反應率可藉由利用高效液相層析法(HPLC)追蹤所投入之1,2-環己基二羧酸酐之殘量而容易地算出。其後，將上述反應液於高速攪拌下滴加至2 L之水中而使聚合物分散析出，將其回收，經適當水洗，脫水後實施真空乾燥，而獲得藉由凝膠滲透層析(GPC)法所測得之重量平均分子量9,000(聚苯乙烯換算)之粗製前驅物。使上述獲得之粗聚苯并㗁唑前驅物再溶解於γ-丁內酯(GBL)後，對其利用陽離子交換樹脂及陰離子交換樹脂進行處理，將藉此獲得之溶液投入至離子交換水中後，過濾分離所析出之聚合物，進行水洗並真空乾燥，藉此獲得經精製之聚苯并㗁唑前驅物(聚合物(A)-5)。＜製造例6＞((A)作為聚醯亞胺之聚合物(A)-6之合成) 對裝有Teflon(註冊商標)製錨型攪拌器之玻璃製可分離式四口燒瓶安裝附迪安-斯塔克分離器之冷卻管。一面通入氮氣，一面將上述燒瓶浸於矽油浴中進行攪拌。添加2,2-雙(3-胺基-4-羥基苯基)丙烷(Clariant Japan公司製造)(以下記為BAP)72.28 g(280 mmol)、5-(2,5-二側氧四氫-3-呋喃基)-3-甲基-環己烯-1,2二羧酸酐(東京化成工業股份有限公司製造)(以下記為MCTC)70.29 g(266 mmol)、γ-丁內酯254.6 g、甲苯60 g，於室溫下以100 rpm攪拌4小時後，添加5-降𦯉烯-2,3-二羧酸酐(東京化成工業股份有限公司製造)4.6 g(28 mmol)，一面通入氮氣一面於矽浴溫度50℃下以100 rpm加熱攪拌8小時。其後，加熱至矽浴溫度180℃，以100 rpm加熱攪拌2小時。去除於反應中所餾出之甲苯、水。醯亞胺化反應結束後恢復至室溫。其後將上述反應液於高速攪拌下滴加至3 L之水中而使聚合物分散析出，將其回收，經適當水洗，脫水後實施真空乾燥，而獲得藉由凝膠滲透層析(GPC)法所測得之重量平均分子量23,000(聚苯乙烯換算)之粗聚醯亞胺(聚合物(A)-6)。＜製造例7＞((A)作為酚樹脂之聚合物(A)-8之合成) 對容積1.0 L之附迪安-斯塔克裝置之可分離式燒瓶進行氮氣置換，其後，於該可分離式燒瓶中將間苯二酚81.3 g(0.738 mol)、BMMB 84.8 g(0.35 mol)、對甲苯磺酸3.81 g(0.02 mol)、丙二醇單甲醚(以下亦稱為PGME)116 g於50℃下進行混合攪拌，而使固形物溶解。藉由油浴將混合溶液加熱至120℃，確認自反應液生成了甲醇。直接於120℃下將反應液攪拌3小時。繼而，於另一容器中將2,6-雙(羥基甲基)對甲酚24.9 g(0.150 mol)、PGME 249 g進行混合攪拌，使之均勻溶解，將所獲得之溶液使用滴液漏斗歷時1小時滴加至該可分離式燒瓶內，滴液後進而攪拌2小時。反應結束後，進行與製造例7相同之處理，而以產率77%獲得包含間苯二酚/BMMB/2,6-雙(羥基甲基)對甲酚之共聚物(聚合物H)。該聚合物H之藉由GPC法之標準聚苯乙烯換算所求出之重量平均分子量為9,900。＜實施例1＞使用聚合物(A)-1、(A)-2，藉由以下之方法製備負型感光性樹脂組合物，並進行感光性樹脂組合物之評價。將作為聚醯亞胺前驅物之聚合物(A)-1 50 g與(A)-2 50 g(相當於(A)樹脂)與1H,1H,8H,8H-全氟四乙二醇二丙烯酸酯(以下述式(B-3-1)表示，Exfluor公司製造)8 g、1-苯基-1,2-丙烷二酮-2-(O-乙氧基羰基)-肟(表1中記為「PDO」)(相當於(C)感光劑)4 g、四乙二醇二甲基丙烯酸酯8 g、N-[3-(三乙氧基矽烷基)丙基]苯二甲醯胺酸1.5 g一併溶解於包含N-甲基-2-吡咯啶酮(以下記為NMP)80 g與乳酸乙酯20 g之混合溶劑。藉由進而添加少量之上述混合溶劑而將所獲得之溶液之黏度調整為約35泊(poise)，製成負型感光性樹脂組合物。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得3.1%之結果。再者，(B-3)-1化合物(表示下述式(B-3-1)之化合物。以下將下述式(B-3-X)(X為1～9)所表示之化合物記為(B-3)-X)之分子中之氟原子之重量比率為44質量%。＜實施例2＞上述實施例1中，將(B-3)成分變為1H,1H,6H,6H-全氟-1,6-己二醇二丙烯酸酯(以(下述式(B-2)表示，Exfluor公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得3.3%之結果。再者，(B-3)-2化合物之分子中之氟原子之重量比率為41質量%。＜實施例3＞上述實施例1中，將(B-3)成分變為甲基丙烯酸1H,1H-全氟正癸酯(以下述式(B-3-3)表示，Exfluor公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得3.4%之結果。再者，(B-3)-3化合物之分子中之氟原子之重量比率為64質量%。＜實施例4＞上述實施例1中，將(B-3)成分變為全氟癸酸(以下述式(B-3-4)表示，Exfluor公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得6.2%之結果。再者，(B-3)-4化合物之分子中之氟原子之重量比率為70質量%。＜實施例5＞上述實施例1中，將(B-3)成分變為1H,1H-全氟-1-癸醇(以下述式(B-3-5)表示，Exfluor公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得6.9%之結果。再者，(B-3)-5化合物之分子中之氟原子之重量比率為72質量%。＜實施例6＞上述實施例1中，將(B-3)成分變為全氟十三烷(以下述式(B-3-6)表示，Exfluor公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得7.7%之結果。再者，(B-3)-6化合物之分子中之氟原子之重量比率為77質量%。＜實施例7＞上述實施例1中，將(B-3)成分變為全氟癸酸甲酯(以下述式(B-7)表示，Exfluor公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得6.9%之結果。再者，(B-3)-7化合物之分子中之氟原子之重量比率為68質量%。＜實施例8＞上述實施例1中，將(B-3)成分變為全氟四乙二醇二甲醚(以下述式(B-3-8)表示，Exfluor公司製造)，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得6.8%之結果。再者，(B-3)-8化合物之分子中之氟原子之重量比率為68質量%。＜實施例9＞上述實施例1中，將(B-3)-1成分之添加量變為2 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.5%之結果。＜實施例10＞上述實施例1中，將(B-3)-1成分之添加量變為20 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行230℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得3.8%之結果。＜實施例11＞上述實施例1中，將固化溫度自230℃變為350℃，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.2%之結果。＜實施例12＞上述實施例1中，作為(A)樹脂，將聚合物(A)-1 50 g與聚合物(A)-2 50 g變為聚合物(A)-1 100 g，將(C)成分自PDO變為1,2-辛烷二酮-1-{4-(苯硫基)-2-(O-苯甲醯基肟)}(Irgacure OXE01(BASF公司製造，商品名))2.5 g，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.6%之結果。＜實施例13＞上述實施例12中，將溶劑變為γ-丁內酯85 g與二甲基亞碸15 g，除此以外，藉由與實施例12相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.8%之結果。＜實施例14＞上述實施例1中，作為(A)樹脂，將聚合物(A)-1 50 g與聚合物(A)-2 50 g變為聚合物(A)-3 100 g，並將固化溫度自230℃變為350℃，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.7%之結果。＜實施例15＞上述實施例1中，作為(A)樹脂，將聚合物(A)-1 50 g與聚合物(A)-2 50 g變為聚合物(A)-4 100 g，並將固化溫度自230℃變為250℃，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物溶液。針對該組合物，於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.4%之結果。＜實施例16＞使用聚合物(A)-5，藉由以下之方法製備正型感光性樹脂組合物，並對所製備之感光性樹脂組合物進行評價。將作為聚㗁唑前驅物之聚合物(A)-5 100 g(相當於(A)樹脂)與下述式(96)： [化129]

所表示之77%之酚性羥基經萘醌二疊氮-4-磺酸酯化之感光性重氮醌化合物(東洋合成公司製造，相當於(C)成分)(C1)15 g溶解於γ-丁內酯(作為溶劑)100 g。藉由進而添加少量之γ-丁內酯而將所獲得之溶液之黏度調整為約20泊(poise)，製成正型感光性樹脂組合物。針對該組合物，藉由上述方法進行350℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.2%之結果。＜實施例17＞上述實施例16中，作為(A)樹脂，將聚合物(A)-5 100 g變為聚合物(A)-6 100 g，除此以外，藉由與實施例11相同之方式製備正型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行250℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.5%之結果。＜實施例18＞上述實施例16中，作為(A)樹脂，將聚合物(A)-5 100 g變為聚合物(A)-7(酚醛清漆樹脂，聚苯乙烯換算重量平均分子量(Mw)＝10,600(旭有機材公司製造，製品名EP-4080G)100 g，除此以外，藉由與實施例11相同之方式製備正型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行250℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得4.8%之結果。＜實施例19＞上述實施例16中，作為(A)樹脂，將聚合物(A)-5 100 g變為聚合物(A)-8 100 g，除此以外，藉由與實施例11相同之方式製備正型感光性樹脂組合物溶液。針對該組合物，藉由上述方法進行250℃固化而於Cu層上製作硬化浮凸圖案，進行高溫保存試驗後，評價空隙於Cu層之表面所占之面積比率，而獲得5.1%之結果。＜比較例1＞於實施例1之組成中，不添加(B)-1成分，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物，並進行與實施例1相同之評價。由於不含本發明之(B)含氟疏水性化合物，故評價結果為15.2%。＜比較例2＞使用四乙二醇二甲基丙烯酸酯(以下述式(B-9)表示，東京化成工業股份有限公司製造)代替實施例1之(B)-1成分，除此以外，藉由與實施例1相同之方式製備負型感光性樹脂組合物，並進行與實施例1相同之評價。由於不含本發明之(B)含氟疏水性化合物，故評價結果為15.5%。再者，(B)-9化合物之分子中之氟原子之重量比率為0質量%。＜比較例3＞使用四乙二醇二甲基丙烯酸酯((B)-9，東京化成工業股份有限公司製造)代替實施例15之(B)-1成分，除此以外，藉由與實施例15相同之方式製備負型感光性樹脂組合物，並進行與實施例15相同之評價。由於不含本發明之(B)含氟疏水性化合物，故評價結果為14.3%。＜比較例4＞使用四乙二醇二甲基丙烯酸酯((B)-9，東京化成工業股份有限公司製造)代替實施例12之(B)-1成分，除此以外，藉由與實施例12相同之方式製備負型感光性樹脂組合物，並進行與實施例12相同之評價。由於不含本發明之(B)含氟疏水性化合物，故評價結果為15.7%。＜比較例5＞使用四乙二醇二甲基丙烯酸酯((B)-9，東京化成工業股份有限公司製造)代替實施例17之(B)-1成分，除此以外，藉由與實施例17相同之方式製備正型感光性樹脂組合物，並進行與實施例17相同之評價。由於不含本發明之(B)含氟疏水性化合物，故評價結果為16.3%。以下，將(B-3)-1～(B-3)-9化合物之分子中之氟原子之重量比率彙總示於表4。 [表4]

[化130]

[化131]

[化132]

[化133]

[化134]

[化135]

[化136]

[化137]

[化138]

將實施例1～19、比較例1～5之結果彙總示於表5。 [表5]

[產業上之可利用性] 本發明之感光性樹脂組合物可較佳地用於例如對半導體裝置、多層配線基板等電氣・電子材料之製造有用之感光性材料領域。The form for implementing the present invention (hereinafter simply referred to as "this embodiment") will be described in detail below. In addition, this embodiment is the illustration for demonstrating this invention, and is not intended to limit this invention. The present invention can be implemented with appropriate changes within the scope of its gist. In addition, in the present specification, when a plurality of structures represented by the same symbol in the general formula exist in a molecule, they may be the same or different from each other. <Photosensitive resin composition> In this embodiment, the following components are essential components, that is, (A) is selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, and polyamino group At least one resin in the group consisting of amide, polyamide, polyamide imide, polyimide, polybenzoxazole, and novolac, polyhydroxystyrene and phenol resin: 100 parts by mass, (B) Plasticizer: 0.1-50 parts by mass based on (A) 100 parts by mass of resin, (C) Sensitizer: 1-50 parts by mass based on (A) 100 parts by mass of resin. <Photosensitive resin composition> In addition, another embodiment includes the following components as essential components, that is, (A) is selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, At least one resin from the group consisting of polyamino amide, poly amide, poly amide amide imide, poly amide imide, polybenzoxazole, and novolac, polyhydroxystyrene, and phenol resin: 100 Parts by mass, (B-1) nanoparticles: 0.01 to 10 parts by mass based on (A) 100 parts by mass of resin, (C) photosensitizer: 1 to 50 parts by mass based on (A) 100 parts by mass of resin Copies. <Photosensitive resin composition> Moreover, another embodiment is a negative photosensitive resin composition which has the following components as an essential component, (A) is selected from the group consisting of polyamic acid, polyamic acid ester and polyacrylic acid At least one resin in the group consisting of amine salts: 100 parts by mass, (B-2) Thermal crosslinking agent: 0.01 to 10 parts by mass based on (A) 100 parts by mass of resin, (C) Sensitizer: 1 to 50 parts by mass based on (A) 100 parts by mass of resin. <Photosensitive resin composition> In addition, another embodiment includes the following components as essential components, that is, (A) is selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, At least one resin from the group consisting of polyamino amide, poly amide, poly amide amide imide, poly amide imide, polybenzoxazole, and novolac, polyhydroxystyrene, and phenol resin: 100 Parts by mass, (B-3) fluorine-containing hydrophobic compound: 0.01 to 50 parts by mass based on (A) 100 parts by mass of the resin, (C) photosensitizer: 1 based on (A) 100 parts by mass of the resin ~50 parts by mass. (A) Resin The (A) resin used in the present invention will be described. The (A) resin of the present invention is selected from the group consisting of polyamic acid, polyamic acid ester, polyamidate, polyhydroxyamide, polyaminoamide, polyamide, polyamidoamide, At least one resin of the group consisting of polyimide, polybenzoxazole, novolac, polyhydroxystyrene, and phenol resin serves as a main component. Here, the main component means that the resin accounts for 60% by mass or more of the entire resin, preferably 80% by mass or more. In addition, other resins may be contained as needed. The weight average molecular weight of these resins is preferably 200 or more, more preferably 5,00 or more in terms of heat resistance and mechanical properties after heat treatment in terms of polystyrene based on gel permeation chromatography. It is preferably 1,000 or more, and more preferably 1,000 or more. The upper limit is preferably 500,000 or less. In the case of preparing a photosensitive resin composition, from the viewpoint of solubility in a developing solution, it is more preferably 20,000 or less. In the present invention, in order to form the relief pattern, the (A) resin is preferably a photosensitive resin. The photosensitive resin is used together with the following (C) sensitizer to form a photosensitive resin composition, and causes a phenomenon of dissolution or undissolution in the subsequent development step. As photosensitive resins, in polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamide imide, polyimide, Among polybenzoxazoles and phenol resins containing novolak and polyhydroxystyrene, polyimide precursors can be preferably used in terms of excellent heat resistance and mechanical properties of the resin after heat treatment ( Polyamide, Polyamide, Polyamide), Polyamide, Polyhydroxyamide, Polyimide and phenol resin. In addition, these photosensitive resins can be selected to prepare any negative-type or positive-type photosensitive resin composition together with the following (C) photosensitizer according to the intended use. [(A) Polyamide, Polyamide, Polyamide] Among the photosensitive resin compositions of the present invention, one example of the (A) resin is the best from the viewpoint of heat resistance and photosensitive characteristics For the above general formula (1): [Chem 45]

{Where, X ₁ Is a 4-valent organic radical, Y ₁ Is a divalent organic radical, n ₁ Is an integer from 2 to 150, R ₁ And R ₂ Each independently represents a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, or the above general formula (2): [Chem 46]

(Where R ₃ , R ₄ And R ₅ Are independently hydrogen atoms or organic groups with 1 to 3 carbon atoms, and m ₁ Is an integer of 2 to 10) a monovalent organic group represented by a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms} or a monovalent organic group represented by the following general formula (3): [Chem 47]

(Where R ₆ , R ₇ And R ₈ Are independently hydrogen atoms or organic groups with 1 to 3 carbon atoms, and m ₂ Is an integer of 2 to 10) represented by a monovalent ammonium ion} as a precursor of polyimide, such as a polyamic acid, a polyamic acid ester or a polyamic acid salt. The polyimide precursor is converted into polyimide by performing a cyclization process of heating (for example, 200° C. or higher). The polyimide precursor is suitable for negative photosensitive resin compositions. In the above general formula (1), X ₁ The represented tetravalent organic group is preferably an organic group having 6 to 40 carbon atoms, and more preferably -COOR in terms of having both heat resistance and photosensitive characteristics ₁ Base and -COOR ₂ The aromatic group or alicyclic aliphatic group in which the group and the -CONH- group are adjacent to each other. As X ₁ The represented tetravalent organic group is preferably an organic group having 6 to 40 carbon atoms containing an aromatic ring, and more preferably, the following formula (30) is listed:

{In the formula, R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group, and a C1-C10 fluorine-containing hydrocarbon group, l is an integer selected from 0-2, and m is selected from 0-3 Integer, n is an integer selected from 0 to 4} The structure represented, but not limited to these. Again, X ₁ The structure may be one kind or a combination of two or more kinds. X with the structure represented by the above formula ₁ The base is particularly good in terms of both heat resistance and photosensitive properties. In the above general formula (1), Y ₁ The represented divalent organic group is preferably an aromatic group having 6 to 40 carbon atoms in terms of having both heat resistance and photosensitive properties, and examples include the following formula (31):

{In the formula, R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group, and a C1-C10 fluorine-containing hydrocarbon group, and n is an integer selected from 0-4.} Not limited to these. Again, Y ₁ The structure may be one kind or a combination of two or more kinds. Y with the structure represented by the above formula (31) ₁ The base is particularly good in terms of both heat resistance and photosensitive properties. R in the above general formula (2) ₃ Preferably hydrogen atom or methyl group, R ₄ And R ₅ From the viewpoint of photosensitive characteristics, a hydrogen atom is preferred. Again, m ₁ From the viewpoint of photosensitive characteristics, it is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less. When a polyimide precursor is used as the (A) resin, examples of the method of imparting sensitivity to the photosensitive resin composition include ester bond type and ion bond type. The former is a method of introducing a compound having a photopolymerizable group, that is, an olefinic double bond, into the side chain of the polyimide precursor through an ester bond, and the latter is a method that combines the carboxyl group of the polyimide precursor with an amine group A method of giving a photopolymerizable group by bonding an amine group of a (meth)acrylic compound through an ionic bond. The ester-bonded polyimide precursor is obtained as follows. First, the above-mentioned tetravalent organic group X ₁ The tetracarboxylic dianhydride reacts with photopolymerizable unsaturated double bond alcohols and any saturated aliphatic alcohols having 1 to 4 carbon atoms to prepare partially esterified tetracarboxylic acids (hereinafter also referred to as Acid/ester body), it is combined with the above-mentioned divalent organic group Y ₁ The diamines undergo condensation polymerization of amides. (Preparation of acid/ester body) In the present invention, a tetravalent organic group X is contained as a precursor of an ester-bonded polyimide ₁ The tetracarboxylic dianhydride includes, for example, pyromellitic dianhydride and diphenyl ether-3,3',4,4 represented by the tetracarboxylic dianhydride having the structure represented by the general formula (30) '-Tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, di Phenylbenzene-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4 -Phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferably listed is pyromellitic acid Dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3, 3',4,4'-tetracarboxylic dianhydride, but not limited to these. Of course, these can of course be used alone, but two or more kinds can be used in combination. In the present invention, examples of alcohols having a photopolymerizable unsaturated double bond suitable for preparing ester-bonded polyimide precursors include, for example, 2-propenyloxyethanol and 1-propenyloxy -3-propanol, 2-acrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-acrylate Butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-third butoxypropyl acrylate, 2-acrylate Hydroxy-3-cyclohexyloxypropyl ester, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacryloylaminoethanol, hydroxymethylvinyl Ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-methacrylate Phenoxypropyl ester, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-third butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyl methacrylate Propyl ester and so on. A part of the above-mentioned alcohols may also be used as a saturated aliphatic alcohol having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and third butanol. The tetracarboxylic dianhydride suitable for the present invention and the alcohol described above are dissolved in the presence of an alkaline catalyst such as pyridine in a solvent as described below at a temperature of 20 to 50°C for 4 to 10 hours to dissolve, By mixing, the esterification reaction of the acid anhydride is carried out to obtain the desired acid/ester body. (Preparation of Polyimide Precursor) To the above acid/ester body (typically a solution in the following solvent), an appropriate dehydrating condensing agent such as dicyclocarbodiimide is added under ice bath cooling Dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzo After triazole, N,N'-dibutylenediimido carbonate, etc. are mixed to make the acid/ester body into a polyanhydride, the organic acid containing divalent is added dropwise to make it suitable for use in the present invention. Base Y ₁ Those obtained by dissolving or dispersing diamines in a solvent are subjected to polycondensation of amides, whereby the target polyimide precursor can be obtained. Alternatively, after chlorinating the acid portion of the acid/ester body using sulfenyl chloride or the like, and reacting with a diamine compound in the presence of a base such as pyridine, the target polyimide precursor can be obtained. Suitable for use in the present invention include a divalent organic group Y ₁ The diamines include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3, represented by the diamine having the structure represented by the general formula (31). 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3, 3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4' -Diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 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] phenanthrene, bis[4-(3-aminophenoxy)phenyl] phenanthrene, 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-aminopropyl) Dimethylsilyl)benzene, o-tolidine, 9,9-bis(4-aminophenyl) stilbene, and part of the hydrogen atoms on the benzene ring are methyl, ethyl, hydroxymethyl Group, hydroxyethyl, halogen and other substitutions, such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl Benzene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-Dimethoxy-4,4'-diaminobiphenyl,3,3'-dichloro-4,4'-diaminobiphenyl,2,2'-dimethylbenzidine, 2,2 '-Bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diamino Octafluorobiphenyl, etc.; preferably listed are: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 2,2'-dimethylbenzidine, 2,2'-bis (Trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl Benzene, etc., and mixtures thereof, but not limited to this. In addition, in order to improve the adhesion between the resin layer formed on the substrate by coating the photosensitive resin composition of the present invention and various substrates, when preparing a polyimide precursor, it can also be combined with 1,3- Diaminosiloxanes such as bis(3-aminopropyl)tetramethyldisilaxane and 1,3-bis(3-aminopropyl)tetraphenyldisilaxane are copolymerized. After the amide condensation polymerization reaction is completed, if necessary, the water-absorbing by-products of the dehydrating condensation agent coexisting in the reaction solution are filtered and separated, and then water, aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component The poor solvent causes the polymer to be analyzed, and then it is repeatedly subjected to re-dissolution, re-precipitation and precipitation operations, etc., whereby the polymer is purified and vacuum dried to isolate the target polyimide precursor. In order to improve the fineness system, the solution of the polymer can also be passed through a column filled with anion and/or cation exchange resin swelled with a suitable organic solvent to remove ionic impurities. On the other hand, the ionic bond type polyimide precursor is typically obtained by reacting tetracarboxylic dianhydride and diamine. In this case, R in the above general formula (1) ₁ And R ₂ At least one of them is a hydroxyl group. The tetracarboxylic dianhydride is preferably an anhydride of a tetracarboxylic acid containing the structure of the above formula (30), and the diamine is preferably a diamine containing the structure of the above formula (31). By adding the following (meth)acrylic compound having an amine group to the obtained polyamidoamine precursor, a photopolymerizable group is given by ion bonding of the carboxyl group and the amine group. As the (meth)acrylic compound having an amine group, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylamino methacrylate Ethyl ester, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, methacrylic acid Dialkylaminobutyl acrylate, diethylaminobutyl acrylate, diethylaminobutyl methacrylate, dialkylaminoalkyl acrylate or other dialkylaminoalkyl methacrylate, wherein, From the viewpoint of photosensitive characteristics, a dialkylaminoalkyl acrylate or dimethacrylic acid alkyl ester having an alkyl group of 1 to 10 carbon atoms and an alkyl chain of 1 to 10 carbon atoms is preferred Alkylaminoalkyl esters. The amount of the (meth)acrylic compound having an amine group is 1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and from the viewpoint of light sensitivity characteristics, it is preferably 2 to 15 Quality parts. Relative to 100 parts by mass of (A) resin, by blending at least 1 part by mass of (meth)acrylic compound having an amine group as the (C) sensitizer, the photosensitivity is excellent, and by blending 20 parts by mass or less, a thick film Excellent hardenability. The molecular weight of the ester bond type and the ion bond type polyimide precursor is preferably 8,000 to 150,000 when measured in the form of weight average molecular weight converted to polystyrene based on gel permeation chromatography , More preferably from 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 relief performance of the relief pattern is good. As a developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the weight average molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to choose from the standard sample STANDARD SM-105 of organic solvents manufactured by Showa Denko. [(A) Polyamide] Another example of the preferred (A) resin in the photosensitive resin composition of the present invention has the following general formula (4):

{Where, X ₂ It is a trivalent organic group with 6 to 15 carbon atoms, Y ₂ It is a divalent organic group with 6 to 35 carbon atoms, and can have the same structure or have multiple structures, R ₉ It is an organic group having at least one radically polymerizable unsaturated bonding group having 3 to 20 carbon atoms, and n ₂ It is an integer of 1 to 1000} Polyamide with the structure represented by. The polyamide is suitable for negative photosensitive resin compositions. In the above general formula (4), as R ₉ The base represented is preferably the following general formula (32) in terms of both photosensitivity and chemical resistance.

{Where R ₃₂ It is a group represented by an organic group having at least one radically polymerizable unsaturated bonding group having 2 to 19 carbon atoms. In the above general formula (4), as X ₂ The trivalent organic group represented is preferably a trivalent organic group having 6 to 15 carbon atoms, for example, preferably selected from the following formula (33): [化52]

The aromatic group in the represented group is further preferably an aromatic group obtained by removing a carboxyl group and an amine group from an amine group-substituted isophthalic acid structure. In the above general formula (4), as Y ₂ The divalent organic group represented is preferably an organic group having 6 to 35 carbon atoms, and more preferably a cyclic organic group having 1 to 4 aromatic rings or aliphatic rings which may be substituted, or not having Aliphatic group or siloxane group of ring structure. As Y ₂ Examples of the divalent organic group represented include the following general formula (I) and the following general formulas (34) and (35):

[化54]

{Where R ₃₃ And R ₃₄ Independently selected from the group consisting of hydroxyl and methyl (-CH ₃ ), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ) Or butyl (-C ₄ H ₉ ) A group in the group, and the propyl and butyl include various isomers} [Chem 55]

{Where m ₇ It is an integer from 0 to 8, m ₈ And m ₉ Are independently integers from 0 to 3, m ₁₀ And m ₁₁ Are independently integers from 0 to 10, and R ₃₅ And R ₃₆ Methyl (-CH ₃ ), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ), butyl (-C ₄ H ₉ ) Or such isomers}. Regarding the aliphatic group or the siloxyalkyl group which does not have a cyclic structure, the following general formula (36) may be mentioned as preferred: [Chem. 56]

{Where m ₁₂ Is an integer from 2 to 12, m ₁₃ Is an integer from 1 to 3, m ₁₄ Is an integer from 1 to 20, and R ₃₇ , R ₃₈ , R ₃₉ And R ₄₀ Respectively, independently C 1-3 alkyl or substituted phenyl}. The polyamide resin of the present invention can be synthesized, for example, as follows. (Synthesis of Terephthalic Acid Compound End Block) The first step is to make trivalent aromatic group X ₂ Compounds such as at least one compound selected from the group consisting of phthalic acid substituted with amine groups, phthalic acid substituted with amine groups and terephthalic acid substituted with amine groups (hereinafter referred to as It is a "phthalic acid compound") 1 mole, and compound 1 which will react with an amine group is reacted, and the amine group for synthesizing the phthalic acid compound is a group containing a radical polymerizable unsaturated bond as described below Modified and blocked compounds (hereinafter referred to as "phthalic acid compound blocked bodies"). These can be used alone or mixed. If the phthalic acid compound is blocked by the radical-polymerizable unsaturated bond-containing group, the polyamide resin can be given negative sensitivity (photocurability). As a group containing a radically polymerizable unsaturated bond, an organic group having a radically polymerizable unsaturated bond group having 3 to 20 carbon atoms is preferred, and a methacryl group or acryl group is particularly preferred. Basis. The above-mentioned phthalic acid compound-terminated body can be obtained by using an amine group of a phthalic acid compound, an acetyl chloride, an isocyanate, or an epoxy compound with an unsaturated bonding group having at least one radical polymerizable group having 3 to 20 carbon atoms Obtained through the reaction. Examples of suitable acetyl chloride include: (meth)acryloyl chloride, 2-[(meth)acryloyloxy] acetyl chloride, 3-[(meth)acryloyl oxy]propyl chloride, and chlorine 2-[((meth)acryloyloxy] ethyl formate, 3-[(meth)acryloyloxypropyl] chloroformate, etc. Examples of suitable isocyanates include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[(meth)acryloyloxymethyl]ethyl isocyanate, isocyanic acid 2-[2-(meth)acryloyloxyethoxy]ethyl ester and the like. Examples of suitable epoxy compounds include glycidyl (meth)acrylate. These can be used alone or in combination, but it is particularly preferred to use methacryloyl chloride and/or 2-(methacryloyloxy)ethyl isocyanate. Furthermore, as these phthalic acid compound-terminated bodies, those having a phthalic acid compound of 5-aminoisophthalic acid can obtain not only excellent photosensitivity but also film properties after heat-hardening, which is preferable. . The above-mentioned end-capping reaction can be carried out by stirring and dissolving the phthalic acid compound and the end-capping agent in a solvent as described below in the presence of an alkaline catalyst such as pyridine or a tin catalyst such as di-n-butyltin dilaurate. Mixed. According to the type of end-capping agent, acetyl chloride etc. will generate by-product hydrogen chloride during the end-capping reaction. In this case, in order to prevent pollution to the subsequent steps, it is preferable to properly refine, that is, temporarily re-precipitate it in water and wash it to dryness, or let it pass through a column filled with ion exchange resin to remove the reduced ions Ingredients etc. (Synthesis of Polyamide) The above-mentioned phthalic acid compound-terminated body and divalent organic group Y ₂ The diamine compound is mixed in a solvent as described below in the presence of a basic catalyst such as pyridine or triethylamine to carry out condensation polymerization of the amide, thereby obtaining the polyamide of the present invention. Examples of the amide condensation polymerization method include a method of using a dehydrating condensing agent to form a phthalic acid compound-terminated body into a symmetric polyanhydride, and then mixing it with a diamine compound, or a known method for terminating a phthalic acid compound-terminated body. A method of mixing with a diamine compound after chlorination, a method of reacting a dicarboxylic acid component with an active esterifying agent in the presence of a dehydrating condensing agent, and mixing with a diamine compound after achieving active esterification. As the dehydrating condensation agent, for example, preferred ones include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, and 1,1′- Carbonyldioxy-di-1,2,3-benzotriazole, N,N'-dibutanediimide carbonate, etc. Examples of the chlorinating agent include thionyl chloride and the like. Examples of the active esterifying agent include: N-hydroxybutadiene imide or 1-hydroxybenzotriazole, N-hydroxy-5-norbenzene-2,3-dicarboxyamide, 2-hydroxyimide Ethylamino-2-cyanoacetate, 2-hydroxyimino-2-cyanoacetamide, etc. As having an organic group Y ₂ The diamine compound is preferably selected from the group consisting of aromatic diamine compounds, aromatic bisaminophenol compounds, alicyclic diamine compounds, linear aliphatic diamine compounds, and siloxane diamine compounds At least one diamine compound may be used in combination as needed. Examples of the aromatic diamine compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 3,3′-diamine. Amino diphenyl ether, 4,4'-diamino diphenyl sulfide, 3,4'-diamino diphenyl sulfide, 3,3'-diamino diphenyl sulfide, 4,4'- Diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'- Diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diamine Benzophenone, 4,4'-diaminodiphenylmethane, 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] phenanthrene, bis[4-(3-aminophenoxy)phenyl] phenanthrene, 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-toluidine, 9,9-bis(4-aminophenyl) stilbene, and one part of the hydrogen atom on the benzene ring is selected from the group consisting of methyl, ethyl, hydroxymethyl, hydroxyethyl and halogen atoms A diamine compound substituted with more than one group in the group. Examples of the diamine compound in which the hydrogen atom on the benzene ring is substituted include: 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 ,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodi Phenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, etc. Examples of aromatic bisaminophenol compounds include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, and 3,3'-dihydroxy-4 ,4'-diaminodiphenylbenzene, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2, 2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(3-hydroxy-4-aminophenyl)hexafluoropropane, bis-(3-hydroxy-4 -Aminophenyl)methane, 2,2-bis-(3-hydroxy-4-aminophenyl)propane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3 ,3'-Dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,5-dihydroxy-1,4- Diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane, 4,4-(α-methylbenzylidene )-Bis(2-aminophenol), etc. Examples of the alicyclic diamine compound include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, and 3 ,5-Diamino-1,1-dimethylcyclohexane, 1,5-diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl- 4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2,5-diethyl Cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2-(3-aminocyclopentyl)-2-propane Amine, menthane diamine, isophorone diamine, norbornane diamine, 1-cycloheptene-3,7-diamine, 4,4'-methylenebis (cyclohexylamine), 4 ,4'-methylenebis(2-methylcyclohexylamine), 1,4-bis(3-aminopropyl)piper, 3,9-bis(3-aminopropyl)-2, 4,8,10-tetraoxaspiro-[5,5]-undecane and so on. Examples of linear aliphatic diamine compounds include 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, and 1,8-diaminooctane. Alkane, 1,10-diaminodecane, 1,12-diaminododecane and other hydrocarbon diamines, or 2-(2-aminoethoxy)ethylamine, 2,2'-( Alkoxy type diamines such as ethylenedioxy)diethylamine, bis[2-(2-aminoethoxy)ethyl]ether, etc. Examples of the siloxane diamine compound include dimethyl (poly) siloxane diamine, for example, trade names PAM-E, KF-8010, X-22-161A manufactured by Shin-Etsu Chemical Industries. After the amide condensation polymerization reaction is completed, the precipitates and the like derived from the dehydration condensing agent that are precipitated in the reaction liquid are filtered and separated as necessary. Then, a poor solvent of polyamide such as water or aliphatic lower alcohol or a mixed solution thereof is added to the reaction solution to precipitate polyamide. Furthermore, the precipitated polyamide was dissolved in the solvent again, and the reprecipitation precipitation operation was repeatedly performed to purify and vacuum-dry the target polyamide. Furthermore, in order to further improve the refinement system, the solution of polyamide can be passed through a column filled with ion exchange resin to remove ionic impurities. The weight average molecular weight of polyamide based on gel permeation chromatography (hereinafter referred to as "GPC") in terms of polystyrene is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. If the polystyrene-equivalent weight average molecular weight is 7,000 or more, the basic physical properties of the hardened relief pattern are ensured. In addition, if the polystyrene-equivalent weight average molecular weight is 70,000 or less, the development solubility when forming the relief pattern is ensured. As the dissolution liquid of GPC, it is recommended to use tetrahydrofuran or N-methyl-2-pyrrolidone. In addition, the weight average molecular weight value is obtained from a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to choose from STANDARD SM-105, a standard sample of organic solvents manufactured by Showa Denko. [(A) Polyhydroxyamide] Another example of the preferred (A) resin in the photosensitive resin composition of the present invention has the following general formula (5): [Chem 57]

{Where, Y ₃ It is a tetravalent organic group having carbon atoms, preferably a tetravalent organic group having 2 or more carbon atoms, Y ₄ , X ₃ And X ₄ Are independently divalent organic groups with more than 2 carbon atoms, n ₃ Is an integer from 1 to 1000, n ₄ Is an integer from 0 to 500, n ₃ /(n ₃ ＋n ₄ )>0.5, and contains X ₃ And Y ₃ Of n ₃ Dihydroxydiamide units and containing X ₄ And Y ₄ Of n ₄ The arrangement order of the two diamide units is any polyhydroxyamide (the precursor of polyazole) (hereinafter sometimes the polyhydroxyamide represented by the above general formula (5) is abbreviated as "polyoxazole"Precursor")). The polyoxazole precursor is n in the general formula (5) ₃ A polymer of two dihydroxydiamide units (hereinafter sometimes simply referred to as dihydroxydiamide units) may also have n in the above general formula (5) ₄ Diamide units (hereinafter sometimes simply referred to as diamide units). X ₃ The number of carbon atoms is preferably 2 or more and 40 or less for the purpose of obtaining photosensitive characteristics, X ₄ The number of carbon atoms is preferably 2 or more and 40 or less for the purpose of obtaining photosensitive characteristics, Y ₃ The number of carbon atoms is preferably 2 or more and 40 or less for the purpose of obtaining photosensitive characteristics, and Y ₄ The number of carbon atoms is preferably 2 or more and 40 or less for the purpose of obtaining photosensitive characteristics. The dihydroxydiamide unit can be obtained by having Y ₃ (NH ₂ ) ₂ (OH) ₂ The structure of the diaminodihydroxy compound (preferably bisaminophenol) and having X ₃ (COOH) ₂ The structure of dicarboxylic acid is synthesized and formed. Hereinafter, a typical aspect will be described by taking the case where the above-mentioned diaminodihydroxy compound is bisaminophenol as an example. The two groups of amino groups of the diaminophenol and the hydroxyl group are located adjacent to each other respectively, and the dihydroxydiamide unit is closed-looped under heating at about 250-400°C to be converted into a heat-resistant polyoxazole structure. N in general formula (5) ₃ It is 1 or more for the purpose of obtaining photosensitive characteristics, and 1000 or less for the purpose of obtaining photosensitive characteristics. n ₃ The range is preferably 2 to 1,000, more preferably 3 to 50, and most preferably 3 to 20. If necessary, it can be condensed on the precursor of polyazole ₄ The above diamide units. The diamide unit can be obtained by having Y ₄ (NH ₂ ) ₂ The structure of diamine and has X ₄ (COOH) ₂ The structure of dicarboxylic acid is synthesized and formed. N in general formula (5) ₄ Is in the range of 0 to 500, with n ₄ It is below 500 to obtain good photosensitive characteristics. n ₄ More preferably, it is in the range of 0-10. If the ratio of the diamide unit to the dihydroxydiamide unit is too high, the solubility in the alkaline aqueous solution used as a developer decreases, so n in general formula (5) ₃ /(n ₃ ＋n ₄ ) Value exceeds 0.5, more preferably 0.7 or more, and most preferably 0.8 or more. About as having Y ₃ (NH ₂ ) ₂ (OH) ₂ The diaminophenol of the diaminodihydroxy compound of the structure can be exemplified by 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4, 4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylbenzene, 4,4'-diamino-3,3 '-Dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis -(3-Amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl) hexafluoropropane, bis-(4-amino-3-hydroxy Phenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-Diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4' -Dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6 -Dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination of two or more. As Y in the diaminophenol ₃ In terms of photosensitive characteristics, the following formula (37) is preferred:

{In the formula, Rs1 and Rs2 independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a trifluoromethyl group}. Also, as having Y ₄ (NH ₂ ) ₂ Examples of the diamine of the structure include aromatic diamine and silicon diamine. Among them, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, 3,3'-diaminodiphenyl ether, and 3,4'-diamino group. Diphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diamine Diphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-di Amino diphenyl sulfide, 3,3'-diamino diphenyl ketone, 4,4'-diamino diphenyl ketone, 3,4'-diamino diphenyl ketone, 2,2' -Bis(4-aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4-methyl-2,4-bis(4-aminophenyl)-1-pentane Ene, 4-methyl-2,4-bis(4-aminophenyl)-2-pentene, 1,4-bis(α,α-dimethyl-4-aminobenzyl)benzene, Aminodi-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis(4-aminophenyl)pentane, 5 (or 6)-Amino-1-(4-aminophenyl)-1,3,3-trimethylindane, bis(p-aminophenyl)phosphine oxide, 4,4'-diaminoazo Benzene, 4,4'-diaminodiphenylurea, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis(4-(4-aminophenoxy) Phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]di Benzophenone, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 4,4'-bis(4-(α,α-dimethyl-4-aminobenzyl)benzene Oxy]benzophenone, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy]diphenylbenzene, 4,4'-diamine Biphenyl, 4,4'-diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-di Methyl-4,4'-diaminobiphenyl, o-toluidine satin, 2,2-bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl) satin , Bis(4-aminophenoxyphenyl) sulfide, 1,4-(4-aminophenoxyphenyl)benzene, 1,3-(4-aminophenoxyphenyl)benzene, 9,9-bis(4-aminophenyl) stilbene, 4,4'-di-(3-aminophenoxy)diphenyl sulfone, 4,4'-diaminobenzylanilide, etc., And the hydrogen atom of the aromatic nucleus of these aromatic diamines is substituted with at least one group or atom selected from the group consisting of chlorine atom, fluorine atom, bromine atom, methyl group, methoxy group, cyano group and phenyl group Compound. In addition, as the above-mentioned diamine, in order to improve the adhesion with the base material, silicon diamine can be selected. Examples of silicon diamines include bis(4-aminophenyl) dimethyl silane, bis(4-aminophenyl) tetramethyl siloxane, bis(4-aminophenyl) tetra Methyldisilaxane, bis(γ-aminopropyl)tetramethyldisilaxane, 1,4-bis(γ-aminopropyldimethylsilyl)benzene, bis(4-amino Butyl)tetramethyldisilaxane, bis(γ-aminopropyl)tetraphenyldisilaxane, etc. Also, as having X ₃ (COOH) ₂ Or X ₄ (COOH) ₂ The preferred dicarboxylic acid of the structure can be X ₃ And X ₄ They are aliphatic groups or aromatic groups with linear, branched or cyclic structures, respectively. Among them, an organic group having 2 or more carbon atoms and 40 or less carbon atoms which may contain an aromatic ring or an aliphatic ring is preferred, X ₃ And X ₄ It can be preferably selected from the following formula (38): [化59]

{Where R ₄₁ Means selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO- and -C(CF ₃ ) ₂ -It is preferable to select the aromatic group represented by the divalent group in the group} which is equivalent to the photosensitive property. The polyazole precursor may also be a terminal group capped by a specific organic group. In the case of using a polyazole precursor blocked with an end-capping group, it is expected that the mechanical properties (especially elongation) and the shape of the cured relief pattern of the coating film of the photosensitive resin composition of the present invention after heat hardening will Well. As a preferred example of such a terminal group, the following formula (39) can be cited:

Expressed by. The polystyrene precursor weight average molecular weight in terms of polystyrene based on gel permeation chromatography is preferably 3,000 to 70,000, more preferably 6,000 to 50,000. From the viewpoint of the physical properties of the cured relief pattern, the weight average molecular weight is preferably 3,000 or more. From the viewpoint of resolution, it is preferably 70,000 or less. As a developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to choose from the standard sample STANDARD SM-105 of organic solvents manufactured by Showa Denko. [(A) Polyimide] Another example of the preferred (A) resin in the photosensitive resin composition of the present invention is that having the above general formula (6): [Chem. 61]

{Where, X ₅ Represents an organic group with a price of 4-14, Y ₅ Represents an organic group of 2-12 valences, R ₁₀ And R ₁₁ Represents an organic group having at least one group selected from a phenolic hydroxyl group, a sulfonic acid group or a thiol group, and may be the same or different, n ₅ Is an integer from 3 to 200, and m ₃ And m ₄ It is an integer from 0 to 10} Polyimide of the structure represented by. Here, the resin represented by the general formula (6) does not need to undergo a chemical change through a heat treatment step when exhibiting sufficient film characteristics, and therefore is suitable for treatment at a lower temperature, which is particularly preferable in this respect. X in the structural unit represented by the above general formula (6) ₅ It is preferably a 4- to 14-valent organic group having a carbon number of 4 to 40, and further preferably has a carbon number of 5 to 40 containing an aromatic ring or an aliphatic ring in terms of having both heat resistance and photosensitive characteristics The organic base. The polyimide represented by the above general formula (6) can make tetracarboxylic acid, the corresponding tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, etc. with diamine, the corresponding diisocyanate compound, trimethylsilane It is obtained by reacting the acylated diamine. Polyimide can generally be chemically treated by heating, acid or alkali, etc., as one of the precursors of polyimide obtained from the reaction of tetracarboxylic dianhydride and diamine. Obtained by dehydration closed loop. Examples of suitable tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyl Tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydrate, 2,2-bis(2,3-dicarboxyphenyl ) Propane dihydrate, 1,1-bis(3,4-dicarboxyphenyl)ethane dihydrate, 1,1-bis(2,3-dicarboxyphenyl)ethane dihydrate, bis( 3,4-dicarboxyphenyl)methane dianhydrate, bis(2,3-dicarboxyphenyl)methane dianhydrate, bis(3,4-dicarboxyphenyl) dihydrate, bis(3, 4-dicarboxyphenyl) ether dianhydrate, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl) stilbene dianhydride, 9,9 -Bis{4-(3,4-dicarboxyphenoxy)phenyl} cinnamic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic acid Aromatic tetracarboxylic dianhydrides such as acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dihydrate, or Butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride and other aliphatic tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ash tetracarboxylic acid Dianhydride and the following general formula (40): [Chemical 62]

{Where R ₄₂ It is selected from oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ Or SO ₂ In the base, and R ₄₃ And R ₄₄ It may be the same or different, and represents a compound selected from the group consisting of a hydrogen atom, a hydroxyl group, or a thiol group. Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2' are preferable ,3,3'-Biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetra Carboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydrate, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydrate, 1,1-bis (3,4-dicarboxyphenyl)ethane dihydrate, 1,1-bis(2,3-dicarboxyphenyl)ethane dihydrate, bis(3,4-dicarboxyphenyl)methanedi Anhydrous, bis(2,3-dicarboxyphenyl)methane dianhydrate, bis(3,4-dicarboxyphenyl) lanthanum dihydrate, bis(3,4-dicarboxyphenyl)ether dianhydrate , 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydrate, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 9,9-bis(3 ,4-dicarboxyphenyl) cis dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl} cis dianhydride and the following general formula (41) [Chem 63 ]

{Where R ₄₅ It is selected from oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ Or SO ₂ In the base, and R ₄₆ And R ₄₇ It may be the same or different, and represents an acid dianhydride having a structure selected from a group represented by a hydrogen atom, a hydroxyl group, or a thiol group. These can be used alone or in combination of two or more. Y of the above general formula (6) ₅ It represents the structural component of a diamine. As this diamine, it represents a 2-12 valence organic group containing an aromatic ring or an aliphatic ring, and among them, an organic group having 5 to 40 carbon atoms is preferred. Specific examples of diamines include: 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4 ,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, phenylyne, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2 ,6-Naphthalenediamine, bis(4-aminophenoxyphenyl) satin, bis(3-aminophenoxyphenyl) satin, bis(4-aminophenoxyphenyl) biphenyl, bis{ 4-(4-aminophenoxy)phenyl) ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diamine Benzene, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl -4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl -4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl) stilbene Or a compound in which the aromatic ring is substituted with an alkyl group or a halogen atom, or an aliphatic cyclohexyldiamine, methylene biscyclohexylamine, and the following general formula (42): [Chem 64]

{Where R ₄₈ It is selected from oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ Or SO ₂ In the base, and R ₄₉ ~R ₅₂ It may be the same or different, and represents a diamine selected from a structure represented by a group selected from a hydrogen atom, a hydroxyl group, or a thiol group. Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4 '-Diaminodiphenyl sulfide, m-phenylenediamine, P-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl) Fu and the following general formula (43): [Chem 65]

{Where R ₅₃ It is selected from oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ Or SO ₂ In the base, and R ₅₄ ~R ₅₇ It may be the same or different, and represents a diamine of a structure selected from a group represented by a hydrogen atom, a hydroxyl group, or a thiol group. Among these, particularly preferred are 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 1,4-bis(4-aminophenoxy)benzene, And the following general formula (44): [Chem 66]

{Where R ₅₈ It is selected from oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ Or SO ₂ In the base, and R ₅₉ And R ₆₀ It may be the same or different, and represents a diamine of a structure selected from a group represented by a hydrogen atom, a hydroxyl group, or a thiol group. These can be used alone or in combination of two or more. R of general formula (6) ₁₀ And R ₁₁ It represents a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. In the present invention, as R ₁₀ And R ₁₁ , Phenolic hydroxyl group, sulfonic acid group and/or thiol group can be mixed. By controlling R ₁₀ And R ₁₁ The amount of the alkali-soluble group changes in the dissolution rate in the alkaline aqueous solution, and therefore the photosensitive resin composition having a moderate dissolution rate can be obtained by this adjustment. Furthermore, in order to improve the adhesion with the substrate, it can also be used as X within the range that does not reduce the heat resistance. ₅ , Y ₅ The aliphatic group with a siloxane structure is copolymerized. Specifically, bis(3-aminopropyl)tetramethyldisilaxane and bis(p-aminophenyl)octamethylpentasiloxane as diamine components with 1 to 10 mole% Copolymers such as alkanes. The above-mentioned polyimide can be obtained by using the following methods after obtaining the polyimide precursor, and then using a known method of imidization to make the polyimide precursor completely imidized, or stopping the midway. The method of introducing a part of the amide imide structure (polyamide amide imide in this case) by amination reaction, or by blending the fully amide imidized polymer with the polyimide precursor It is synthesized by introducing a part of the amide imide structure. The method for obtaining the polyimide precursor described above is as follows: for example, a tetracarboxylic dianhydride and a diamine compound (a part of which is substituted with a terminal blocking agent as a monoamine) at a low temperature Reaction; reacting tetracarboxylic dianhydride (a part of which is substituted with an end-capping agent that is an acid anhydride or a monochloride compound or a single active ester compound) with a diamine compound at a low temperature; dicarboxylic acid dianhydride and alcohol are used to obtain di Ester, which is then reacted with a diamine (a part of which is substituted by a terminal blocking agent as a monoamine) in the presence of a condensing agent; a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is carried out Acyl chloride is reacted with diamine (a part of which is replaced by a terminal blocking agent as a monoamine). The above-mentioned polyimide preferably has polyimide so that the degree of imidization is 15% or more with respect to the entire resin constituting the photosensitive resin composition. Furthermore, it is preferably 20% or more. Here, the imidate ratio refers to the ratio of imidate present in the entire resin constituting the photosensitive resin composition. If the imidate ratio is less than 15%, the amount of shrinkage during heat curing becomes large, which is not suitable for thick film production. The imidate ratio can be easily calculated by the following method. First, the infrared absorption spectrum of the polymer was measured, and it was confirmed that there was an absorption peak (near 1780 cm-1, near 1377 cm-1) derived from the amide imide structure of the polyimide. Then, the polymer was heat-treated at 350°C for 1 hour, the infrared absorption spectrum after the heat treatment was measured, and the peak intensity near 1377 cm-1 was compared with the intensity before the heat treatment, thereby calculating the Rate of amide imidization. The molecular weight of the above-mentioned polyimide is preferably 3,000 to 200,000, and more preferably 5,000 to 50,000 when measured in terms of weight average molecular weight in terms of polystyrene based on gel permeation chromatography. When the weight average molecular weight is 3,000 or more, the mechanical properties are good, and when it is 50,000 or less, the dispersibility in the developer is good, and the relief performance of the relief pattern is good. As a developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to choose from the standard sample STANDARD SM-105 of organic solvents manufactured by Showa Denko. Furthermore, in the present invention, a phenol resin can also be preferably used. [(A) Phenolic resin] The phenol resin in this embodiment means a resin having a repeating unit containing a phenolic hydroxyl group. (A) The phenol resin does not undergo structural changes such as the cyclization (polyimidization) of the polyimide precursor during thermal curing, and therefore has the advantage of being able to be cured at a low temperature (eg, 250°C or lower). In the present embodiment, the weight average molecular weight of (A) phenol resin is preferably 700 to 100,000, more preferably 1,500 to 80,000, and still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of applicability of the reflow process of the cured film, and on the other hand, preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition. The measurement of the weight average molecular weight herein can be performed by gel permeation chromatography (GPC) and calculated based on a calibration curve prepared using standard polystyrene. (A) The phenol resin is preferably selected from the group consisting of novolak and polyhydroxystyrene from the viewpoints of solubility in an alkaline aqueous solution, sensitivity and resolution when forming a resist pattern, and residual stress of a cured film , With the following general formula (7): [Chem 67]

{In the formula, a is an integer from 1 to 3, b is an integer from 0 to 3, 1≦(a+b)≦4, R ₂₆ Represents a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group. When b is 2 or 3, plural R ₁₂ They may be the same as or different from each other. X represents a divalent aliphatic group selected from the group consisting of a carbon number of 2 to 10 and a carbon number of 3 to 20, which may have an unsaturated bond, and the following general formula ( 8): [Chemical 68]

(In the formula, p is an integer of 1-10) The divalent organic group represented by the divalent alkoxy group represented by the divalent organic group and the divalent organic group having an aromatic ring having 6 to 12 carbon atoms At least one phenol resin of the phenol resin of the repeating unit represented by the group} and the phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms. (Novolak) As used herein, novolak means the entire polymer obtained by condensing phenols and formaldehyde in the presence of a catalyst. Generally speaking, novolac can be obtained by condensing 1 mol of phenol with less than 1 mol of formaldehyde relative to the phenol. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butyl Phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol , 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol, etc. Specific novolaks include, for example, phenol/formaldehyde condensed novolak resins, cresol/formaldehyde condensed novolak resins, phenol-naphthol/formaldehyde condensed novolak resins, and the like. The weight average molecular weight of the novolak is preferably 700 to 100,000, more preferably 1,500 to 80,000, and still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of applicability of the reflow process of the cured film, and on the other hand, preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition. (Polyhydroxystyrene) As used herein, polyhydroxystyrene means the entire polymer containing hydroxystyrene as a polymerization unit. Preferable examples of polyhydroxystyrene include poly-p-vinylphenol. Poly-p-vinylphenol means the entire polymer containing p-vinylphenol as a polymerization unit. Therefore, as long as the object of the present invention is not violated, polymerized units other than hydroxystyrene (for example, p-vinylphenol) can be used to constitute polyhydroxystyrene (for example, polyp-vinylphenol). In the polyhydroxystyrene, the ratio of the number of moles of hydroxystyrene units based on the number of moles of all the polymerized units is preferably 10 mol% to 99 mol%, more preferably 20 to 97 mol%, Furthermore, it is preferably 30 to 95 mol%. When the above ratio is 10 mol% or more, it is advantageous from the viewpoint of alkali solubility of the photosensitive resin composition, and when it is 99 mol% or less, the composition containing the following copolymerization component is hardened The viewpoint of the reflow solderability of the cured film formed is advantageous. The polymerization unit other than hydroxystyrene (for example, p-vinylphenol) may be any polymerization unit capable of copolymerizing with hydroxystyrene (for example, p-vinylphenol). The copolymerization component forming a polymerization unit other than hydroxystyrene (for example, p-vinylphenol) is not limited, and examples thereof include methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, and acrylic acid. Octyl ester, 2-ethoxyethyl methacrylate, third butyl acrylate, 1,5-pentanediol diacrylate, N,N-diethylaminoethyl acrylate, ethylene glycol diacrylate , 1,3-Propanediol diacrylate, Decanediol diacrylate, Decanediol dimethacrylate, 1,4-Cyclohexanediol diacrylate, 2,2-Dimethylolpropane diacrylate , Glycerin diacrylate, tripropylene glycol diacrylate, glycerin triacrylate, 2,2-di (p-hydroxyphenyl) propane dimethacrylate, triethylene glycol diacrylate, polyoxyethyl-2- 2-Di(p-hydroxyphenyl)propane dimethacrylate, triethylene glycol dimethacrylate, polyoxypropyltrimethylolpropane triacrylate, ethylene glycol dimethacrylate, succinic acid Alcohol dimethacrylate, 1,3-propanediol dimethacrylate, butanediol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethyl Acrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol trimethacrylate, 1,2-dimethacrylate 1-phenylethylene glycol, pentaerythritol Acrylic esters such as tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate, and 1,4-benzenediol dimethacrylate; benzene Ethylene and substituted styrenes such as 2-methylstyrene and vinyltoluene; vinylester monomers such as vinyl acrylate and vinyl methacrylate; and o-vinylphenol, m-vinylphenol Wait. In addition, as the novolak and polyhydroxystyrene described above, one type may be used alone, or two or more types may be used in combination. The weight average molecular weight of polyhydroxystyrene is preferably 700 to 100,000, more preferably 1,500 to 80,000, and still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of applicability of the reflow process of the cured film, and on the other hand, preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition. (Phenolic resin represented by general formula (7)) In this embodiment, (A) the phenol resin preferably also includes the following general formula (7):

{In the formula, a is an integer from 1 to 3, b is an integer from 0 to 3, 1≦(a+b)≦4, R ₁₂ Represents a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group. When b is 2 or 3, plural R ₁₂ They may be the same as or different from each other. X represents a divalent aliphatic group selected from the group consisting of a carbon number of 2 to 10 and a carbon number of 3 to 20, which may have an unsaturated bond, and the following general formula ( 8): [Chemical 70]

(In the formula, p is an integer of 1-10) The divalent organic group represented by the divalent alkoxy group represented by the divalent organic group and the divalent organic group having an aromatic ring having 6 to 12 carbon atoms The phenol resin of the repeating unit represented by the group }. The phenol resin having the above-mentioned repeating unit can be hardened at a low temperature compared with, for example, polyimide resin and polybenzoxazole resin previously used, and can form a cured film having good elongation, which is especially in this respect favorable. The above-mentioned repeating units present in the phenol resin molecule may be one kind or a combination of two or more kinds. In the above general formula (7), R ₁₂ From the viewpoint of reactivity when synthesizing the resin of the general formula (7), it is a monovalent substitution selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group base. R ₁₂ From the viewpoint of alkali solubility, it is preferably selected from a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, and an aromatic group having 6 to 20 carbon atoms, and The following general formula (45): [Chem. 71]

{Where R ₆₁ , R ₆₂ And R ₆₃ Each independently represents a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms, and R ₆₄ Represents a divalent aliphatic group having 1 to 10 carbon atoms, a divalent alicyclic group having 3 to 20 carbon atoms, or a divalent aromatic group having 6 to 20 carbon atoms which may have an unsaturated bond} One-valent substituent in the group consisting of the four groups. In the present embodiment, in the general formula (7), a is an integer of 1 to 3, but from the viewpoint of alkali solubility and elongation, 2 is preferable. In addition, when a is 2, the substitution positions of the hydroxyl groups may be any positions of the ortho position, meta position and para position. In addition, when a is 3, the substitution positions of the hydroxyl groups may be any positions such as 1,2,3-position, 1,2,4-position and 1,3,5-position. In this embodiment, in the above general formula (7), when a is 1, in order to improve alkali solubility, a phenol resin having a repeating unit represented by general formula (7) (hereinafter also referred to as (a1 ) Resin) A phenol resin selected from novolac and polyhydroxystyrene (hereinafter also referred to as (a2) resin) is further mixed. The mixing ratio of (a1) resin and (a2) resin is preferably in the range of (a1)/(a2)=10/90 to 90/10 in terms of mass ratio. The mixing ratio is preferably (a1)/(a2)=10/90 to 90/10, and more preferably (a1)/ from the viewpoint of solubility in the alkaline aqueous solution and the elongation of the cured film. (a2)=20/80 to 80/20, more preferably (a1)/(a2)=30/70 to 70/30. Regarding the novolak and polyhydroxystyrene as the above-mentioned (a2) resin, the same resins as those shown in the above (novolac) and (polyhydroxystyrene) can be used. In the present embodiment, in the above general formula (7), b is an integer of 0 to 3. However, from the viewpoint of alkali solubility and elongation, it is preferably 0 or 1. In addition, when b is 2 or 3, a plurality of R ₁₂ They may be the same or different from each other. Furthermore, in the present embodiment, in the above general formula (7), a and b satisfy the relationship of 1≦(a+b)≦4. In the present embodiment, in the above general formula (7), X is selected from the group consisting of divalent fats having 2 to 10 carbon atoms which may have an unsaturated bond from the viewpoint of the shape of the cured relief pattern and the elongation of the cured film It consists of a group, a divalent alicyclic group having 3 to 20 carbon atoms, an alkoxy group represented by the above general formula (8), and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms The two-valent organic group in the group. Among these divalent organic groups, from the viewpoint of the strength and toughness of the cured film, X is preferably selected from the following general formula (9):

{Where R ₁₃ , R ₁₄ , R ₁₅ And R ₁₆ Each is independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a monovalent aliphatic group having 1 to 10 carbon atoms in which a part or all of a hydrogen atom is substituted with a fluorine atom, n ₆ Is an integer from 0 to 4, and n ₆ R when it is an integer from 1 to 4 ₁₇ It is a halogen atom, a hydroxyl group, or a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ Is hydroxyl, n ₆ In the case of an integer from 2 to 4, plural R ₁₇ They may be the same or different from each other, the divalent group represented by }, and the following general formula (10): [化73]

{Where R ₁₈ , R ₁₉ , R ₂₀ And R _{twenty one} Each independently represents a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a monovalent aliphatic group having 1 to 10 carbon atoms in which a part or all of the hydrogen atoms are substituted with fluorine atoms, and W is a monovalent Bond, selected from aliphatic groups having 1 to 10 carbon atoms which may be substituted with fluorine atoms, alicyclic groups having 3 to 20 carbon atoms which may be substituted with fluorine atoms, the following general formula (8): [Chem 74]

(In the formula, p is an integer of 1 to 10) The divalent alkoxy group represented by and the following formula (11): [Chem 75]

The divalent organic group in the group consisting of the represented divalent base} The divalent organic group in the group consisting of the represented divalent base}. The carbon number of the divalent organic group X having the aromatic ring having 6 to 12 carbon atoms is preferably 8 to 75, more preferably 8 to 40. Furthermore, the structure of the above-mentioned divalent organic group X having an aromatic ring having 6 to 12 carbon atoms is generally different from the aromatic ring in the general formula (7) in which an OH group and any R are bonded ₁₂ The structure of the base. Furthermore, the divalent organic group represented by the above general formula (10) is more preferably the following formula (12) from the viewpoints that the patternability of the resin composition and the elongation of the cured film after curing are good: [化76]

The represented divalent organic group is further preferably the following formula (13): [Chem 77]

The indicated divalent organic group. Among the structures represented by the general formula (7), X is particularly preferably the structure represented by the above formula (12) or (13), and the ratio of the positions represented by the structure represented by the formula (12) or (13) in X is From the viewpoint of elongation, it is preferably 20% by mass or more, and more preferably 30% by mass or more. From the viewpoint of alkali solubility of the composition, the above ratio is preferably 80% by mass or less, and more preferably 70% by mass or less. In addition, among the phenol resins having the structure represented by the above general formula (7), from the viewpoint of the alkali solubility of the composition and the elongation of the cured film, it is particularly preferable to have the following The structure represented by the formula (14) and the structure represented by the following general formula (15) are both structures. [Chemical 78]

{Where R _{twenty one} It is a monovalent group of 1 to 10 carbon atoms selected from the group consisting of hydrocarbon groups and alkoxy groups, n ₇ 2 or 3, n ₈ It is an integer from 0 to 2, m ₅ It is an integer from 1 to 500, 2≦(n ₇ ＋n ₈ )≦4, at n ₈ In the case of 2, plural R _{twenty one} Mutually the same or different} [Chem. 79]

{Where R _{twenty two} And R _{twenty three} Each is independently a monovalent group with a carbon number of 1 to 10 selected from the group consisting of a hydrocarbon group and an alkoxy group, n ₉ Is an integer from 1 to 3, n ₁₀ Is an integer from 0 to 2, n ₁₁ It is an integer from 0 to 3, m ₆ It is an integer from 1 to 500, 2≦(n ₉ ＋n ₁₀ )≦4, at n ₁₀ In the case of 2, plural R _{twenty two} Mutually the same or different, in n ₁₁ In the case of 2 or 3, plural R _{twenty three} May be the same or different from each other} m of the above general formula (14) ₅ And m of the above general formula (15) ₆ Represents the total number of each repeating unit in the main chain of the phenol resin. That is, in the phenol resin (A), for example, the repeating unit in the brackets in the structure represented by the above general formula (14) and the repeating unit in the brackets in the structure represented by the above general formula (15) may be random, embedded Arranged in the form of paragraphs or a combination of these. m ₅ And m ₆ Each is independently an integer of 1 to 500, the lower limit value is preferably 2, more preferably 3, and the upper limit value is preferably 450, more preferably 400, and further preferably 350. m ₅ And m ₆ From the viewpoint of the strength and toughness of the cured film, it is preferably independently 2 or more, and from the viewpoint of solubility in an alkaline aqueous solution, it is preferably 450 or less. m ₅ With m ₆ The total amount is preferably 2 or more, more preferably 4 or more, and even more preferably 6 or more from the viewpoint of the strength and toughness of the cured film, and preferably from the viewpoint of solubility in an alkaline aqueous solution It is 200 or less, more preferably 175 or less, and still more preferably 150 or less. Among (A) phenol resins having both the structure represented by the above general formula (14) and the structure represented by the above general formula (15) in the same resin skeleton, the structure represented by the above general formula (14) The higher the ear ratio, the better the film properties after curing and the better the heat resistance. On the other hand, the higher the molar ratio of the structure represented by the above general formula (15), the better the alkali solubility, after curing The better the pattern shape. Therefore, the ratio m of the structure represented by the general formula (14) to the structure represented by the general formula (15) ₅ /m ₆ From the viewpoint of the film physical properties after curing, it is preferably 20/80 or more, more preferably 40/60 or more, and particularly preferably 50/50 or more, and from the viewpoint of alkali solubility and the shape of the cured relief pattern, It is preferably 90/10 or less, more preferably 80/20 or less, and still more preferably 70/30 or less. The phenol resin having a repeating unit represented by the general formula (7) typically contains a phenol compound and a copolymerization component (specifically, it is selected from compounds having an aldehyde group (including compounds that decompose to form aldehyde compounds like trioxane) , A compound with a ketone group, a compound with 2 hydroxymethyl groups in the molecule, a compound with 2 alkoxymethyl groups in the molecule, and a compound with 2 haloalkyl groups in the molecule The above compounds) are more typically synthesized by subjecting the monomer components containing these to polymerization reaction. For example, the following phenol and/or phenol derivatives (hereinafter collectively referred to as "phenol compounds") and aldehyde compounds, ketone compounds, methylol compounds, alkoxymethyl compounds, diene compounds or haloalkyl groups Copolymerization components such as compounds are polymerized to obtain (A) a phenol resin. In this case, in the above general formula (7), an OH group and an arbitrary R are bonded to the aromatic ring ₁₂ The part represented by the structure of the group is derived from the above-mentioned phenol compound, and the part represented by X is derived from the above-mentioned copolymerization component. From the viewpoints of reaction control and the stability of the obtained (A) phenol resin and photosensitive resin composition, the mole ratio of the phenol compound and the above-mentioned copolymer component (phenol compound): (copolymer component) is preferably 5:1 to 1.01:1: more preferably 2.5:1 to 1.1:1. The weight average molecular weight of the phenol resin having the repeating unit represented by the general formula (7) is preferably 700 to 100,000, more preferably 1,500 to 80,000, and still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of applicability of the reflow process of the cured film, and on the other hand, preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition. Examples of phenol compounds that can be used to obtain a phenol resin having a repeating unit represented by general formula (7) include cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, and hydroxyl groups. Biphenyl, benzylphenol, nitrobenzylphenol, cyanobenzylphenol, adamantanephenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N-(hydroxyphenyl)- 5-Norton-2,3-dicarboxylimide, N-(hydroxyphenyl)-5-methyl-5-North-2,3-dicarboxylimide, trifluoromethylphenol , Hydroxybenzoic acid, methyl hydroxybenzoate, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzoyl amide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, m Resorcinol, xylenol, catechol, methyl catechol, ethyl catechol, hexyl catechol, benzyl catechol, nitrobenzyl catechol, methyl resorcinol, Ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, dihydroxybenzene Ethyl formate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzoyl amide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, Dihydroxybenzonitrile, N-(dihydroxyphenyl)-5-norbornene-2,3-dicarboxyacetylimide, N-(dihydroxyphenyl)-5-methyl-5-norbornene -2,3-dicarboxyacetylimide, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol Diphenol, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, resorcinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, tris Methyl hydroxybenzoate, ethyl trihydroxybenzoate, butyl trihydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxybenzene ethyl Ketone, trihydroxybenzophenone, trihydroxybenzonitrile, etc. Examples of the aldehyde compound include acetaldehyde, propionaldehyde, trimethylacetaldehyde, butyraldehyde, valeraldehyde, hexanal, trioxane, glyoxal, cyclohexanal, diphenylacetaldehyde, ethyl Butyraldehyde, benzaldehyde, glyoxylic acid, 5-north-2-en aldehyde, malondialdehyde, succinaldehyde, glutaraldehyde, salicylaldehyde, naphthalene formaldehyde, terephthalaldehyde, etc. Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, dicyclohexanone, and cyclic Hexanedione, 3-butyn-2-one, 2-norone, adamantone, 2,2-bis(4-oxetanyl)propane, etc. Examples of the hydroxymethyl compound include 2,6-bis(hydroxymethyl)p-cresol, 2,6-bis(hydroxymethyl)-4-ethylphenol, and 2,6-bis(hydroxymethyl) Yl)-4-propylphenol, 2,6-bis(hydroxymethyl)-4-n-butylphenol, 2,6-bis(hydroxymethyl)-4-third butylphenol, 2,6- Bis(hydroxymethyl)-4-methoxyphenol, 2,6-bis(hydroxymethyl)-4-ethoxyphenol, 2,6-bis(hydroxymethyl)-4-propoxyphenol, 2,6-bis(hydroxymethyl)-4-n-butoxyphenol, 2,6-bis(hydroxymethyl)-4-third butoxyphenol, 1,3-bis(hydroxymethyl)urea , Ribitol, arabitol, allitol, 2,2-bis (hydroxymethyl) butanoic acid, 2-benzyloxy-1,3-propanediol, 2,2-dimethyl-1,3-propanediol , 2,2-diethyl-1,3-propanediol, glycerol monoacetate, 2-methyl-2-nitro-1,3-propanediol, 5-northene-2,2-dimethanol, 5 -Norpho-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis (hydroxymethyl) are all four Toluene, 2-nitro-p-phenylenediethanol, 1,10-dihydroxydecane, 1,12-dihydroxydodecane, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-bis( Hydroxymethyl) cyclohexene, 1,6-bis(hydroxymethyl)adamantane, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 2,6-bis(hydroxymethyl)-1, 4-dimethoxybenzene, 2,3-bis(hydroxymethyl)naphthalene, 2,6-bis(hydroxymethyl)naphthalene, 1,8-bis(hydroxymethyl)anthracene, 2,2'-bis (Hydroxymethyl) diphenyl ether, 4,4'-bis (hydroxymethyl) diphenyl ether, 4,4'-bis (hydroxymethyl) diphenyl sulfide, 4,4'-bis (hydroxymethyl) ) Benzophenone, 4-hydroxymethylbenzoic acid-4'-hydroxymethylphenyl ester, 4-hydroxymethylbenzoic acid-4'-hydroxymethylaniline, 4,4'-bis(hydroxymethyl) Phenylurea, 4,4'-bis(hydroxymethyl)phenylcarbamate, 1,8-bis(hydroxymethyl)anthracene, 4,4'-bis(hydroxymethyl)biphenyl, 2 ,2'-Dimethyl-4,4'-bis(hydroxymethyl)biphenyl, 2,2-bis(4-hydroxymethylphenyl)propane, ethylene glycol, diethylene glycol, triethylenedioxide Alcohol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, etc. Examples of the alkoxymethyl compound include 2,6-bis(methoxymethyl)p-cresol, 2,6-bis(methoxymethyl)-4-ethylphenol, and 2, 6-bis(methoxymethyl)-4-propylphenol, 2,6-bis(methoxymethyl)-4-n-butylphenol, 2,6-bis(methoxymethyl)- 4-tert-butylphenol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 2,6-bis(methoxymethyl)-4-ethoxyphenol, 2, 6-bis(methoxymethyl)-4-propoxyphenol, 2,6-bis(methoxymethyl)-4-n-butoxyphenol, 2,6-bis(methoxymethyl) )-4-Third butoxyphenol, 1,3-bis(methoxymethyl)urea, 2,2-bis(methoxymethyl)butanoic acid, 2,2-bis(methoxymethoxy) Radicals)-5-northrene, 2,3-bis(methoxymethyl)-5-northene, 1,4-bis(methoxymethyl)cyclohexane, 1,4-bis( Methoxymethyl)cyclohexene, 1,6-bis(methoxymethyl)adamantane, 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl) )Benzene, 2,6-bis(methoxymethyl)-1,4-dimethoxybenzene, 2,3-bis(methoxymethyl)naphthalene, 2,6-bis(methoxymethoxy) Group) naphthalene, 1,8-bis(methoxymethyl)anthracene, 2,2'-bis(methoxymethyl)diphenyl ether, 4,4'-bis(methoxymethyl)diphenyl Ether, 4,4'-bis(methoxymethyl)diphenyl sulfide, 4,4'-bis(methoxymethyl)benzophenone, 4-methoxymethylbenzoic acid-4' -Methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'-methoxymethylaniline, 4,4'-bis(methoxymethyl)phenylurea, 4,4' -Bis(methoxymethyl)phenylcarbamate, 1,8-bis(methoxymethyl)anthracene, 4,4'-bis(methoxymethyl)biphenyl, 2,2 '-Dimethyl-4,4'-bis(methoxymethyl)biphenyl, 2,2-bis(4-methoxymethylphenyl)propane, ethylene glycol dimethyl ether, diethylenedioxide Alcohol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, etc. Examples of the diene compounds include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, and 1,3-butanediol. -Dimethacrylate, 2,4-hexadien-1-ol, methylcyclohexadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentadiene Ene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2, 5-northrene, tetrahydroindene, 5-ethylene-2-northene, 5-vinyl-2-northene, triallyl cyanurate, isocyanuric diene Propyl ester, triallyl isocyanurate, diallyl isocyanurate, etc. Examples of the above-mentioned haloalkyl compounds include dichloroxylene, bischloromethyldimethoxybenzene, bischloromethyl mesitylene, bischloromethylbiphenyl, and bischloromethyl-biphenylcarboxy Acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, bischloromethyl-dimethylbiphenyl, bischloromethylanthracene, ethylene glycol bis(chloroethyl) Ether, diethylene glycol bis(chloroethyl) ether, triethylene glycol bis(chloroethyl) ether, tetraethylene glycol bis(chloroethyl) ether, etc. (A) Phenolic resin can be obtained by condensing the above-mentioned phenol compound and copolymerization component by dehydration, dehydrohalogenation, or dealcoholization, or breaking the unsaturated bond, while using a catalyst during polymerization . Examples of acidic catalysts include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylene -1,1'-bisphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride-phenol complex, boron trifluoride-ether complex, etc. On the other hand, examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N,N- Dimethylaminopyridine, piperidine, piperidine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, 1 ,5-diazabicyclo[4.3.0]-5-nonene, ammonia, hexamethylenetetramine, etc. The amount of catalyst used to obtain a phenol resin having a repeating structure represented by the general formula (7) is preferably an aldehyde compound or a ketone compound with respect to the total number of moles of copolymerization components (that is, components other than phenol compounds) , The total number of moles of methylol compounds, alkoxymethyl compounds, diene compounds and haloalkyl compounds is 100 mole%, preferably in the range of 0.01 mole% to 100 mole%. (A) In the synthesis reaction of phenol resin, the reaction temperature is usually preferably 40°C to 250°C, more preferably 100°C to 200°C, and the reaction time is preferably about 1 hour to 10 hours. If necessary, a solvent that can sufficiently dissolve the resin can be used. In addition, the phenol resin having the repeating structure represented by the general formula (7) may be a phenol compound that is polymerized with a raw material that does not become the structure of the general formula (7) within a range that does not impair the effects of the present invention. The range that does not impair the effect of the present invention is, for example, 30% or less of the total number of moles of the phenol compound that becomes the raw material of the (A) phenol resin. (Phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms) Phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms is phenol or its derivative and having 4 to 4 carbon atoms Polycondensation products of reaction products (hereinafter also referred to as "unsaturated hydrocarbon group modified phenol derivatives") and aldehydes of 100 unsaturated hydrocarbon group compounds (hereinafter sometimes referred to as "unsaturated hydrocarbon group-containing compounds"), or It is the reaction product of phenol resin and unsaturated hydrocarbon group-containing compound. The phenol derivative may be the same as the phenol derivative described above as the raw material of the phenol resin having the repeating unit represented by the general formula (7). Regarding the unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound, from the viewpoint of the residual stress of the cured film and the applicability of the reflow soldering treatment, it is preferable to include two or more unsaturated groups. In addition, from the viewpoint of compatibility and residual stress of the cured film when forming the resin composition, the unsaturated hydrocarbon group preferably has a carbon number of 4 to 100, more preferably a carbon number of 8 to 80, and further preferably a carbon number 10～60. Examples of the unsaturated hydrocarbon group-containing compound include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linoleyl alcohol, oleyl alcohol, unsaturated fatty acids and unsaturated fats Acid ester. Examples of suitable unsaturated fatty acids include butenoic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, isoleic acid, cod oleic acid, erucic acid, tetracosenoic acid, and linoleic acid. , Α-linolenic acid, tungstic acid, octadecadecanoic acid, arachidonic acid, eicosapentaenoic acid, herring acid and docosahexaenoic acid. Among these, particularly from the viewpoint of the elongation of the cured film and the flexibility of the cured film, vegetable oils as unsaturated fatty acid esters are particularly preferred. Vegetable oils usually contain esters of glycerin and unsaturated fatty acids. There are non-drying oils with an iodine value of 100 or less, semi-drying oils of more than 100 and less than 130, or dry oils of 130 or more. Examples of non-drying oils include olive oil, morning glory seed oil, Polygonum multiflorum oil, tea plum oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of the drying oil include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, razor seed oil, and mustard oil. Furthermore, processed vegetable oils processed from these vegetable oils can also be used. Among the vegetable oils described above, it is preferable to use non-drying oils from the viewpoint of preventing gelation caused by excessive reaction during the reaction of phenol or its derivative or phenol resin with vegetable oil, and improving yield. On the other hand, from the viewpoint of improving the adhesion, mechanical characteristics, and thermal shock resistance of the resist pattern, it is preferable to use a dry oil. Among the dry oils, in terms of more effective and reliable effects of the present invention, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are preferred, and tung oil and linseed oil are more preferred. These vegetable oils can be used alone or in combination of two or more. The reaction of phenol or its derivative with a compound containing an unsaturated hydrocarbon group is preferably carried out at 50 to 130°C. Regarding the reaction ratio of phenol or its derivatives and unsaturated hydrocarbon group-containing compound, from the viewpoint of reducing the residual stress of the cured film, the unsaturated hydrocarbon group-containing compound is preferably 1 relative to 100 parts by mass of phenol or its derivative. ~100 parts by mass, more preferably 5-50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. may be used as a catalyst as necessary. The unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction is subjected to polycondensation with aldehydes, thereby generating a phenol resin modified with an unsaturated hydrocarbon group-containing compound. Aldehydes such as formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde , Acetone, glyceraldehyde, glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, methyl acetic acid, methyl methyl acetyl acetate, 2-methyl acetyl propionic acid, 2 -Methyl methyl propionate, pyruvic acid, acetyl propionic acid, 4-acetyl butyric acid, acetone dicarboxylic acid and 3,3'-4,4'-benzophenone tetracarboxylic acid. In addition, formaldehyde precursors such as paraformaldehyde and trioxane can also be used. These aldehydes can be used alone or in combination of two or more. The reaction between the aldehydes and the unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and previously known synthesis conditions of phenol resins can be used. The reaction is preferably carried out in the presence of a catalyst such as an acid or an alkali. From the viewpoint of the degree of polymerization (molecular weight) of the resin, it is more preferable to use an acid catalyst. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used alone or in combination of two or more. The above reaction is usually preferably carried out at a reaction temperature of 100 to 120°C. In addition, the reaction time varies depending on the type or amount of catalyst used, and is usually 1 to 50 hours. After the reaction is completed, a phenol resin modified with an unsaturated hydrocarbon group-containing compound is obtained by dehydrating the reaction product under reduced pressure at a temperature of 200° C. or lower. Furthermore, solvents such as toluene, xylene, and methanol can be used for the reaction. The phenol resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by subjecting a compound other than phenol such as m-xylene and aldehydes to polycondensation with the unsaturated hydrocarbon group-modified phenol derivative. In this case, the addition mole of the compound other than phenol to the compound obtained by reacting the phenol derivative with the unsaturated hydrocarbon group-containing compound is preferably less than 0.5. The phenol resin modified with the unsaturated hydrocarbon group-containing compound can also be obtained by reacting the phenol resin with the unsaturated hydrocarbon group-containing compound. The phenol resin used in this case is a polycondensation product of a phenol compound (ie, phenol and/or phenol derivative) and aldehydes. In this case, as the phenol derivatives and aldehydes, the same ones as the above phenol derivatives and aldehydes can be used, and the phenol resin can be synthesized under the previously known conditions as described above. Specific examples of phenol resins obtained from phenol compounds and aldehydes suitable for forming phenol resins modified with unsaturated hydrocarbon group-containing compounds include phenol/formaldehyde novolak resins and cresol/formaldehyde novolak resins. , Resorcinol/formaldehyde novolak resin, resorcinol/formaldehyde novolak resin and phenol-naphthol/formaldehyde novolak resin. The unsaturated hydrocarbon group-containing compound that reacts with the phenol resin can be the same as the above-mentioned unsaturated hydrocarbon group-containing compound that participates in the production of the unsaturated hydrocarbon group-modified phenol derivative that reacts with aldehydes. The reaction of the phenol resin and the unsaturated hydrocarbon group-containing compound is usually preferably carried out at 50 to 130°C. Further, regarding the reaction ratio of the phenol resin and the unsaturated hydrocarbon group-containing compound, from the viewpoint of improving the flexibility of the cured film (resist pattern), the unsaturated hydrocarbon group-containing compound is preferable to 100 parts by mass of the phenol resin. It is 1 to 100 parts by mass, more preferably 2 to 70 parts by mass, and still more preferably 5 to 50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, there is a tendency for the flexibility of the cured film to decrease. If it exceeds 100 parts by mass, there is a tendency that the possibility of gelation during the reaction becomes high, and the cured film The heat resistance tends to decrease. When the phenol resin reacts with the unsaturated hydrocarbon group-containing compound, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. can also be used as a catalyst as needed. In addition, solvents such as toluene, xylene, methanol, and tetrahydrofuran can be used for the reaction, which will be described in detail below. An acid-modified phenol resin can also be used by reacting a phenolic hydroxyl group remaining in a phenol resin modified with an unsaturated hydrocarbon group-containing compound produced by the above method and reacting with a polybasic acid anhydride. By acid modification with a polybasic acid anhydride to introduce a carboxyl group, the solubility in an alkaline aqueous solution (used as a developer) is further improved. The polyanhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of the carboxyl group of the polyacid containing a plurality of carboxyl groups. Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, and hexahydrogen Phthalic Anhydride, Methyl Tetrahydrophthalic Anhydride, Methyl Hexahydrophthalic Anhydride, Diacid Anhydride, 3,6-Nimethylene Tetrahydrophthalic Anhydride, Methyl Nya Dibasic acid anhydrides such as methyltetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride Anhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride and other aromatic tetrabasic acid dianhydride. These can be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more kinds selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, there is an advantage that a better-shaped resist pattern can be formed. The reaction of phenolic hydroxyl group and polybasic acid anhydride can be carried out at 50～130℃. In this reaction, it is preferred to react a polyanhydride of 0.10 to 0.80 moles relative to 1 mole of phenolic hydroxyl groups, more preferably to react 0.15 to 0.60 moles, and more preferably to 0.20 to 0.40 moles. The ear reacts. If the polyacid anhydride is less than 0.10 moles, the developability tends to decrease, and if it exceeds 0.80 moles, the alkali resistance of the unexposed portion tends to decrease. Furthermore, from the viewpoint of making the reaction proceed quickly, the above reaction may contain a catalyst as necessary. Examples of the catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine. . Further, the acid value of the phenol resin modified with polybasic acid anhydride is preferably 30 to 200 mgKOH/g, more preferably 40 to 170 mgKOH/g, and still more preferably 50 to 150 mgKOH/g. If the acid value is less than 30 mgKOH/g, there is a tendency for the alkaline development time to be longer than when the acid value is in the above range, and if it exceeds 200 mgKOH/g, it is similar to the case where the acid value is in the above range There is a tendency for the developer resistance of the unexposed portion to decrease. The molecular weight of the phenol resin modified with an unsaturated hydrocarbon group-containing compound is preferably 1,000 to 100,000 in terms of weight average molecular weight in consideration of the solubility in an alkaline aqueous solution or the balance between the photosensitive characteristics and the physical properties of the cured film. Preferably, it is 2000 to 100,000. As the (A) phenol resin of this embodiment, it is also preferably selected from phenol resins having a repeating unit represented by the above general formula (7) and the above compounds modified with an unsaturated hydrocarbon group having a carbon number of 4 to 100 A mixture of at least one phenol resin (hereinafter also referred to as (a3) resin) and a phenol resin selected from novolac and polyhydroxystyrene (hereinafter also referred to as (a4) resin). (a3) The mixing ratio of the resin and (a4) resin is in the range of (a3)/(a4)=5/95 to 95/5 in terms of mass ratio. The mixing ratio is preferably (a3)/(in terms of solubility in an alkaline aqueous solution, sensitivity and resolution when forming a resist pattern, residual stress of a cured film, and applicability of reflow soldering treatment) a4)=5/95 to 95/5, more preferably (a3)/(a4)=10/90 to 90/10, further preferably (a3)/(a4)=15/85 to 85/15. Regarding the novolak and polyhydroxystyrene as the above-mentioned (a4) resin, the same resins as those shown in the above (novolac) and (polyhydroxystyrene) can be used. (B) Plasticizer Hereinafter, (B) the plasticizer in this embodiment will be described in detail. (B) The plasticizer is used to improve (A) the fluidity of the resin and increase the (A) the polymer bulk of the resin when the relief pattern formed using the photosensitive resin composition of this embodiment is heat-cured Compound. By improving the stackability, it is possible to suppress the occurrence of voids in the high-temperature storage test, and to suppress the decrease in the adhesion at the interface between the Cu layer and the resin layer. (B) The plasticizer is not particularly limited as long as it meets the above conditions. Regarding the compound that functions as a (B) plasticizer, the following general formula (7) can be preferably used: [Chem. 80]

{In the formula, X is a structure containing saturated or unsaturated hydrocarbons or aromatic hydrocarbons having a carbon number of 1 or more and 15 or less, n is an integer of 1 to 4, and when n is 2 or more, R may be the same It may be different, and it is a compound represented by saturated or unsaturated hydrocarbons or aromatic hydrocarbons having a carbon number of 2 or more and 15 or less. Among them, as the plasticizer of the present invention, it is preferably selected from the following general formula (8):

{In the formula, m is an integer of 1 to 4, and when m is 2 or more, R may be the same or different, indicating a saturated or unsaturated hydrocarbon or aromatic hydrocarbon with a carbon number of 2 or more and 15 or less} Represented by, or the following general formula (9): [Chem 82]

{In the formula, Y is a structure containing a saturated hydrocarbon or an unsaturated hydrocarbon or an aromatic hydrocarbon having a carbon number of 1 or more and 10 or less, and R may be the same or different, and represents a saturated hydrocarbon or a carbon number of 2 or more and 15 or less At least one of the group consisting of unsaturated hydrocarbons or aromatic hydrocarbons. Examples of the plasticizer represented by the general formula (7) include benzoate, phthalate, isophthalate, terephthalate, trimellitate, and Pyromellitic acid ester and fatty acid tetrahydrofurfuryl ester etc. Specific examples of benzoate compounds include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, amyl benzoate, heptyl benzoate, n-octyl benzoate, Nonyl benzoate, isononyl benzoate, isodecyl benzoate, 2-ethylhexyl benzoate, isodecyl benzoate, butyl benzyl benzoate, cyclopropyl benzoate, cyclobutyl benzoate , Cyclopentyl benzoate, cyclohexyl benzoate, cycloheptyl benzoate, allyl benzoate, butyl benzyl benzoate, phenyl benzoate. Among them, 2-ethylhexyl benzoate, cyclohexyl benzoate, and phenyl benzoate are particularly suitable. Specific examples of phthalate compounds include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, and o-benzene Dipentyl dicarboxylate, diheptyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, ortho Bis(2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, dicyclopropyl phthalate, dicyclobutyl phthalate, ortho Dicyclopentyl phthalate, dicyclohexyl phthalate, dicycloheptyl phthalate, diallyl phthalate, dibutyl benzyl phthalate, diphthalic phthalate Phenyl ester. Among them, bis(2-ethylhexyl) phthalate, dicyclohexyl phthalate, and diphenyl phthalate are particularly suitable. Specific examples of isophthalate compounds include dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, and isobenzene Dipentyl dicarboxylate, diheptyl isophthalate, di-n-octyl isophthalate, dinonyl isophthalate, diisononyl isophthalate, diisodecyl isophthalate, m Bis(2-ethylhexyl) phthalate, diisodecyl isophthalate, butyl benzyl isophthalate, dicyclopropyl isophthalate, dicyclobutyl isophthalate, m Dicyclopentyl phthalate, dicyclohexyl isophthalate, dicycloheptyl isophthalate, diallyl isophthalate, dibutyl benzyl isophthalate, diisophthalate Phenyl ester. Among them, bis(2-ethylhexyl) isophthalate, dicyclohexyl isophthalate, and diphenyl isophthalate are particularly suitable. Examples of specific compounds of terephthalate include dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, and p-benzene Dipentyl dicarboxylate, diheptyl terephthalate, di-n-octyl terephthalate, dinonyl terephthalate, diisononyl terephthalate, diisodecyl terephthalate, para Bis(2-ethylhexyl) phthalate, diisodecyl terephthalate, butyl benzyl terephthalate, dicyclopropyl terephthalate, dicyclobutyl terephthalate, para Dicyclopentyl phthalate, dicyclohexyl terephthalate, dicycloheptyl terephthalate, diallyl terephthalate, dibutyl benzyl terephthalate, dibutyl terephthalate Phenyl ester. Among them, bis(2-ethylhexyl) terephthalate, dicyclohexyl terephthalate, and diphenyl terephthalate are particularly suitable. Examples of specific compounds of trimellitate include trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, and trimellitate Tripentyl formate, triheptyl trimellitate, tri-n-octyl trimellitate, trinonyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate, partial benzene Tris(2-ethylhexyl) tricarboxylate, triisodecyl trimellitate, tributyl benzyl trimellitate, tricyclopropyl trimellitate, tricyclobutyl trimellitate, partial Tricyclopentyl trimellitate, tricyclohexyl trimellitate, tricycloheptyl trimellitate, triallyl trimellitate, tributyl benzyl trimellitate, tri trimellitate Phenyl ester. Among them, tris(2-ethylhexyl) trimellitate, tricyclohexyl trimellitate, and triphenyl trimellitate are particularly suitable. Examples of specific compounds of pyromellitic acid esters include tetramethyl pyromellitic acid, tetraethyl pyromellitic acid, tetrapropyl pyromellitic acid, tetrabutyl pyromellitic acid, and homobenzene Tetrapentyl tetracarboxylic acid, tetraheptyl pyromellitic acid, tetra-n-octyl pyromellitic acid, tetranonyl pyromellitic acid, tetraisononyl pyromellitic acid, tetraisodecyl pyromellitic acid, homo Tetra (2-ethylhexyl) pyromellitic acid, tetraisodecyl pyromellitic acid, tetrabutyl benzyl pyromellitic acid, tetracyclopropyl pyromellitic acid, tetracyclobutyl pyromellitic acid, Tetracyclopentyl pyromellitic acid, tetracyclohexyl pyromellitic acid, tetracycloheptyl pyromellitic acid, tetraallyl pyromellitic acid, tetrabutyl benzyl pyromellitic acid, pyromellitic acid Tetraphenylester. Among them, tetrakis(2-ethylhexyl) pyromellitic acid, tetracyclohexyl pyromellitic acid, and tetraphenyl pyromellitic acid are particularly suitable. As the plasticizer represented by the above general formula (8), malonate, succinate, glutarate, adipate, pimelate, suberate, azelate, Sebacate, etc. Examples of specific compounds of malonate include dimethyl malonate, diethyl malonate, dipropyl malonate, dibutyl malonate, dipentyl malonate, and malonate. Diheptyl diacid, di-n-octyl malonate, dinonyl malonate, diisononyl malonate, diisodecyl malonate, bis(2-ethylhexyl) malonate, Diisodecyl malonate, butyl benzyl malonate, dicyclopropyl malonate, dicyclobutyl malonate, dicyclopentyl malonate, dicyclohexyl malonate, malonate Dicycloheptyl acid, diallyl malonate, dibutylbenzyl malonate, diphenyl malonate. Among them, bis(2-ethylhexyl) malonate, dicyclohexyl malonate, and diphenyl malonate are particularly suitable. Specific examples of compounds of succinate include dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dipentyl succinate, diheptyl succinate, and succinate Di-n-octyl acid, dinonyl succinate, diisononyl succinate, diisodecyl succinate, bis(2-ethylhexyl) succinate, diisodecyl succinate, butylbenzyl succinate Ester, dicyclopropyl succinate, dicyclobutyl succinate, dicyclopentyl succinate, dicyclohexyl succinate, dicycloheptyl succinate, diallyl succinate, dibutylbenzyl succinate Ester, diphenyl succinate. Among them, bis(2-ethylhexyl) succinate, dicyclohexyl succinate, and diphenyl succinate are particularly suitable. Examples of specific compounds of glutaric acid esters include dimethyl glutarate, diethyl glutarate, dipropyl glutarate, dibutyl glutarate, dipentyl glutarate, and glutaric acid. Diheptyl diacid, di-n-octyl glutarate, dinonyl glutarate, diisononyl glutarate, diisodecyl glutarate, bis(2-ethylhexyl) glutarate, Diisodecyl glutarate, butyl benzyl glutarate, dicyclopropyl glutarate, dicyclobutyl glutarate, dicyclopentyl glutarate, dicyclohexyl glutarate, glutarate Dicycloheptyl acid, diallyl glutarate, dibutyl benzyl glutarate, diphenyl glutarate. Among them, bis(2-ethylhexyl) glutarate, dicyclohexyl glutarate, and diphenyl glutarate are particularly suitable. Examples of specific compounds of adipate include dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dipentyl adipate, and hexane. Diheptyl diacid, di-n-octyl adipate, dinonyl adipate, diisononyl adipate, diisodecyl adipate, bis(2-ethylhexyl) adipate, Diisodecyl adipate, butyl benzyl adipate, dicyclopropyl adipate, dicyclobutyl adipate, dicyclopentyl adipate, dicyclohexyl adipate, adipic acid Dicycloheptyl acid, diallyl adipate, dibutylbenzyl adipate, diphenyl adipate. Among them, bis(2-ethylhexyl) adipate, dicyclohexyl adipate, and diphenyl adipate are particularly suitable. Examples of specific compounds of pimelate include dimethyl pimelate, diethyl pimelate, dipropyl pimelate, dibutyl pimelate, dipentyl pimelate, and heptane Diheptyl diacid, di-n-octyl pimelate, dinonyl pimelate, diisononyl pimelate, diisodecyl pimelate, bis(2-ethylhexyl) pimelate, Diisodecyl pimelate, butyl benzyl pimelate, dicyclopropyl pimelate, dicyclobutyl pimelate, dicyclopentyl pimelate, dicyclohexyl pimelate, pimelic acid Dicycloheptyl acid, diallyl pimelate, dibutyl benzyl pimelate, diphenyl pimelate. Among them, bis(2-ethylhexyl) pimelate, dicyclohexyl pimelate, and diphenyl pimelate are particularly suitable. Examples of specific compounds of suberic acid esters include dimethyl suberate, diethyl suberate, dipropyl suberate, dibutyl suberate, dipentyl suberate, and octyl. Diheptyl diacid, di-n-octyl suberate, dinonyl suberate, diisononyl suberate, diisodecyl suberate, bis(2-ethylhexyl) suberate, Diisodecyl suberate, butyl benzyl suberate, dicyclopropyl suberate, dicyclobutyl suberate, dicyclopentyl suberate, dicyclohexyl suberate, suberic Dicycloheptyl acid, diallyl suberate, dibutyl benzyl suberate, diphenyl suberate. Among them, bis(2-ethylhexyl) suberate, dicyclohexyl suberate, and diphenyl suberate are particularly suitable. Examples of specific compounds of azelaic acid esters include dimethyl azelate, diethyl azelate, dipropyl azelate, dibutyl azelate, dipentyl azelate, and nonane Diheptyl diacid, di-n-octyl azelate, dinonyl azelate, diisononyl azelate, diisodecyl azelate, bis(2-ethylhexyl) azelate, Diisodecyl azelate, butyl benzyl azelate, dicyclopropyl azelate, dicyclobutyl azelate, dicyclopentyl azelate, dicyclohexyl azelate, azela Dicycloheptyl acid, diallyl azelate, dibutyl benzyl azelate, diphenyl azelate. Among them, bis(2-ethylhexyl) azelate, dicyclohexyl azelate, and diphenyl azelate are particularly preferably used. Examples of specific compounds of sebacate include dimethyl sebacate, diethyl sebacate, dipropyl sebacate, dibutyl sebacate, dipentyl sebacate, and decane Diheptyl diacid, di-n-octyl sebacate, dinonyl sebacate, diisononyl sebacate, diisodecyl sebacate, bis(2-ethylhexyl) sebacate, Diisodecyl sebacate, butyl benzyl sebacate, dicyclopropyl sebacate, dicyclobutyl sebacate, dicyclopentyl sebacate, dicyclohexyl sebacate, sebacic acid Dicycloheptyl acid, diallyl sebacate, dibutyl benzyl sebacate, diphenyl sebacate. Among them, bis(2-ethylhexyl) sebacate, dicyclohexyl sebacate, and diphenyl sebacate are particularly suitable. Examples of specific compounds of the tetrahydrofurfuryl fatty acid ester include tetrahydrofurfuryl formate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, and tetrahydrofurfuryl isobutyrate. , Tetrahydrofurfuryl valerate, Tetrahydrofurfuryl isovalerate, Tetrahydrofurfuryl hexanoate, etc. Among them, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, and tetrahydrofurfuryl isobutyrate are particularly suitable. The content of the plasticizer (B) is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and still more preferably 1 to 30 parts by mass relative to 100 parts by mass of the resin (A). If the content is more than this range, the glass transition temperature is lowered, which is unsatisfactory. If the content is less than this range, sufficient plasticization cannot be obtained, and voids are easily generated with the copper surface. The role of the plasticizer (B) in this embodiment is to increase (A) the fluidity of the resin and improve (A) when heating and curing the relief pattern formed using the photosensitive resin composition of this embodiment. ) The stackability of the resin polymer. By this, a strong cured film can be obtained, voids can be suppressed during the high-temperature storage test, and the decrease in the adhesion at the interface between the Cu layer and the resin layer can be suppressed. The photosensitive resin composition of this embodiment may contain any one of (B-1) nanoparticles, (B-2) thermal crosslinking agent, and (B-3) fluorine-containing hydrophobic compound instead of (B) Plasticizer or used together. By combining a photosensitive resin with specific (B-1) nanoparticles, (B-2) thermal crosslinking agent, or (B-3) fluorine-containing hydrophobic compound, a photosensitive resin combination can be provided And the method of forming a hardened relief pattern using the photosensitive resin composition, the photosensitive resin composition can be obtained after a high temperature storage test, at the interface between the Cu layer and the resin layer A photosensitive resin that has voids and has high adhesion. (B-1) Nanoparticles (B-1) Nanoparticles are solid at room temperature, and from the viewpoint of light transmittance are particles having an average primary particle diameter of 1 μm or less, preferably 300 nm or less. The primary particle size can be obtained by SEM observation or laser diffraction. In addition, from the viewpoint of Cu migration resistance during HTS, it is preferably plate-like, scaly, needle-like or fibrous particles with an aspect ratio of 5 or more, and from the viewpoint of compatibility with (A) resin It is preferable to use a silane coupling agent or the like for surface treatment. Furthermore, from the viewpoint of water resistance, the nanoparticles preferably include oxides, composite oxides, doped oxides, oxyacids, oxyacid salts, nitrides, carbides, or sulfides. Examples of the (B-1) nanoparticles usable in the present invention include SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZrO ₂ , HfO ₂ , V ₂ O ₅ , WO ₃ , In ₂ O ₃ , SnO ₂ , Sb ₂ O ₃ , Nb ₂ O ₅ , MoO ₃ , Fe ₂ O ₃ , CuO, ZnO, CaO, MgO, Aerosil, silica alumina, mica, montmorillonite, talc, clay, gibbsite, kaolin, (poly) zirconium phosphate, barium titanate, calcium carbonate, (poly) Zirconium tungstate, PZT (Lead Zirconium Titanate), glass, aluminum borate, aluminum nitride, titanium nitride, silicon nitride, boron nitride, or a mixture of these. By adding nanoparticles, the coefficient of thermal expansion of the photosensitive resin can be reduced. The reduction in thermal expansion coefficient suppresses the thermal expansion of the resin during the high-temperature storage test, and suppresses the occurrence of copper migration. In this case, as nanoparticles, those with a relatively high aspect ratio can reduce the coefficient of thermal expansion by adding a smaller amount, which is preferable. In addition, those with a relatively high aspect ratio tend to have fewer voids on the copper surface, and tend to have better developability or chemical resistance, which is better. From the viewpoint of the number of voids on the copper surface, developability, or chemical resistance, the aspect ratio of the nanoparticles is preferably greater than 1, the aspect ratio is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more. The aspect ratio is more preferably 5 or more, more preferably 8 or more, more preferably 10 or more, more preferably 12 or more, more preferably 15 or more, and particularly preferably 20 or more. The aspect ratio represents the value of the length of the long axis/length of the short axis of the nanoparticles. When the nanoparticles are standard spheres, the aspect ratio becomes 1. When the nanoparticle is not a standard sphere or a standard ellipsoid, the diameter of the smallest sphere that can completely enclose the nanoparticle in the inner sphere is used as the long axis of the nanoparticle to be completely contained in the nanoparticle The diameter of the largest sphere in the size sphere inside the rice particle serves as the short axis of the nanoparticle. The formulation amount of (B-1) nanoparticles is 0.1 to 50 parts by mass, preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of (A) resin. From the viewpoint of migration resistance, it is more preferably 0.1 part by mass or more, and from the viewpoint of solubility, it is more preferably less than 50 parts by mass. (B-2) Thermal crosslinking agent The (B-2) thermal crosslinking agent used in the present invention will be described. (B-2) Thermal cross-linking agent means that when the relief pattern formed using the photosensitive resin composition of this embodiment is heat-cured, it can cross-link with (A) the resin or the cross-linking agent itself. Network-like compounds. (B) The thermal crosslinking agent is not particularly limited as long as it satisfies the above conditions, and it is preferably any of the following (B-2-1) to (B-2-12). (B-2-1) Compound containing hydroxymethyl and/or alkoxymethyl group The so-called compound containing hydroxymethyl and/or alkoxymethyl group contains the following general formula (TS2) in the molecule: 83]

{In the formula, Rs3 is a monovalent organic group or a hydrogen atom} A compound represented by an organic group. Specifically, the following general formula (TS1) can be cited: [Chem 84]

{In the formula, Rs1 is a hydrogen atom, a monovalent group selected from the group consisting of methyl, ethyl, n-propyl, and isopropyl, and Rs2 is selected from the group consisting of a hydroxyl group and an alkyl group having 1 to 10 carbon atoms. , A group consisting of an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a carbamate group, mm1 is an integer of 1 to 5, mm2 is 0 to 4 An integer. Here, 1≦(mm1+mm2)≦5, nn1 is an integer from 1 to 4, V ₁ CH when nn1=1 ₂ ORs1, when nn1=2~4, it is a single bond or an organic group of 2~4 valence. Yu CH ₂ ORs1 and R ₁₀ When there are multiple situations, these may be the same or different}, and the general formulas (TS3) and (TS4): [化85]

{In the formula, Rs3 and Rs4 are independently a hydrogen atom and a monovalent organic group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms} [Chem 86]

{In the formula, Rs5 is independently a hydrogen atom and a monovalent organic group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms} N-hydroxymethyl compound and N-alkoxy group represented by the structure Methyl group, etc., but not limited to these. Preferred examples include: Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300, Micoat 102, 105 (above manufactured by Mitsui Cytec), NIKALAC (registered trademark) MX-270, -280, -290, NIKALAC MS-11, NIKALAC MW-30, -100, -300,- 390, -750 (made by SANWA CHEMICAL), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML-PTBP, DML-PCHP, DML-POP, DML -PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAFMF, TM-BIP-A , HMOM-TP-HAP (above manufactured by the State Chemical Industry Company), benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether , Bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylphenyl ester, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl) Group) benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenyl Benzophenone, methoxymethyl benzoic acid methoxymethyl phenyl ester, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, novolac hydroxymethyl Incarnation, etc. Among them, those having the structure represented by the above general formula (12) are more preferable, and specific examples include DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, and DML -PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM -BPA, TML-BPAFMF, TM-BIP-A, HMOM-TP-HAP (manufactured above by Honshu Chemical Industry Co., Ltd.), benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxy Benzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylphenyl ester, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxyl) Methyl) biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)bis Phenyl ether, bis (methoxymethyl) benzophenone, methoxymethyl benzoic acid methoxymethyl phenyl ester, bis (methoxymethyl) biphenyl, dimethyl bis (methoxy) Methyl) biphenyl and novolac hydroxymethylated form. Among these, particularly preferred are TMOM-BP, TMOM-BPA, TML-BPAFMF, TM-BIP-A, HMOM-TP-HAP. (B-2-2) Ethylene oxide compound As the ethylene oxide (epoxy) compound, there is no particular limitation as long as it contains an epoxy group in the molecule, and specific examples include phenol novolak Type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, triphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-benzene Dimethyl epoxy resin, phenol-naphthol epoxy resin, phenol-dicyclopentadiene epoxy resin, alicyclic epoxy resin, chain aliphatic epoxy resin, diethylene glycol dishrinkage Glycerol ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether, glycerol triglyceride Glycidyl ether, o-second butyl phenyl glycidyl ether, 1,6-bis(2,3-glycidoxy)naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB- 340, YDB-412, YDF-2001, YDF-2004 (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), GAN, GOT, NC-3000-H, EPPN-501H, EPPN-502H, EOCN-1020, NC -6000, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (trade name, manufactured by Nippon Kayaku Co., Ltd.), Epikote (registered trademark) 1001, Epikote 1007, Epikote 1009, Epikote 5050, Epikote 5051, Epikote 1031S, Epikote 180S65, Epikote 157H70, YX-315-75 (trade name, manufactured by Japan Epoxy Resins Co., Ltd.), EHPE3150, PLACCEL G402, PUE101, PUE105 (trade name, manufactured by Diacel Chemical Industries Co., Ltd.), EPICLON ( Registered trademark) 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-850CRP, 860, EXA-4701, EXA-4850-1000 (commodity Name, manufactured by DIC), DENACOL (registered trademark) EX-201, EX-212L, EX-214L, EX-216L, EX-251, EX-203, EX-313, EX-314, EX-321, EX- 411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-711, EX-731, EX-810, EX-850L, EX-911, EM-150 (trade name, Nagase che mteX), Epolight (registered trademark) 70P, 40E, 100E, 100MF, 200E, 400E, 200P, 400P, 1500NP, 80MF, 4000, 3002 (trade name, manufactured by Kyoeisha Chemical), jER (registered trademark) 828 , 834, 1001, 1002, 1003, 1004, 1005, 1007, 1010, 1100L, 630, ESCN-220L, 220F, 220H, 220HH, 180H65, 1032H60, YX4000H, 152, 157S70, 1031 (manufactured by Mitsubishi Chemical), Adeka Resin (Registered trademark) EP-4000s, EP-4003s (manufactured by Adeka), etc. Among these, from the viewpoint of reliability after the HTS test, particularly preferred are triglycidyl isocyanurate, EPICLON 830, 850, 1050, N-680, N-690, N-695, N -770, HP-7200, HP-820, EXA-4850-1000, DENACOL EX-201, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, Epoxy compounds of EX-614, EX-614B, EX-731, EX-810, EX-911, and EM-150. (B-2-3) As the isocyanate group-containing compound, the isocyanate group-containing compound is not particularly limited as long as the compound contains an isocyanate group in the molecule. From the viewpoint of reliability after the HTS test, it is preferably 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 1,3-xylylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexa Asia Methyl diisocyanate, Takenate (registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, ND (trade name, manufactured by Mitsui Chemicals) Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF- K60X, E402-B80T (trade name, manufactured by Asahi Kasei Chemicals), etc. (B-2-4) bis-cis-butadiene diimide compound As the bis-cis-butadiene diimide compound, as long as it is a compound containing a cis-butadiene diimide group in its molecule, there is no particular limitation. From the viewpoint of reliability after the HTS test, 4,4'-diphenylmethane bis-cis-butadiene diimide, phenylmethane-cis-butadiene-diimide, and m-phenylene bis-cis-butane are preferred Enildiimide, bisphenol A diphenyl ether bis-cis-butenediimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane biscis Butene diimide, 4-methyl-1,3-phenylene bis-cis-butadiene diimide, 1,6'-bis-cis-butadiene diimide-(2,2,4-tri Methyl) hexane, 4,4'-diphenyl ether bis-cis-butadiene diimide, 4,4'-diphenyl bis-cis-butadiene di-imide, 1,3-bis(3-cis Butenediimidephenoxy)benzene, 1,3-bis(4-cisbutadieneimidephenoxy)benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI -3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (trade name, manufactured by Daiwa Chemical Industry Co., Ltd.), etc. (B-2-5) Compounds containing aldehyde groups are not particularly limited as long as they are compounds containing aldehyde groups in the molecule, and from the viewpoint of reliability after HTS test, it is preferably Formaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde , M-tolualdehyde, p-tolualdehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, m-phthalaldehyde, hexamethylenetetramine, trioxane, malondialdehyde, succinic acid Aldehyde and so on. (B-2-6) Compound containing oxetane ring The compound called oxetane ring contains the following formula: [Chem 87]

The compound represented by the divalent base. The compound containing an oxetane ring is not particularly limited as long as it contains an oxetanyl group in the molecule, and examples include 1,4-bis{[(3-ethyl-3-oxetanyl )Methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)] methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl) Methoxymethyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl ) Ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, bis(3-ethyl-3-oxetanylmethyl) diphenolate, trimethylolpropane tris (3-ethyl-3-oxetanyl methyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanyl methyl) ether, 3-ethyl-3{[(3-ethyloxetan Butane-yl)methoxy]methyl}oxetane, 3-ethyl-3-hydroxymethyloxetane (OXT-101), 2-ethyl Hexyl oxetane (OXT-212), xylylene dioxetane (OXT-121), 3-ethyl-3-{[(3-ethyloxetane-3- Group) methoxy] methyl} oxetane (OXT-221), OX-SQ-H, OXT-191, PNOX-1009, RSOX, the following: [Chem 88]

, Etanacol EHO, OXBP, OXMA, OXIPA, HBOX, OXTP, etc. Among them, OXBP, OXIPA, OXT-121, and OXT-221 are preferred from the viewpoint of solubility in the developer and elongation of the obtained cured film. (B-2-7) As a compound containing a benzo 㗁𠯤 ring, as long as it is a compound containing a benzo 㗁𠯤 ring in the molecule, there is no particular limitation, and it is reliable after the HTS test From the viewpoint of sex, the compounds disclosed in Japanese Patent Laid-Open No. 2006-335671, and bisphenol F-type benzo BF-BXZ, bisphenol A-type benzo 㗁𠯤 BA-BXZ, bisphenol are preferred S type benzo 㗁𠯤 BS-BXZ (trade name, manufactured by Konishi Chemical Industry), etc. (B-2-8) Compound containing oxazoline ring As the compound containing oxazoline ring, as long as it is a compound containing oxazoline ring in the molecule, it is not particularly limited, and examples include 2-oxazoline, 2-amino-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, 1,4- Bis(4,5-dihydro-2-oxazolyl)benzene, 1,3,5-tris(4,5-dihydro-2-oxazolyl)benzene, 2,2'-(2,6- Pyridinediyl)bis(4-isopropyl-2-oxazoline), 2,2'-(2,6-pyridinyl)bis(4-phenyl-2-oxazoline), 2-benzene (2-oxazoline), 4,4-dimethyl-2-oxazoline, 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2-ethyl -2-oxazoline, 2,2'-isopropylidene bis(4-third butyl-2-oxazoline), 2-isopropyl-2-oxazoline, 4-methoxymethyl 2-methyl-5-phenyl-2-oxazoline, 2-methyl-2-oxazoline, 2,4,4-trimethyl-2-oxazoline, manufactured by Japan Catalyst The Epocros series K-1010E, K-2010E, K-1020E, K-2020E, K-1030E, K-2030E, WS-500, WS-700, RPS-1005, RAS-1005, etc. From the viewpoint of the reliability after the HTS test, for example, 2,2'-bis(2-oxazoline), 1,3-bis(4,5-dihydro-2-oxazolyl)benzene is preferred , 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3,5-tris(4,5-dihydro-2-oxazolyl)benzene, 2-phenyl( 2-㗁azoline), Epocros WS-500, etc. In addition, the compound containing an oxazoline ring is more preferably the following general formula (TS5): [Chem 89]

{In the formula, Rs6 is an organic group having 1 to 10 carbon atoms, and nn2 is an integer from 0 to 4} The compound represented by 1,3-bis(4,5-dihydro-2-㗁azolyl) is the most preferable Benzene and 1,3,5-tris(4,5-dihydro-2-oxazolyl)benzene. (B-2-9) The compound containing a carbodiimide group is not particularly limited as long as it is a compound containing a carbodiimide group in the molecule, as for the HTS test From the standpoint of reliability, bis(2,6-diisopropylphenyl)carbodiimide, Carbodilite SV-02, V-01, V-02, V-03, V- 04, V-05, V-07, V-09, E-01, E-02, LA-1 (trade name, manufactured by Nisshinbo Chemical Company), etc. (B-2-10) Allyl compound The allyl compound is not particularly limited as long as it contains an allyl group in the molecule, and examples include trimethylolpropane trimethacrylate, 1,3,5 -Triallyl trimellitate, triallyl trimellitate, tetraallyl pyromellitate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, NK Ester 1G, 2G, 3G, 4G, 9G, 14G, NPG, BPE-100, BPE-200, BPE-500, BPE-1400 , A-200, A-400, A-600, TMPT, A-TMM-3 (trade name, manufactured by Shin Nakamura Chemical Industry Company), BANI-M, BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) )Wait. Among these, from the viewpoint of reliability after the HTS test, particularly preferred are vinyl acetate, trimethylolpropane trimethacrylate, triallyl 1,3,5-benzenetricarboxylate, Triallyl trimellitate, tetraallyl pyromellitate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, di Trimethylolpropane tetraacrylate, BANIM and BANI-X. (B-2-11) Trithiol compound As the trithiol compound, as long as it contains a trimer thiocyanate group in the molecule, it is not particularly limited, and it is preferable from the viewpoint of reliability after the HTS test 2,4,6-trithiol-1,3,5-tris, 2-dimethylamino-4,6-dithiol-1,3,5-tris, 2-dibutyl Amino-4,6-dithiol-1,3,5-tris, 2-phenylamino-4,6-dithiol-1,3,5-tris, etc. (B-2-12) Metal chelate compounds Examples of metal chelate compounds include aluminum chelate compounds, titanium chelate compounds, zirconium chelate compounds, chromium chelate compounds, magnesium chelate compounds, nickel chelate compounds, etc. From the standpoint of reliability after the HTS test, it is preferably aluminum (III) acetone salt, titanium (IV) acetone salt, chromium (III) acetone salt, and magnesium (II) acetone acetone Salt, nickel (II) acetone salt, zirconium (IV) acetone salt, aluminum (III) trifluoroacetone salt, titanium (IV) trifluoroacetone salt, chromium (III) acetone trifluoroacetone ) Salt, trifluoroacetone magnesium (II) salt, trifluoroacetone nickel (II) salt, trifluoroacetone zirconium (IV) salt, diisopropoxybis (acetylacetonate) titanium, Titanium tetraacetatepyruvate, di-2-ethylhexyloxybis(2-ethyl-3-hydroxyhexanol) titanium, diisopropoxybis(ethylacetoacetate) titanium, etc. Among these compounds, from the viewpoint of reliability after the HTS test, acetone aluminum (III) salt, acetone titanium (IV) salt, acetone zirconium (IV) salt, acetone are preferred Nickel (II) acetone salt, aluminum (III) trifluoroacetone salt, titanium (IV) trifluoroacetone salt, nickel (II) trifluoroacetone salt, zirconium (IV) trifluoroacetone salt , Titanium diisopropoxide bis(acetylpyruvate), titanium tetraacetate pyruvate, titanium di-2-ethylhexyloxybis(2-ethyl-3-hydroxyhexanol), and diisopropyl Oxybis (ethyl acetoacetate) titanium is preferably aluminum (III) acetone salt, titanium (IV) acetone salt, acetone acetone from the viewpoint of adhesion on a silicon wafer Zirconium (IV) salt, aluminum (III) trifluoroacetone salt, titanium (IV) trifluoroacetone salt, zirconium (IV) trifluoroacetone salt, and diisopropoxybis (acetone acetone) Acid) titanium. Among the crosslinking agents described in (B-2-1) to (B-2-12), from the viewpoint of reliability after the HTS test, (B-2-1) containing hydroxymethyl Group and/or alkoxymethyl compound, (B-2-2) ethylene oxide compound, (B-2-3) isocyanate group-containing compound, (B-2-4) bis-cis-butene Diimino compound, (B-2-5) compound containing aldehyde group, (B-2-6) compound containing oxetane ring, (B-2-7) compound containing benzo 㗁𠯤 Ring compound, (B-2-8) compound containing oxazoline ring, (B-2-10) allyl compound, more preferably (B-2-1) containing hydroxymethyl and/or alkoxy Compounds containing methyl groups, (B-2-3) compounds containing isocyanate groups, (B-2-4) compounds containing bismaleimide groups, (B-2-6) oxygen-containing heterocycles Butane ring compounds, (B-2-7) compounds containing benzo 㗁𠯤 rings, (B-2-10) allyl compounds, preferably (B-2-1) containing hydroxymethyl and/ Or alkoxymethyl compounds. These crosslinking agents (B-2) can be used alone or in combination of two or more. Among the above (B-2) crosslinking agents, the present invention preferably uses (B-2-1) compounds containing hydroxymethyl and/or alkoxymethyl groups, and more preferably uses the following general formula ( 12): [Chem 90]

{In the formula, Rs1 is a hydrogen atom, a monovalent group selected from the group consisting of methyl, ethyl, n-propyl, and isopropyl, and Rs2 is selected from the group consisting of a hydroxyl group and an alkyl group having 1 to 10 carbon atoms. , A group consisting of an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a carbamate group, mm1 is an integer of 1 to 5, mm2 is 0 to 4 An integer. Here, 1≦(mm1+mm2)≦5, nn1 is an integer from 1 to 4, V ₁ CH when nn1=1 ₂ ORs1, when nn1=2~4, it is a single bond or an organic group of 2~4 valence. Yu CH ₂ ORs1 and R ₁₀ When there are a plurality of cases, these may be the same as or different from each other} hydroxymethyl compounds and alkoxymethyl compounds. By adding a cross-linking agent, the glass transition temperature of the resin at the same curing temperature can be increased. By increasing the glass transition temperature of the resin, the migration of copper into the resin is suppressed. The compounding amount of the crosslinking agent (B-2) is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 5 to 20 parts by mass relative to 100 parts by mass of the resin (A). . (B-3) Fluorine-containing hydrophobic compound The following describes (B-3) the fluorine-containing hydrophobic compound in this embodiment in detail. (B) The fluorine-containing hydrophobic compound is not particularly limited as long as it contains a fluorine atom in the molecule and is hydrophobic. Compounds that can be preferably used as the (B-3) fluorine-containing hydrophobic compound of the present embodiment are acid fluoride, fluorinated acrylate, fluorinated methacrylate, fluorinated alcohol, fluorinated alkane , Fluorinated esters and fluorinated ethers. <Acyl Fluoride> As a specific compound example of the acyl fluoride as the (B-3) fluorine-containing hydrophobic compound, perfluoropentyl fluoride, perfluorohexyl fluoride, perfluoroheptane fluoride, Perfluorooctyl fluoride, perfluoro succinyl fluoride, hexafluoropentane difluoride, octafluorohexadiacetyl fluoride, perfluoromethoxypropyl fluoride, perfluorobutoxyethoxyacetyl fluoride, perfluoropoly Ether dipropylene fluoride (n=1), perfluoropolyether dipropylene fluoride (n=2), perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluorodecane Monoacid, perfluorododecanoic acid, perfluorotetradecanoic acid, perfluorohexadecanoic acid, perfluoro-3,5,5-trimethylhexanoic acid, perfluoro-3,7-dimethyloctanoic acid, perfluoro Succinic acid, perfluoroglutaric acid, perfluoroadipic acid, perfluorooctanedioic acid, perfluoroazelaic acid, perfluorosebacic acid, perfluorododecanedioic acid, perfluoro-3,6-dioxane Heteroheptanoic acid, perfluoro-3,6,9-trioxadecanoic acid, perfluoro-3,6-dioxadecanoic acid, perfluoro-3,6,9-trioxatridecanoic acid, perfluoro -3,6-dioxaoctane-1,8-dioic acid, perfluoro-3,6,9-trioxaundecane-1,11-dioic acid, etc. <Fluorinated Acrylate> As a specific compound example of the fluorinated acrylate as the (B-3) fluorine-containing hydrophobic compound, 1H,1H-perfluoro n-butyl acrylate, 1H,1H- Perfluoro-n-octyl ester, 1H, 1H-perfluoro-n-decyl acrylate, 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diacrylate, 1H, 1H, 8H, 8H-perfluorotetra Ethylene glycol diacrylate, 1H, 1H, 6H, 6H-perfluorotriethylene glycol diacrylate, 1H, 1H, 4H, 4H-perfluorodiethylene glycol diacrylate, 1H, 1H, 10H, 10H -Pentaethylene glycol diacrylate, 1H, 1H, 18H, 18H-nonaglycol diacrylate, perfluoro-1,6-hexanediol diacrylate, perfluorotetraethylene glycol diacrylate, perfluoroethylene Fluorotriethylene glycol diacrylate, perfluorodiethylene glycol diacrylate, pentaethylene glycol diacrylate, nonaethylene glycol diacrylate, etc. Among them, 1H,1H,6H,6H-perfluoro-1,6-hexanediol diacrylate and 1H,1H,8H,8H-perfluorotetraethylene glycol diacrylate can be used particularly well as Obtained the product name C6DIACRY and product name DA-F4EO manufactured by Exfluor. <Fluorinated Methacrylate> As a specific compound example of the fluorinated methacrylate as the (B-3) fluorine-containing hydrophobic compound, 1H,1H-perfluoro-n-butyl methacrylate can be preferably used , 1H, 1H-perfluoro-n-octyl methacrylate, 1H, 1H-perfluoro-n-decyl methacrylate, 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol dimethacrylate , 1H, 1H, 8H, 8H-perfluorotetraethylene glycol dimethacrylate, 1H, 1H, 6H, 6H-perfluorotriethylene glycol dimethacrylate, 1H, 1H, 4H, 4H-full Fluorinated diethylene glycol dimethacrylate, 1H, 1H, 10H, 10H-pentaethylene glycol dimethacrylate, 1H, 1H, 18H, 18H-nonaethylene glycol dimethacrylate, perfluoro- 1,6-hexanediol dimethacrylate, perfluorotetraethylene glycol dimethacrylate, perfluorotriethylene glycol dimethacrylate, perfluorodiethylene glycol dimethacrylate, five Ethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, etc. <Fluorinated Alcohol> As a specific compound example of the fluorinated alcohol as the (B-3) fluorine-containing hydrophobic compound, 1H,1H-perfluoro-1-hexanol, 1H,1H-perfluoro can be preferably used -1-heptanol, 1H, 1H-perfluoro-1-octanol, 1H, 1H-perfluoro-1-nonanol, 1H, 1H-perfluoro-1-decanol, 1H, 1H-perfluoro-1 -Undecyl alcohol, 1H,1H-perfluoro-1-dodecanol, 1H,1H-perfluoro-1-tetradecanol, 1H,1H-perfluoro-1-hexadecanol, perfluoro-3,5 ,5-trimethylhexane-1-ol, perfluoro-3,7-dimethyloctan-1-ol, 1H,1H,4H,4H-perfluoro-1,4-butanediol, 1H ,1H,5H,5H-perfluoro-1,5-pentanediol, 1H,1H,5H,5H-perfluoro-1,5-pentanediol, 1H,1H,6H,6H-perfluoro-1, 6-hexanediol, 1H, 1H, 8H, 8H-perfluoro-1,8-octanediol, 1H, 1H, 9H, 9H-perfluoro-1,9-nonanediol, 1H, 1H, 10H, 10H-perfluoro-1,10-decanediol, 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, perfluoro-third butanol, fluorinated diethylene glycol monomethyl Ether, fluorinated triethylene glycol monomethyl ether, fluorinated diethylene glycol monobutyl ether, fluorinated triethylene glycol monobutyl ether, fluorinated triethylene glycol, fluorinated tetraethylene glycol, etc. <Fluorinated Alkanes> As specific examples of fluorinated alkanes as (B-3) fluorine-containing hydrophobic compounds, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane can be preferably used Trioxane, perfluoropentadecane, 1H-perfluoropentane, 1H-perfluorohexane, 1H-perfluoroheptane, 1H-perfluorooctane, 1H-perfluorononane, 1H-perfluorodecane , 1H-perfluoroundecane, 1H-perfluorotridecane, 1H-perfluoropentadecane, 1H-perfluoro-2,4,4-trimethylpentane, 1H-perfluoro-2,6 -Dimethylheptane, 1H, 4H-perfluorobutane, 1H, 6H-perfluorohexane, 1H, 7H-perfluoroheptane, 1H, 8H-perfluorooctane, 1H, 10H-perfluorodecane Alkane etc. <Fluorinated ester> As a specific compound example of the fluorinated ester as the (B-3) fluorine-containing hydrophobic compound, methyl perfluorovalerate, methyl perfluorohexanoate, and perfluoroheptanoic acid can be preferably used Methyl ester, methyl perfluorooctanoate, methyl perfluorononanoate, methyl perfluorodecanoate, methyl perfluoroundecanoate, methyl perfluorododecanoate, methyl perfluoromyristate, perfluorohexadecanoic acid Methyl ester, dimethyl perfluorosuccinate, dimethyl perfluoroglutarate, dimethyl perfluoroadipate, dimethyl perfluorosuberate, dimethyl perfluoroazelaate, perfluorodecane Dimethyl diorate, dimethyl perfluoro-1,12-sebacate, methyl perfluoro-3,6-dioxaheptanoate, methyl perfluoro-3,6,9-trioxadecanoate Ester, methyl perfluoro-3,6-dioxadecanoate, methyl perfluoro-3,6,9-trioxatridecanoate, perfluoro-3,6-dioxaoctane-1, 8-Dicarboxylic acid dimethyl ester, perfluoro-3,6,9-trioxaundecane-1,11-dioic acid dimethyl ester, etc. <Fluorinated Ether> As a specific compound example of the fluorinated ether as the (B-3) fluorine-containing hydrophobic compound, perfluoro (diethylene glycol dimethyl ether), perfluoro (triethylenedioxide) can be preferably used Alcohol dimethyl ether), perfluoro (triethylene glycol dimethyl ether), etc. (B-3) The weight ratio of fluorine atoms in the molecules of the fluorine-containing hydrophobic compound is preferably 30% by mass or more and 80% by mass or less. If the weight ratio of fluorine is less than this range, sufficient hydrophobicity cannot be obtained. In addition, if fluorine is more than this range, the compatibility with the solvent is reduced, and it is difficult to obtain a coating film with uniform surface flatness, which is not good. The range of the fluorine weight content ratio is more preferably 35% by mass or more and 75% by mass or less. The (B-3) fluorine-containing hydrophobic compound in this embodiment preferably has at least one unsaturated double bond in the molecule. If there is an unsaturated double bond, in the exposure step, a crosslinking reaction is performed between the molecules of (B-3) fluorine-containing hydrophobic compounds and the molecules of (A) resin. By this, the fluorine-containing hydrophobic compound (B-3) is not easily volatilized during the heat treatment, and can exhibit a sufficient hydrophobic effect. Preferred examples of unsaturated double bonds are acrylate and methacrylate. The content of the (B-3) fluorine-containing hydrophobic compound is preferably 0.01 to 50 parts by mass, more preferably 0.02 to 30 parts by mass, and still more preferably 0.05 to 20 parts by mass relative to 100 parts by mass of the resin (A). Copies. If the content is more than this range, the compatibility with the solvent is reduced, and it is difficult to obtain a coating film with uniform surface flatness. Therefore, it is not good. If the content is less than this range, a sufficient hydrophobic effect cannot be obtained. It is easy to create voids. (C) Sensitizer The (C) sensitizer used in the present invention will be described. (C) Photosensitizer The photosensitive resin composition according to the present invention is, for example, a polyimide precursor and/or polyamide as the negative type of (A) resin, or is a polyoxazole precursor, for example, At least one of soluble polyimide, novolak, polyhydroxystyrene and phenol resin is different as the positive type of (A) resin. The formulation amount of the (C) photosensitive agent in the photosensitive resin composition is 1 to 50 parts by mass with respect to 100 parts by mass of the (A) photosensitive resin. The above formulation amount is 1 part by mass or more from the viewpoint of light sensitivity or patternability, and is 50 parts by mass or less from the viewpoint of the curability of the photosensitive resin composition or the physical properties of the photosensitive resin layer after curing. [(C) Negative Type Photosensitizer: Polymerization Initiator, Photoacid Generator] First, the case where the negative type is desired will be described. In this case, a photopolymerization initiator and/or photoacid generator is used as the (C) sensitizer. As the photopolymerization initiator, it is preferably a photoradical polymerization initiator, preferably listed as: diphenyl Benzophenone derivatives such as methyl ketone, methyl phthalate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, stilbene, etc., 2,2'-di Acetophenone derivatives such as ethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexyl phenyl ketone, 9-oxythio 𠮿

、2-Methyl 9-Oxysulfur 𠮿

、2-Isopropyl 9-oxygen sulfur 𠮿

、Diethyl 9-oxysulfur 𠮿

Wait 9-oxygen sulfur

Derivatives, benzoyl derivatives such as benzoyl benzene, benzoyl dimethyl ketal, benzoyl-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-benzoyl)oxime, 1,3-diphenyl Propane trione-2-(o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropane trione-2-(o-benzoyl)oxime and other oximes, N-phenylglycine Peroxides such as N-arylglycinates, benzyl perchlorides, aromatic biimidazoles, titanocenes, α-(n-octylsulfonylimido)-4-methyl Photoacid generators such as oxybenzyl cyanide and the like are not limited thereto. Among the above-mentioned photopolymerization initiators, especially in terms of light sensitivity, oximes are more preferable. In the case where a photoacid generator is used as the (C) photosensitive agent in the negative photosensitive resin composition, it exhibits acidity under the irradiation of active light such as ultraviolet rays, and has the following effects due to this effect The role of the crosslinking agent and the resin as the component (A) to crosslink or polymerize the crosslinking agents with each other. As examples of the photoacid generator, diarylammonium salts, triarylammonium salts, dialkylbenzylmethylammonium salts, diarylphosphonium salts, aryldiazonium salts, aromatic tetracarboxylates can be used Acid esters, aromatic sulfonates, nitrobenzyl esters, oxime sulfonates, aromatic N-oxyamide sulfonates, aromatic sulfonamides, halogenated alkyl-containing hydrocarbon compounds, halogen-containing Heterocyclic compounds of alkyl, naphthoquinone diazide-4-sulfonate, etc. These compounds can be used in combination of 2 or more types as needed, or in combination with other sensitizers. Among the above-mentioned photoacid generators, particularly in terms of light sensitivity, aromatic oxime sulfonate and aromatic N-oxyimidimide sulfonate are more preferable. In the case of a negative type, the compounding amount of these sensitizers is 1 to 50 parts by mass with respect to 100 parts by mass of (A) resin, and preferably 2 to 15 parts by mass from the viewpoint of light sensitivity characteristics. By blending (C) a photosensitizer that is 1 part by mass or more with respect to 100 parts by mass of (A) resin, the photosensitivity is excellent, and by blending 50 parts by mass or less, the thick film curability is excellent. Furthermore, as described above, when the (A) resin represented by the general formula (1) is an ionic bond type, an amine group is used to impart a photopolymerizable group to the side chain of the (A) resin via an ionic bond (Meth)acrylic compound. In this case, the (meth)acrylic compound having an amine group is used as the (C) sensitizer, as described above, for example, preferably dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate , Diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethyl methacrylate Dialkylaminoalkyl acrylates such as aminopropyl esters, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, diethylaminobutyl methacrylate Or dialkylaminoalkyl methacrylate, from the viewpoint of photosensitive characteristics, it is preferable that the carbon number of the alkyl group on the amine group is 1-10, and the carbon number of the alkyl chain is 1-10 The dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate. The amount of the (meth)acrylic compound having an amine group is 1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and from the viewpoint of light sensitivity characteristics, it is preferably 2 to 15 parts by mass Copies. By blending (meth)acrylic compound having an amine group with 1 part by mass or more with respect to 100 parts by mass of (A) resin as (C) photosensitizer, excellent photosensitivity, by blending 20 parts by mass or less, thick film Excellent hardenability. Next, the case where the expectation is positive will be described. In this case, a photoacid generator is used as the (C) sensitizer. Specifically, a diazoquinone compound, an onium salt, a halogen-containing compound, etc. can be used. From the viewpoint of solvent solubility and storage stability, The compound having a diazoquinone structure is preferred. [(C) Positive type photosensitizer: compound having a quinonediazide group] As (C) a compound having a quinonediazide group (hereinafter also referred to as "(C) quinonediazide compound"), there can be exemplified Compounds with 1,2-benzoquinone diazide structure and compounds with 1,2-naphthoquinone diazide structure are US Patent No. 2,772,972, US Patent No. 2,797,213, and US Patent No. 3,669,658 Known substances in The (C) quinonediazide compound is preferably selected from 1,2-naphthoquinonediazide-4-sulfonate of a polyhydroxy compound having a specific structure described in detail below, and 1, of the polyhydroxy compound, At least one compound in the group consisting of 2-naphthoquinonediazide-5-sulfonate (hereinafter also referred to as "NQD compound"). The NQD compound is obtained by chlorinating the naphthoquinone diazide sulfonic acid compound with chlorosulfonic acid or thionyl chloride according to a conventional method to make the obtained naphthoquinone diazide sulfonyl chloride Condensation reaction with polyhydroxy compounds. For example, it can be obtained by combining a polyhydroxy compound with a specific amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in dioxan In a solvent such as alkane, acetone or tetrahydrofuran, it is reacted in the presence of an alkaline catalyst such as triethylamine to perform esterification, and the obtained product is washed with water and dried. In this embodiment, from the viewpoint of sensitivity and resolution when forming a resist pattern, (C) the compound having a quinonediazide group is preferably represented by the following general formulas (70) to (74) 1,2-naphthoquinonediazide-4-sulfonate and/or 1,2-naphthoquinonediazide-5-sulfonate of the hydroxy compound. The general formula (70) is represented by [Chem. 91]

{Where, X ₁₁ And X ₁₂ Each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably 1 to 30 carbon atoms), X ₁₃ And X ₁₄ Each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably 1 to 30 carbon atoms), r1, r2, r3, and r4 are independently integers of 0 to 5, and at least one of r3 and r4 It is an integer of 1 to 5, represented by (r1+r3)≦5, and (r2+r4)≦5}. The general formula (71) consists of [Chem 92]

{In the formula, Z represents an organic group of 4 to 4 carbon atoms, X ₁₅ , X ₁₆ , X ₁₇ And X ₁₈ Each independently represents a monovalent organic group having 1 to 30 carbon atoms, r6 is an integer of 0 or 1, r5, r7, r8 and r9 are independently integers of 0 to 3, and r10, r11, r12 and r13 are independently 0 An integer of ~2, and r10, r11, r12, and r13 are not all represented by 0}. And the general formula (72) is represented by [Chem. 93]

{In the formula, r14 represents an integer of 1-5, r15 represents an integer of 3-8, (r14×r15) L independently represent a monovalent organic group with a carbon number of 1-20, (r15) T ¹ And (r15) T ² Each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms}. And the general formula (73) is represented by [Chem 94]

{In the formula, A represents an aliphatic divalent organic group containing a tertiary or quaternary carbon, and M represents a divalent organic group, preferably represents a chemical formula selected from the following: [Chem 95]

The two-valent base among the three bases represented by} is represented. Furthermore, the general formula (74) is represented by [Chem 96]

{In the formula, r17, r18, r19 and r20 are independently integers from 0 to 2, and at least one of r17, r18, r19 and r20 is 1 or 2, X ₂₀ ~X ₂₉ Each independently represents a hydrogen atom, a halogen atom, a monovalent group selected from the group consisting of alkyl, alkenyl, alkoxy, allyl, and acetyl, and Y ₁₀ , Y ₁₁ And Y ₁₂ Respectively represent a single bond, selected from -O-, -S-, -SO-, -SO ₂ -, -CO-, -CO ₂ -, represented by a divalent group in the group consisting of cyclopentylene, cyclohexylene, phenylene, and a divalent organic group having 1 to 20 carbon atoms}. In another embodiment, in the above general formula (74), Y ₁₀ ~Y ₁₂ It is preferable to independently from the following general formula: [Chem 97]

[化98]

[Chem 99]

{Where, X ₃₀ And X ₃₁ Each independently represents a hydrogen atom, at least one monovalent group selected from the group consisting of alkyl, alkenyl, aryl, and substituted aryl, X ₃₂ , X ₃₃ , X ₃₄ And X ₃₅ Each independently represents a hydrogen atom or an alkyl group, r21 is an integer of 1 to 5, and X ₃₆ , X ₃₇ , X ₃₈ And X ₃₉ It is independently selected from three divalent organic groups represented by hydrogen atom or alkyl group}. Examples of the compound represented by the general formula (70) include hydroxy compounds represented by the following formulas (75) to (79). Here, the general formula (75) is [Chem100]

{In the formula, r16 is independently an integer from 0 to 2, and X ₄₀ Each independently represents a hydrogen atom or a monovalent organic group with a carbon number of 1 to 20, in X ₄₀ When there are plural situations, plural X ₄₀ May be the same or different from each other, and X ₄₀ The following general formula is preferred: [Chem 101]

(In the formula, r18 is an integer from 0 to 2, X ₄₁ Represents a hydrogen atom, a monovalent organic group selected from the group consisting of alkyl groups and cycloalkyl groups, and when r18 is 2, 2 X ₄₁ May be the same or different from each other) represented by a monovalent organic group}, general formula (76) is represented by [Chem 102]

{Where, X ₄₂ It represents a hydrogen atom, a monovalent organic group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms. Moreover, the general formula (77) is [Chem 103]

{In the formula, r19 is independently an integer of 0~2, X ₄₃ Each independently represents a hydrogen atom or the following general formula: [Chem 104]

(In the formula, r20 is an integer from 0 to 2, X ₄₅ It is selected from the group consisting of hydrogen atom, alkyl group and cycloalkyl group, and when r20 is 2, 2 X ₄₅ May be the same or different from each other) the monovalent organic group represented by, and X ₄₄ It is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms. Formulas (78) and (79) have the following structures. [化105]

[化106]

As the compound represented by the above general formula (70), in terms of high sensitivity when made into an NQD compound and low precipitation in the photosensitive resin composition, the following formula (80) is preferable ~ The hydroxy compound represented by (82). The structures of formulas (80) to (82) are shown below. [化107]

[化108]

[化109]

As the compound represented by the above general formula (76), in terms of high sensitivity when made into an NQD compound and low precipitation in the photosensitive resin composition, the following formula (83) is preferable : [Chem 110]

The hydroxy compound represented. As the compound represented by the above general formula (77), in terms of high sensitivity when made into an NQD compound and low precipitation in the photosensitive resin composition, the following formula (84) is preferable ~ The hydroxy compound represented by (86). The structures of formulas (84) to (86) are shown below. [化111]

[化112]

[化113]

In the above general formula (71), Z is not particularly limited as long as it is a tetravalent organic group having 1 to 20 carbon atoms. From the viewpoint of sensitivity, it is preferable to have the following formula:

The four-valent base of the structure shown. Among the compounds represented by the above general formula (71), in terms of high sensitivity when made into NQD compounds and low precipitation in the photosensitive resin composition, the following formula (87) is preferable ) To hydroxy compounds represented by (90). The structures of formulas (87) to (90) are shown below. [化115]

[化116]

[化117]

[化118]

As the compound represented by the above general formula (72), in terms of high sensitivity when made into an NQD compound and low precipitation in the photosensitive resin composition, the following formula (91) is preferable : [Chem119]

{In the formula, r40 is independently an integer of 0-9} hydroxy compound represented by. As the compound represented by the above general formula (73), in terms of high sensitivity when made into an NQD compound and low precipitation in the photosensitive resin composition, the following formula (92) is preferable And the hydroxy compound represented by (93). The structures of equations (92) and (93) are shown below. [化120]

[化121]

As the compound represented by the above general formula (74), in terms of high sensitivity and low precipitation in the photosensitive resin composition, specifically, the following formula (94) is preferable: 122]

The NQD compound of the indicated polyhydroxy compound. In the case where (C) the compound having a quinonediazide group has 1,2-naphthoquinonediazidesulfonamide group, the group may be 1,2-naphthoquinonediazide-5-sulfonamide group or 1 , Any of 2-naphthoquinonediazide-4-sulfonyl. 1,2-Naphthoquinonediazide-4-sulfonamide can absorb the i-ray region of the mercury lamp, so it is suitable for exposure with i-rays. On the other hand, 1,2-naphthoquinonediazide-5-sulfonyl can absorb even the g-ray region of mercury lamps, so it is suitable for exposure with g-rays. In this embodiment, it is preferable to select one of 1,2-naphthoquinonediazide-4-sulfonate compound and 1,2-naphthoquinonediazide-5-sulfonate compound according to the wavelength of exposure. Or both. In addition, 1,2-naphthoquinone diazide having 1,2-naphthoquinonediazide-4-sulfonyl and 1,2-naphthoquinonediazide-5-sulfonyl in the same molecule can also be used The sulfazo compound can also be used by mixing a 1,2-naphthoquinonediazide-4-sulfonate compound and a 1,2-naphthoquinonediazide-5-sulfonate compound. (C) Among the compounds having a quinonediazide group, the average esterification rate of the naphthoquinonediazidesulfonyl ester of the hydroxy compound is preferably 10% to 100% from the viewpoint of developing contrast, and more preferably 20%～100%. From the viewpoint of the physical properties of the cured film such as sensitivity and elongation, preferred examples of the NQD compound include those represented by the following general formula groups. [化123]

Examples include {where Q is a hydrogen atom, or the following group of formulas: [Chem 124]

The naphthoquinone diazide sulfonate group represented by any one of them, but Q does not all represent hydrogen atom at the same time}. In this case, as an NQD compound, it can be used for the naphthoquinone diazide sulfonyl ester compound having 4-naphthoquinone diazide sulfonyl and 5-naphthoquinone diazide sulfonyl in the same molecule. The 4-naphthoquinone diazide sulfonyl ester compound and the 5-naphthoquinone diazide sulfonyl ester compound can be used in combination. Among the naphthoquinone diazide sulfonate groups described in the above paragraph [0243], the following general formula (95) is particularly preferred: [Chem 125]

Expressed by. Examples of the above-mentioned onium salt include: a thionium salt, a cerium salt, a phosphonium salt, an ammonium salt, a diazonium salt, and the like, preferably selected from the group consisting of diarylphosphonium salts, triarylammonium salts, and trialkylammonium salts Onium salt in the group. Examples of the halogen-containing compound include a halogen alkyl-containing hydrocarbon compound and the like, and trichloromethyltriazine is preferred. In the case of the positive type, the amount of the photoacid generator is 1 to 50 parts by mass, preferably 5 to 30 parts by mass relative to 100 parts by mass of the (A) resin. If the compounding amount of the photoacid generator as the (C) photosensitive agent is 1 part by mass or more, the patternability of the photosensitive resin composition is good, and if it is 50 parts by mass or less, the photosensitive resin composition after curing The tensile elongation of the film is good, and the development residue (scum) in the exposed portion is small. The above-mentioned NQD compounds may be used alone or in combination of two or more. In the present embodiment, the compounding amount of (C) compound having a quinonediazide group in the photosensitive resin composition is 0.1 to 70 parts by mass relative to 100 parts by mass of the resin (A), preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, and still more preferably 5 to 30 parts by mass. If the blending amount is 0.1 parts by mass or more, good sensitivity is obtained, while if it is 70 parts by mass or less, the mechanical properties of the cured film are good. The photosensitive resin composition of the present invention may further contain components other than the aforementioned components (A) to (C). This component is preferably based on (A) resins such as the negative type using polyimide precursor and polyimide, or the positive type using polyoxazole precursor, soluble polyimide and phenol resin, etc. And different. In the present embodiment, the above-mentioned polyimide precursor resin composition and polyamide resin composition as the negative resin composition, or the polyazole resin composition and soluble polyamide as the positive photosensitive resin composition The imine resin composition and the phenol resin composition may contain a solvent for dissolving these resins. <Solvent> Examples of the solvent include amides, sulfonamides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. For example, N-methyl 2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl Isobutyl 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, benzene ethylene glycol, tetrahydrofuran methanol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 𠰌 line, dichloromethane, 1,2 -Dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. Among them, from the viewpoints of the solubility of the resin, the stability of the resin composition, and the adhesion to the substrate, N-methyl-2-pyrrolidone, dimethyl sulfoxide, 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, benzene ethylene glycol and tetrahydrofuran methanol. Among such solvents, those that can completely dissolve the resulting polymer are particularly preferred, for example: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl Carboxamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, etc. As a solvent suitable for the above phenol resin, bis(2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, di Ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, etc., but not limited to this Wait. In the photosensitive resin composition of the present invention, the amount of the solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and more preferably 125 to 100 parts by mass of the (A) resin. 500 parts by mass. The photosensitive resin composition of the present invention may further contain components other than the aforementioned components (A) to (C). For example, when the photosensitive resin composition of the present invention is used to form a cured film on a substrate containing copper or a copper alloy, in order to suppress discoloration on the copper, a nitrogen-containing heterocyclic ring such as an azole compound and a purine derivative can be arbitrarily formulated Compound. Examples of azole compounds include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl -1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5- Phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-bis Ethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α -Dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl- 5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-third-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5 '-Third octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 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 group-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred are enumerations: tolutriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. In addition, these azole compounds can be used alone or in a mixture of two or more. Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyl 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-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyl Adenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N -(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-aza Xanthine, 8-azahypoxanthine and their derivatives. The formulation amount when the photosensitive resin composition contains the azole compound or purine derivative is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin. From the viewpoint of light sensitivity characteristics, More preferably, it is 0.5 to 5 parts by mass. If the formulation amount of the azole compound with respect to 100 parts by mass of the (A) resin is 0.1 part by mass or more, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, the generation of the surface of the copper or copper alloy is suppressed On the other hand, if the discoloration is 20 parts by mass or less, the light sensitivity is excellent. In addition, in order to suppress discoloration on the copper surface, a hindered phenol compound can be arbitrarily formulated. Examples of hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, and 3-(3,5-di-tert-butyl- 4-Hydroxyphenyl) propionate octadecyl ester, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate isooctyl ester, 4,4'-methylene bis(2 ,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl- 6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol- Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diextenyl bis[3-(3,5-di-tert-butyl 4-hydroxyphenyl) propionate], N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionamide), 2,2'- Methyl-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), tetrakis[3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, tri-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl -4-isopropylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl (-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri( 4-second-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1, 3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris-2,4,6-(1H, 3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris-2, 4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tri 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxyl -2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris (4-third Butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3 H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tri 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methyl Benzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2 -Methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3- Hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4- Tributyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, etc. Not limited to this. Among these, particularly preferred is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4 ,6-(1H,3H,5H)-trione, etc. The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and more preferably from 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics. If the compounding amount of the hindered phenol compound with respect to 100 parts by mass of the (A) resin 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, the generation of copper or copper alloy is prevented It is discolored or corroded. On the other hand, if it is 20 parts by mass or less, the light sensitivity is excellent. The photosensitive resin composition of this invention may contain a crosslinking agent. The cross-linking agent may be a cross-linking agent capable of cross-linking (A) the resin or forming a cross-linked network structure when the relief pattern formed using the photosensitive resin composition of the present invention is heat-cured Agent. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the photosensitive resin composition. Examples of the crosslinking agent include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, which are compounds containing hydroxymethyl and/or alkoxymethyl. 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300, Micoat 102, 105 (above manufactured by Mitsui Cytec); NIKALAC (registered trademark) MX-270, -280, -290, NIKALAC MS-11, NIKALAC MW-30, -100, -300, -390, -750 (above are manufactured by SANWA CHEMICAL); DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML -PSBP, DML-PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM -BP, TMOM-BPA, TML-BPAF-MF (manufactured by Honshu Chemical Industry Co., Ltd.); benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxyl) Methyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethyl benzoic acid hydroxymethyl phenyl ester, bis (hydroxymethyl) biphenyl, dimethyl bis (hydroxymethyl) biphenyl, Bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methyl Oxymethyl) benzophenone, methoxymethyl benzoic acid methoxymethyl phenyl ester, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, etc. . In addition, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol epoxy resin, triphenol epoxy resin, tetraphenol epoxy resin, Phenol-xylylene epoxy resin, naphthol-xylylene epoxy resin, phenol-naphthol epoxy resin, phenol-dicyclopentadiene epoxy resin, alicyclic epoxy resin , Aliphatic epoxy resin, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 1,1,2,2-tetra Hydroxyphenyl)ethane tetraglycidyl ether, glycerol triglycidyl ether, o-second butylphenyl glycidyl ether, 1,6-bis (2,3-glycidoxy) naphthalene, diglycerol polyglycidyl Glycerin ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (the above are trade names, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN- 501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), Epikote (registered trademark) 1001, Epikote 1007, Epikote 1009, Epikote 5050, Epikote 5051, Epikote 1031S, Epikote 180S65, Epikote 157H70, YX-315-75 (the above are trade names, manufactured by Japan Epoxy Resins Co., Ltd.), EHPE3150, PLACCEL G402, PUE101, PUE105 (above trade names, Diacel Chemical Industries Co., Ltd.), EPICLON (registered trademark) 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (the above are Trade name, manufactured by DIC), DENACOL (registered trademark) EX-201, EX-251, EX-203, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX -612, EX-614, EX-614B, EX-711, EX-731, EX-810, EX-911, EM-150 (the above are trade names, manufactured by Nagase chemteX), Epolight (registered trademark) 70P, Epolight 100MF (the above is a trade name, manufactured by Kyoeisha Chemical), etc. In addition, as the isocyanate group-containing compound, 4,4′-diphenylmethane diisocyanate, toluene diisocyanate, 1,3-xylylene diisocyanate, and dicyclohexylmethane-4,4′- Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate (registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, ND (the above are trade names, manufactured by Mitsui Chemicals), Duranate (registered trademark) ) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (the above are trade names, manufactured by Asahi Kasei Chemicals), etc. In addition, 4,4'-diphenylmethane bis-cis-butadiene diimide, phenylmethane-cis-butadiene diimide, m-phenylene bis bis Maleimide diimide, bisphenol A diphenyl ether bismaleimide diimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane Bis-cis-butadiene diimide, 4-methyl-1,3-phenylene bis-cis-butadiene diimide, 1,6'-bis-cis-butadiene diimide-(2,2,4 -Trimethyl)hexane, 4,4'-diphenyl ether bis-cis-butadiene diimide, 4,4'-diphenyl bis-cis-butadiene-diimide, 1,3-bis(3 -Maleimide phenoxy)benzene, 1,3-bis(4-maleimide phenoxy)benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300 , BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (the above are trade names, manufactured by Daiwa Chemical Industry Co., Ltd.), etc., as long as they are as described above Compounds that are generally thermally cross-linked are not limited to these. The blending amount when using a crosslinking agent is preferably 0.5 to 20 parts by mass, and more preferably 2 to 10 parts by mass relative to 100 parts by mass of the (A) resin. When the blending amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are exhibited. On the other hand, when it is 20 parts by mass or less, the storage stability is excellent. The photosensitive resin composition of this invention may contain an organic titanium compound. By including an organic titanium compound, a photosensitive resin layer excellent in chemical resistance can be formed even when it is cured at a low temperature of about 250°C. In addition, in particular, by containing both the (B) compound and the organic titanium compound in the photosensitive resin composition, the cured resin layer has an effect of not only excellent substrate adhesion but also excellent chemical resistance. In addition, in particular, by containing both (B-1) nanoparticles and an organic titanium compound in the photosensitive resin composition, the cured resin layer not only has excellent substrate adhesion but also excellent chemical resistance. . In addition, in particular, by including (B-2) both a thermal crosslinking agent and an organic titanium compound in the photosensitive resin composition, having the cured resin layer not only has excellent substrate adhesion but also excellent chemical resistance. effect. In addition, in particular, by including both the (B-3) compound and the organic titanium compound in the photosensitive resin composition, the resin layer after curing has an effect of not only excellent substrate adhesion but also excellent chemical resistance. Examples of the organic titanium compound that can be used 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, in terms of storage stability of the negative photosensitive resin composition and obtaining a good pattern, it is more preferably Titanium chelates with more than 2 alkoxy groups, specific examples are as follows: bis(triethanolamine) titanium diisopropoxide, bis(2,4-glutaric acid) titanium di-n-butoxide, bis(2,4 -Glutaric acid) titanium diisopropoxide, bis(tetramethylpimelic acid) titanium diisopropoxide, bis(ethyl acetoacetic acid) titanium diisopropoxide, etc. II) Titanium tetraalkoxy compounds: for example, titanium tetra(n-butanol), titanium tetraethoxide, titanium tetrakis(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxide Titanium methoxypropoxide, titanium tetramethylphenol, tetrakis(n-nonanol) titanium, tetrakis(n-propanol) titanium, titanium tetrastearate, tetrakis[bis{2,2-(allyloxymethyl ) Butanol}] Titanium, etc. III) Titanocene compounds: for example (pentamethylcyclopentadienyl) titanium trimethoxide, bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) titanium, bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium, etc. IV) Monoalkoxy titanium compounds: for example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) titanium isopropoxide, etc. V) Oxytitanium compounds: for example, bis(glutaric acid) titanium oxide, bis(tetramethylpimelic acid) titanium oxide, phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetate pyruvate: for example, titanium tetraacetate pyruvate. VII) Titanate coupling agent: for example, tris(dodecylbenzenesulfonyl)isopropyl titanate and the like. Among them, from the viewpoint of exhibiting better chemical resistance, the organic titanium compound is preferably selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound At least one compound in the group. Particularly preferred are bis(ethyl acetoacetate) titanium diisopropoxide, titanium tetra(n-butanol), and bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium. When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 mass parts, and more preferably 0.1 to 2 mass parts relative to 100 mass parts of the (A) resin. 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, the storage stability is excellent. Furthermore, in order to improve the adhesion between the film and the substrate formed using the photosensitive resin composition of the present invention, an adhesion aid may be arbitrarily formulated. Examples of the adhesion auxiliary agent include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-glycidoxy Propylpropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxy Propyltrimethoxysilane, dimethoxymethyl-3-piperidylpropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethyl Silyl propyl) succinimide, N-[3-(triethoxysilyl) propyl] phthalimide, benzophenone-3,3'-bis(N-[ 3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)- 2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3- Silane coupling agents such as ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, and aluminum tris(ethyl acetoacetate), aluminum tris(acetoacetate), ethyl Aluminum-based adhesives such as ethyl aluminum diisopropyl acetate. Among these adhesives, in terms of adhesion, it is more preferable to use a silane coupling agent. When the photosensitive resin composition contains an adhesion aid, the amount of the adhesion aid is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of (A) resin. 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-mercaptopropyl trimethoxysilane. Ethoxysilane (manufactured by Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Co., Ltd.: trade product Name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.0) , 3-mercaptopropyl diethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyl diethoxypropane Oxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethane Trimethoxysilane, 2-mercaptoethyl diethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyl Tripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4- Mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea (Shin-Etsu Chemical Industry Co., Ltd. Co., Ltd.: trade name LS3610, Azmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxysilylpropyl) urea (Azmax Co., Ltd.: trade name SIU9058.0), N -(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl) )Urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydiepropoxysilylpropyl)urea, N-(3-dimethoxy Propoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethyl Oxydimethoxysilylethyl)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)propyltrimethoxysilane (Azmax shares Co., Ltd. manufacture: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.) : Trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: product Name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl) Pyridine, carbamic acid (3-triethoxysilylpropyl) third butyl ester, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, Tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetrabutoxysilane, tetra(methoxyethoxysilane), tetra(meth) Oxy-n-propoxy silane), tetra (ethoxy ethoxy silane), tetra (methoxy ethoxy ethoxy silane), bis (trimethoxy silane) ethane, bis (trimethoxy) Silane)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane Alkane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetra Thioether, di-third butoxydiethoxysilane, diisobutoxyaluminumoxytriethoxysilane, bis(glutaric acid) titanium-O,O'-bis(oxyethyl) -Aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol , N-butylphenylsilanediol, isobutylphenylsilanediol, third butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydi Phenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol , Isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutyl Ethyl ethyl phenyl silanol, tertiary butyl ethyl phenyl silanol, methyl diphenyl silanol, ethyl diphenyl silanol, n-propyl diphenyl silanol, isopropyl diphenyl Silanol, n-butyl diphenyl silanol, isobutyl diphenyl silanol, third butyl diphenyl silanol, triphenyl silanol, etc., but not limited to these. These can be used alone or in combination. As the silane coupling agent, among the above silane coupling agents, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenyl are preferred Silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and silane coupling agent represented by the following structure. [化126]

The blending amount when using the silane coupling agent is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the (A) resin. The photosensitive resin composition of the present invention may further contain components other than the above components. The preferred of this component is based on the negative type using (a) resin such as polyimide precursor and polyimide or the positive type using polyoxazole precursor, soluble polyimide and phenol resin, etc. different. In the case of using a polyimide precursor, polyamide, or the like as the negative type of (A) resin, a sensitizer may be arbitrarily formulated in order to improve the light sensitivity. Examples of the sensitizer include: Michelerone, 4,4′-bis(diethylamino)benzophenone, and 2,5-bis(4′-diethylaminobenzylidene) ) Cyclopentane, 2,6-bis(4'-diethylaminobenzylidene) cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methyl Cyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone , P-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenyl biphenylene) benzothiazole, 2-(p-dimethylaminophenyl vinylidene) benzothiazole , 2-(p-dimethylaminophenyl vinylidene) isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-bis (Ethylaminobenzylidene) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetoxy-7-dimethylaminocoumarin, 3- Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin Element, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-benzene Ethanolamine, 4-𠰌olinyl benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto Tetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl) benzoxazole, 2-(p-dimethylaminostyryl) benzothiazole, 2-(p-di Methylaminostyryl) naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, etc. These can be used alone or in a combination of 2 to 5, for example. When the photosensitive resin composition contains a sensitizer for improving photosensitivity, it is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of (A) resin. In addition, in order to improve the resolvability of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be arbitrarily formulated. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferred, and it is not particularly limited to those listed below, and examples include diethylene glycol dimethyl Mono- or diacrylate and methacrylate of ethylene glycol or polyethylene glycol such as acrylic acid ester, tetraethylene glycol dimethacrylate, mono- or diacrylate and methacrylate of propylene glycol or polypropylene glycol, Glycerin mono-, di- or triacrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylate and dimethacrylate, 1,6- Diacrylate and dimethacrylate of hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono or diacrylate and methacrylate of bisphenol A, benzenetrimethacrylate , Isopropyl acrylate and methacrylate, isopropyl amine and its derivatives, methacrylic amine and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol two or three Compounds such as acrylates and methacrylates, pentaerythritol di-, tri- or tetraacrylates and methacrylates, and ethylene oxide or propylene oxide adducts of these compounds. When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond to improve the resolution of the relief pattern, regarding the amount of the monomer having a photopolymerizable unsaturated bond, It is preferably 1 to 50 parts by mass relative to 100 parts by mass of (A) resin. In addition, in the case of using a polyimide precursor or polyamide as the negative type of (A) resin, it is especially for improving the viscosity and light of the photosensitive resin composition when stored in a state containing a solution containing a solvent The stability of sensitivity can be arbitrarily formulated thermal polymerization inhibitor. As thermal polymerization inhibitors, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic 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-phenylhydroxyl Ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt, etc. When the thermal polymerization inhibitor is blended in the photosensitive resin composition, the blending amount is preferably in the range of 0.005 to 12 mass parts relative to 100 mass parts of the (A) resin. On the other hand, in the photosensitive resin composition of the present invention, when a polyoxazole precursor, soluble polyimide, phenol resin, or the like is used as the positive type of (A) resin, it may be appropriately added previously as a photosensitive Dyes, surfactants, thermal acid generators, dissolution accelerators, adhesion aids used to improve the adhesion to the substrate, etc. used as additives to the resin composition. If the above additives are described more specifically, examples of the dye include methyl violet, crystal violet, and malachite green. In addition, examples of the surfactant include nonionic surfactants including polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether or derivatives thereof, such as Fluorad (trade name, manufactured by Sumitomo 3M), MEGAFAC ( Trade name, Dainippon Ink & Chemical Industry Co., Ltd. or Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants, such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso) , Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and other organosiloxane surfactants. Examples of the adhesion auxiliary agent include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, tertiary butyl novolac, epoxy silane, epoxy polymer, etc., and Various silane coupling agents. The amount of the above-mentioned dye and surfactant is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the (A) resin. In addition, from the viewpoint of showing good thermal properties and mechanical properties of the cured product even when the curing temperature is lowered, a thermal acid generator can be arbitrarily formulated. From the viewpoint of showing good thermal properties and mechanical properties of the cured product even when the curing temperature is lowered, it is preferable to formulate a thermal acid generator. Examples of the thermal acid generator include salts formed of strong acids and bases such as onium salts having a function of generating acid by heat, or amide imine sulfonate. Examples of the onium salt include diaryliodonium salts such as aryldiazonium salts and diphenylphosphonium salts; di(alkylaryl)phosphonium salts such as di(third butylphenyl) phosphonium salts; tri Trialkylammonium salts such as methylammonium salts; dialkylmonoarylammonium salts such as dimethylphenylammonium salts; diarylmonoalkylammonium salts such as diphenylmethylammonium salts; triarylammonium salts Salt etc. Among these, the bis (third butylphenyl) onium salt of p-toluenesulfonic acid, the bis (third butylphenyl) onium salt of trifluoromethanesulfonic acid, and the three of trifluoromethanesulfonic acid are preferred Methyl saccharinium salt, trifluoromethanesulfonic acid dimethylphenyl alkane salt, trifluoromethanesulfonic acid diphenylmethyl sammonium salt, nonafluorobutane sulfonic acid bis (third butylphenyl) iodonium salt 、Diphenylphosphonium salt of camphor sulfonic acid, Diphenyl sulfonium salt of ethanesulfonic acid, Dimethylphenyl sulfonium salt of benzenesulfonic acid, Diphenylmethyl sulfonium salt of toluenesulfonic acid, etc. In addition, as the salt formed of a strong acid and a base, in addition to the above-mentioned onium salt, a salt formed of the following strong acid and a base, such as a pyridinium salt, can also be used. Examples of strong acids include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid, and methanesulfonic acid. , Alkylsulfonic acid such as ethanesulfonic acid, butanesulfonic acid, etc. Examples of the base include pyridine, alkylpyridine such as 2,4,6-trimethylpyridine, N-alkylpyridine such as 2-chloro-N-methylpyridine, and halogenated-N-alkylpyridine. Wait. As the imide sulfonate, for example, naphthalene imide sulfonate, o-xylylene imide sulfonate and the like can be used, and it is not limited as long as it is a compound that generates an acid under the action of heat. When the thermal acid generator is used, the blending amount is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass relative to (A) 100 parts by mass of the resin. . In the case of a positive photosensitive resin composition, a dissolution accelerator may be used in order to promote the removal of useless resin after photosensitive. For example, a compound having a hydroxyl group or a carboxyl group is preferred. Examples of the compound having a hydroxyl group include a ballast used in the above naphthoquinonediazide compounds, and linear chains such as p-cumylphenol, bisphenols, resorcinols, and MtrisPC, MtetraPC Phenolic compounds, TrisP-HAP, TrisP-PHBA, TrisP-PA and other non-linear phenol compounds (all manufactured by Honshu Chemical Industry Co., Ltd.), 2 to 5 phenol substitutions of diphenylmethane, 3,3-di 1 to 5 phenol substitutions of phenylpropane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane and 5-nor-2,3-dicarboxylic anhydride A compound obtained by reacting with an ear ratio of 1:2, obtained by reacting bis-(3-amino-4-hydroxyphenyl) sulcus with 1,2-cyclohexyldicarboxylic anhydride at a molar ratio of 1:2 Compounds, N-hydroxysuccinimide, N-hydroxyxylylenediimide, N-hydroxy 5-nor-2,3-dicarboxylimide, etc. Examples of compounds having a carboxyl group include 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxy Amygdalic acid, 2-methoxy-2-(1-naphthyl) propionic acid, amygdalic acid, 2-phenyllactic acid, α-methoxyphenylacetic acid, O-acetyl acetyl mandelic acid, Icon Acid and so on. When the dissolution accelerator is used, the blending amount is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the (A) resin. <Manufacturing method of hardened relief pattern and semiconductor device> Furthermore, the present invention provides a method of manufacturing hardened relief pattern, comprising: step (1), which is achieved by coating the above-mentioned photosensitive resin combination of the present invention on a substrate Forming a resin layer on the substrate; step (2), which exposes the resin layer; step (3), which develops the exposed resin layer to form a relief pattern; and step (4 ), which forms a hardened relief pattern by subjecting the relief pattern to heat treatment. The following describes the typical appearance of each step. (1) Step of forming a resin layer on the substrate by coating the photosensitive resin composition on the substrate In this step, the photosensitive resin composition of the present invention is coated on the base material, and then dried if necessary Instead, a resin layer is formed. As the coating method, a method previously used for coating the photosensitive resin composition may be used, for example, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, etc. The method of coating, the method of spray coating with a spray coater, etc. As a method for forming a relief pattern using the photosensitive resin composition of the present invention, not only can the resin layer be formed on the substrate by coating the photosensitive resin composition on the substrate, but also by combining the photosensitive resin After forming the film into a film, a layer of photosensitive resin composition is laminated on the substrate to form a resin layer. In addition, the film of the photosensitive resin composition of the present invention is formed on the support substrate. When the film is used, the support substrate can be removed after lamination, or the support substrate can be removed before lamination. If necessary, the coating film containing the photosensitive resin composition may be dried. As the drying method, methods such as air drying, heat 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 at 20°C to 140°C for 1 minute to 1 hour. The resin layer can be formed on the substrate by the above method. (2) Steps of exposing the resin layer In this step, an exposure device such as a contact exposure machine, a mirror projection exposure machine, a stepper, etc. is used, through a patterned photomask or reticle, Alternatively, the resin layer formed as described above is directly exposed by an ultraviolet light source or the like. Thereafter, in order to improve light sensitivity, etc., post-exposure baking (PEB) and/or pre-development baking under any combination of temperature and time may be performed as necessary. The range of the baking conditions is preferably temperature: 40 to 120°C, time: 10 seconds to 240 seconds, but it is not limited to this range as long as the characteristics of the photosensitive resin composition of the present invention are not impaired. (3) Step of developing the exposed resin layer to form a relief pattern In this step, the exposed portion or unexposed portion of the photosensitive resin layer after exposure is developed and removed. When using a negative type photosensitive resin composition (for example, when using a polyimide precursor or polyamide as the (A) resin), develop and remove the unexposed part, and use a positive type photosensitive resin In the case of the composition (for example, when a polyoxazole precursor or soluble polyimide is used as the (A) resin), the exposed portion is developed and removed. As the development method, any method can be selected and used from a previously known photoresist development method, such as a rotary spray method, a coating method, an immersion method with ultrasonic treatment, and the like. In addition, after development, in order to adjust the shape of the relief pattern, etc., post-development baking under conditions of any combination of temperature and time may be performed as necessary. As the developer used in development, a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent is preferred. For example, in the case of a photosensitive resin composition insoluble in an alkaline aqueous solution, as a good solvent, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethyl Acetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc., as poor solvents, preferably toluene, xylene, methanol, ethanol, isopropanol , Ethyl lactate, propylene glycol methyl ether acetate and water. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. Furthermore, two or more solvents, for example, a plurality of solvents may be used in combination. On the other hand, in the case of a photosensitive resin composition dissolved in an alkaline aqueous solution, the developer used at the time of development is the one in which the soluble polymer of the alkaline aqueous solution is dissolved and removed. Water solution. The alkaline compound dissolved in the developer may be any of inorganic alkaline compounds or organic alkaline compounds. Examples of the inorganic basic compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia. In addition, examples of the organic basic compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, and monoethylamine. , Diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, and triethanolamine. Furthermore, water-soluble organic solvents such as methanol, ethanol, propanol, or ethylene glycol, surfactants, storage stabilizers, resin dissolution inhibitors, etc. may be appropriately added to the alkaline aqueous solution as needed. The relief pattern can be formed in the above manner. (4) Step of forming a hardened relief pattern by subjecting the relief pattern to heat treatment In this step, the relief pattern obtained by the above development is heated to be converted into a hardened relief pattern. As the method of heat hardening, various methods such as those using a hot plate, those using an oven, and those using a temperature-raising oven with a temperature control program can be selected. The heating can be performed under the conditions of, for example, 180°C to 400°C for 30 minutes to 5 hours. As the ambient gas during heat curing, air can be used, and inert gases such as nitrogen and argon can also be used. <Semiconductor device> The present invention also provides a semiconductor device including the hardened relief pattern obtained by the above-described method of manufacturing the hardened relief pattern of the present invention. The present invention also provides a semiconductor device including a substrate as a semiconductor element and a cured relief pattern of a resin formed on the substrate by the above-described cured relief pattern manufacturing method. In addition, the present invention is also applicable to a method of manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method of manufacturing a hardened relief pattern as part of the steps. The semiconductor device of the present invention can be formed by forming a hardened relief pattern formed by the above-mentioned hardened relief pattern manufacturing method as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or having The protective film of the bump-structured semiconductor device is manufactured in combination with a known semiconductor device manufacturing method. The photosensitive resin composition of the present invention is not only suitable for semiconductor devices as described above, but also used for interlayer insulation of multilayer circuits, protective coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. [Examples] Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the photosensitive resin composition were measured and evaluated according to the following methods. (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement was the trade name "Shodex 805M/806M series" manufactured by Showa Denko Co., Ltd., and the standard monodisperse polystyrene was selected as the trade name "Shodex STANDARD SM-105" made by Showa Denko Co., Ltd. It is N-methyl-2-pyrrolidone, and the detector uses the brand name "Shodex RI-930" manufactured by Showa Denko Co., Ltd. (2) The production of the hardened relief pattern on Cu uses a sputtering device (L-440S-FHL type, manufactured by Canon Anelva), on a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm) on which Ti of 200 nm thick and Cu of 400 nm thick are sputtered in sequence. Then, using a coating developer (Coater Developer) (D-Spin60A type, manufactured by SOKUDO), the photosensitive resin composition prepared by the following method was spin-coated on the wafer and dried to form A coating film with a thickness of 10 μm (a coating film with a thickness of 6 to 10 μm is formed in the second embodiment). Using a photomask with a test pattern, align the exposure machine (PLA-501FA type, manufactured by Canon Corporation) with a parallel light mask, and irradiate the coating film with 300 mJ/cm ² Energy. Then, in the case of the negative type, cyclopentanone was used as the developer, in the case of the positive type, 2.38% TMAH (tetramethylammonium hydroxide, tetramethylammonium hydroxide) was used as the developer, and a coating developer (D-Spin60A Type, manufactured by SOKUDO Co., Ltd.) The coating film is spray-developed, and in the case of negative type, propylene glycol methyl ether acetate is used for rinsing, and in the case of positive type, pure water is used for rinsing, thereby obtaining relief on Cu pattern. Using a temperature-programmed curing oven (model VF-2000, manufactured by Koyo Lindberg), under a nitrogen atmosphere, the wafer on which the relief pattern is formed on Cu is heated for 2 hours at the temperature described in each example In this way, a hardened relief pattern containing a resin with a thickness of about 6 to 7 μm is obtained on Cu. (3) The high temperature storage test and subsequent evaluation of the hardened relief pattern on Cu uses a temperature-programmed curing oven (Model VF-2000, manufactured by Koyo Lindberg), in air at 150°C. The wafer with the hardened relief pattern formed on Cu was heated for 168 hours. Then, using a plasma surface treatment device (EXAM type, manufactured by Shinko Seiki Co., Ltd.), all resin layers on Cu were removed by plasma etching. The plasma etching conditions are as follows. Output: 133 W Gas type, flow rate: O ₂ ：40 ml/min＋CF ₄ : 1 ml/min Gas pressure: 50 Pa Mode: Hard mode Etching time: 1800 seconds FE-SEM (field emission-scanning electron microscope) (S-4800 type, Hitachi High -Manufactured by Technologies) Observe the Cu surface from which the resin layer has been completely removed, and use image analysis software (A Xiangjun, manufactured by Asahi Kasei Corporation) to calculate the area ratio of the void to the surface of the Cu layer. <First Example> As the first example, the following experiment was performed. <Production Example 1> ((A) Synthesis of polymer (A)-1 as a precursor of polyimide) Put 4,4'-oxydiphthalic acid in a separable flask with a volume of 2 L 155.1 g of dianhydride (ODPA), 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm generated by the reaction was completed, it was left to cool to room temperature and allowed to stand for 16 hours. Then, under ice-cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes, followed by stirring One side was added by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone over 60 minutes. After 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 formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction solution was added to 3 L of ethanol to produce a precipitate containing crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (Polymer (A)-1). The molecular weight of the polymer (A)-1 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 20,000. In addition, the weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was obtained. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: 2 Shodex KD-806M series mobile phases: 0.1 mol/L LiBr/NMP (N-methylpyrrolidone, N- (Methylpyrrolidone) Flow rate: 1 ml/min. <Production Example 2> ((A) Synthesis of polymer (A)-2 as a precursor of polyimide) Use 3,3',4,4' -147.1 g of biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) of Production Example 1, in addition to the The reaction was carried out in the same manner as described, to obtain polymer (A)-2. The molecular weight of the polymer (A)-2 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 22,000. <Production Example 3> ((A) Synthesis of polymer (A)-3 as a precursor of polyimide) 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl ( TFMB) 147.8 g instead of 9,4 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example 1, except that the polymerization was carried out in the same manner as in the method described in Production Example 1 above to obtain polymerization物(A)-3. The molecular weight of the polymer (A)-3 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 21,000. <Production Example 4> ((A) Synthesis of Polyamide Polymer (A)-4) (Synthesis of Phthalic Acid Compound End Block AIPA-MO) Put 5 into a separable flask with a volume of 5 L -543.5 g of aminoisophthalic acid {hereinafter abbreviated as AIPA} and 1700 g of N-methyl-2-pyrrolidone were mixed and stirred, and heated to 50°C by a water bath. Using a dropping funnel, dilute 512.0 g (3.3 mol) of 2-methacryloxyethyl isocyanate into 500 g of γ-butyrolactone, and stir at 50°C for about 2 hours. . After confirming the completion of the reaction (the disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC}, the reaction solution was poured into 15 L of ion-exchanged water and stirred. It was allowed to stand, after the crystallization of the reaction product appeared, it was filtered and separated, washed with appropriate water, and dried under vacuum at 40°C for 48 hours, thereby obtaining the amine group of 5-aminoisophthalic acid and isocyanide AIPA-MO obtained by isocyanate group of acid 2-methacrylic acid ethyl ester. The low molecular weight GPC purity of the obtained AIPA-MO is about 100%. (Synthesis of polymer (A)-4) In a separable flask with a volume of 2 L, the obtained AIPA-MO 100.89 g (0.3 mol), pyridine 71.2 g (0.9 mol), GBL (butyrolactone, γ -butyrolactone) 400 g, mixed and cooled to 5°C with an ice bath. Under cooling in an ice bath, a solution of dicyclohexylcarbodiimide (DCC) 125.0 g (0.606 mol) dissolved in GBL 125 g was added dropwise in about 20 minutes, and then added dropwise in about 20 minutes 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB} 103.16 g (0.28 mol) dissolved in 168 g of NMP, maintained by ice bath for 3 hours less than 5 ℃, and then The ice bath was removed and stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. A mixed liquid of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction liquid, and the precipitated polymer was separated and dissolved in NMP 650 g again. The obtained crude polymer solution was added dropwise to 5 L of water to precipitate the polymer, and the obtained precipitate was filtered and separated, followed by vacuum drying to obtain a powdery polymer (Polymer (A)-4). The molecular weight of the polymer (A)-4 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 34,700. <Production Example 5> ((A) Synthesis of polymer (A)-5 as a precursor of polyoxazole) In a separable flask with a volume of 3 L, place 2,2-bis(3-amino-4- 183.1 g of hydroxyphenyl)-hexafluoropropane, 640.9 g of N,N-dimethylacetamide (DMAc) and 63.3 g of pyridine were mixed and stirred at room temperature (25°C) to make a homogeneous solution. Using a dropping funnel, 118.0 g of 4,4′-diphenyl ether dimethyl chloride was dissolved in 354 g of diethylene glycol dimethyl ether (DMDG). At this time, the separable flask was cooled in a water bath at 15 to 20°C. The time required for dripping is 40 minutes, and the maximum temperature of the reaction liquid is 30°C. After 3 hours have elapsed after the dripping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride is added to the reaction solution, and the mixture is left under stirring at room temperature for 15 hours to make the polymer chains account for 99% of the total amine The terminal group is capped with a carboxycyclohexyl amide group. The reaction rate at this time can be easily calculated by tracing the residual amount of 1,2-cyclohexyldicarboxylic anhydride charged by high-performance liquid chromatography (HPLC). Thereafter, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with appropriate water, dehydrated and then vacuum dried to obtain a gel permeation chromatography (GPC ) Method to measure the crude polybenzoxazole precursor with a weight average molecular weight of 9,000 (in terms of polystyrene). After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), it is treated with a cation exchange resin and an anion exchange resin, and the solution thus obtained is poured into ion exchange water The polymer precipitated was separated by filtration, washed with water and dried in vacuum, thereby obtaining a purified polybenzoxazole precursor (polymer (A)-5). <Production Example 6> ((A) Synthesis of polymer (A)-6 as polyimide) Attached to a glass separable four-necked flask equipped with an anchor stirrer made of Teflon (registered trademark) The cooling tube of the An-Stark separator. While introducing nitrogen gas, the flask was immersed in a silicone oil bath and stirred. Add 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5-(2,5-bioxytetrahydrogen -3-furyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70.29 g (266 mmol), γ-butyrolactone 254.6 g. Toluene 60 g. After stirring at 100 rpm for 4 hours at room temperature, add 4.6 g (28 mmol) of 5-northene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). The nitrogen gas was heated and stirred at 100 rpm at a silicon bath temperature of 50°C for 8 hours. Thereafter, it was heated to a silicon bath temperature of 180°C, and heated and stirred at 100 rpm for 2 hours. Toluene and water distilled in the reaction are removed. After the amide imidization reaction was completed, the temperature was returned to room temperature. Thereafter, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with appropriate water, dehydrated, and then vacuum-dried to obtain gel permeation chromatography (GPC). The crude polyimide (polymer (A)-6) having a weight average molecular weight of 23,000 (in terms of polystyrene) measured by the method. <Production Example 7> ((A) Synthesis of polymer (A)-8 as phenol resin) A separable flask equipped with a Dean-Stark apparatus with a volume of 1.0 L was replaced with nitrogen, and then In a separable flask, combine resorcinol 81.3 g (0.738 mol), BMMB 84.8 g (0.35 mol), p-toluenesulfonic acid 3.81 g (0.02 mol), and propylene glycol monomethyl ether (hereinafter also referred to as PGME) 116 g in The mixture was stirred at 50°C to dissolve the solid matter. The mixed solution was heated to 120°C with an oil bath, and it was confirmed that methanol was produced from the reaction solution. The reaction solution was directly stirred at 120°C for 3 hours. Then, in another container, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)p-cresol and 249 g of PGME were mixed and stirred to uniformly dissolve, and the obtained solution was used for a dropping funnel for a long time The solution was added dropwise to the separable flask for 1 hour, and the solution was stirred for 2 hours after dropping. After the reaction was completed, the same treatment as in Production Example 7 was carried out to obtain a copolymer (polymer H) containing resorcinol/BMMB/2,6-bis(hydroxymethyl)p-cresol at a yield of 77%. The weight-average molecular weight of the polymer H calculated by standard polystyrene conversion of the GPC method was 9,900. <Example 1> Using polymers (A)-1 and (A)-2, a negative photosensitive resin composition was prepared by the following method, and the photosensitive resin composition was evaluated. Polymers (A)-1 50 g and (A)-2 50 g (equivalent to (A) resin) and dicyclohexyl phthalate (Tokyo Chemical Industry Co., Ltd.) as precursors of polyimide Manufactured, equivalent to (B)-1) 4 g, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 1) (equivalent (C) Sensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g, N-[3-(triethoxysilyl)propyl] phthalimide 1.5 g are dissolved in It contains a mixed solvent of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. By further adding a small amount of the above mixed solvent, the viscosity of the obtained solution was adjusted to about 35 poise to prepare a negative photosensitive resin composition. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 4.1%. <Example 2> In the above Example 1, the component (B) was changed to diphenyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the negative was prepared in the same manner as in Example 1. Type photosensitive resin composition solution. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 4.9%. <Example 3> In Example 1, the component (B) was changed to di-2-ethylhexyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.). The negative photosensitive resin composition solution was prepared in the same manner. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.2%. <Example 4> In Example 1, the component (B) was changed to dicyclohexyl trimellitate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that it was prepared in the same manner as in Example 1. Negative photosensitive resin composition solution. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 4.3%. <Example 5> In the above Example 1, the component (B) was changed to pyromellitic acid dicyclohexyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.), except that it was prepared in the same manner as in Example 1. Negative photosensitive resin composition solution. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 4.2%. <Example 6> In the above Example 1, the component (B) was changed to dicyclohexyl adipate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the negative was prepared in the same manner as in Example 1. Type photosensitive resin composition solution. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.9%. <Example 7> In the above Example 1, the component (B) was changed to dicyclohexyl sebacate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the negative was prepared in the same manner as in Example 1. Type photosensitive resin composition solution. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.8%. <Example 8> In the above Example 1, the component (B) was changed to tetrahydrofurfuryl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.), and the negative form was prepared in the same manner as in Example 1 except for that. Photosensitive resin composition solution. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 4.8%. <Example 9> In Example 1, the negative photosensitive resin composition solution was prepared in the same manner as Example 1 except that the amount of component (B)-1 added was changed to 2 g. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 7.6%. <Example 10> In Example 1, the negative photosensitive resin composition solution was prepared in the same manner as Example 1 except that the amount of component (B)-1 added was 8 g. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 4.8%. <Example 11> In Example 1, the negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the amount of component (B)-1 added was 16 g. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 10.5%. <Example 12> A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the curing temperature was changed from 230°C to 350°C in Example 1 above. For this composition, a hard relief pattern was formed on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.5% was obtained. <Example 13> In the above Example 1, as the (A) resin, the polymer (A)-1 50 g and the polymer (A)-2 50 g were changed to the polymer (A)-1 100 g, and (C) The component changed from PDO to 1,2-octanedione-1-{4-(phenylthio)-2-(O-benzoyl oxime)} (Irgacure OXE01 (manufactured by BASF, trade name )) 2.5 g, except for this, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1. For this composition, a hard relief pattern was formed on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.3% was obtained. <Example 14> In Example 12 above, the negative photosensitive resin was prepared in the same manner as Example 12 except that the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide. Composition solution. For this composition, a hard relief pattern was formed on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.5% was obtained. <Example 15> In the above Example 1, as the (A) resin, the polymer (A)-1 50 g and the polymer (A)-2 50 g were changed to the polymer (A)-3 100 g, and A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that the curing temperature was changed from 230°C to 350°C. For this composition, a hard relief pattern was formed on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.8% was obtained. <Example 16> In the above Example 1, as the (A) resin, the polymer (A)-1 50 g and the polymer (A)-2 50 g were changed to the polymer (A)-4 100 g, except Other than that, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1. For this composition, a hard relief pattern was formed on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 4.9%. <Example 17> Using polymer (A)-5, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. The polymer (A)-5 100 g (corresponding to (A) resin) as a precursor of polyoxazole is represented by the following formula (96):

77% of the indicated phenolic hydroxyl groups are naphthoquinone diazide-4-sulfonate-sensitized diazoquinone compounds (manufactured by Toyo Synthetic, equivalent to (C) component) (C1) 15 g dissolved in γ -Butyrolactone (as solvent) 100 g. By further adding a small amount of γ-butyrolactone, the viscosity of the obtained solution was adjusted to about 20 poise to prepare a positive photosensitive resin composition. The composition was cured at 350° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.1%. <Example 18> In Example 17, the same as Example 17 except that the polymer (A)-5 100 g was changed to the polymer (A)-6 100 g as the (A) resin The positive photosensitive resin composition solution is prepared by this method. With respect to this composition, curing was performed at 250° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 6.2%. <Example 19> In the above Example 17, as the (A) resin, 100 g of the polymer (A)-6 was changed to the polymer (A)-7 (phenolic novolak resin, polystyrene equivalent weight average molecular weight (Mw) ) = 10,600 (manufactured by Asahi Organic Materials Co., Ltd., product name EP-4080G) 100 g, except that a positive photosensitive resin composition solution was prepared in the same manner as in Example 17. For this composition, by the above Method Curing at 250°C to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.2%. <Example 20> The above example In 17, as (A) resin, polymer (A)-6 100 g was changed to polymer (A)-7 (phenolic novolak resin, polystyrene equivalent weight average molecular weight (Mw) = 10,600 (Asahi Organic Materials Co., Ltd. Manufactured, product name EP-4080G) 100 g, (B) component was changed to tetrahydrofurfuryl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the positive form was prepared in the same manner as in Example 17 Photosensitive resin composition solution. This composition was cured at 250°C by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated. A result of 5.6% was obtained. <Example 21> In Example 17 above, as the (A) resin, except that the polymer (A)-6 100 g was changed to the polymer (A)-8 100 g, A positive photosensitive resin composition solution was prepared in the same manner as in Example 17. The composition was cured at 250° C. by the above method to produce a hard relief pattern on the Cu layer, and subjected to a high-temperature storage test to evaluate The ratio of the area occupied by voids on the surface of the Cu layer to obtain a result of 4.6%. <Example 22> In the above Example 17, as the (A) resin, the polymer (A)-6 100 g was changed to a polymer (A)-8 100 g, except that the component (B) was changed to tetrahydrofurfuryl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that a positive photosensitive resin was prepared in the same manner as in Example 17. A composition solution. For this composition, a 250° C. curing was performed by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain 4.3 % Result. <Comparative Example 1> In the composition of Example 1, the negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the component (B)-1 was not added, and was carried out The same evaluation as in Example 1. Since the (B) plasticizer of the present invention was not included, the evaluation result was 15.2%. <Comparative Example 2> In the composition of Example 16, (B)-1 component was not added, Other than this, a negative photosensitive resin composition was prepared in the same manner as in Example 15, And the same evaluation as Example 15 was performed. Since the (B) plasticizer of the present invention is not included, the evaluation result is 14.3%. <Comparative Example 3> In the composition of Example 14, except that the component (B)-1 was not added, a negative photosensitive resin composition was prepared in the same manner as in Example 13 and carried out as in Example 13. The same evaluation. Since the (B) plasticizer of the present invention is not included, the evaluation result is 15.7%. <Comparative Example 4> A positive photosensitive resin composition was prepared in the same manner as in Example 17 except that the component (B)-1 was not added to the composition of Example 18, and was carried out in the same manner as in Example 17. The same evaluation. Since the (B) plasticizer of the present invention is not included, the evaluation result is 16.3%. <Comparative Example 5> In the composition of Example 1, the negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the amount of component (B)-1 added was changed to 0.05 g. The same evaluation as in Example 1 was performed. The evaluation result was 13.1%. <Comparative Example 6> In the composition of Example 1, except that the addition amount of the component (B)-1 was changed to 60 g, a negative photosensitive resin composition was prepared in the same manner as in Example 1, and The same evaluation as in Example 1 was performed. The evaluation result was 15.2%. Table 1 summarizes the results of Examples 1 to 22 and Comparative Examples 1 to 6. [Table 1]

<Second Embodiment> As the second embodiment, the following experiment was performed. <Production Example 1> ((A) Synthesis of polymer A as a precursor of polyimide) Put 4,4'-oxydiphthalic dianhydride (ODPA) in a separable flask with a volume of 2 L ) 155.1 g, adding 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone and stirring at room temperature, adding 81.5 g of pyridine while stirring to obtain a reaction mixture. After the exotherm generated by the reaction was completed, it was left to cool to room temperature and allowed to stand for 16 hours. Then, under ice-cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes, followed by stirring One side was added by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone over 60 minutes. After 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 formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction solution was added to 3 L of ethanol to produce a precipitate containing crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (Polymer A). The molecular weight of polymer A was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000. In addition, the weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was obtained. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: 2 Shodex KD-806M serial mobile phases: 0.1 mol/L LiBr/NMP Flow rate: 1 ml/min. <Production Example 2> ((A) Synthesis of Polyimide Precursor Polymer B) Using 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) 147.1 g instead of the production example 1,4'-oxydiphthalic dianhydride (ODPA) of 155.1 g was used, except that the reaction was carried out in the same manner as in the method described in Production Example 1 above to obtain polymer B. The molecular weight of polymer B was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 22,000. <Production Example 3> ((A) Synthesis of polymer C as a polyimide precursor) 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) 147.8 g was used Instead of 9,3.0 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example 1, a reaction was carried out in the same manner as the method described in Production Example 1 above to obtain polymer C. The molecular weight of polymer C was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 21,000. <Production Example 4> ((A) Synthesis of Polyamide Polymer D) (Synthesis of Phthalic Acid Compound End Block AIPA-MO) In a separable flask with a volume of 5 L, put 5-amine groups Phthalic acid {hereinafter abbreviated as AIPA} 543.5 g and N-methyl-2-pyrrolidone 1700 g were mixed and stirred, and heated to 50°C by a water bath. Using a dropping funnel, dilute 512.0 g (3.3 mol) of 2-methacryloxyethyl isocyanate into 500 g of γ-butyrolactone, and stir at 50°C for about 2 hours. . After confirming the completion of the reaction (the disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC}, the reaction solution was poured into 15 L of ion-exchanged water and stirred. It was allowed to stand, after the crystallization of the reaction product appeared, it was filtered and separated, washed with appropriate water, and dried under vacuum at 40°C for 48 hours, thereby obtaining the amine group of 5-aminoisophthalic acid and isocyanide AIPA-MO obtained by isocyanate group of acid 2-methacrylic acid ethyl ester. The low molecular weight GPC purity of the obtained AIPA-MO is about 100%. (Synthesis of Polymer D) In a separable flask with a volume of 2 L, the obtained AIPA-MO 100.89 g (0.3 mol), pyridine 71.2 g (0.9 mol), and GBL 400 g were mixed and mixed by an ice bath Cool to 5°C. Under cooling in an ice bath, a solution of dicyclohexylcarbodiimide (DCC) 125.0 g (0.606 mol) dissolved in GBL 125 g was added dropwise in about 20 minutes, and then added dropwise in about 20 minutes 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB} 103.16 g (0.28 mol) dissolved in 168 g of NMP, maintained by ice bath for 3 hours less than 5 ℃, and then The ice bath was removed and stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. A mixed liquid of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction liquid, and the precipitated polymer was separated and dissolved in NMP 650 g again. The obtained crude polymer solution was added dropwise to 5 L of water to precipitate the polymer, and the obtained precipitate was filtered and separated, followed by vacuum drying to obtain a powdery polymer (Polymer E). The molecular weight of polymer D was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 34,700. <Production Example 5> ((A) Synthesis of polymer E as a precursor of polyoxazole) In a separable flask with a volume of 3 L, place 2,2-bis(3-amino-4-hydroxyphenyl) -183.1 g of hexafluoropropane, 640.9 g of N,N-dimethylacetamide (DMAc) and 63.3 g of pyridine were mixed and stirred at room temperature (25°C) to make a homogeneous solution. Using a dropping funnel, 118.0 g of 4,4′-diphenyl ether dimethyl chloride was dissolved in 354 g of diethylene glycol dimethyl ether (DMDG). At this time, the separable flask was cooled in a water bath at 15 to 20°C. The time required for dripping is 40 minutes, and the maximum temperature of the reaction liquid is 30°C. After 3 hours have elapsed after the dripping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride is added to the reaction solution, and the mixture is left under stirring at room temperature for 15 hours to make the polymer chains account for 99% of the total amine The terminal group is capped with a carboxycyclohexyl amide group. The reaction rate at this time can be easily calculated by tracing the residual amount of 1,2-cyclohexyldicarboxylic anhydride charged by high-performance liquid chromatography (HPLC). Thereafter, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with appropriate water, dehydrated and then vacuum dried to obtain a gel permeation chromatography (GPC ) Method to measure the crude polybenzoxazole precursor with a weight average molecular weight of 9,000 (in terms of polystyrene). After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), it is treated with a cation exchange resin and an anion exchange resin, and the solution thus obtained is poured into ion exchange water Then, the polymer precipitated was separated by filtration, washed with water and dried in vacuum, thereby obtaining a purified polybenzoxazole precursor (Polymer E). <Production Example 6> ((A) Synthesis of Polyimide Polymer F) Attach a Dean-Star to a glass separable four-necked flask equipped with a Teflon (registered trademark) anchor stirrer Gram separator cooling tube. While introducing nitrogen gas, the flask was immersed in a silicone oil bath and stirred. Add 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5-(2,5-bioxytetrahydrogen -3-furyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70.29 g (266 mmol), γ-butyrolactone 254.6 g. Toluene 60 g. After stirring at 100 rpm for 4 hours at room temperature, add 4.6 g (28 mmol) of 5-northene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). The nitrogen gas was heated and stirred at 100 rpm at a silicon bath temperature of 50°C for 8 hours. Thereafter, it was heated to a silicon bath temperature of 180°C, and heated and stirred at 100 rpm for 2 hours. Toluene and water distilled in the reaction are removed. After the amide imidization reaction was completed, the temperature was returned to room temperature. Thereafter, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with appropriate water, dehydrated, and then vacuum-dried to obtain gel permeation chromatography (GPC). The crude polyimide (polymer F) having a weight average molecular weight of 23,000 (in terms of polystyrene) measured by the method. <Production Example 7> ((A) Synthesis of polymer G as a phenol resin) In a separable flask with a Dean-Stark device with a volume of 0.5 L, methyl 3,5-dihydroxybenzoate was 128.3 g (0.76 mol), 4,4'-bis (methoxymethyl) biphenyl (hereinafter also referred to as "BMMB") 121.2 g (0.5 mol), diethyl sulfuric acid 3.9 g (0.025 mol), diethyl 140 g of glycol dimethyl ether was mixed and stirred at 70°C to dissolve the solid matter. The mixed solution was heated to 140°C with an oil bath, and it was confirmed that methanol was generated from the reaction solution. The reaction solution was directly stirred at 140°C for 2 hours. Then, the reaction vessel was cooled in the atmosphere, and an additional 100 g of tetrahydrofuran was added thereto and stirred. The above reaction diluent was added dropwise to 4 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, washed with appropriate water, dehydrated and then vacuum-dried to obtain a 3,5-dihydroxy group containing 70% yield Copolymer of methyl benzoate/BMMB (Polymer G). The weight-average molecular weight of this polymer G calculated by standard polystyrene conversion in the GPC method was 21,000. <Production Example 8> ((A) Synthesis of polymer H as phenol resin) A separable flask with a Dean-Stark apparatus of 1.0 L in volume was subjected to nitrogen replacement, and thereafter, in the separable flask In the process, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, 3.81 g (0.02 mol) of p-toluenesulfonic acid, and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were conducted at 50°C Mix and stir to dissolve solids. The mixed solution was heated to 120°C with an oil bath, and it was confirmed that methanol was produced from the reaction solution. The reaction solution was directly stirred at 120°C for 3 hours. Then, in another container, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)p-cresol and 249 g of PGME were mixed and stirred to uniformly dissolve, and the obtained solution was used for a dropping funnel for a long time The solution was added dropwise to the separable flask for 1 hour, and the solution was stirred for 2 hours after dropping. After the reaction was completed, the same treatment as in Production Example 7 was carried out to obtain a copolymer (polymer H) containing resorcinol/BMMB/2,6-bis(hydroxymethyl)p-cresol at a yield of 77%. The weight-average molecular weight of the polymer H calculated by standard polystyrene conversion of the GPC method was 9,900. <Example 1> Using polymers A and B, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Plate-like particles of polymer A 50 g and B 50 g (equivalent to (A) resin) and zirconium phosphate (long axis 100 nm, short axis 5 nm), which are precursors of polyimide, correspond to an aspect ratio of 20 (B-1) Nanoparticles) 5 g, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (referred to as “PDO” in Table 1) (equivalent to (C) Photosensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g, and N-[3-(triethoxysilyl)propyl] phthalimide 1.5 g are dissolved in A mixed solvent of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. By further adding a small amount of the above mixed solvent, the viscosity of the obtained solution was adjusted to about 35 poise to prepare a negative photosensitive resin composition. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.5%. <Example 2> In the above Example 1, the negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the addition amount of zirconium phosphate was 1 g as the component (B-1). Solution. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 6.6%. <Example 3> In the above Example 1, as the component (B-1), montmorillonite (long axis 100 nm, short axis 10 nm, aspect ratio 10 plate-like particles) was used instead of zirconium phosphate. A negative photosensitive resin composition solution was prepared in the same manner as in Example 1. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.8%. <Example 4> In the above Example 1, as the component (B-1), 1 g of Aerotech (spherical particles with a particle diameter of 12 nm, aspect ratio 1) 1 g was used instead of 5 g of zirconium phosphate. A negative photosensitive resin composition solution was prepared in the same manner as in Example 1. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.4%. <Example 5> A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, and the composition was cured at 350° C. by the above method to produce a hard relief pattern on the Cu layer and proceeded. After the high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.5% was obtained. <Example 6> In the above Example 1, as the (A) resin, the polymer A 50 g and the polymer B 50 g were changed to the polymer A 100 g, and as the (C) component, the PDO 4 g was changed to 1. , 2-octanedione-1-{4-(phenylthio)-2-(O-benzyl oxime)} (Irgacure OXE01 (manufactured by BASF, trade name)) 2.5 g, other than A negative photosensitive resin composition solution was prepared in the same manner as in Example 1. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.3%. <Example 7> In the above Example 1, as the (A) resin, 50 g of the polymer A and 50 g of the polymer B were changed to 100 g of the polymer A, and as the (C) component, PDO 4 g was changed to 1. ,2-octanedione-1-{4-(phenylthio)-2-(O-benzoyl oxime)} (Irgacure OXE01 (manufactured by BASF, trade name)) 2.5 g, and then the solvent was changed A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide were used. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.3%. <Example 8> In the above Example 1, as the (A) resin, in the same manner as in Example 1, except that the polymer A 50 g and the polymer B 50 g were changed to the polymer C 100 g. A negative photosensitive resin composition solution was prepared. Regarding this composition, a 350° C. curing was performed by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 4.8%. <Example 9> In the above Example 1, as the (A) resin, in the same manner as in Example 1, except that the polymer A 50 g and the polymer B 50 g were changed to the polymer D 100 g. A negative photosensitive resin composition solution was prepared. With respect to this composition, curing was performed at 250° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.6%. <Example 10> Using polymer E, the positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. The polymer E 100 g (corresponding to (A) resin) which is a precursor of polyoxazole is represented by the following formula (96):

The represented 77% of the phenolic hydroxyl group is naphthoquinone diazide-4-sulfonate-sensitized diazoquinone compound (manufactured by Toyo Synthetic, equivalent to (C) sensitizer) (C1) 15 g, phosphoric acid Zirconium (plate-like particles with a long diameter of 100 nm and a thickness of 5 nm, equivalent to (B) nanoparticles) 5 g, and 3-third butoxycarbonylaminopropyltriethoxysilane 6 g are dissolved together γ-butyrolactone (as solvent) 100 g. By further adding a small amount of γ-butyrolactone, the viscosity of the obtained solution was adjusted to about 20 poise to prepare a positive photosensitive resin composition. The composition was cured at 350° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.7%. <Example 11> In Example 10 above, a positive photosensitive resin was prepared in the same manner as in Example 10 except that the polymer E 100 g was changed to polymer F 100 g as the (A) resin. Composition solution. With respect to this composition, curing was performed at 250° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.7%. <Example 12> In the above Example 10, a positive photosensitive resin was prepared in the same manner as in Example 10 except that (A) resin was changed from polymer E 100 g to polymer G 100 g. Composition solution. The composition was cured at 220° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.4%. <Example 13> In the above Example 10, a positive photosensitive resin was prepared in the same manner as in Example 10 except that (A) resin was changed from polymer E 100 g to polymer H 100 g. Composition solution. With respect to this composition, curing was performed at 220° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.5%. <Comparative Example 1> In the composition of Example 1, except that zirconium phosphate was not added, a negative photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. Since the (B) compound of the present invention was not included, the evaluation result was 14.3%. <Comparative Example 2> In the composition of Example 8, the negative photosensitive resin composition was prepared in the same manner as in Example 8 except that zirconium phosphate was not added, and the same evaluation as in Example 10 was performed. Since the (B) compound of the present invention was not included, the evaluation result was 14.9%. <Comparative Example 3> In the composition of Example 10, a positive photosensitive resin composition was prepared in the same manner as in Example 10 except that zirconium phosphate was not added, and the same evaluation as in Example 10 was performed. Since the (B) compound of the present invention was not included, the evaluation result was 14.6%. Table 2 summarizes these results. [Table 2]

<Third Embodiment> As the third embodiment, the following experiment was performed. <Production Example 1> ((A) Synthesis of polymer A as a precursor of polyimide) Put 4,4'-oxydiphthalic dianhydride (ODPA) in a separable flask with a volume of 2 L ) 155.1 g, adding 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone and stirring at room temperature, adding 81.5 g of pyridine while stirring to obtain a reaction mixture. After the exotherm generated by the reaction was completed, it was left to cool to room temperature and allowed to stand for 16 hours. Then, under ice-cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes, followed by stirring One side was added by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone over 60 minutes. After 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 formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction solution was added to 3 L of ethanol to produce a precipitate containing crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (Polymer A). The molecular weight of polymer A was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000. In addition, the weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was obtained. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: 2 Shodex KD-806M serial mobile phases: 0.1 mol/L LiBr/NMP Flow rate: 1 ml/min. <Production Example 2> ((A) Synthesis of Polyimide Precursor Polymer B) Using 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) 147.1 g instead of the production example 1,4'-oxydiphthalic dianhydride (ODPA) of 155.1 g was used, except that the reaction was carried out in the same manner as in the method described in Production Example 1 above to obtain polymer B. The molecular weight of polymer B was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 22,000. <Production Example 3> ((A) Synthesis of polymer C as a polyimide precursor) 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) 147.8 g was used Instead of 9,3.0 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example 1, a reaction was carried out in the same manner as the method described in Production Example 1 above to obtain polymer C. The molecular weight of polymer C was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 21,000. <Production Example 4> ((A) Synthesis of Polyamide Polymer D) (Synthesis of Phthalic Acid Compound End Block AIPA-MO) In a separable flask with a volume of 5 L, put 5-amine groups Phthalic acid {hereinafter abbreviated as AIPA} 543.5 g and N-methyl-2-pyrrolidone 1700 g were mixed and stirred, and heated to 50°C by a water bath. Using a dropping funnel, dilute 512.0 g (3.3 mol) of 2-methacryloxyethyl isocyanate into 500 g of γ-butyrolactone, and stir at 50°C for about 2 hours. . After confirming the completion of the reaction (the disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC}, the reaction solution was poured into 15 L of ion-exchanged water and stirred. It was allowed to stand, after the crystallization of the reaction product appeared, it was filtered and separated, washed with appropriate water, and dried under vacuum at 40°C for 48 hours, thereby obtaining the amine group of 5-aminoisophthalic acid and isocyanide AIPA-MO obtained by isocyanate group of acid 2-methacrylic acid ethyl ester. The low molecular weight GPC purity of the obtained AIPA-MO is about 100%. (Synthesis of Polymer D) In a separable flask with a volume of 2 L, the obtained AIPA-MO 100.89 g (0.3 mol), pyridine 71.2 g (0.9 mol), and GBL 400 g were mixed and mixed by an ice bath Cool to 5°C. Under cooling in an ice bath, a solution of dicyclohexylcarbodiimide (DCC) 125.0 g (0.606 mol) dissolved in GBL 125 g was added dropwise in about 20 minutes, and then added dropwise in about 20 minutes 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB} 103.16 g (0.28 mol) dissolved in 168 g of NMP, maintained by ice bath for 3 hours less than 5 ℃, and then The ice bath was removed and stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. A mixed liquid of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction liquid, and the precipitated polymer was separated and dissolved in NMP 650 g again. The obtained crude polymer solution was added dropwise to 5 L of water to precipitate the polymer, and the obtained precipitate was filtered and separated, followed by vacuum drying to obtain a powdery polymer (Polymer E). The molecular weight of polymer D was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 34,700. <Example 1> Using polymers A and B, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Polymers A 50 g and B 50 g (equivalent to (A) resin) and TMOM-BP (trade name, Honshu Chemicals, equivalent to (B-2) thermal crosslinking agent) as precursors of polyimide g, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (marked as "PDO" in Table 1) (equivalent to (C) sensitizer) 4 g, four 8 g of ethylene glycol dimethacrylate and 1.5 g of N-[3-(triethoxysilyl)propyl]phthalimide are dissolved in N-methyl-2-pyrrolidone (Hereinafter referred to as NMP) a mixed solvent of 80 g and 20 g of ethyl lactate. By further adding a small amount of the above mixed solvent, the viscosity of the obtained solution was adjusted to about 35 poise to prepare a negative photosensitive resin composition. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.7%. <Example 2> In the above Example 1, as the component (B-2), the addition amount of TMOM-BP was changed to 20 g, and a negative photosensitive resin combination was prepared in the same manner as in Example 1 except that the amount of TMOM-BP was added to 20 g.物液。 Material solution. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 3.8%. <Example 3> In Example 1, the negative photosensitive resin combination was prepared in the same manner as Example 1 except that the amount of TMOM-BP was changed to 5 g as the component (B-2).物液。 Material solution. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 9.3%. <Example 4> In the above Example 1, TM-BIP-A (trade name, Honshu Chemical) was used instead of TMOM-BP as the component (B-2), except that in the same manner as Example 1 A negative photosensitive resin composition solution was prepared. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.2%. <Example 5> In the above Example 1, HMOM-TP-HAP (trade name, Honshu Chemical) was used instead of TMOM-BP as the component (B-2), except that in the same manner as Example 1 A negative photosensitive resin composition solution was prepared. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.8%. <Example 6> In the above Example 1, NIKALAC MW-390 (trade name, SANWA CHEMICAL) was used instead of TMOM-BP as the component (B-2), except that it was prepared in the same manner as in Example 1. Negative photosensitive resin composition solution. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 10.3%. <Example 7> In the above Example 1, as the (A) resin, in the same manner as in Example 1, except that the polymer A 50 g and the polymer B 50 g were changed to the polymer A 100 g. A negative photosensitive resin composition solution was prepared. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.3%. <Example 8> In the above Example 1, as the (A) resin, the polymer A 50 g and the polymer B 50 g were changed to the polymer A 100 g, and as the (C) component, the PDO 4 g was changed to 1. ,2-octanedione-1-{4-(phenylthio)-2-(O-benzyl oxime)} (Irgacure OXE01 (manufactured by BASF, trade name)) 2.0 g, and then the solvent was changed A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that 80 g of γ-butyrolactone and 20 g of dimethyl sulfoxide were used. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.8%. <Example 9> In the above Example 1, as the (A) resin, in the same manner as in Example 1, except that the polymer A 50 g and the polymer B 50 g were changed to the polymer C 100 g. A negative photosensitive resin composition solution was prepared. The composition was cured at 350° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.0%. <Example 10> In the above Example 1, as the (A) resin, in the same manner as in Example 1, except that the polymer A 50 g and the polymer B 50 g were changed to the polymer D 100 g. A negative photosensitive resin composition solution was prepared. The composition was cured at 250° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 6.9%. <Comparative Example 1> In the composition of Example 1, except that TMOM-BP was not added, a negative photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. . Since the (B) compound of the present invention was not included, the evaluation result was 14.3%. <Comparative Example 2> In the composition of Example 10, except that TMOM-BP was not added, a negative photosensitive resin composition was prepared in the same manner as in Example 10, and the same evaluation as in Example 11 was performed . Since the (B) compound of the present invention was not included, the evaluation result was 15.5%. Table 3 summarizes the results of Examples 1 to 10 and Comparative Examples 1 to 2. [table 3]

<Fourth Example> As the fourth example, the following experiment was performed. <Production Example 1> ((A) Synthesis of polymer (A)-1 as a precursor of polyimide) Put 4,4'-oxydiphthalic acid in a separable flask with a volume of 2 L 155.1 g of dianhydride (ODPA), 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm generated by the reaction was completed, it was left to cool to room temperature and allowed to stand for 16 hours. Then, under ice-cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes, followed by stirring One side was added by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone over 60 minutes. After 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 formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction solution was added to 3 L of ethanol to produce a precipitate containing crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum dried to obtain a powdery polymer (Polymer (A)-1). The molecular weight of the polymer (A)-1 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 20,000. In addition, the weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was obtained. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: 2 Shodex KD-806M serial mobile phases: 0.1 mol/L LiBr/NMP Flow rate: 1 ml/min. <Production Example 2> ((A) Synthesis of polymer (A)-2 as a polyimide precursor) 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) 147.1 is used g instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) of Production Example 1, except that the reaction was carried out in the same manner as the method described in Production Example 1 above to obtain a polymer (A)-2. The molecular weight of the polymer (A)-2 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 22,000. <Production Example 3> ((A) Synthesis of polymer (A)-3 as a precursor of polyimide) 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl ( TFMB) 147.8 g instead of 9,4 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example 1, except that the polymerization was carried out in the same manner as in the method described in Production Example 1 above to obtain polymerization物(A)-3. The molecular weight of the polymer (A)-3 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 21,000. <Production Example 4> ((A) Synthesis of Polyamide Polymer (A)-4) (Synthesis of Phthalic Acid Compound End Block AIPA-MO) Put 5 into a separable flask with a volume of 5 L -543.5 g of aminoisophthalic acid {hereinafter abbreviated as AIPA} and 1700 g of N-methyl-2-pyrrolidone were mixed and stirred, and heated to 50°C by a water bath. Using a dropping funnel, dilute 512.0 g (3.3 mol) of 2-methacryloxyethyl isocyanate into 500 g of γ-butyrolactone, and stir at 50°C for about 2 hours. . After confirming the completion of the reaction (the disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC}, the reaction solution was poured into 15 L of ion-exchanged water and stirred. It was allowed to stand, after the crystallization of the reaction product appeared, it was filtered and separated, washed with appropriate water, and dried under vacuum at 40°C for 48 hours, thereby obtaining the amine group of 5-aminoisophthalic acid and isocyanide AIPA-MO obtained by isocyanate group of acid 2-methacrylic acid ethyl ester. The low molecular weight GPC purity of the obtained AIPA-MO is about 100%. (Synthesis of polymer (A)-4) 100.89 g (0.3 mol) of obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were put into a separable flask with a volume of 2 L, and mixed, Cool to 5°C with an ice bath. Under cooling in an ice bath, a solution of dicyclohexylcarbodiimide (DCC) 125.0 g (0.606 mol) dissolved in GBL 125 g was added dropwise in about 20 minutes, and then added dropwise in about 20 minutes 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB} 103.16 g (0.28 mol) dissolved in 168 g of NMP, maintained by ice bath for 3 hours less than 5 ℃, and then The ice bath was removed and stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. A mixed liquid of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction liquid, and the precipitated polymer was separated and dissolved in NMP 650 g again. The obtained crude polymer solution was added dropwise to 5 L of water to precipitate the polymer, and the obtained precipitate was filtered and separated, followed by vacuum drying to obtain a powdery polymer (Polymer (A)-4). The molecular weight of the polymer (A)-4 was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 34,700. <Production Example 5> ((A) Synthesis of polymer (A)-5 as a precursor of polyoxazole) In a separable flask with a volume of 3 L, place 2,2-bis(3-amino-4- 183.1 g of hydroxyphenyl)-hexafluoropropane, 640.9 g of N,N-dimethylacetamide (DMAc) and 63.3 g of pyridine were mixed and stirred at room temperature (25°C) to make a homogeneous solution. Using a dropping funnel, 118.0 g of 4,4′-diphenyl ether dimethyl chloride was dissolved in 354 g of diethylene glycol dimethyl ether (DMDG). At this time, the separable flask was cooled in a water bath at 15 to 20°C. The time required for dripping is 40 minutes, and the maximum temperature of the reaction liquid is 30°C. After 3 hours have elapsed after the dripping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride is added to the reaction solution, and the mixture is left under stirring at room temperature for 15 hours to make the polymer chains account for 99% of the total amine The terminal group is capped with a carboxycyclohexyl amide group. The reaction rate at this time can be easily calculated by tracing the residual amount of 1,2-cyclohexyldicarboxylic anhydride charged by high-performance liquid chromatography (HPLC). Thereafter, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with appropriate water, dehydrated and then vacuum dried to obtain a gel permeation chromatography (GPC ) Method to measure the crude precursor with a weight average molecular weight of 9,000 (in terms of polystyrene). After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), it is treated with a cation exchange resin and an anion exchange resin, and the solution thus obtained is poured into ion exchange water The polymer precipitated was separated by filtration, washed with water and dried in vacuum, thereby obtaining a purified polybenzoxazole precursor (polymer (A)-5). <Production Example 6> ((A) Synthesis of polymer (A)-6 as polyimide) Attached to a glass separable four-necked flask equipped with an anchor stirrer made of Teflon (registered trademark) The cooling tube of the An-Stark separator. While introducing nitrogen gas, the flask was immersed in a silicone oil bath and stirred. Add 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5-(2,5-bioxytetrahydrogen -3-furyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70.29 g (266 mmol), γ-butyrolactone 254.6 g. Toluene 60 g. After stirring at 100 rpm for 4 hours at room temperature, add 4.6 g (28 mmol) of 5-northene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). The nitrogen gas was heated and stirred at 100 rpm at a silicon bath temperature of 50°C for 8 hours. Thereafter, it was heated to a silicon bath temperature of 180°C, and heated and stirred at 100 rpm for 2 hours. Toluene and water distilled in the reaction are removed. After the amide imidization reaction was completed, the temperature was returned to room temperature. Thereafter, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with appropriate water, dehydrated, and then vacuum-dried to obtain gel permeation chromatography (GPC). The crude polyimide (polymer (A)-6) having a weight average molecular weight of 23,000 (in terms of polystyrene) measured by the method. <Production Example 7> ((A) Synthesis of polymer (A)-8 as phenol resin) A separable flask equipped with a Dean-Stark apparatus with a volume of 1.0 L was replaced with nitrogen, and then In a separable flask, combine resorcinol 81.3 g (0.738 mol), BMMB 84.8 g (0.35 mol), p-toluenesulfonic acid 3.81 g (0.02 mol), and propylene glycol monomethyl ether (hereinafter also referred to as PGME) 116 g in The mixture was stirred at 50°C to dissolve the solid matter. The mixed solution was heated to 120°C with an oil bath, and it was confirmed that methanol was produced from the reaction solution. The reaction solution was directly stirred at 120°C for 3 hours. Then, in another container, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)p-cresol and 249 g of PGME were mixed and stirred to uniformly dissolve, and the obtained solution was used for a dropping funnel for a long time The solution was added dropwise to the separable flask for 1 hour, and the solution was stirred for 2 hours after dropping. After the reaction was completed, the same treatment as in Production Example 7 was carried out to obtain a copolymer (polymer H) containing resorcinol/BMMB/2,6-bis(hydroxymethyl)p-cresol at a yield of 77%. The weight-average molecular weight of the polymer H calculated by standard polystyrene conversion of the GPC method was 9,900. <Example 1> Using polymers (A)-1 and (A)-2, a negative photosensitive resin composition was prepared by the following method, and the photosensitive resin composition was evaluated. Combine the polymers (A)-1 50 g and (A)-2 50 g (equivalent to (A) resin) as the precursors of polyimide with 1H, 1H, 8H, 8H-perfluorotetraethylene glycol di Acrylate (expressed by the following formula (B-3-1), manufactured by Exfluor Corporation) 8 g, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (Table 1 (Denoted as "PDO" in the middle) (equivalent to (C) sensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g, N-[3-(triethoxysilyl)propyl] xylylene Acetic acid 1.5 g was dissolved in a mixed solvent containing 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. By further adding a small amount of the above mixed solvent, the viscosity of the obtained solution was adjusted to about 35 poise to prepare a negative photosensitive resin composition. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 3.1%. Furthermore, the compound (B-3)-1 (represents the compound of the following formula (B-3-1). The compound represented by the following formula (B-3-X) (X is 1 to 9) is described below The weight ratio of fluorine atoms in the molecule of (B-3)-X) is 44% by mass. <Example 2> In the above Example 1, the (B-3) component was changed to 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diacrylate (in the following formula (B- 2) Shown by Exfluor Corporation), except that a negative photosensitive resin composition solution was prepared in the same manner as in Example 1. The composition was cured at 230°C on the Cu layer by the above method After making a hardened relief pattern and performing a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 3.3%. Furthermore, the fluorine atom in the molecule of (B-3)-2 compound The weight ratio is 41% by mass. <Example 3> In the above Example 1, the component (B-3) was changed to 1H,1H-perfluoro-n-decyl methacrylate (in the following formula (B-3-3) Means, manufactured by Exfluor Co., Ltd.), except for this, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1. The composition was cured at 230°C by the above method to produce a hardening on the Cu layer After conducting the high-temperature storage test on the relief pattern, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 3.4%. Furthermore, the weight ratio of fluorine atoms in the molecule of (B-3)-3 compound It is 64% by mass. <Example 4> In Example 1, the component (B-3) was changed to perfluorodecanoic acid (expressed by the following formula (B-3-4), manufactured by Exfluor), except for A negative photosensitive resin composition solution was prepared in the same manner as in Example 1. The composition was cured at 230°C by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, The area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 6.2%. Furthermore, the weight ratio of fluorine atoms in the molecule of (B-3)-4 compound was 70% by mass. <Example 5> In the above Example 1, the (B-3) component was changed to 1H,1H-perfluoro-1-decanol (represented by the following formula (B-3-5), manufactured by Exfluor), except that A negative photosensitive resin composition solution was prepared in the same manner as in Example 1. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after performing a high-temperature storage test, the void was evaluated The area ratio of the surface of the Cu layer obtained a result of 6.9%. Furthermore, the weight ratio of fluorine atoms in the molecule of the (B-3)-5 compound was 72% by mass. <Example 6> The above example In 1, the component (B-3) was changed to perfluorotridecane (represented by the following formula (B-3-6), manufactured by Exfluor Corporation), except that the negative electrode was prepared in the same manner as in Example 1. Type photosensitive resin composition solution. This composition was cured at 230°C by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated ,and Get a 7.7% result. In addition, the weight ratio of fluorine atoms in the molecule of (B-3)-6 compound was 77% by mass. <Example 7> In the above Example 1, the component (B-3) was changed to methyl perfluorodecanoate (represented by the following formula (B-7), manufactured by Exfluor Corporation). In Example 1, a negative photosensitive resin composition solution was prepared in the same manner. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 6.9%. Furthermore, the weight ratio of fluorine atoms in the molecule of (B-3)-7 compound was 68% by mass. <Example 8> In the above Example 1, the component (B-3) was changed to perfluorotetraethylene glycol dimethyl ether (represented by the following formula (B-3-8), manufactured by Exfluor Corporation), except for In the same manner as in Example 1, a negative photosensitive resin composition solution was prepared. The composition was cured at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 6.8%. Furthermore, the weight ratio of fluorine atoms in the molecule of (B-3)-8 compound was 68% by mass. <Example 9> In Example 1, the negative photosensitive resin composition solution was prepared in the same manner as Example 1 except that the amount of (B-3)-1 component added was 2 g. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 4.5%. <Example 10> In Example 1, the negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the amount of (B-3)-1 component added was 20 g. With respect to this composition, curing was performed at 230° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 3.8%. <Example 11> A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the curing temperature was changed from 230°C to 350°C in the above Example 1. For this composition, a hard relief pattern was formed on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.2% was obtained. <Example 12> In the above Example 1, as the (A) resin, the polymer (A)-1 50 g and the polymer (A)-2 50 g were changed to the polymer (A)-1 100 g, and (C) The component changed from PDO to 1,2-octanedione-1-{4-(phenylthio)-2-(O-benzoyl oxime)} (Irgacure OXE01 (manufactured by BASF, trade name )) 2.5 g, except for this, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1. For this composition, a hard relief pattern was formed on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.6% was obtained. <Example 13> In Example 12 above, the negative photosensitive resin was prepared in the same manner as in Example 12 except that the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide. Composition solution. For this composition, a hard relief pattern was formed on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.8% was obtained. <Example 14> In the above Example 1, as the (A) resin, the polymer (A)-1 50 g and the polymer (A)-2 50 g were changed to the polymer (A)-3 100 g, and A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that the curing temperature was changed from 230°C to 350°C. For this composition, a hard relief pattern was formed on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.7% was obtained. <Example 15> In the above Example 1, as the (A) resin, the polymer (A)-1 50 g and the polymer (A)-2 50 g were changed to the polymer (A)-4 100 g, and A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that the curing temperature was changed from 230°C to 250°C. For this composition, a hard relief pattern was formed on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.4% was obtained. <Example 16> Using polymer (A)-5, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. The polymer (A)-5 as a precursor of polyoxazole (100) (equivalent to (A) resin) and the following formula (96): [Chem. 129]

77% of the indicated phenolic hydroxyl groups are naphthoquinone diazide-4-sulfonate-sensitized diazoquinone compounds (manufactured by Toyo Synthetic, equivalent to (C) component) (C1) 15 g dissolved in γ -Butyrolactone (as solvent) 100 g. By further adding a small amount of γ-butyrolactone, the viscosity of the obtained solution was adjusted to about 20 poise to prepare a positive photosensitive resin composition. The composition was cured at 350° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.2%. <Example 17> In Example 16, the same as Example 11 except that the polymer (A)-5 100 g was changed to the polymer (A)-6 100 g as the (A) resin The positive photosensitive resin composition solution is prepared by this method. With respect to this composition, curing was performed at 250° C. by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 5.5%. <Example 18> In the above-mentioned Example 16, as the (A) resin, 100 g of the polymer (A)-5 was changed to the polymer (A)-7 (novolac resin, polystyrene equivalent weight average molecular weight (Mw) )=10,600 (manufactured by Asahi Organic Materials Co., Ltd., product name EP-4080G) 100 g, except that a positive photosensitive resin composition solution was prepared in the same manner as in Example 11. For this composition, by the above Method Curing at 250°C to produce a hard relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain a result of 4.8%. <Example 19> The above example In 16, as the (A) resin, except that the polymer (A)-5 100 g was changed to the polymer (A)-8 100 g, a positive photosensitive resin was prepared in the same manner as in Example 11 Composition solution: For this composition, a 250° C. curing was performed by the above method to produce a hard relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated to obtain 5.1 % Result. <Comparative Example 1> In the composition of Example 1, the negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the component (B)-1 was not added, and was carried out The same evaluation as in Example 1. Since the (B) fluorine-containing hydrophobic compound of the present invention is not included, the evaluation result is 15.2%. <Comparative Example 2> Tetraethylene glycol dimethacrylate (using the following formula ( B-9) indicates that Tokyo Chemical Industry Co., Ltd.) replaces the component (B)-1 of Example 1, except that the negative photosensitive resin composition is prepared in the same manner as in Example 1 and carried out The same evaluation as in Example 1. Since the (B) fluorine-containing hydrophobic compound of the present invention is not included, the evaluation result is 15.5%. Furthermore, the weight ratio of fluorine atoms in the molecule of (B)-9 compound is 0 % By mass. <Comparative Example 3> Instead of the component (B)-1 of Example 15, tetraethylene glycol dimethacrylate ((B)-9, manufactured by Tokyo Chemical Industry Co., Ltd.) was used. A negative photosensitive resin composition was prepared in the same manner as in Example 15, and the same evaluation as in Example 15. Since the (B) fluorine-containing hydrophobic compound of the present invention was not included, the evaluation result was 14.3%. Comparative Example 4> In addition to the component (B)-1 of Example 12, tetraethylene glycol dimethacrylate ((B)-9, manufactured by Tokyo Chemical Industry Co., Ltd.) was used. 12 The negative photosensitive resin composition was prepared in the same manner and evaluated in the same manner as in Example 12. Since the (B) fluorine-containing hydrophobic compound of the present invention was not included, the evaluation result was 15.7%. <Comparative Example 5> Tetraethylene glycol dimethacrylate ((B)-9, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of component (B)-1 of Example 17 A positive photosensitive resin composition was prepared in the same manner as in Example 17, and the same evaluation as in Example 17 was performed. Since the (B) fluorine-containing hydrophobic compound of the present invention is not contained, the evaluation result is 16.3%. The weight ratio of fluorine atoms in the molecules of the compounds (B-3)-1 to (B-3)-9 is shown in Table 4 below. [Table 4]

[化130]

[化131]

[化132]

[化133]

[化134]

[化135]

[化136]

[化137]

[化138]

Table 5 summarizes the results of Examples 1 to 19 and Comparative Examples 1 to 5. [table 5]

[Industrial Applicability] The photosensitive resin composition of the present invention can be preferably used in the field of photosensitive materials useful for manufacturing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

A photosensitive resin composition, comprising: (A) selected from the group consisting of polyamic acid, polyamic acid ester, polyamidate, polyhydroxyamide, polyaminoamide, polyamide, polyamide Amide imine, polyimide, polybenzo

At least one resin in the group consisting of azole, novolac, polyhydroxystyrene and phenol resin: 100 parts by mass, (B-1) nanoparticles: 0.01 to 100 parts by mass of the above (A) resin 10 parts by mass, and (C) photosensitive agent: 1 to 50 parts by mass based on 100 parts by mass of (A) resin.

The photosensitive resin composition according to claim 1, wherein the resin (A) is selected from the group consisting of a polyimide precursor containing the following general formula (1), a polyamide containing the following general formula (4), and Polymerization of the following general formula (5)

At least one of the group consisting of an azole precursor, a polyimide containing the following general formula (6), and novolac, polyhydroxystyrene, and a phenol resin containing the following general formula (7). Equation (1) is

{In the formula, X ₁ is a 4-valent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are independently hydrogen atoms and saturated with 1 to 30 carbon atoms. An aliphatic group, an aromatic group, or the following general formula (2):

(In the formula, R ₃ , R ₄ and R ₅ 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) a monovalent organic group represented by 1 or a carbon number 1 ~4 saturated aliphatic group, or the following general formula (3):

(In the formula, R ₆ , R ₇ and R ₈ are independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10) The monovalent ammonium ion represented by} The polyimide precursor, polyamic acid, polyamic acid ester or polyamic acid salt, the following general formula (4) has [Chem 19]

{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or have multiple structures, and R ₉ has at least An organic group having a radical polymerizable unsaturated bonding group with a carbon number of 3 to 20, and n ₂ is an integer of 1 to 1000), a polyamide having a structure represented by the following general formula (5):

{In the formula, Y ₃ is a tetravalent organic group with carbon atoms, Y ₄ , X ₃ and X ₄ are each independently a divalent organic group with 2 or more carbon atoms, and n ₃ is an integer from 1 to 1000 , n ₄ is an integer of 0 to _{_{500., n 3 / (n 3 +}} n 4)> 0.5, and comprises X ₃ and Y ₃ of n ₃ dihydroxy two Amides unit and comprising X n ₄ and Y ₄ of ₄ The arrangement order of the two diamide units is arbitrary}

The polyhydroxyamide of the azole precursor is represented by the following general formula (6):

{In the formula, X ₅ is an organic group of 4 to 14 valences, Y ₅ is an organic group of 2 to 12 valences, R ₁₀ and R ₁₁ independently represent at least one selected from phenolic hydroxyl group, sulfonic acid group or thiol The organic group of the base in the group, n ₅ is an integer of 3 to 200, and m ₃ and m ₄ represent an integer of 0 to 10) polyimide of the structure represented by }, and the following general formula (7) is

{In the formula, a is an integer of 1~3, b is an integer of 0~3, 1≦(a+b)≦4, R ₁₂ represents a monovalent organic group selected from carbon number 1-20, halogen atom, A monovalent substituent in the group consisting of nitro and cyano, when b is 2 or 3, a plurality of R ₁ may be the same as or different from each other, X represents selected from carbons that may have an unsaturated bond The divalent aliphatic group having 2 to 10 carbon atoms, the divalent alicyclic group having 3 to 20 carbon atoms, and the following general formula (8): [Chem 23]-C _p H _2p O- (8) (formula Where p is an integer from 1 to 10) a divalent organic group represented by a divalent alkoxy group represented by a divalent organic group having an aromatic ring having 6 to 12 carbon atoms and a divalent organic group) The indicated phenol resin.

The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition includes a phenol resin having a repeating unit represented by the general formula (7), and X in the general formula (7) is selected from General formula (9):

{In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon in which a part or all of a hydrogen atom is substituted with a fluorine atom In the case of a monovalent aliphatic group of 1 to 10, n ₆ is an integer of 0 to 4, and n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or 1 of carbon number 1 to 12. Valent organic group, when at least one R ₁₇ is a hydroxyl group, and n ₆ is an integer of 2 to 4, the plural R ₁₇ groups may be the same or different from each other. (10):

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ independently represent a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a carbon in which a part or all of a hydrogen atom is substituted with a fluorine atom 1 to 10 monovalent aliphatic groups, W is a single bond, selected from aliphatic groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, and 3 to 20 alicyclic formulas which may be substituted by fluorine atoms Group, the following general formula (8): [Chem 26]-C _p H _2p O- (8) (where p is an integer of 1 to 10) represented by a divalent alkoxy group, and the following Formula (11):

The divalent base in the group consisting of the represented divalent base} The divalent organic group in the group consisting of the represented divalent base}.

A method for manufacturing a hardened relief pattern, including: (1) The step of forming a photosensitive resin layer on the substrate by coating the photosensitive resin composition according to any one of claims 1 to 3 on the substrate; (2) Exposure of the photosensitive resin layer Step; (3) The step of developing the photosensitive resin layer after the exposure to form a relief pattern; and (4) The step of forming a hardened relief pattern by subjecting the relief pattern to heat treatment.

The method of claim 4, wherein the substrate is formed of copper or copper alloy.

A semiconductor device including the hardened relief pattern obtained by the manufacturing method as in claim 4 or 5.