TW202348687A

TW202348687A - Resin composition, method for manufacturing polyimide, method for manufacturing cured relief pattern, and semiconductor device capable of obtaining a polyimide film (cured relief pattern) that has a good coloration degree (low transmittance) and maintains sufficient film elongation before and after a heating (curing) step

Info

Publication number: TW202348687A
Application number: TW112121581A
Authority: TW
Inventors: 中村光孝; 岩田隆志; 和田佳祐
Original assignee: 日商旭化成股份有限公司
Priority date: 2022-06-13
Filing date: 2023-06-09
Publication date: 2023-12-16
Also published as: TWI839243B; JP2023181982A

Abstract

The present invention provides a resin composition capable of obtaining a polyimide film (cured relief pattern) that has a good coloration degree (low transmittance) and maintains sufficient film elongation before and after a heating (curing) step. The resin composition of the present invention contains the following components: (A) a polyimide precursor represented by general formula (A1); (B) an organic dye; and (C) an organic solvent. After applying the resin composition by spin coating, a pre-baked film obtained by drying at 110 DEG C for 240 seconds exhibits a UV transmittance rate (a) of 40% or less at 532 nm when calculated based on a film thickness of 10 [mu]m, and a polyimide film obtained by heating the pre-baked film in a nitrogen atmosphere at 230 DEG C for 2 hours exhibits a UV transmittance (b) of 0.4 or less at 532 nm when calculated based on a film thickness of 10 [mu]m.

Description

樹脂組合物、聚醯亞胺之製造方法、硬化浮凸圖案之製造方法、及半導體裝置Resin composition, method for manufacturing polyimide, method for manufacturing hardened relief pattern, and semiconductor device

本發明係關於一種樹脂組合物、聚醯亞胺之製造方法、硬化浮凸圖案之製造方法、及半導體裝置。The present invention relates to a resin composition, a method of manufacturing polyimide, a method of manufacturing a hardened relief pattern, and a semiconductor device.

半導體裝置(以下，於本說明書中有時簡稱為「元件」)係根據目的，藉由各種方法安裝於印刷基板。先前之元件通常係藉由打線接合法來製作，該打線接合法係利用較細之導線自元件之外部端子(焊墊)連接至引線框架。然而，如今隨著元件不斷高速化，動作頻率已達到GHz，以至於安裝時各端子之佈線長度差異會對元件動作產生影響。因此，高端用途之元件安裝中，需要準確控制安裝佈線之長度。然而，於打線接合中，難以滿足該要求。Semiconductor devices (hereinafter, sometimes simply referred to as "devices" in this specification) are mounted on printed circuit boards by various methods depending on the purpose. Previous components were usually made by wire bonding, which used thinner wires to connect from the external terminals (soldering pads) of the component to the lead frame. However, as the speed of components continues to increase, the operating frequency has reached GHz, so that the difference in wiring length of each terminal during installation will affect the operation of the component. Therefore, in the installation of components for high-end applications, it is necessary to accurately control the length of the installation wiring. However, in wire bonding, it is difficult to meet this requirement.

因此，業界提出了覆晶安裝，於半導體晶片之表面形成再佈線層，再於其上形成凸塊(電極)後，將該晶片翻轉(flip)並直接安裝於印刷基板。該覆晶安裝中，可準確控制佈線距離。因此，覆晶安裝用於處理高速信號之高端用途之元件，或因安裝尺寸較小而用於行動電話等，其需求正急速增加。Therefore, the industry has proposed flip-chip mounting, which involves forming a rewiring layer on the surface of a semiconductor chip, forming bumps (electrodes) on it, and then flipping the chip and mounting it directly on a printed circuit board. In this flip-chip installation, the wiring distance can be accurately controlled. Therefore, flip-chip mounting is used for high-end components that process high-speed signals, or for mobile phones due to smaller mounting sizes, and the demand is increasing rapidly.

先前，於電子零件之絕緣材料、以及半導體裝置之鈍化膜、表面保護膜、及層間絕緣膜等中，使用兼具優異之耐熱性及電特性之聚醯亞胺。為了於構成鈍化膜、表面保護膜、及層間絕緣膜等之樹脂之表面形成浮凸圖案，以及於該表面刻印半導體裝置之製品規格、批號及製造年月日等目的，通常使用雷射裝置。為了於雷射處理時，可形成且可刻印所需之浮凸圖案，要求鈍化膜、表面保護膜、及層間絕緣膜等對雷射波長具有吸收。 Previously, polyimide, which has both excellent heat resistance and electrical properties, has been used in insulating materials for electronic components, as well as passivation films, surface protective films, and interlayer insulating films of semiconductor devices. Laser devices are generally used to form relief patterns on the surfaces of resins constituting passivation films, surface protection films, interlayer insulating films, etc., and to imprint product specifications, batch numbers, and manufacturing dates of semiconductor devices on the surfaces. In order to form and engrave the required relief pattern during laser processing, the passivation film, surface protection film, and interlayer insulating film are required to absorb the laser wavelength.

此處，已知有藉由使聚醯亞胺膜著色而使該聚醯亞胺膜具有適度之光吸收之方法。例如，專利文獻1中揭示有如下意旨：藉由含有C.I.(Color Index，染料索引)顏料藍或碳黑等顏料，使聚醯亞胺膜著色。又，專利文獻2中揭示有如下意旨：藉由含有苝系或苯并呋喃酮系顏料，使聚醯亞胺膜著色。再者，作為顏料，除上述以外，還可例舉：鈦黑、石墨、苝黑、苯胺黑等。 [先前技術文獻] [專利文獻] Here, a method of coloring a polyimide film so that the polyimide film has appropriate light absorption is known. For example, Patent Document 1 discloses that a polyimide film is colored by containing pigments such as C.I. (Color Index) pigment blue or carbon black. Furthermore, Patent Document 2 discloses that a polyimide film is colored by containing a perylene-based or benzofuranone-based pigment. Furthermore, examples of the pigment include, in addition to the above, titanium black, graphite, perylene black, aniline black, and the like. [Prior technical literature] [Patent Document]

[專利文獻1]國際公開第2020/175150號 [專利文獻2]日本專利第6418248號公報 [Patent Document 1] International Publication No. 2020/175150 [Patent Document 2] Japanese Patent No. 6418248

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

然而，添加顏料而著色之聚醯亞胺膜於受到拉伸應力之情形時，顏料成分容易達到斷裂點，因此，存在無法達成良好之膜伸長率之問題。對於此方面，亦已知有使用有機染料使聚醯亞胺膜著色之方法。另一方面，認為經200℃以上之加熱後，有機染料會分解及揮發，結果會使樹脂明顯褪色。又，於有機染料藉由加熱進行聚合而明顯著色之情形時，存在難以控制藉由加熱所進行之著色情況之問題。另一方面，有如下背景。近年來，要求使用輸出能量較小之532 nm之雷射(綠色雷射)，於樹脂表面進行刻印。為了使用綠色雷射於樹脂表面進行刻印，較理想為該樹脂具有良好之著色程度(低透過率)，但至今尚未對用以獲得適於綠色雷射之使用之樹脂之樹脂組合物進行充分研究。 However, when a polyimide film colored by adding pigments is subjected to tensile stress, the pigment components easily reach the breaking point. Therefore, there is a problem that good film elongation cannot be achieved. In this regard, a method of coloring a polyimide film using an organic dye is also known. On the other hand, it is believed that after heating above 200°C, organic dyes will decompose and volatilize, resulting in significant discoloration of the resin. Furthermore, when an organic dye is polymerized by heating and is significantly colored, there is a problem that it is difficult to control the coloring by heating. On the other hand, there is the following background. In recent years, it has been required to use a 532 nm laser (green laser) with a smaller output energy to engrave on the resin surface. In order to use a green laser to engrave a resin surface, it is ideal for the resin to have a good degree of coloring (low transmittance). However, resin compositions to obtain a resin suitable for use with a green laser have not yet been fully studied. .

本發明之目的在於提供一種樹脂組合物，其可獲得於加熱(固化)步驟前後均具有良好之著色程度(低透過率)且保持充分之膜伸長率之聚醯亞胺膜(硬化浮凸圖案)。又，本發明之目的在於提供使用該樹脂組合物之聚醯亞胺之製造方法、硬化浮凸圖案之製造方法、及半導體裝置。 [解決問題之技術手段] The object of the present invention is to provide a resin composition that can obtain a polyimide film (hardened relief pattern) that has a good degree of coloration (low transmittance) and maintains sufficient film elongation before and after the heating (curing) step. ). Furthermore, an object of the present invention is to provide a method for manufacturing polyimide using the resin composition, a method for manufacturing a hardened relief pattern, and a semiconductor device. [Technical means to solve problems]

本發明之一形態如下。 [1] 一種樹脂組合物，其包含以下成分： (A)下述通式(A1)所表示之聚醯亞胺前驅物： [化1] {式中，X為四價有機基，Y為二價有機基，R ₁及R ₂為氫原子、下述通式(R _h)： [化2] (式中，R ₃、R ₄及R ₅為氫原子或碳數1～3之有機基，p為選自2～10之整數)所表示之一價有機基、或碳數1～4之飽和脂肪族基；其中，R ₁及R ₂並不同時為氫原子}； (B)有機染料；及 (C)有機溶劑；且旋轉塗佈上述樹脂組合物後，於110℃下歷經240秒進行乾燥而獲得之預烘烤膜於532 nm下之以10 μm膜厚換算之UV(ultraviolet，紫外線)透過率(a)為40%以下，於230℃下將上述預烘烤膜歷經2小時於氮氣氛圍下加熱而獲得之聚醯亞胺膜於532 nm下之以10 μm膜厚換算之UV透過率(b)為40%以下。 [2] 如項目1所記載之樹脂組合物，其中UV透過率之差Δ(b－a)滿足-10%≦Δ(b－a)≦10%之關係。 [3] 如項目1或2所記載之樹脂組合物，其中於上述通式(A1)中，上述X包含下述式(2)所表示之結構。 [化3] [4] 如項目1至3中任一項所記載之樹脂組合物，其中於上述通式(A1)中，上述Y包含下述式(8)： [化4] 及/或下述式(9)： [化5] 所表示之結構。 [5] 如項目1至4中任一項所記載之樹脂組合物，其中上述(B)成分之含量相對於(A)成分100質量份為0.5～30質量份。 [6] 如項目1至5中任一項所記載之樹脂組合物，其中上述樹脂組合物包含相對於上述(A)成分100質量份為1～50質量份之(D)光聚合起始劑。 [7] 如項目1至6中任一項所記載之樹脂組合物，其中上述(B)成分包含吖𠯤系染料衍生物、及蒽系染料衍生物之至少一者。 [8] 如項目1至7中任一項所記載之樹脂組合物，其中上述(C)成分包含選自由N-甲基-2-吡咯啶酮(NMP)、γ-丁內酯(GBL)、二甲基亞碸(DMSO)、3-甲氧基-N,N-二甲基丙醯胺、及乳酸乙酯所組成之群中之至少1者。 [9] 如項目1至8中任一項所記載之樹脂組合物，其進而包含以下成分： (D)光聚合起始劑，且上述(D)成分為肟類。 [10] 一種硬化浮凸圖案之製造方法，其包括如下步驟： (1)藉由將如項目1至9中任一項所記載之樹脂組合物塗佈於基板，而形成樹脂組合物膜； (2)藉由對上述樹脂組合物膜進行曝光及顯影之步驟、或雷射照射上述樹脂組合物膜之步驟，而形成浮凸圖案；及 (3)對上述浮凸圖案加熱，而形成硬化浮凸圖案。 [11] 如項目10所記載之硬化浮凸圖案之製造方法，其中上述基板由銅或銅合金形成。 [12] 一種半導體裝置，其具有由如項目1至9中任一項所記載之樹脂組合物獲得之硬化浮凸圖案作為絕緣層。 [13] 一種聚醯亞胺之製造方法，其使用包含以下成分之樹脂組合物： (A)下述通式(A1)所表示之聚醯亞胺前驅物： [化6] {式中，X為四價有機基，Y為二價有機基，R ₁及R ₂為氫原子、下述通式(R _h)： [化7] (式中，R ₃、R ₄及R ₅為氫原子或碳數1～3之有機基，p為選自2～10之整數)所表示之一價有機基、或碳數1～4之飽和脂肪族基；其中，R ₁及R ₂並不同時為氫原子}； (B)有機染料；及 (C)有機溶劑；且旋轉塗佈上述樹脂組合物後，於110℃下歷經240秒進行乾燥而獲得之預烘烤膜於532 nm下之以10 μm膜厚換算之UV透過率(a)為40%以下，於230℃下將上述預烘烤膜歷經2小時於氮氣氛圍下加熱而獲得之上述聚醯亞胺膜於532 nm下之以10 μm膜厚換算之UV透過率(b)為40%以下。 [14] 如項目13所記載之聚醯亞胺之製造方法，其中UV透過率之差Δ(b－a)滿足-10%≦Δ(b－a)≦10%之關係。 [發明之效果] One aspect of the present invention is as follows. [1] A resin composition containing the following components: (A) A polyimide precursor represented by the following general formula (A1): [Chemical 1] {In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are hydrogen atoms, and the following general formula (R _h ): [Chemical 2] (In the formula, R ₃ , R ₄ and R ₅ are hydrogen atoms or organic groups with 1 to 3 carbon atoms, and p is an integer selected from 2 to 10), or a monovalent organic group with 1 to 4 carbon atoms. Saturated aliphatic group; wherein, R ₁ and R ₂ are not hydrogen atoms at the same time}; (B) organic dye; and (C) organic solvent; and after spin-coating the above resin composition, at 110°C for 240 seconds The UV (ultraviolet, ultraviolet) transmittance (a) of the dried pre-baked film at 532 nm based on the film thickness of 10 μm is less than 40%. The pre-baked film is dried at 230°C for 2 hours. The UV transmittance (b) of the polyimide film obtained by heating in a nitrogen atmosphere at 532 nm and converted to a film thickness of 10 μm is less than 40%. [2] The resin composition according to item 1, wherein the difference in UV transmittance Δ(b-a) satisfies the relationship of -10%≦Δ(b-a)≦10%. [3] The resin composition according to item 1 or 2, wherein in the general formula (A1), the X includes a structure represented by the following formula (2). [Chemical 3] [4] The resin composition according to any one of items 1 to 3, wherein in the general formula (A1), the Y includes the following formula (8): [Chemical 4] And/or the following formula (9): [Chemistry 5] the structure represented. [5] The resin composition according to any one of items 1 to 4, wherein the content of the component (B) is 0.5 to 30 parts by mass relative to 100 parts by mass of the component (A). [6] The resin composition according to any one of items 1 to 5, wherein the resin composition contains 1 to 50 parts by mass of the photopolymerization initiator (D) based on 100 parts by mass of the component (A). . [7] The resin composition according to any one of items 1 to 6, wherein the component (B) contains at least one of an azine-based dye derivative and an anthracene-based dye derivative. [8] The resin composition according to any one of items 1 to 7, wherein the component (C) contains a compound selected from the group consisting of N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL). At least one of the group consisting of, dimethylsulfoxide (DMSO), 3-methoxy-N,N-dimethylpropionamide, and ethyl lactate. [9] The resin composition according to any one of items 1 to 8, further comprising the following components: (D) a photopolymerization initiator, and the component (D) is an oxime. [10] A method for manufacturing a hardened relief pattern, which includes the following steps: (1) forming a resin composition film by applying the resin composition as described in any one of items 1 to 9 on a substrate; (2) Forming a relief pattern by exposing and developing the above-mentioned resin composition film or irradiating the above-mentioned resin composition film with laser; and (3) Heating the above-mentioned relief pattern to form a hardened Embossed pattern. [11] The method of manufacturing a hardened relief pattern as described in item 10, wherein the substrate is formed of copper or copper alloy. [12] A semiconductor device having as an insulating layer a hardened relief pattern obtained from the resin composition described in any one of items 1 to 9. [13] A method for producing polyimide, which uses a resin composition containing the following components: (A) A polyimide precursor represented by the following general formula (A1): [Chemical 6] {In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are hydrogen atoms, and the following general formula (R _h ): [Chemical 7] (In the formula, R ₃ , R ₄ and R ₅ are hydrogen atoms or organic groups with 1 to 3 carbon atoms, and p is an integer selected from 2 to 10), or a monovalent organic group with 1 to 4 carbon atoms. Saturated aliphatic group; wherein, R ₁ and R ₂ are not hydrogen atoms at the same time}; (B) organic dye; and (C) organic solvent; and after spin-coating the above resin composition, at 110°C for 240 seconds The prebaked film obtained by drying has a UV transmittance (a) of 10 μm film thickness at 532 nm of less than 40%. The prebaked film is heated at 230°C for 2 hours in a nitrogen atmosphere. The UV transmittance (b) of the obtained polyimide film at 532 nm calculated from a film thickness of 10 μm is less than 40%. [14] The manufacturing method of polyimide as described in item 13, wherein the difference in UV transmittance Δ(b-a) satisfies the relationship of -10%≦Δ(b-a)≦10%. [Effects of the invention]

根據本發明，可提供一種樹脂組合物，其可獲得於加熱(固化)步驟前後均具有良好之著色程度(低透過率)且保持充分之膜伸長率之聚醯亞胺膜(硬化浮凸圖案)。又，根據本發明，可提供使用該樹脂組合物之聚醯亞胺之製造方法、硬化浮凸圖案之製造方法、及半導體裝置。According to the present invention, a resin composition can be provided that can obtain a polyimide film (hardened relief pattern) that has a good degree of coloration (low transmittance) and maintains sufficient film elongation before and after the heating (curing) step. ). Furthermore, according to the present invention, it is possible to provide a method for manufacturing polyimide using the resin composition, a method for manufacturing a hardened relief pattern, and a semiconductor device.

以下，對本發明之實施方式(以下稱為「本實施方式」)進行具體說明，但本發明並不限定於此，可於不脫離其主旨之範圍內進行各種變化。本說明書中，某通式中以同一元件符號所表示之結構於其在分子中存在複數個之情形時，彼此可相同亦可不同。本說明書中，使用「～」記載之數值範圍表示包含「～」前後之數值作為下限值及上限值之數值範圍。又，本說明書中，於階段性記載之數值範圍中，某數值範圍中記載之上限值或下限值可置換為其他階段性記載之數值範圍之上限值或下限值。又，本說明書中，某數值範圍中記載之上限值或下限值可置換為實施例中示出之值。Hereinafter, an embodiment of the present invention (hereinafter referred to as "this embodiment") will be described in detail. However, the present invention is not limited thereto, and various changes can be made without departing from the gist of the invention. In this specification, the structures represented by the same element symbol in a certain general formula may be the same or different from each other when there are plural structures in the molecule. In this specification, the numerical range described using "～" means the numerical range including the numerical values before and after "～" as the lower limit and the upper limit. In this specification, among the numerical ranges described in stages, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of the numerical range described in other stages. In addition, in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in an Example.

[樹脂組合物] 本實施方式之樹脂組合物含有(A)聚醯亞胺前驅物、(B)有機染料、及(C)有機溶劑。根據本實施方式之樹脂組合物，可不使膜物性變差，而藉由添加少量有機染料，於加熱(固化)後亦表現出良好之著色程度。 [Resin composition] The resin composition of this embodiment contains (A) a polyimide precursor, (B) an organic dye, and (C) an organic solvent. According to the resin composition of this embodiment, the physical properties of the film are not deteriorated, and by adding a small amount of organic dye, a good degree of coloring can be achieved even after heating (curing).

此處，本實施方式之樹脂組合物包含以下成分： (A)下述通式(A1)所表示之聚醯亞胺前驅物： [化8] {式中，X為四價有機基，Y為二價有機基，R ₁及R ₂為氫原子、下述通式(R _h)： [化9] (式中，R ₃、R ₄及R ₅為氫原子或碳數1～3之有機基，p為選自2～10之整數)所表示之一價有機基、或碳數1～4之飽和脂肪族基；其中，R ₁及R ₂並不同時為氫原子}； (B)有機染料；及 (C)有機溶劑；且旋轉塗佈上述樹脂組合物後，於110℃下歷經240秒進行乾燥而獲得之預烘烤膜(樹脂膜)於532 nm下之以10 μm膜厚換算之UV透過率(a)為40%以下，於230℃下將上述預烘烤膜歷經2小時於氮氣氛圍下加熱而獲得之聚醯亞胺膜於532 nm下之以10 μm膜厚換算之UV透過率(b)為40%以下。根據此種樹脂組合物，可獲得於加熱(固化)步驟前後均具有良好之著色程度(低透過率)且保持充分之膜伸長率之聚醯亞胺膜(硬化浮凸圖案)。 Here, the resin composition of this embodiment contains the following components: (A) A polyimide precursor represented by the following general formula (A1): [Chemical 8] {In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are hydrogen atoms, and the following general formula (R _h ): [Chemical 9] (In the formula, R ₃ , R ₄ and R ₅ are hydrogen atoms or organic groups with 1 to 3 carbon atoms, and p is an integer selected from 2 to 10), or a monovalent organic group with 1 to 4 carbon atoms. Saturated aliphatic group; wherein, R ₁ and R ₂ are not hydrogen atoms at the same time}; (B) organic dye; and (C) organic solvent; and after spin-coating the above resin composition, at 110°C for 240 seconds The UV transmittance (a) of the prebaked film (resin film) obtained by drying based on the film thickness of 10 μm at 532 nm is 40% or less. The above prebaked film is dried at 230°C for 2 hours. The UV transmittance (b) of the polyimide film obtained by heating in a nitrogen atmosphere at 532 nm and converted to a film thickness of 10 μm is less than 40%. According to this resin composition, it is possible to obtain a polyimide film (hardened relief pattern) that has a good degree of coloring (low transmittance) and maintains sufficient film elongation before and after the heating (curing) step.

＜＜UV透過率＞＞＜UV透過率(a)＞本實施方式中，上述UV透過率(a)為40%以下。UV透過率(a)可定位為表示預烘烤膜中之著色程度之指標，UV透過率(a)為40%以下則表示預烘烤膜適宜地著色。就該觀點而言，UV透過率(a)較佳為35%以下，更佳為30%以下。＜＜UV transmittance＞＞＜UV transmittance (a)＞ In this embodiment, the UV transmittance (a) is 40% or less. UV transmittance (a) can be positioned as an indicator of the degree of coloring in the pre-baked film. If the UV transmittance (a) is 40% or less, it means that the pre-baked film is suitably colored. From this viewpoint, the UV transmittance (a) is preferably 35% or less, more preferably 30% or less.

UV透過率(a)可藉由樹脂組合物之原料種類、及其等之含量比等進行控制。UV透過率(a)可基於實施例之方法計算出。再者，乾燥條件(110℃、及240秒)係以適宜地獲得預烘烤膜之觀點進行選擇。The UV transmittance (a) can be controlled by the types of raw materials of the resin composition, their content ratios, etc. UV transmittance (a) can be calculated based on the method of the Example. In addition, the drying conditions (110° C. and 240 seconds) are selected from the viewpoint of appropriately obtaining a prebaked film.

＜UV透過率(b)＞本實施方式中，上述UV透過率(b)為40%以下。UV透過率(b)可定位為表示聚醯亞胺膜中之著色程度之指標，UV透過率(b)為40%以下則表示聚醯亞胺膜適宜地著色。就該觀點而言，UV透過率(b)較佳為35%以下，更佳為30%以下。＜UV transmittance (b)＞ In this embodiment, the UV transmittance (b) is 40% or less. UV transmittance (b) can be positioned as an index indicating the degree of coloring in the polyimide film. If the UV transmittance (b) is 40% or less, it means that the polyimide film is suitably colored. From this viewpoint, the UV transmittance (b) is preferably 35% or less, more preferably 30% or less.

UV透過率(b)可藉由樹脂組合物之原料種類、及其等之含量比等進行控制。UV透過率(a)可基於實施例之方法計算出。再者，加熱(固化)條件(230℃、2小時、及氮氣氛圍下)係以適宜地獲得聚醯亞胺膜之觀點進行選擇。The UV transmittance (b) can be controlled by the types of raw materials of the resin composition, their content ratios, etc. UV transmittance (a) can be calculated based on the method of the Example. In addition, the heating (curing) conditions (230°C, 2 hours, and nitrogen atmosphere) are selected from the viewpoint of appropriately obtaining a polyimide film.

＜UV透過率之差Δ(b－a)＞於樹脂組合物中，上述UV透過率之差Δ(b－a)較佳為滿足-10%≦Δ(b－a)≦10%之關係。UV透過率之差Δ(b－a)可定位為表示預烘烤膜經加熱(固化)時之膜之變色程度之指標，UV透過率之差Δ(b－a)滿足上述關係則表示即便經加熱(固化)，聚醯亞胺膜仍充分維持了預烘烤膜之著色性。本實施方式中，預烘烤膜具有規定之著色性，且於聚醯亞胺膜中亦可適宜地保持其著色性程度，故而容易於預烘烤膜之時點調整聚醯亞胺膜中之光吸收程度。就該觀點而言，UV透過率之差Δ(b－a)更佳為-8%≦Δ(b－a)≦8%，進而較佳為-6%≦Δ(b－a)≦6%。 <Difference in UV transmittance Δ(b-a)> In the resin composition, the UV transmittance difference Δ(b-a) preferably satisfies the relationship of -10%≦Δ(b-a)≦10%. The difference in UV transmittance Δ(b-a) can be positioned as an indicator of the degree of discoloration of the pre-baked film when it is heated (cured). If the difference in UV transmittance Δ(b-a) satisfies the above relationship, it means that even if After heating (curing), the polyimide film still fully maintains the coloring properties of the pre-baked film. In this embodiment, the pre-baked film has a predetermined coloring property, and its coloring property can be appropriately maintained in the polyimide film. Therefore, it is easy to adjust the coloring properties in the polyimide film at the time of pre-baking the film. Degree of light absorption. From this point of view, the difference in UV transmittance Δ(b-a) is more preferably -8%≦Δ(b-a)≦8%, and further preferably -6%≦Δ(b-a)≦6 %.

UV透過率之差Δ(b－a)超過0%，即，上述UV透過率(b)＞上述UV透過率(a)則意味著儘管因加熱(固化)導致膜之褪色加深，但可充分抑制其加深程度。 UV透過率之差Δ(b－a)未達0%，即，上述UV透過率(b)＜上述UV透過率(a)則意味著利用加熱(固化)可使膜進一步著色。 The difference in UV transmittance Δ(b-a) exceeds 0%, that is, the above-mentioned UV transmittance (b) > the above-mentioned UV transmittance (a) means that although the fading of the film is deepened due to heating (curing), it can be fully Suppress its deepening. The difference in UV transmittance Δ(b-a) does not reach 0%, that is, the above-mentioned UV transmittance (b) < the above-mentioned UV transmittance (a) means that the film can be further colored by heating (curing).

UV透過率之差Δ(b－a)係基於波長532 nm下之紫外線(UV)而獲得之值，因此，本實施方式中之聚醯亞胺膜(硬化浮凸)容易判斷對搭載有532 nm之綠色雷射之雷射裝置之利用合適性。該雷射裝置有時用於在構成鈍化膜、表面保護膜、及層間絕緣膜等之樹脂之表面形成浮凸圖案，以及於該表面刻印半導體裝置之製品規格、批號及製造年月日等目的。與本實施方式之如下特性，即，容易於預烘烤膜之時點調整聚醯亞胺膜中之光吸收程度相輔相成，本實施方式之樹脂組合物可用於形成高端用途之元件中之聚醯亞胺膜，尤其是作為鈍化膜、表面保護膜、及層間絕緣膜等之聚醯亞胺膜。The difference in UV transmittance Δ(b-a) is a value based on ultraviolet (UV) at a wavelength of 532 nm. Therefore, it is easy to judge whether the polyimide film (hardened embossment) in this embodiment is equipped with 532 nm. Suitability of using nm green laser laser device. The laser device is sometimes used to form a relief pattern on the surface of the resin constituting the passivation film, surface protective film, interlayer insulating film, etc., and to engrave the product specifications, batch number, and manufacturing date of the semiconductor device on the surface. . Complementing the characteristics of this embodiment, that is, it is easy to adjust the light absorption degree in the polyimide film at the time of pre-baking the film, the resin composition of this embodiment can be used to form polyimide in devices for high-end applications. Amine films, especially polyimide films used as passivation films, surface protective films, and interlayer insulating films.

＜＜(A)成分；聚醯亞胺前驅物＞＞本實施方式之(A)成分為上述通式(A1)所表示之聚醯亞胺前驅物。藉此，於曝光時容易使(C)光聚合起始劑有效地發揮作用，結果容易獲得各種特性優異之硬化浮凸圖案。＜＜(A) component; polyimide precursor＞＞ The component (A) of this embodiment is the polyimide precursor represented by the general formula (A1). This makes it easy for the (C) photopolymerization initiator to effectively function during exposure, and as a result, it is easy to obtain a hardened relief pattern excellent in various characteristics.

＜上述通式(A1)中之X＞上述通式(A1)中，X所表示之四價有機基例如為源自作為(A)成分之原料之四羧酸二酐之有機基。該有機基較佳為碳數6～40之有機基，進而較佳為滿足以下兩者之四價芳香族基或四價脂環式脂肪族基： (1)-COOR ₁基及-CONH-基鍵結於同一環； (2)-COOR ₁基及-CONH-基彼此處於鄰位。上述(1)中，-COOR ₁基所鍵結之芳香環與-COOR ₂基所鍵結之芳香環可相同亦可不同。該語境中之「環」較佳為苯環。又，該語境中之-COOR ₁基中之R ₁較佳為上述通式(R _h)所表示之一價有機基。 <X in the general formula (A1)> In the general formula (A1), the tetravalent organic group represented by X is, for example, an organic group derived from the tetracarboxylic dianhydride which is the raw material of the component (A). The organic group is preferably an organic group having 6 to 40 carbon atoms, and more preferably a tetravalent aromatic group or a tetravalent alicyclic aliphatic group satisfying both of the following: (1) -COOR ₁ group and -CONH- The groups are bonded to the same ring; (2) -COOR ₁ group and -CONH- group are in ortho position to each other. In the above (1), the aromatic ring to which the -COOR ₁ group is bonded and the aromatic ring to which the -COOR ₂ group is bonded may be the same or different. "Ring" in this context is preferably a benzene ring. In addition, R ₁ in the -COOR ₁ group in this context is preferably a monovalent organic group represented by the general formula (R _h ).

作為X所表示之四價有機基，尤佳可例舉下述式所表示之結構。 [化10] X可為1種，亦可為2種以上之組合。 Particularly preferred examples of the tetravalent organic group represented by X include structures represented by the following formulas. [Chemical 10] X may be one type or a combination of two or more types.

本實施方式中，就表現出良好之膜物性之觀點而言，上述X較佳為包含選自下述式(1)～(3)所表示之群中之至少一種結構。 [化11] [化12] [化13] In this embodiment, from the viewpoint of exhibiting good film physical properties, the above-mentioned X preferably contains at least one structure selected from the group represented by the following formulas (1) to (3). [Chemical 11] [Chemical 12] [Chemical 13]

本實施方式中，就表現出良好之膜物性(例如，膜伸長率)之觀點而言，較佳為於(A)成分中，上述X包含下述式(2)所表示之結構。 [化14] 即，較佳為，(A)成分包含源自ODPA(4,4'-氧二鄰苯二甲酸酐)之結構。 In this embodiment, from the viewpoint of exhibiting good film physical properties (for example, film elongation), it is preferable that in the component (A), the above-mentioned X includes a structure represented by the following formula (2). [Chemical 14] That is, it is preferable that (A) component contains a structure derived from ODPA (4,4'-oxydiphthalic anhydride).

於上述通式(A1)中之R ₁及R ₂、X之至少一者為上述通式(R _h)所表示之一價有機基之情形時，該通式(R _h)中之R ₃較佳為氫原子或甲基，就感光特性之觀點而言，R ₄及R ₅分別較佳為氫原子。又，就感光特性之觀點而言，p較佳為2以上10以下之整數，更佳為2以上4以下之整數。 When at least one of R ₁ , R ₂ and X in the above general formula (A1) is a monovalent organic group represented by the above general formula (R _h ), R ₃ in the general formula (R _h ) A hydrogen atom or a methyl group is preferred, and from the viewpoint of photosensitive characteristics, R ₄ and R ₅ are each preferably a hydrogen atom. Furthermore, from the viewpoint of photosensitive characteristics, p is preferably an integer of 2 to 10 and more preferably 2 to 4.

＜上述通式(A1)中之Y＞上述通式(A1)中，Y所表示之二價有機基例如為源自作為(A)成分之原料之二胺之有機基。該有機基較佳為碳數6～40之芳香族基，例如可例舉下述式所表示之結構： [化15] {上述式中，A分別獨立地為甲基(-CH ₃)、乙基(-C ₂H ₅)、丙基(-C ₃H ₇)、丁基(-C ₄H ₉)、或三氟甲基(-CF ₃)}。Y可為1種，亦可為2種以上之組合。 <Y in the general formula (A1)> In the general formula (A1), the divalent organic group represented by Y is, for example, an organic group derived from the diamine which is the raw material of the component (A). The organic group is preferably an aromatic group having 6 to 40 carbon atoms. Examples thereof include a structure represented by the following formula: [Chemical 15] {In the above formula, A is independently methyl (-CH ₃ ), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ), butyl (-C ₄ H ₉ ), or tris Fluoromethyl(-CF ₃ )}. Y may be one type or a combination of two or more types.

本實施方式中，就表現出良好之膜物性之觀點而言，上述Y較佳為包含選自下述通式(4)～(7)所表示之群中之至少一種結構： [化16] [化17] [化18] [化19] {上述式中，A分別獨立地為甲基(-CH ₃)、乙基(-C ₂H ₅)、丙基(-C ₃H ₇)、丁基(-C ₄H ₉)、或三氟甲基(-CF ₃)}。 In this embodiment, from the viewpoint of exhibiting good film physical properties, the above-mentioned Y preferably contains at least one structure selected from the group represented by the following general formulas (4) to (7): [Chemical 16] [Chemical 17] [Chemical 18] [Chemical 19] {In the above formula, A is independently methyl (-CH ₃ ), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ), butyl (-C ₄ H ₉ ), or tris Fluoromethyl(-CF ₃ )}.

其中，本實施方式中，就表現出良好之膜物性(例如，膜伸長率)之觀點而言，較佳為於(A)成分中，上述Y包含下述式(8)： [化20] 及/或下述式(9)： [化21] 所表示之結構。即，較佳為，(A)成分包含源自DADPE(4,4'-二胺基二苯醚)之結構、及/或源自m-TB(2,2'-二甲基-4,4'-二胺基聯苯)之結構。 Among them, in this embodiment, from the viewpoint of expressing good film physical properties (for example, film elongation), it is preferable that in the component (A), the above-mentioned Y includes the following formula (8): [Chemical 20] And/or the following formula (9): [Chemical 21] the structure represented. That is, it is preferable that component (A) contains a structure derived from DADPE (4,4'-diaminodiphenyl ether) and/or derived from m-TB (2,2'-dimethyl-4, 4'-diaminobiphenyl) structure.

＜上述通式(A1)中之X及Y之組合之一例＞本實施方式中，就進一步提高接著性且表現出良好之膜物性之觀點而言，較佳為於通式(A1)中，上述X包含下述式(2)所表示之結構， [化22] 且上述Y包含下述式(8)所表示之結構。 [化23] <An example of the combination of X and Y in the general formula (A1)> In this embodiment, from the viewpoint of further improving the adhesiveness and expressing good film physical properties, it is preferable that in the general formula (A1), The above-mentioned X includes a structure represented by the following formula (2), [Chemical Formula 22] And the above-mentioned Y includes a structure represented by the following formula (8). [Chemistry 23]

又，本實施方式中，就表現出良好之膜物性之觀點而言，較佳為於通式(A1)中，上述X包含下述式(2)所表示之結構， [化24] 且上述Y包含選自下述式(8)： [化25] 及下述式(10)： [化26] 所表示之群中之至少一種結構。 Moreover, in this embodiment, from the viewpoint of expressing good film physical properties, it is preferable that in the general formula (A1), the above-mentioned X includes a structure represented by the following formula (2), [Chemical 24] And the above-mentioned Y includes the following formula (8): [Chemical 25] And the following formula (10): [Chemical 26] At least one structure in the represented group.

包括上述在內，本實施方式中之上述X及上述Y之組合之一例如下所述。根據該等組合，容易對樹脂組合物、及/或由此所獲得之硬化浮凸圖案實現各種特性之提昇。規定編號中之X及Y之組合與其他編號中之X及Y之組合可併用。Including the above, an example of the combination of the above-mentioned X and the above-mentioned Y in this embodiment is as follows. These combinations make it easy to improve various characteristics of the resin composition and/or the hardened relief pattern obtained thereby. The combination of X and Y in the specified number can be used together with the combination of X and Y in other numbers.

[表1-1] 編號 X Y 1 源自ODPA之骨架源自DADPE之骨架 2 源自ODPA之骨架源自mTB之骨架 3 源自ODPA之骨架源自TFMB之骨架 4 源自ODPA之骨架上述式(5)所表示之骨架 5 源自ODPA之骨架上述式(6)所表示之骨架 (其中，源自p-PD之骨架) 6 源自BPDA之骨架源自DADPE之骨架 7 源自BPDA之骨架源自mTB之骨架 8 源自BPDA之骨架源自TFMB之骨架 [Table 1-1] No. X Y 1 Derived from the skeleton of ODPA Derived from the skeleton of DADPE 2 Derived from the skeleton of ODPA Derived from the skeleton of mTB 3 Derived from the skeleton of ODPA Derived from the skeleton of TFMB 4 Derived from the skeleton of ODPA The skeleton represented by the above formula (5) 5 Derived from the skeleton of ODPA The skeleton represented by the above formula (6) (where the skeleton is derived from p-PD) 6 Derived from the skeleton of BPDA Derived from the skeleton of DADPE 7 Derived from the skeleton of BPDA Derived from the skeleton of mTB 8 Derived from the skeleton of BPDA From the skeleton of TFMB

[表1-2] 編號 X Y 9 源自BPDA之骨架上述式(5)所表示之骨架 [Table 1-2] No. X Y 9 Derived from the skeleton of BPDA The skeleton represented by the above formula (5)

＜(A)成分之物性＞就加熱(固化)後所獲得之聚醯亞胺膜之耐熱性及機械特性之觀點而言，(A)成分之重量平均分子量較佳為1,000以上，更佳為5,000以上，又，較佳為100,000以下。就對有機溶劑之溶解性之觀點而言，(A)成分之重量平均分子量更佳為50,000以下。本實施方式之樹脂組合物具有感光性時，就兼顧曝光感光度、以及曝光及顯影後所獲得之圖案之解像度與對該圖案加熱(固化)後之膜物性之觀點而言，(A)成分之重量平均分子量較佳為6,000以上、7,000以上、8,000以上，又，較佳為40,000以下、30,000以下、22,000以下。「重量平均分子量」係作為藉由凝膠滲透層析法所得之聚苯乙烯換算值而計算出。＜Physical properties of component (A)＞ From the viewpoint of the heat resistance and mechanical properties of the polyimide film obtained after heating (curing), the weight average molecular weight of component (A) is preferably 1,000 or more, more preferably 5,000 or more, and more preferably Below 100,000. From the viewpoint of solubility in organic solvents, the weight average molecular weight of component (A) is more preferably 50,000 or less. When the resin composition of the present embodiment has photosensitivity, from the viewpoint of balancing the exposure sensitivity, the resolution of the pattern obtained after exposure and development, and the film physical properties after heating (curing) the pattern, the component (A) The weight average molecular weight is preferably 6,000 or more, 7,000 or more, or 8,000 or more, and more preferably 40,000 or less, 30,000 or less, or 22,000 or less. The "weight average molecular weight" is calculated as a polystyrene-converted value obtained by gel permeation chromatography.

＜＜(B)成分；有機染料＞＞本實施方式之樹脂組合物包含上述(B)成分。作為(B)成分之染料(dye)在溶解於溶劑(主要為水)方面，與定義為不與溶劑發生作用且不溶解於溶劑之「顏料(pigment)」不同。作為(B)成分，較佳可例舉於波長400～800 nm附近具有極大吸收波長之有機染料。＜＜(B)Component; organic dye＞＞ The resin composition of this embodiment contains the above-mentioned component (B). The dye (dye) as the component (B) is different from the "pigment" which is defined as not interacting with the solvent and being insoluble in the solvent in terms of being soluble in the solvent (mainly water). As the component (B), an organic dye having a maximum absorption wavelength near a wavelength of 400 to 800 nm is preferably used.

作為(B)成分，具體可例舉選自由吖𠯤系、次甲基偶氮系、蒽系、喹吖啶酮系、二㗁𠯤系、吡咯并吡咯二酮系、蒽吡啶酮系、異吲哚啉酮系、陰丹士林系、芘酮系、苝系、靛藍系、硫靛藍系、喹酞酮系、喹啉系、及三苯甲烷系所組成之群中之至少一種染料衍生物。其中，作為(B)成分之較佳例，可例舉吖𠯤系染料衍生物、及蒽系染料衍生物之至少一者。該等(B)成分與(A)成分顯示出較高之相容性，故而容易實現聚醯亞胺膜之膜伸長率之提昇。Specific examples of the component (B) include those selected from the group consisting of azine series, methine azo series, anthracene series, quinacridone series, diketon series, diketopyrrolopyrrole series, anthrapyridone series, and iso-series. At least one dye derived from the group consisting of indolinone series, indanthryne series, pyrenone series, perylene series, indigo series, thioindigo series, quinphthalone series, quinoline series, and triphenylmethane series things. Among them, preferred examples of the component (B) include at least one of an azine-based dye derivative and an anthracene-based dye derivative. The component (B) and the component (A) show high compatibility, so it is easy to increase the film elongation of the polyimide film.

(B)成分較佳為將滿足如下條件中之至少一項之有機染料組合複數種所得者：適宜地吸收可見光範圍之波長；具有與諸如(A)成分之聚合物之適宜之相容性；及對雷射光之散射特性較低。進而，(B)成分較佳為具有滿足如下條件中之至少一項之有機染料：曝露於(A)成分之加熱(固化)步驟中之高溫、或藉由雷射光照射進行之熔融時之高溫下時不易褪色；具有優異之耐熱性；及適宜地吸收雷射光之波長。此處所謂「雷射光」，例如可為利用波長532 nm之綠色雷射之雷射光。Component (B) is preferably obtained by combining a plurality of organic dyes that meet at least one of the following conditions: suitably absorb wavelengths in the visible light range; have suitable compatibility with polymers such as component (A); And the scattering characteristics of laser light are low. Furthermore, component (B) is preferably an organic dye that satisfies at least one of the following conditions: exposure to high temperatures in the heating (curing) step of component (A) or high temperatures in melting by laser irradiation. It is not easy to fade when exposed to heat; it has excellent heat resistance; and it can appropriately absorb the wavelength of laser light. The so-called “laser light” here may be, for example, laser light using a green laser with a wavelength of 532 nm.

作為吖𠯤系染料衍生物，可例舉於染料索引中記載為C.I.溶劑黑(Solvent Black)5、C.I.溶劑黑7、及C.I.酸性黑(Acid Black)2之類之黑色吖𠯤系縮合混合物。此種吖𠯤系染料衍生物例如可藉由如下方式獲得：於氯化鐵之存在下，以160～180℃之反應溫度使苯胺、苯胺鹽酸鹽、及硝基苯氧化及脫水縮合。Examples of the azine-based dye derivatives include black azine-based condensation mixtures such as C.I. Solvent Black 5, C.I. Solvent Black 7, and C.I. Acid Black 2, which are listed in the dye index. Such azine-based dye derivatives can be obtained, for example, by oxidizing and dehydrating condensation of aniline, aniline hydrochloride, and nitrobenzene in the presence of ferric chloride at a reaction temperature of 160 to 180°C.

作為蒽系染料衍生物，下述所示之蒽系染料衍生物由於容易獲得顯示出良好之耐熱性，且於加熱(固化)步驟前後均具有良好之著色程度(低透過率)之膜，故而尤佳。即，作為蒽系染料衍生物，較佳為蒽系油溶性染料，具體而言，較佳可例舉：以C.I.溶劑藍(Solvent Blue)11、12、13、14、26、35、36、44、45、48、49、58、59、63、68、69、70、78、79、83、87、90、94、97、98、101、102、104、105、122、129、及132； C.I.分散藍(Disperse Blue)14、35、102、及197；C.I.溶劑綠(Solvent Green)3、19、20、23、24、25、26、28、31、33、及65； C.I.溶劑紫(Solvent Violet)13、14、15、26、30、31、33、34、36、37、38、40、41、42、45、47、48、51、59、及60之染料索引市售之染料。 As anthracene-based dye derivatives, the anthracene-based dye derivatives shown below are easy to obtain films that exhibit good heat resistance and have good coloring (low transmittance) before and after the heating (curing) step. Excellent. That is, the anthracene-based dye derivative is preferably an anthracene-based oil-soluble dye. Specifically, preferred examples include: C.I. Solvent Blue (Solvent Blue) 11, 12, 13, 14, 26, 35, 36, 44, 45, 48, 49, 58, 59, 63, 68, 69, 70, 78, 79, 83, 87, 90, 94, 97, 98, 101, 102, 104, 105, 122, 129, and 132 ; C.I. Disperse Blue (Disperse Blue) 14, 35, 102, and 197; C.I. Solvent Green (Solvent Green) 3, 19, 20, 23, 24, 25, 26, 28, 31, 33, and 65; Dye index for C.I. Solvent Violet 13, 14, 15, 26, 30, 31, 33, 34, 36, 37, 38, 40, 41, 42, 45, 47, 48, 51, 59, and 60 Commercially available dyes.

其中，更佳可例舉選自由如下化合物所組成之群中之至少一種蒽系染料衍生物。 B-4：下式所表示之化合物； [化27] B-5：下式所表示之化合物； [化28] B-6：下式所表示之化合物； [化29] B-7：下式所表示之化合物； [化30] B-8：下式所表示之化合物； [化31] B-9：下式所表示之化合物； [化32] B-10：下式所表示之化合物； [化33] B-11：下式所表示之化合物。 [化34] Among them, at least one anthracene dye derivative selected from the group consisting of the following compounds is more preferred. B-4: Compound represented by the following formula; [Chemical 27] B-5: Compound represented by the following formula; [Chemical 28] B-6: Compound represented by the following formula; [Chemical 29] B-7: Compound represented by the following formula; [Chemical 30] B-8: Compound represented by the following formula; [Chemical 31] B-9: Compound represented by the following formula; [Chemical 32] B-10: Compound represented by the following formula; [Chemical 33] B-11: Compound represented by the following formula. [Chemical 34]

就容易發揮本發明之效果之觀點而言，(B)成分之含量相對於(A)成分100質量份，較佳為0.5～30質量份，更佳為1～20質量份，進而較佳為1～5質量份。若(B)成分之含量少於上述下限值，則於預烘烤膜階段無法充分獲得著色性。若(B)成分之含量多於上述上限值，則所獲得之聚醯亞胺膜之膜物性容易變差。(B)成分可單獨使用，亦可併用2種以上。From the viewpoint of easily exhibiting the effects of the present invention, the content of component (B) is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of component (A), and still more preferably 1 to 5 parts by mass. If the content of component (B) is less than the above lower limit, sufficient coloring properties cannot be obtained in the pre-baked film stage. If the content of component (B) exceeds the above upper limit, the film physical properties of the obtained polyimide film are likely to deteriorate. (B) Component can be used individually or in combination of 2 or more types.

＜＜(C)成分；有機溶劑＞＞本實施方式之樹脂組合物包含上述(C)成分。作為(C)成分，例如，就對(A)成分之溶解性之觀點而言，較佳可例舉具有極性之有機溶劑。具體可例舉：N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N,N-二甲基乙醯胺、二甲基亞碸(DMSO)、二乙二醇二甲醚、環戊酮、γ-丁內酯(GBL)、α-乙醯基-γ-丁內酯、四甲基脲、1,3-二甲基-2-咪唑啉酮、N-環己基-2-吡咯啶酮等。該等可單獨使用或以2種以上之組合使用。＜＜(C)Component; organic solvent＞＞ The resin composition of this embodiment contains the above-mentioned component (C). As the component (C), for example, from the viewpoint of the solubility of the component (A), a polar organic solvent can be preferably used. Specific examples include: N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylformamide, Methylsulfoxide (DMSO), diglyme, cyclopentanone, γ-butyrolactone (GBL), α-acetyl-γ-butyrolactone, tetramethylurea, 1,3- Dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidinone, etc. These can be used alone or in combination of two or more.

又，作為(C)成分，就提昇樹脂組合物之保存穩定性之觀點而言，較佳可例舉醇類。適宜之醇類係於分子內具有醇性羥基且不具有烯烴系雙鍵之醇。具體可例舉：甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第三丁醇等烷基醇類；乳酸乙酯等乳酸酯類；丙二醇-1-甲醚、丙二醇-2-甲醚、丙二醇-1-***、丙二醇-2-***、丙二醇-1-(正丙基)醚、丙二醇-2-(正丙基)醚等丙二醇單烷基醚類；乙二醇甲醚、乙二醇***、乙二醇正丙基醚等單醇類； 2-羥基異丁酸酯類；乙二醇、丙二醇等二醇類；等。其中，較佳為乳酸酯類、丙二醇單烷基醚類、2-羥基異丁酸酯類、及乙醇，尤其更佳為乳酸乙酯、丙二醇-1-甲醚、丙二醇-1-***、及丙二醇-1-(正丙基)醚。 Moreover, as (C) component, from a viewpoint of improving the storage stability of a resin composition, alcohol is preferably mentioned. Suitable alcohols are those which have an alcoholic hydroxyl group in the molecule and do not have an olefinic double bond. Specific examples include: Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol and other alkyl alcohols; Lactic acid esters such as ethyl lactate; Propylene glycol monomethyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-(n-propyl) ether, propylene glycol-2-(n-propyl) ether, etc. Alkyl ethers; Monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol n-propyl ether; 2-Hydroxyisobutyrate; Diols such as ethylene glycol and propylene glycol; wait. Among them, lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethanol are preferred, and ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and Propylene glycol-1-(n-propyl) ether.

根據樹脂組合物之塗佈膜厚、及/或黏度，(C)成分相對於(A)成分之100質量份，以30～1,500質量份、較佳為100～1,000質量份使用。於(C)成分包含不具有烯烴系雙鍵之醇之情形時，不具有烯烴系雙鍵之醇於(C)成分總量中所占之比率較佳為5～50質量%，更佳為10～30質量%。於不具有烯烴系雙鍵之醇之上述比率為5質量%以上之情形時，樹脂組合物之保存穩定性變得良好，於50質量%以下之情形時，(A)成分之溶解性變得良好。Depending on the coating film thickness and/or viscosity of the resin composition, component (C) is used in an amount of 30 to 1,500 parts by mass, preferably 100 to 1,000 parts by mass relative to 100 parts by mass of component (A). When the component (C) contains an alcohol without an olefinic double bond, the ratio of the alcohol without an olefinic double bond to the total amount of the component (C) is preferably 5 to 50% by mass, more preferably 10～30% by mass. When the above-mentioned ratio of the alcohol having no olefinic double bond is 5 mass % or more, the storage stability of the resin composition becomes good, and when it is 50 mass % or less, the solubility of the component (A) becomes good.

綜上所述，(C)成分之中，選自由N-甲基-2-吡咯啶酮、GBL、DMSO、3-甲氧基-N,N-二甲基丙醯胺、及乳酸乙酯所組成之群中之至少1種尤佳。(C)成分可單獨使用，亦可併用2種以上。In summary, component (C) is selected from N-methyl-2-pyrrolidinone, GBL, DMSO, 3-methoxy-N,N-dimethylpropylamide, and ethyl lactate At least one species from the group is preferred. (C) Component can be used individually or in combination of 2 or more types.

＜＜(D)成分；光聚合起始劑＞＞本實施方式之樹脂組合物可進而包含上述(D)成分。(D)成分藉由吸收特定波長並進行分解，可產生自由基。本實施方式之樹脂組合物藉由進而包含(D)成分，可適宜地用作感光性樹脂組合物。＜＜(D) component; photopolymerization initiator＞＞ The resin composition of this embodiment may further contain the above-mentioned component (D). Component (D) can generate free radicals by absorbing specific wavelengths and decomposing them. The resin composition of this embodiment can be suitably used as a photosensitive resin composition by further containing the component (D).

作為(D)成分，較佳可例舉：二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯基酮、二苄基酮、茀酮等二苯甲酮衍生物； 2,2'-二乙氧基苯乙酮、2-羥基-2-甲基苯丙酮、1-羥基環己基苯基酮等苯乙酮衍生物； 9-氧硫𠮿、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-丁二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰乙氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰苯甲醯基)肟、1,3-二苯基丙三酮-2-(鄰乙氧基羰基)肟、1-苯基-3-乙氧基丙三酮-2-(鄰苯甲醯基)肟等肟類； N-苯基甘胺酸等N-芳基甘胺酸類；過氯化苯甲醯等過氧化物類；芳香族聯咪唑類；二茂鈦類； α-(正辛基磺醯氧基亞胺基)-4-甲氧基苄基氰化物等光酸產生劑類；等。其中，就光敏度之方面而言，更佳為肟類。 Preferable examples of the component (D) include benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and benzyl ketone. Benzophenone derivatives such as ketone; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone and other acetophenone derivatives; 9- oxygen sulfur𠮿 , 2-Methyl-9-oxosulfide𠮿 , 2-isopropyl-9-oxosulfide𠮿 , diethyl-9-oxosulfide𠮿 Etc. 9-oxysulfur𠮿 Derivatives; Benzyl derivatives such as Benzyl, Benzyl dimethyl ketal, Benzyl-β-methoxyethyl acetal; Benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl -1,2-Butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1 ,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropane Triketone-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxyglycerin-2-(o-benzoyl)oxime and other oximes; N-phenylglycine, etc. N-arylglycines; peroxides such as benzyl perchloride; aromatic biimidazoles; titanocenes; α-(n-octylsulfonyloxyimino)-4-methoxy Photoacid generators such as benzyl cyanide; etc. Among them, in terms of photosensitivity, oximes are more preferred.

肟類之中，就樹脂組合物與基板之接著性之觀點而言，進而較佳為含有選自由下述式(D1)～(D6)所表示之群中之至少一種結構者： [化35-1] [化35-2] (式中，R39為甲基或苯基，R40分別獨立地為碳數1～12之一價有機基，Z為硫或氧原子，R ₄₁為甲基、苯基或二價有機基，R ₄₂～R ₄₄為氫原子或一價有機基)。 Among the oximes, from the viewpoint of adhesion between the resin composition and the substrate, those containing at least one structure selected from the group represented by the following formulas (D1) to (D6) are more preferred: [Chemical 35 -1] [Chemical 35-2] (In the formula, R39 is a methyl or phenyl group, R40 is independently a monovalent organic group with 1 to 12 carbon atoms, Z is a sulfur or oxygen atom, R ₄₁ is a methyl, phenyl or divalent organic group, R ₄₂ to R ₄₄ are hydrogen atoms or monovalent organic groups).

就適宜地表現(D)成分之功能之觀點、甚至容易發揮本發明之效果之觀點而言，樹脂組合物較佳為包含相對於(A)成分100質量份為0.1～100質量份之(D)成分，更佳為包含相對於(A)成分100質量份為1～50質量份之(D)成分。From the viewpoint of suitably expressing the function of component (D) and even easily exhibiting the effects of the present invention, the resin composition preferably contains 0.1 to 100 parts by mass of (D) based on 100 parts by mass of component (A). ) component, and more preferably contains 1 to 50 parts by mass of component (D) relative to 100 parts by mass of component (A).

＜＜(E)成分；其他成分＞＞本實施方式之樹脂組合物可既包含(A)～(C)成分、或(A)～(D)成分，又進而包含除上述(A)～(D)以外之成分((E)成分；其他成分)。＜＜(E) Ingredients; other ingredients＞＞ The resin composition of this embodiment may contain both components (A) to (C) or components (A) to (D), and may further contain components other than the above (A) to (D) (component (E); other ingredients).

作為(E)成分，例如可例舉具有不飽和鍵之交聯劑。藉此，於進而含有(D)成分之情形時，容易將本實施方式之樹脂組合物更適宜地用作感光性樹脂組合物。此外，作為(E)成分，可例舉：除(A)成分以外之樹脂；增感劑；接著助劑；聚合抑制劑；唑類化合物；受阻酚化合物；等。(E)成分可單獨使用，亦可併用2種以上。 Examples of the component (E) include a cross-linking agent having an unsaturated bond. Thereby, when further containing (D)component, it becomes easy to use the resin composition of this embodiment more suitably as a photosensitive resin composition. In addition, examples of the component (E) include: Resins other than component (A); sensitizer; Then add auxiliaries; polymerization inhibitor; Azole compounds; Hindered phenolic compounds; wait. (E) Component may be used individually, or 2 or more types may be used together.

((E-1)交聯劑) 就提昇聚醯亞胺膜(硬化浮凸圖案)之物性、及解像性之觀點而言，本實施方式之樹脂組合物可含有具有光聚合性不飽和鍵之交聯劑。作為此種交聯劑，可例舉可藉由(D)成分進行自由基聚合反應之(甲基)丙烯酸化合物。作為此種化合物，較佳可例舉：以二乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯為代表之乙二醇或聚乙二醇之單或二(甲基)丙烯酸酯；丙二醇或聚丙二醇之單或二(甲基)丙烯酸酯；甘油之單、二或三(甲基)丙烯酸酯；環己烷二(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(甲基)丙烯酸酯；新戊二醇之二(甲基)丙烯酸酯；雙酚A之單或二(甲基)丙烯酸酯；苯三甲基丙烯酸酯； (甲基)丙烯酸異𦯉基酯；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(甲基)丙烯酸酯；甘油之二或三(甲基)丙烯酸酯；季戊四醇之二、三、或四(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。 ((E-1) Cross-linking agent) From the viewpoint of improving the physical properties and resolution of the polyimide film (hardened relief pattern), the resin composition of this embodiment may contain a crosslinking agent having a photopolymerizable unsaturated bond. Examples of such a cross-linking agent include (meth)acrylic compounds capable of radical polymerization by component (D). Preferable examples of such compounds include: Mono- or di(meth)acrylates of ethylene glycol or polyethylene glycol represented by diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; Mono- or di(meth)acrylates of propylene glycol or polypropylene glycol; Mono, di or tri(meth)acrylate of glycerol; Cyclohexane di(meth)acrylate; 1,4-butanediol diacrylate and dimethacrylate, 1,6-hexanediol di(meth)acrylate; Neopentyl glycol di(meth)acrylate; Mono- or di(meth)acrylate of bisphenol A; Trimethacrylate; (Meth)acrylic acid isoester; Acrylamide and its derivatives; Methacrylamide and its derivatives; Trimethylolpropane tri(meth)acrylate; Glycerol di- or tri(meth)acrylate; Pentaerythritol di, tri, or tetra(meth)acrylate; and ethylene oxide or propylene oxide adducts of such compounds; wait.

具有光聚合性不飽和鍵之交聯劑之含量相對於(A)成分100質量份，較佳為1～100質量份，更佳為2～50質量份。具有光聚合性不飽和鍵之交聯劑可單獨使用，亦可併用2種以上。The content of the cross-linking agent having a photopolymerizable unsaturated bond is preferably 1 to 100 parts by mass, and more preferably 2 to 50 parts by mass based on 100 parts by mass of component (A). The cross-linking agent having a photopolymerizable unsaturated bond can be used alone, or two or more types can be used in combination.

((E-2)除(A)成分以外之樹脂) 本實施方式之樹脂組合物可含有除(A)成分以外之樹脂成分。此種樹脂成分例如：聚醯亞胺、聚㗁唑、聚㗁唑前驅物、酚樹脂、聚醯胺、環氧樹脂、矽氧烷樹脂、丙烯酸樹脂等。於含有聚醯亞胺作為(E)成分之情形時，該聚醯亞胺可為骨架源自(A)成分之骨架之聚醯亞胺，又，亦可為不具有該骨架之聚醯亞胺。 ((E-2) Resins other than component (A)) The resin composition of this embodiment may contain resin components other than component (A). Examples of such resin components include: polyimide, polyethazole, polyethazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, acrylic resin, etc. When polyimide is contained as component (E), the polyimide may be a polyimide whose skeleton is derived from the skeleton of component (A), or may be a polyimide which does not have such a skeleton. amine.

除(A)成分以外之樹脂成分之調配量相對於(A)成分100質量份，較佳為0.01～20質量份。除(A)成分以外之樹脂成分可單獨使用，亦可併用2種以上。The compounding amount of the resin component other than component (A) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of component (A). Resin components other than component (A) may be used alone, or two or more types may be used in combination.

((E-3)增感劑) 於將本實施方式之樹脂組合物用作感光性樹脂組合物之情形時，為了提昇光敏度，該樹脂組合物可任意地含有增感劑。作為該增感劑，例如可例舉：米其勒酮、4,4'-雙(二乙胺基)二苯甲酮、2,5-雙(4'-二乙胺基苯亞甲基)環戊烷、2,6-雙(4'-二乙胺基苯亞甲基)環己酮、2,6-雙(4'-二乙胺基苯亞甲基)-4-甲基環己酮、4,4'-雙(二甲胺基)查耳酮、4,4'-雙(二乙胺基)查耳酮、對二甲胺基亞桂皮基茚滿酮、對二甲胺基亞苄基茚滿酮、2-(對二甲胺基苯基聯伸苯)-苯并噻唑、2-(對二甲胺基苯基伸乙烯基)苯并噻唑、2-(對二甲胺基苯基伸乙烯基)異萘并噻唑、1,3-雙(4'-二甲胺基苯亞甲基)丙酮、1,3-雙(4'-二乙胺基苯亞甲基)丙酮、3,3'-羰基-雙(7-二乙胺基香豆素)、3-乙醯基-7-二甲胺基香豆素、3-乙氧基羰基-7-二甲胺基香豆素、3-苄氧基羰基-7-二甲胺基香豆素、3-甲氧基羰基-7-二乙胺基香豆素、3-乙氧基羰基-7-二乙胺基香豆素、N-苯基-N'-乙基乙醇胺、N-苯基二乙醇胺、N-對甲苯基二乙醇胺、N-苯基乙醇胺、4-𠰌啉基二苯甲酮、二甲胺基苯甲酸異戊酯、二乙胺基苯甲酸異戊酯、2-巰基苯并咪唑、1-苯基-5-巰基四唑、2-巰基苯并噻唑、2-(對二甲胺基苯乙烯基)苯并㗁唑、2-(對二甲胺基苯乙烯基)苯并噻唑、2-(對二甲胺基苯乙烯基)萘并(1,2-d)噻唑、2-(對二甲胺基苯甲醯基)苯乙烯、二苯基乙醯胺、苯甲醯苯胺、N-甲基乙醯苯胺、3',4'-二甲基乙醯苯胺等。 ((E-3) Sensitizer) When the resin composition of this embodiment is used as a photosensitive resin composition, the resin composition may optionally contain a sensitizer in order to improve photosensitivity. Examples of the sensitizer include Michelone, 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-dimethylaminocinnaminylindanone, p-dimethylaminocinnaminylindanone, Methylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzothiazole, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole Dimethylaminophenylvinyl)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene) base) acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-di Methylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-𠰌linylbenzophenone , isoamyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p- Dimethylaminostyryl)benzozoazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d) Thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzyl aniline, N-methylacetyl aniline, 3',4'-dimethylacetyl aniline wait.

增感劑之含量相對於(A)成分100質量份，較佳為0.1～25質量份。增感劑可單獨使用，亦可併用2種以上。The content of the sensitizer is preferably 0.1 to 25 parts by mass based on 100 parts by mass of component (A). The sensitizer can be used alone, or two or more types can be used in combination.

((E-4)接著助劑) 為了提昇樹脂組合物與基板之接著性，該樹脂組合物可任意地含有接著助劑。作為接著助劑，例如可例舉：γ-胺基丙基二甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基二甲氧基甲基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、二甲氧基甲基-3-哌啶基丙基矽烷、二乙氧基-3-縮水甘油氧基丙基甲基矽烷、N-(3-二乙氧基甲基矽烷基丙基)丁二醯亞胺、N-[3-(三乙氧基矽烷基)丙基]鄰苯二甲醯胺酸、二苯甲酮-3,3'-雙(N-[3-三乙氧基矽烷基]丙基醯胺)-4,4'-二羧酸、苯-1,4-雙(N-[3-三乙氧基矽烷基]丙基醯胺)-2,5-二羧酸、3-(三乙氧基矽烷基)丙基丁二酸酐、N-苯基胺基丙基三甲氧基矽烷等矽烷偶合劑、及三(乙醯乙酸乙基)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。其中，就接著性之觀點而言，較佳為矽烷偶合劑。 ((E-4) Adhesion additive) In order to improve the adhesion between the resin composition and the substrate, the resin composition may optionally contain an adhesion assistant. Examples of adhesion aids include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyldimethoxysilane, and γ-aminopropyldimethoxysilane. Glyceroxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacrylyl Oxypropyltrimethoxysilane, dimethoxymethyl-3-piperidylpropylsilane, diethoxy-3-glycidyloxypropylmethylsilane, N-(3-diethoxy Methylmethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamide, benzophenone-3,3'-bis( N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide) Amine)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane and other silane coupling agents, and tris(acetyl acetic acid) Aluminum-based adhesion additives such as ethyl)aluminum, tris(acetylpyruvate)aluminum, and ethylaluminum acetylacetate diisopropyl. Among them, from the viewpoint of adhesiveness, a silane coupling agent is preferred.

接著助劑之含量相對於(A)成分100質量份，較佳為0.5～25質量份。接著助劑可單獨使用，亦可併用2種以上。Next, the content of the auxiliary agent is preferably 0.5 to 25 parts by mass based on 100 parts by mass of component (A). The subsequent additives can be used alone or two or more types can be used in combination.

((E-5)聚合抑制劑) 本實施方式之樹脂組合物由於包含有機溶劑作為(C)成分，故而處於溶液狀態。於此情形時，為了提昇保存時之黏度及光敏度之穩定性，該樹脂組合物可任意地含有熱聚合抑制劑。作為熱聚合抑制劑，例如可例舉：對苯二酚、N-亞硝基二苯胺、對第三丁基兒茶酚、啡噻𠯤、N-苯基萘胺、乙二胺四乙酸、1,2-環己烷二胺四乙酸、乙二醇醚二胺四乙酸、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-苯基羥胺銨鹽、N-亞硝基-N(1-萘基)羥胺銨鹽、2,2,6,6-四甲基哌啶-1-氧自由基等。 ((E-5)Polymerization inhibitor) Since the resin composition of this embodiment contains an organic solvent as the (C) component, it is in a solution state. In this case, in order to improve the stability of viscosity and photosensitivity during storage, the resin composition may optionally contain a thermal polymerization inhibitor. Examples of thermal polymerization inhibitors include: hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, thiophene, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-Cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso -N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, 2,2,6,6-tetramethylpiperidine-1-oxygen free radical, etc.

熱聚合抑制劑之含量相對於(A)成分100質量份，較佳為0.005～12質量份。熱聚合抑制劑可單獨使用，亦可併用2種以上。The content of the thermal polymerization inhibitor is preferably 0.005 to 12 parts by mass relative to 100 parts by mass of component (A). The thermal polymerization inhibitor may be used alone, or two or more types may be used in combination.

((E-6)唑類化合物) 於塗佈本實施方式之樹脂組合物之基板含有銅或銅合金之情形時，為了抑制銅表面之變色，該樹脂組合物可任意地含有唑類化合物。作為唑類化合物，例如可例舉：1H-***、5-甲基-1H-***、5-乙基-1H-***、4,5-二甲基-1H-***、5-苯基-1H-***、4-第三丁基-5-苯基-1H-***、5-羥基苯基-1H-***、苯基***、對乙氧基苯基***、5-苯基-1-(2-二甲基胺基乙基)***、5-苄基-1H-***、羥基苯基***、1,5-二甲基***、4,5-二乙基-1H-***、1H-苯并***、2-(5-甲基-2-羥基苯基)苯并***、2-[2-羥基-3,5-雙(α,α-二甲基苄基)苯基]-苯并***、2-(3,5-二-第三丁基-2-羥基苯基)苯并***、2-(3-第三丁基-5-甲基-2-羥基苯基)-苯并***、2-(3,5-二-第三戊基-2-羥基苯基)苯并***、2-(2'-羥基-5'-第三辛基苯基)苯并***、羥基苯基苯并***、甲苯并***、5-甲基-1H-苯并***、4-甲基-1H-苯并***、4-羧基-1H-苯并***、5-羧基-1H-苯并***、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。其中，較佳為選自由甲苯并***、5-甲基-1H-苯并***、及4-甲基-1H-苯并***所組成之群中之至少一種以上。 ((E-6)azole compounds) When the substrate on which the resin composition of the present embodiment is applied contains copper or a copper alloy, the resin composition may optionally contain an azole compound in order to suppress discoloration of the copper surface. 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 -Diethyl-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-tertiary butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tertiary Butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2' -Hydroxy-5'-tertiary octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, toluenzotriazole, 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 Azole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Among them, at least one selected from the group consisting of toluenzotriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole is preferred.

就接著性之觀點而言，唑類化合物之含量相對於(A)成分100質量份，較佳為0.1～20質量份，更佳為0.5～5質量份。於唑類化合物之含量為0.1質量份以上之情形時，容易於將本實施方式之樹脂組合物形成於基板上時，抑制該基板中所含之銅或銅合金之變色，且於唑類化合物之含量為20質量份以下之情形時，該樹脂組合物容易顯示出良好之保存穩定性。唑類化合物可單獨使用，亦可併用2種以上。From the viewpoint of adhesiveness, the content of the azole compound is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 5 parts by mass based on 100 parts by mass of component (A). When the content of the azole compound is 0.1 parts by mass or more, when the resin composition of the present embodiment is formed on a substrate, it is easy to suppress discoloration of copper or copper alloy contained in the substrate, and the azole compound When the content is 20 parts by mass or less, the resin composition tends to exhibit good storage stability. The azole compound may be used alone, or two or more types may be used in combination.

((E-7)受阻酚化合物) 為了抑制基板表面之變色，本實施方式之樹脂組合物可任意地含有受阻酚化合物來代替上述唑類化合物，或者除含有唑類化合物以外還任意地含有受阻酚化合物。作為受阻酚化合物，例如可例舉：2,6-二-第三丁基-4-甲基苯酚、2,5-二-第三丁基-對苯二酚、十八烷基-3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯、異辛基-3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯、4,4'-亞甲基雙(2,6-二-第三丁基苯酚)、4,4'-硫基-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-硫基-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-氫化苯丙烯醯胺)、2,2'-亞甲基-雙(4-甲基-6-第三丁基苯酚)、2,2'-亞甲基-雙(4-乙基-6-第三丁基苯酚)、季戊四醇基-四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、三-(3,5-二-第三丁基-4-羥基苄基)-異氰尿酸酯、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。其中，較佳為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。 ((E-7)Hindered phenol compound) In order to suppress discoloration of the substrate surface, the resin composition of the present embodiment may optionally contain a hindered phenol compound instead of the azole compound, or may optionally contain a hindered phenol compound in addition to the azole compound. Examples of hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, and octadecyl-3- (3,5-Di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4 '-Butylene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propanol acid ester], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenediol Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'hexamethylene bis(3,5-di-tert-butyl-4- Hydroxy-hydrogenated phenylacrylamide), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl- 6-tert-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-tert. Butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tertiary 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-tris(4-dibutyl-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-dimethyl Benzyl]-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy- 2,6-Dimethylbenzyl]-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2 ,6-Dimethyl-4-phenylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4 -Tertibutyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-( 1H,3H,5H)-triketone, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tristrione -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl base)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl) -3-Hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4- tert-Butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-trione (4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H ,5H)-triketone, etc. Among them, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6- (1H,3H,5H)-Triketone.

就樹脂組合物與基板之接著性之觀點而言，受阻酚化合物之含量相對於(A)成分100質量份，較佳為0.1～20質量份，更佳為0.5～10質量份。於受阻酚化合物之含量為0.1質量份以上之情形時，容易於將本實施方式之樹脂組合物形成於基板上時，抑制該基板中所含之銅或銅合金之變色，又，於受阻酚化合物之含量為20質量份以下之情形時，該樹脂組合物容易顯示出良好之保存穩定性。From the viewpoint of the adhesiveness between the resin composition and the substrate, the content of the hindered phenol compound is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass based on 100 parts by mass of component (A). When the content of the hindered phenol compound is 0.1 parts by mass or more, it is easier to suppress the discoloration of copper or copper alloy contained in the substrate when the resin composition of the present embodiment is formed on the substrate, and the hindered phenol compound When the content of the compound is 20 parts by mass or less, the resin composition tends to exhibit good storage stability.

＜＜(A)成分之製備方法＞＞ (A)成分可藉由各步驟而製備。 (1)使具有所需之四價有機基X之四羧酸二酐與具有光聚合性基(例如，不飽和雙鍵)之醇類反應，而製備部分酯化之四羧酸(以下亦稱為「酸/酯體」)。 (2)使酸/酯體與具有二價有機基Y之二胺類進行醯胺縮聚。於上述(1)中，可除使用具有光聚合性基之醇類以外，還任意地併用飽和脂肪族醇類。該等化合物可單獨使用，亦可併用2種以上。＜＜Preparation method of component (A)＞＞ Component (A) can be prepared through various steps. (1) React tetracarboxylic dianhydride having the desired tetravalent organic group called "acid/ester body"). (2) Carry out amide polycondensation between acid/ester body and diamines having divalent organic group Y. In the above (1), in addition to using alcohols having a photopolymerizable group, saturated aliphatic alcohols may be optionally used in combination. These compounds may be used individually or in combination of 2 or more types.

＜酸/酯體之製備＞ (具有四價有機基X之四羧酸二酐) 作為適於製備酸/酯體之具有四價有機基X之四羧酸二酐，例如可例舉：均苯四甲酸酐、二苯醚-3,3',4,4'-四羧酸二酐、二苯甲酮-3,3',4,4'-四羧酸二酐、聯苯-3,3',4,4'-四羧酸二酐、二苯碸-3,3',4,4'-四羧酸二酐、二苯基甲烷-3,3',4,4'-四羧酸二酐、2,2-雙(3,4-鄰苯二甲酸酐)丙烷、2,2-雙(3,4-鄰苯二甲酸酐)-1,1,1,3,3,3-六氟丙烷。＜Preparation of acid/ester body＞ (tetracarboxylic dianhydride with tetravalent organic group X) Examples of the tetracarboxylic dianhydride having a tetravalent organic group Dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl-3,3 ',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride) Propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane.

(具有光聚合性基之醇類) 作為適於製備酸/酯體之具有光聚合性基之醇類，例如可例舉：2-丙烯醯氧基乙醇、1-丙烯醯氧基-3-丙醇、2-丙烯醯胺乙醇、羥甲基乙烯基酮、2-羥基乙基乙烯基酮、丙烯酸2-羥基-3-甲氧基丙酯、丙烯酸2-羥基-3-丁氧基丙酯、丙烯酸2-羥基-3-苯氧基丙酯、丙烯酸2-羥基-3-丁氧基丙酯、丙烯酸2-羥基-3-第三丁氧基丙酯、丙烯酸2-羥基-3-環己氧基丙酯、2-甲基丙烯醯氧基乙醇、1-甲基丙烯醯氧基-3-丙醇、2-甲基丙烯醯胺乙醇、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。 (Alcohols with photopolymerizable groups) Examples of alcohols having photopolymerizable groups suitable for preparing acid/ester bodies include: 2-acryloxyethanol, 1-acryloxy-3-propanol, 2-acrylamideethanol, Hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-benzene acrylate Oxypropyl ester, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methyl Acryloxyethanol, 1-methacryloxy-3-propanol, 2-methacrylamideethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-methacrylate Hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-methacrylate Tributoxypropyl ester, 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

(飽和脂肪族醇類) 作為可任意地使用之飽和脂肪族醇類，例如可例舉碳數1～4之飽和脂肪族醇。具體而言，例如較佳為甲醇、乙醇、正丙醇、異丙醇、正丁醇、第三丁醇。 (Saturated aliphatic alcohols) Examples of arbitrarily usable saturated aliphatic alcohols include saturated aliphatic alcohols having 1 to 4 carbon atoms. Specifically, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol are preferred.

(反應溶劑及反應條件) 上述四羧酸二酐與上述醇類可較佳為於吡啶等鹼性觸媒之存在下，且較佳為於適當之反應溶劑中於溫度20～50℃下歷經4～10小時進行攪拌及混合。藉此，可進行酸酐之酯化反應，而適宜地獲得所需之酸/酯體。 (Reaction solvent and reaction conditions) The above-mentioned tetracarboxylic dianhydride and the above-mentioned alcohols can preferably be stirred in the presence of an alkaline catalyst such as pyridine and in an appropriate reaction solvent at a temperature of 20 to 50° C. for 4 to 10 hours. mix. Thereby, the esterification reaction of the acid anhydride can be carried out, and the desired acid/ester body can be appropriately obtained.

作為上述反應溶劑，較佳為可溶解原料(四羧酸二酐及醇類)、及作為產物之酸/酯體之溶劑。更佳為可溶解作為酸/酯體與二胺之醯胺縮聚產物之聚醯亞胺前驅物之溶劑。作為此種反應溶劑，例如可例舉：N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、DMSO、四甲基脲、酮類、酯類、內酯類、醚類、鹵化烴類、烴類等。其中，作為酮類，例如可例舉：丙酮、甲基乙基酮、甲基異丁基酮、環己酮；作為酯類，例如可例舉：乙酸甲酯、乙酸乙酯、乙酸丁酯、草酸二乙酯；作為內酯類，例如可例舉：GBL；作為醚類，例如可例舉：乙二醇二甲醚、二乙二醇二甲醚、四氫呋喃；作為鹵化烴類，例如可例舉：二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、氯苯、鄰二氯苯；作為烴類，例如可例舉：己烷、庚烷、苯、甲苯、二甲苯；等。 The reaction solvent is preferably a solvent that can dissolve the raw materials (tetracarboxylic dianhydride and alcohols) and the acid/ester body of the product. More preferably, it is a solvent that can dissolve the polyimide precursor which is the amide condensation polymerization product of acid/ester body and diamine. Examples of such reaction solvents include N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, DMSO, and tetramethylurea. , ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. in, Examples of ketones include: acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Examples of esters include: methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate; Examples of lactones include: GBL; Examples of ethers include: glycol dimethyl ether, diglyme, and tetrahydrofuran; Examples of halogenated hydrocarbons include: methylene chloride, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, and o-dichlorobenzene; Examples of hydrocarbons include: hexane, heptane, benzene, toluene, and xylene; wait.

＜(A)成分之製備＞向酸/酯體(典型地為處於溶解於上述反應溶劑中之溶液狀態下之酸/酯體)中，較佳為於冰浴冷卻下，投入適當之脫水縮合劑加以混合，而將酸/酯體轉換為作為中間物之聚酸酐。向其中滴加使具有二價有機基Y之二胺類另行溶解或分散於溶劑中而成者，而使兩者進行醯胺縮聚，藉此獲得目標之(A)成分。＜Preparation of component (A)＞ To the acid/ester body (typically the acid/ester body in a solution state dissolved in the above reaction solvent), preferably under cooling in an ice bath, an appropriate dehydration condensing agent is added and mixed, and the acid/ester body is mixed. The ester body is converted into polyanhydride as an intermediate. A diamine having a divalent organic group Y that has been separately dissolved or dispersed in a solvent is added dropwise thereto, and the two are subjected to amide polycondensation to obtain the target component (A).

作為脫水縮合劑，例如可例舉：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***、N,N'-二丁二醯亞胺基碳酸酯。Examples of the dehydration condensation agent include dicyclohexylcarbodiamide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, and 1,1-carbonyldioxy- Di-1,2,3-benzotriazole, N,N'-dibutylene imide carbonate.

作為具有二價有機基Y之二胺類，例如可例舉：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'-二胺基二苯甲烷、3,4'-二胺基二苯甲烷、3,3'-二胺基二苯甲烷、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、聯鄰甲苯胺碸、9,9-雙(4-胺基苯基)茀等；該等苯環上之一部分氫原子經甲基、乙基、羥甲基、羥乙基、鹵素原子等取代者(取代體)；該等之混合物；等。 Examples of diamines having a divalent organic group Y include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl ether. , 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide Ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide Benzene, 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]terine, bis[4-(3-aminophenoxy)phenyl]terine, 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, orthotoluidine Trichosanthes, 9,9-bis(4-aminophenyl)fen, etc.; Part of the hydrogen atoms on the benzene ring is substituted by methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen atoms, etc. (substituted form); mixtures of such; wait.

作為取代體之具體例，例如可例舉：3,3'-二甲基-4,4'-二胺基聯苯、2,2'-二甲基-4,4'-二胺基聯苯、2,2'-雙(三氟甲基)聯苯胺、3,3'-二甲基-4,4'-二胺基二苯甲烷、2,2'-二甲基-4,4'-二胺基二苯甲烷、3,3'-二甲氧基-4,4'-二胺基聯苯、3,3'-二氯-4,4'-二胺基聯苯等；該等混合物；等。 Specific examples of the substituent include: 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl Benzene, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4 '-Diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, etc.; such mixtures; wait.

為了提昇樹脂組合物與基板之接著性，二胺基矽氧烷類於製備(A)成分時可與含有二價有機基Y之二胺類併用。作為二胺基矽氧烷類之具體例，例如可例舉：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。In order to improve the adhesion between the resin composition and the substrate, diaminosiloxanes can be used together with diamines containing divalent organic groups Y when preparing component (A). Specific examples of diaminosiloxanes include: 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(3-aminopropyl) ) Tetraphenyldisiloxane, etc.

醯胺縮聚結束後，可於視需要將反應液中所共存之脫水縮合劑之吸水副產物過濾分離後，向包含聚合物之溶液中投入適當之不良溶劑(例如，水、脂肪族低級醇、其混合液)，使聚合物成分析出。進而，可於視需要重複進行再溶解、及再沈澱操作將聚合物純化後，進行真空乾燥，藉此單離出目標之(A)成分。為了提昇純化度，可使包含該聚合物之溶液通過管柱，而去除離子性雜質，該管柱係填充有用適當之有機溶劑使陰離子及/或陽離子交換樹脂膨潤者。After the amide polycondensation is completed, if necessary, the water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution can be filtered and separated, and then an appropriate poor solvent (for example, water, aliphatic lower alcohol, etc.) can be added to the solution containing the polymer. its mixture) to separate out the polymer components. Furthermore, the polymer can be purified by repeating the re-dissolving and reprecipitating operations as necessary, and then vacuum drying, thereby isolating the target component (A). In order to improve the degree of purification, the solution containing the polymer can be passed through a column to remove ionic impurities. The column is filled with an appropriate organic solvent to swell the anion and/or cation exchange resin.

就加熱後所獲得之聚醯亞胺膜(硬化浮凸圖案)之耐熱性、及機械特性之觀點而言，(A)成分之重量平均分子量以藉由凝膠滲透層析法所得之聚苯乙烯換算值計，較佳為1,000以上，更佳為5,000以上，又，較佳為100,000以下。就對顯影液之溶解性之觀點而言，重量平均分子量更佳為50,000以下。就兼顧感度與解像度之觀點而言，重量平均分子量較佳為6,000～40,000，更佳為7,000～30,000，進而較佳為8,000～22,000。凝膠滲透層析法之展開溶劑推薦四氫呋喃或N-甲基-2-吡咯啶酮。分子量係根據使用標準單分散聚苯乙烯製作之校準曲線而求出。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。From the viewpoint of the heat resistance and mechanical properties of the polyimide film (hardened relief pattern) obtained after heating, the weight average molecular weight of component (A) is based on the polyphenylene glycol obtained by gel permeation chromatography. In terms of ethylene conversion value, it is preferably 1,000 or more, more preferably 5,000 or more, and more preferably 100,000 or less. From the viewpoint of solubility in a developer, the weight average molecular weight is more preferably 50,000 or less. From the viewpoint of balancing sensitivity and resolution, the weight average molecular weight is preferably 6,000 to 40,000, more preferably 7,000 to 30,000, and still more preferably 8,000 to 22,000. The recommended developing solvent for gel permeation chromatography is tetrahydrofuran or N-methyl-2-pyrrolidinone. The molecular weight was determined based on a calibration curve prepared using standard monodisperse polystyrene. The standard monodisperse polystyrene is recommended to be selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko Co., Ltd.

＜＜硬化浮凸圖案之製造方法＞＞本實施方式之一形態為硬化浮凸圖案之製造方法。本實施方式之製造方法具有以下步驟： (1)藉由將上述樹脂組合物塗佈於基板，而形成樹脂組合物膜； (2)藉由對樹脂組合物膜進行曝光及顯影之步驟、或雷射照射樹脂組合物膜之步驟，而形成浮凸圖案；及 (3)對浮凸圖案加熱，而形成硬化浮凸圖案。＜＜Method for manufacturing hardened relief pattern＞＞ One form of this embodiment is a method of manufacturing a hardened relief pattern. The manufacturing method of this embodiment has the following steps: (1) Forming a resin composition film by applying the above-mentioned resin composition to a substrate; (2) Forming a relief pattern through the steps of exposing and developing the resin composition film, or the step of irradiating the resin composition film with laser; and (3) The embossed pattern is heated to form a hardened embossed pattern.

(1)塗佈步驟本步驟中，藉由將上述樹脂組合物塗佈於基板，而形成樹脂組合物膜。將樹脂組合物塗佈於基板後，可視需要進行乾燥。 (1) Coating step In this step, the resin composition film is formed by coating the above-mentioned resin composition on the substrate. After the resin composition is applied to the substrate, it may be dried if necessary.

作為基板，例如可例舉：包含矽、鋁、銅、銅合金等之金屬基板；環氧樹脂、聚醯亞胺、聚苯并㗁唑等之樹脂基板；於上述樹脂基板形成有金屬電路之基板；將複數種金屬、或金屬與樹脂積層多層而成之基板；等。 Examples of substrates include: Metal substrates including silicon, aluminum, copper, copper alloys, etc.; Resin substrates such as epoxy resin, polyimide, polybenzoconazole, etc.; A substrate with a metal circuit formed on the above-mentioned resin substrate; A substrate made of multiple types of metals or multiple layers of metals and resins; wait.

作為塗佈方法，可例舉先前用於塗佈樹脂組合物之方法，例如：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；用噴霧塗佈機進行噴霧塗佈之方法；等。 As a coating method, a method previously used for coating a resin composition can be exemplified, for example: Coating methods using spin coaters, rod coaters, blade coaters, curtain coaters, screen printing machines, etc.; The method of spray coating using a spray coater; wait.

於使樹脂組合物乾燥之情形時，作為該乾燥方法，可例舉：風乾；用烘箱或加熱板進行之加熱乾燥；真空乾燥；等方法。再者，乾燥較理想為於不易引起(A)成分之醯亞胺化之條件下進行。具體而言，於進行風乾或加熱乾燥之情形時，可於20℃～140℃且於1分鐘～1小時之條件下進行乾燥。 When the resin composition is dried, examples of the drying method include: air dry; Heating and drying using an oven or heating plate; vacuum drying; and other methods. Furthermore, drying is preferably performed under conditions that do not easily cause imidization of component (A). Specifically, when air drying or heat drying is performed, drying can be performed at 20°C to 140°C for 1 minute to 1 hour.

(2)形成浮凸圖案之步驟本步驟中，藉由對樹脂組合物膜進行曝光及顯影之步驟、或雷射照射樹脂組合物膜之步驟，而形成浮凸圖案。本步驟於將上述樹脂組合物用作感光性樹脂之情形時較為適宜。即，藉由進行光微影步驟(曝光及顯影步驟)，或藉由進行使用二氧化碳雷射、UV雷射、綠色雷射等高能量密度之雷射鑽孔加工之步驟(雷射鑽孔加工步驟)，可適宜地形成浮凸圖案。 (2) Steps to form relief patterns In this step, a relief pattern is formed by exposing and developing the resin composition film or irradiating the resin composition film with laser. This step is suitable when the above-mentioned resin composition is used as a photosensitive resin. That is, by performing a photolithography step (exposure and development step), or by performing a high-energy-density laser drilling process (laser drilling process) using carbon dioxide laser, UV laser, green laser, etc. step), the relief pattern can be appropriately formed.

(光微影步驟) 光微影步驟可藉由曝光裝置進行。作為曝光裝置，可例舉：接觸式對準機、鏡面投影曝光機、步進機等曝光裝置。 (Photolithography step) The photolithography step can be performed by an exposure device. Examples of the exposure device include exposure devices such as contact aligners, mirror projection exposure machines, and stepper machines.

曝光步驟中，向樹脂組合物膜照射來自光線之曝光之光。向樹脂組合物膜照射曝光之光可經由形成有圖案之光罩或主光罩進行，或者直接進行。曝光所使用之光線為紫外線光源等。In the exposure step, the resin composition film is irradiated with exposure light from light. The resin composition film can be irradiated with exposure light through a patterned photomask or a master photomask, or directly. The light used for exposure is ultraviolet light source, etc.

曝光步驟後，出於提昇光敏度等目的，可視需要實施以任意溫度、及任意時間之組合進行之曝光後烘烤(PEB)、及/或顯影前烘烤。烘烤條件之一例係溫度為40～120℃，時間為10秒～240秒。After the exposure step, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) and/or pre-development baking at any temperature and any combination of time may be implemented as needed. An example of the baking conditions is that the temperature is 40 to 120°C and the time is 10 seconds to 240 seconds.

顯影步驟中，藉由顯影液去除曝光後之樹脂組合物膜中之未曝光部。作為顯影方法，可例舉先前已知之光阻之顯影方法，例如：旋轉噴霧法；覆液法；伴隨超音波處理之浸漬法；等。In the development step, the unexposed portion of the exposed resin composition film is removed using a developer. As the development method, there can be exemplified previously known photoresist development methods, such as: rotary spray method; liquid coating method; dipping method accompanied by ultrasonic treatment; etc.

顯影步驟後，出於調整浮凸圖案之形狀等目的，可視需要實施以任意溫度、及任意時間之組合進行之顯影後烘烤。顯影後烘烤之條件之一例係例如溫度為80～130℃，又，時間為0.5～10分鐘。After the development step, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking at any temperature and any combination of time may be implemented as necessary. An example of post-development baking conditions is that the temperature is 80 to 130°C and the time is 0.5 to 10 minutes.

顯影液較佳為對樹脂組合物之良溶劑、或該良溶劑與不良溶劑之組合。作為良溶劑，較佳為N-甲基-2-吡咯啶酮、N-環己基-2-吡咯啶酮、N,N-二甲基乙醯胺、環戊酮、環己酮、γ-丁內酯、α-乙醯基-γ-丁內酯等。作為不良溶劑，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、水等。於將良溶劑與不良溶劑混合使用之情形時，可根據樹脂組合物中之樹脂成分之溶解性，調整不良溶劑相對於良溶劑之比率。各溶劑可單獨使用，亦可併用2種以上。The developer is preferably a good solvent for the resin composition, or a combination of the good solvent and a poor solvent. As a good solvent, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ- Butyrolactone, α-acetyl-γ-butyrolactone, etc. As the poor solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. are preferred. When a good solvent and a poor solvent are mixed and used, the ratio of the poor solvent to the good solvent can be adjusted according to the solubility of the resin component in the resin composition. Each solvent can be used alone, or two or more types can be used in combination.

(雷射鑽孔加工步驟) 雷射鑽孔加工步驟中，於使用532 nm之綠色雷射波長之情形時，容易實現高產能，且容易將對半導體裝置之損害抑制為最小限度，故而較佳。本實施方式之樹脂組合物於532 nm具有吸收波長，故而可藉由綠色雷射適宜地形成浮凸圖案。 (Laser drilling processing steps) In the laser drilling process, it is preferable to use a green laser wavelength of 532 nm because it is easy to achieve high productivity and to minimize damage to the semiconductor device. The resin composition of this embodiment has an absorption wavelength at 532 nm, so it can suitably form a relief pattern using a green laser.

(3)加熱步驟本步驟中，對上述藉由顯影所獲得之浮凸圖案加熱，而形成硬化浮凸圖案。此時，使(A)成分醯亞胺化，轉換為包含聚醯亞胺之硬化浮凸圖案。 (3)Heating step In this step, the relief pattern obtained by development is heated to form a hardened relief pattern. At this time, component (A) is imidized and converted into a hardened relief pattern containing polyimide.

作為加熱方法，可例舉：利用加熱板進行之加熱方法；使用烘箱之加熱方法；使用可設定溫控程式之升溫型烘箱之加熱方法；等各種方法。加熱條件之一例係溫度為200℃～400℃，時間為30分鐘～5小時。作為加熱時之氣氛中之氣體，可為空氣，亦可為氮氣、氬氣等惰性氣體。Examples of heating methods include: heating using a heating plate; heating using an oven; heating using a temperature-increasing oven with a settable temperature control program; and other various methods. An example of the heating conditions is that the temperature is 200°C to 400°C and the time is 30 minutes to 5 hours. As the gas in the atmosphere during heating, it can be air or inert gases such as nitrogen and argon.

＜＜半導體裝置＞＞本實施方式之一形態係具有由上述樹脂組合物所獲得之硬化浮凸圖案作為絕緣層之半導體裝置。半導體裝置例如具有作為半導體元件之基板、及配置於該基板上之上述硬化浮凸圖案。＜＜Semiconductor Devices＞＞ One aspect of this embodiment is a semiconductor device having a hardened relief pattern obtained from the above resin composition as an insulating layer. A semiconductor device has, for example, a substrate as a semiconductor element and the above-mentioned hardened relief pattern arranged on the substrate.

上述半導體裝置例如可藉由使用半導體元件作為基板，且於該半導體裝置之一部分製造步驟中包含上述硬化浮凸圖案之製造方法之方法進行製造。半導體裝置可藉由如下方式進行製造：將藉由上述硬化浮凸圖案製造方法所形成之硬化浮凸圖案例如形成為表面保護膜、層間絕緣膜、再佈線用絕緣膜、覆晶裝置用保護膜、或具有凸塊結構之半導體裝置之保護膜等，進而，與公知之半導體裝置之製造方法組合。 [實施例] The above-mentioned semiconductor device can be manufactured, for example, by using a semiconductor element as a substrate and including the above-mentioned manufacturing method of the hardened relief pattern in a part of the manufacturing steps of the semiconductor device. Semiconductor devices can be manufactured by forming the hardened embossed pattern formed by the above-described hardened embossed pattern manufacturing method into, for example, a surface protective film, an interlayer insulating film, an insulating film for rewiring, and a protective film for a flip-chip device. , or a protective film of a semiconductor device having a bump structure, etc., and further combined with a known manufacturing method of a semiconductor device. [Example]

以下，例舉實施例對本發明進行具體說明，但本發明並不僅限定於下述實施例。實施例欄中之樹脂組合物之物性係依照下述方法進行測定及評估。Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited only to the following examples. The physical properties of the resin compositions in the Example column were measured and evaluated according to the following methods.

(1)硬化浮凸圖案之UV透過率使用塗佈顯影機(D-Spin60A型，SOKUDO公司製造)並藉由旋轉塗佈法，將依照以下製造例製備之樹脂組合物塗佈於石英板上，獲得樹脂組合物之膜。於大氣氛圍下且於110℃下，歷經240秒對該膜進行乾燥(預烘烤)，藉此於石英板上獲得10 μm厚之預烘烤膜。藉由紫外可見分光光度計(島津製作所股份有限公司製造，UV-1800)，計算出上述預烘烤膜於532 nm下之以10 μm膜厚換算之UV透過率(a)。 (1) UV transmittance of hardened relief pattern Using a coating developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), the resin composition prepared according to the following production examples was applied on a quartz plate by the spin coating method to obtain a film of the resin composition. The film was dried (pre-baked) in an atmospheric atmosphere at 110° C. for 240 seconds, thereby obtaining a 10 μm-thick pre-baked film on the quartz plate. Using a UV-visible spectrophotometer (UV-1800 manufactured by Shimadzu Corporation), the UV transmittance (a) of the above-mentioned pre-baked film at 532 nm was calculated based on a film thickness of 10 μm.

使用升溫程式型固化爐(VF-2000型，Koyo Lindberg公司製造)，於230℃下歷經2小時，於氮氣氛圍下對預烘烤膜加熱(固化)，藉此於石英板上獲得約6～7 μm厚之聚醯亞胺膜(硬化浮凸圖案)。藉由紫外可見分光光度計(島津製作所股份有限公司製造，UV-1800)，計算出上述聚醯亞胺膜於532 nm下之以10 μm膜厚換算之UV透過率(b)。Using a temperature-increasing programmed curing oven (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.), the pre-baked film was heated (cured) in a nitrogen atmosphere at 230°C for 2 hours, thereby obtaining about 6~6% on the quartz plate. 7 μm thick polyimide film (hardened embossed pattern). Using a UV-visible spectrophotometer (UV-1800 manufactured by Shimadzu Corporation), the UV transmittance (b) of the above-mentioned polyimide film at 532 nm was calculated based on a film thickness of 10 μm.

將上述(a)、(b)均為40%以下者設為評估對象。而且，基於以下基準，對下述式所表示之上述加熱(固化)前後之UV透過率之差Δ(b－a)進行評估。 UV透過率之差Δ(b－a)＝UV透過率(b)－UV透過率(a) 符合「優」及「良」兩者之評估結果均視為「優」。「優」：-5%≦Δ(b－a)≦5% 「良」：-10%≦Δ(b－a)≦10% 「可」：Δ(b－a)＜-10%，或Δ(b－a)＞10% Those with the above-mentioned (a) and (b) both being 40% or less are targeted for evaluation. Furthermore, the difference Δ(b-a) in UV transmittance before and after the above-mentioned heating (curing) represented by the following formula was evaluated based on the following criteria. Difference in UV transmittance Δ(b-a)=UV transmittance (b)-UV transmittance (a) Evaluation results that meet both "Excellent" and "Good" are considered "Excellent". "Excellent": -5%≦Δ(b-a)≦5% "Good": -10%≦Δ(b-a)≦10% "Yes": Δ(b-a)＜-10%, or Δ(b-a)＞10%

(2)硬化浮凸圖案之伸長率以上述加熱(固化)後之膜厚成為約7 μm之方式獲得硬化浮凸圖案。即，藉由旋轉塗佈法，將依照以下製造例製備之樹脂組合物塗佈於6英吋之矽晶圓上，並對其進行乾燥(預烘烤)。其後，使用升溫程式型固化爐(VF-2000型，日本，Koyo Lindberg公司製造)，於230℃下歷經2小時，於氮氣氛圍下進行加熱(固化)，藉此獲得聚醯亞胺膜(硬化浮凸圖案)。 (2) Elongation of hardened relief pattern A hardened relief pattern is obtained so that the film thickness after the above heating (curing) becomes about 7 μm. That is, the resin composition prepared according to the following production examples was coated on a 6-inch silicon wafer by a spin coating method, and dried (prebaked). Thereafter, a temperature-increasing programmed curing oven (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd., Japan) was used to heat (cure) the film in a nitrogen atmosphere at 230° C. for 2 hours, thereby obtaining a polyimide film ( Hardened relief pattern).

使用切割機(DAD3350型，DISCO公司製造)，將所獲得之聚醯亞胺膜切割為3 mm寬之短條狀後，使用46%氫氟酸將其自矽晶圓剝離，藉此獲得聚醯亞胺膠帶。使用拉伸試驗機(UTM-II-20型，Orientec公司製造)，依照ASTM D882-09測定所獲得之聚醯亞胺膠帶之伸長率。而且，基於以下基準評估伸長率。「優」：50%以上「良」：20%以上且未達50% 「不可」：未達20% Using a cutting machine (DAD3350 model, manufactured by DISCO), the obtained polyimide film was cut into short strips with a width of 3 mm, and then peeled off from the silicon wafer using 46% hydrofluoric acid to obtain the polyimide film. Imide tape. A tensile testing machine (model UTM-II-20, manufactured by Orientec) was used to measure the elongation of the obtained polyimide tape in accordance with ASTM D882-09. Furthermore, the elongation rate was evaluated based on the following criteria. "Excellent": above 50% "Good": more than 20% and less than 50% "Impossible": less than 20%

＜製造例1＞((A)聚醯亞胺前驅物(聚合物A-1)之合成) 將4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g放入2 L容量之可分離式燒瓶中，再加入甲基丙烯酸2-羥基乙酯(HEMA)134.0 g及γ-丁內酯400 ml，並一面於室溫下攪拌一面加入吡啶79.1 g，使其等反應。於反應所引起之發熱結束後，自然冷卻至室溫，進而靜置16小時，從而獲得反應混合物。 <Production Example 1> ((A) Synthesis of polyimide precursor (polymer A-1)) Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a 2 L separable flask, then add 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and γ-butanyl 400 ml of lactone was added, and 79.1 g of pyridine was added while stirring at room temperature, and allowed to react. After the heat generated by the reaction ends, the reaction mixture is naturally cooled to room temperature and left to stand for 16 hours to obtain a reaction mixture.

繼而，準備使二環己基碳二醯亞胺(DCC)206.3 g溶解於γ-丁內酯180 ml中所得之溶液、及於γ-丁內酯350 ml中懸浮有4,4'-二胺基二苯醚(DADPE)93.0 g之懸浮液。於冰浴冷卻下，將上述溶液一面攪拌一面歷時40分鐘加入至反應混合物中，繼而，將上述懸浮液一面攪拌一面歷時60分鐘加入。其後，進而於室溫下攪拌2小時後，加入乙醇30 ml並攪拌1小時，其後加入γ-丁內酯400 ml，從而獲得混合液。藉由過濾除去混合液中產生之沈澱物，獲得反應液。Next, a solution was prepared in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone, and 4,4'-diamine was suspended in 350 ml of γ-butyrolactone. 93.0 g suspension of DADPE. Under cooling in an ice bath, the above solution was added to the reaction mixture while stirring for 40 minutes, and then, the above suspension was added while stirring for 60 minutes. Thereafter, after further stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added to obtain a mixed liquid. The precipitate generated in the mixed solution is removed by filtration to obtain a reaction solution.

將所獲得之反應液加入至3 L之乙醇中，生成含有粗聚合物之沈澱物。將所生成之粗聚合物過濾取出，並溶解於四氫呋喃1.5 L中，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，使聚合物沈澱，將沈澱物過濾取出後進行真空乾燥，藉此獲得粉末狀之聚合物A-1。聚合物A-1之重量平均分子量(Mw)為20,000。The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing crude polymer. The generated crude polymer was filtered out 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. The precipitate was filtered out and then dried under vacuum to obtain powdery polymer A-1. Polymer A-1 has a weight average molecular weight (Mw) of 20,000.

＜製造例2＞(聚醯亞胺前驅物(聚合物A-2)之合成) 除於上述製造例1中，使用3,3'4,4'-聯苯四羧酸二酐(BPDA)147.1 g來代替4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g以外，藉由與製造例1同樣之方法獲得聚合物A-2。聚合物A-2之重量平均分子量(Mw)為22,000。 <Production Example 2> (Synthesis of polyimide precursor (polymer A-2)) In addition to the above production example 1, 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA). Except for this, polymer A-2 was obtained in the same manner as in Production Example 1. Polymer A-2 has a weight average molecular weight (Mw) of 22,000.

＜製造例3＞(聚醯亞胺前驅物(聚合物A-3)之合成) 除於上述製造例1中，使用2,2-雙[4-(4-胺基苯氧基)苯基]丙烷(BAPP)(190.7 g)來代替4,4'-二胺基二苯醚(DADPE)93.0 g以外，藉由與製造例1同樣之方法獲得聚合物A-3。聚合物A-3之重量平均分子量(Mw)為21,000。 <Production Example 3> (Synthesis of polyimide precursor (polymer A-3)) In addition to the above production example 1, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) (190.7 g) was used instead of 4,4'-diaminodiphenyl ether. Polymer A-3 was obtained in the same manner as in Production Example 1 except for 93.0 g of (DADPE). Polymer A-3 has a weight average molecular weight (Mw) of 21,000.

＜製造例4＞(聚醯亞胺前驅物(聚合物A-4)之合成) 除於上述製造例1中，使用2,2'-二甲基-4,4'-二胺基聯苯(m-TB)(98.6 g)來代替4,4'-二胺基二苯醚(DADPE)93.0 g以外，藉由與製造例1同樣之方法獲得聚合物A-4。聚合物A-4之重量平均分子量(Mw)為21,000。 <Production Example 4> (Synthesis of polyimide precursor (polymer A-4)) In addition to the above production example 1, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) (98.6 g) was used instead of 4,4'-diaminodiphenyl ether. Polymer A-4 was obtained in the same manner as in Production Example 1 except for 93.0 g of (DADPE). Polymer A-4 has a weight average molecular weight (Mw) of 21,000.

＜製造例5＞(聚醯亞胺前驅物(聚合物A-5)之合成) 除於上述製造例1中，使用對苯二胺(p-PD)(50.2 g)來代替4,4'-二胺基二苯醚(DADPE)93.0 g以外，藉由與製造例1同樣之方法獲得聚合物A-5。聚合物A-5之重量平均分子量(Mw)為21,000。 <Production Example 5> (Synthesis of polyimide precursor (polymer A-5)) In the above-mentioned Production Example 1, except that p-phenylenediamine (p-PD) (50.2 g) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE), the method was the same as in Production Example 1. Method to obtain polymer A-5. Polymer A-5 has a weight average molecular weight (Mw) of 21,000.

＜製造例6＞(聚醯亞胺前驅物(聚合物A-6)之合成) 除於上述製造例1中，使用2,2'-雙(三氟甲基)聯苯胺(TFMB)160.1 g來代替4,4'-二胺基二苯醚(DADPE)93.0 g以外，藉由與製造例1同樣之方法獲得聚合物A-6。聚合物A-6之重量平均分子量(Mw)為21,000。 <Production Example 6> (Synthesis of polyimide precursor (polymer A-6)) Except that in the above-mentioned Production Example 1, 160.1 g of 2,2'-bis(trifluoromethyl)benzidine (TFMB) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE), by Polymer A-6 was obtained in the same manner as in Production Example 1. Polymer A-6 has a weight average molecular weight (Mw) of 21,000.

＜製造例7＞(聚醯亞胺前驅物(聚合物A-7)之合成) 於上述製造例1中，使用均苯四甲酸酐(PMDA)54.5 g及4,4'-氧二鄰苯二甲酸二酐(ODPA)77.6 g來代替4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g，又，使用2,2'-二甲基-4,4'-二胺基聯苯(m-TB)98.6 g來代替4,4'-二胺基二苯醚(DADPE)93.0 g，除此以外藉由與製造例1同樣之方法獲得聚合物A-7。聚合物A-7之重量平均分子量(Mw)為21,000。 <Production Example 7> (Synthesis of polyimide precursor (polymer A-7)) In the above production example 1, 54.5 g of pyromellitic anhydride (PMDA) and 77.6 g of 4,4'-oxydiphthalic dianhydride (ODPA) were used instead of 4,4'-oxydiphthalic acid. 155.1 g of dianhydride (ODPA), and 98.6 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) was used instead of 4,4'-diaminodiphenyl ether (DADPE) 93.0 g, except that polymer A-7 was obtained in the same manner as in Production Example 1. Polymer A-7 has a weight average molecular weight (Mw) of 21,000.

＜製造例8＞(聚醯亞胺前驅物(聚合物A-8)之合成) 除於上述製造例1中，使用4,4'-氧二鄰苯二甲酸二酐(ODPA)77.6 g及3,3'4,4'-聯苯四羧酸二酐(BPDA)73.6 g來代替4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g以外，藉由與製造例1同樣之方法獲得聚合物A-8。聚合物A-8之重量平均分子量(Mw)為20,000。 <Production Example 8> (Synthesis of polyimide precursor (polymer A-8)) In addition to the above production example 1, 77.6 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 73.6 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride (BPDA) were used. Polymer A-8 was obtained by the same method as Production Example 1 except that 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was substituted. Polymer A-8 has a weight average molecular weight (Mw) of 20,000.

＜製造例9＞(聚醯亞胺前驅物(聚合物A-9)之合成) 於上述製造例1中，使用均苯四甲酸酐(PMDA)109.1 g來代替4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g，且使用對苯二胺(p-PD)50.2 g來代替4,4'-二胺基二苯醚(DADPE)93.0 g，除此以外藉由與製造例1同樣之方法獲得聚合物A-9。聚合物A-9之重量平均分子量(Mw)為20,000。 <Production Example 9> (Synthesis of polyimide precursor (polymer A-9)) In the above production example 1, 109.1 g of pyromellitic anhydride (PMDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA), and p-phenylenediamine (p-PD) was used Polymer A-9 was obtained in the same manner as in Production Example 1 except that 50.2 g was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE). Polymer A-9 has a weight average molecular weight (Mw) of 20,000.

＜實施例1＞將作為(A)成分之聚合物A-1(100質量份)、作為(B)成分之B-1(溶劑黑7；3.0質量份)、以及作為其他成分之四乙二醇二甲基丙烯酸酯(8質量份)及N-苯基二乙醇胺(4質量份) 溶解於作為(C)成分之C-1(GBL及DMSO之重量比80：20混合物)中，從而獲得樹脂組合物。樹脂組合物之黏度為約3.5 Pa･s。藉由上述方法對該樹脂組合物進行評估。評估結果示於下表中。 <Example 1> Polymer A-1 (100 parts by mass) as component (A), B-1 (solvent black 7; 3.0 parts by mass) as component (B), and As other components, tetraethylene glycol dimethacrylate (8 parts by mass) and N-phenyldiethanolamine (4 parts by mass) It was dissolved in C-1 (a mixture of GBL and DMSO in a weight ratio of 80:20) as component (C) to obtain a resin composition. The viscosity of the resin composition is approximately 3.5 Pa･s. The resin composition was evaluated by the above method. The evaluation results are shown in the table below.

＜實施例2～36、及比較例1～11＞除將如下所述之各原料混合以外，藉由與實施例1同樣之方法獲得實施例2～36及比較例1～11之樹脂組合物。藉由上述方法對所獲得之樹脂組合物進行評估。評估結果示於下表中。 <Examples 2 to 36 and Comparative Examples 1 to 11> The resin compositions of Examples 2 to 36 and Comparative Examples 1 to 11 were obtained in the same manner as Example 1, except that the respective raw materials described below were mixed. The obtained resin composition was evaluated by the above method. The evaluation results are shown in the table below.

下表中記載之各編號分別意指下述化合物。 (A)成分；聚醯亞胺前驅物 A-1/A-2：A-1與A-2各使用50質量份之混合物 A-1/A-5：A-1與A-5各使用50質量份之混合物 Each number described in the table below means the following compound respectively. (A) Component; polyimide precursor A-1/A-2: A-1 and A-2 each use 50 parts by mass of the mixture. A-1/A-5: Use a mixture of 50 parts by mass each of A-1 and A-5.

(B)成分；有機染料 B-1：溶劑黑7 B-2：溶劑黑3 B-3：酸性黑2 B-4：下式所表示之蒽衍生物化合物 [化35] B-5：下式所表示之蒽衍生物化合物 [化36] B-6：下式所表示之蒽衍生物化合物 [化37] B-7：下式所表示之蒽衍生物化合物 [化38] B-8：下式所表示之蒽衍生物化合物 [化39] B-9：下式所表示之蒽衍生物化合物 [化40] B-10：下式所表示之蒽衍生物化合物 [化41] B-11：下式所表示之蒽衍生物化合物 [化42] b-12：下式所表示之隱色結晶紫(4,4',-次甲基三(N,N-二甲基苯胺)) [化43] b-13：下式所表示之結晶紫(4,4',4''-次甲基三(N,N-二甲基苯胺)) [化44] b-14：二苯基蒽 b-15：9-苯基吖啶 (B) Component; organic dye B-1: solvent black 7 B-2: solvent black 3 B-3: acid black 2 B-4: anthracene derivative compound represented by the following formula [Chemical 35] B-5: Anthracene derivative compound represented by the following formula [Chemical 36] B-6: Anthracene derivative compound represented by the following formula [Chemical 37] B-7: Anthracene derivative compound represented by the following formula [Chemical 38] B-8: Anthracene derivative compound represented by the following formula [Chemical 39] B-9: Anthracene derivative compound represented by the following formula [Chemical 40] B-10: Anthracene derivative compound represented by the following formula [Chemical 41] B-11: Anthracene derivative compound represented by the following formula [Chemical 42] b-12: Leuco crystal violet (4,4',-methinetris(N,N-dimethylaniline)) represented by the following formula [Chemical 43] b-13: Crystal violet represented by the following formula (4,4',4''-methinetris(N,N-dimethylaniline)) [Chemical 44] b-14: diphenylanthracene b-15: 9-phenyl acridine

(b)顏料 b-16：碳黑 b-17：石墨 b-18：鈦黑 b-19：氧化鐵 (b)Pigment b-16: carbon black b-17: graphite b-18: titanium black b-19: Iron oxide

(C)成分；有機溶劑 C-2：N-甲基吡咯啶酮 C-3：N-甲基吡咯啶酮及乳酸乙酯之重量比80：20混合物 C-4：Equamide C-5：Equamide及DMSO之重量比80：20混合物 C-6：丙酮 C-7：己烷 (C)Component; organic solvent C-2: N-methylpyrrolidone C-3: A mixture of N-methylpyrrolidone and ethyl lactate in a weight ratio of 80:20 C-4: Equamide C-5: A mixture of Equamide and DMSO with a weight ratio of 80:20 C-6: Acetone C-7: Hexane

(D)成分；光聚合起始劑 D-1：下式所表示之光聚合起始劑 [化45] D-2：式(D4)所表示之光聚合起始劑 D-3：式(D6)所表示之光聚合起始劑 (D) Component; Photopolymerization initiator D-1: Photopolymerization initiator represented by the following formula [Chemical 45] D-2: Photopolymerization initiator represented by formula (D4) D-3: Photopolymerization initiator represented by formula (D6)

[表2] [表2] (A)聚醯亞胺前驅物 (B)有機染料 (B)有機染料(質量份) (C)有機溶劑 (D)光聚合起始劑預烘烤膜之UV透過率(a) 聚醯亞胺膜之UV透過率(b) Δ(b－a) UV透過率之判定膜伸長率實施例1 A-1 B-1 3 C-1 - 0.15 0.15 0.00 優優實施例2 A-2 B-1 3 C-1 - 0.17 0.18 0.01 優優實施例3 A-3 B-1 3 C-1 - 0.18 0.20 0.02 優優實施例4 A-4 B-1 3 C-1 - 0.14 0.14 0.00 優優實施例5 A-5 B-1 3 C-1 - 0.20 0.21 0.01 優優實施例6 A-6 B-1 3 C-1 - 0.15 0.16 0.01 優優實施例7 A-7 B-1 3 C-1 - 0.21 0.22 0.01 優優實施例8 A-8 B-1 3 C-1 - 0.16 0.16 0.00 優優實施例9 A-1/A-2 B-1 3 C-1 - 0.16 0.17 0.01 優優實施例10 A-1/A-5 B-1 3 C-1 - 0.18 0.20 0.02 優優實施例11 A-1 B-1 0.1 C-1 - 0.40 0.40 0.00 良優實施例12 A-1 B-1 0.5 C-1 - 0.35 0.33 -0.02 良優實施例13 A-1 B-1 1 C-1 - 0.28 0.29 0.01 優優實施例14 A-1 B-1 2 C-1 - 0.22 0.21 -0.01 優優實施例15 A-1 B-1 4 C-1 - 0.11 0.10 -0.01 優優實施例16 A-1 B-1 5 C-1 - 0.08 0.09 0.01 優優實施例17 A-1 B-1 10 C-1 - 0.06 0.06 0.00 優優實施例18 A-1 B-1 20 C-1 - 0.04 0.05 0.01 優優實施例19 A-1 B-1 30 C-1 - 0.02 0.02 0.00 優良實施例20 A-1 B-2 3 C-1 - 0.10 0.13 0.03 優優實施例21 A-1 B-3 3 C-1 - 0.13 0.20 0.06 優優實施例22 A-1 B-4 3 C-1 - 0.16 0.14 -0.02 優優實施例23 A-1 B-5 1 C-1 - 0.18 0.21 0.03 優優實施例24 A-1 B-6 3 C-1 - 0.30 0.31 0.01 優優實施例25 A-1 B-7 10 C-1 - 0.09 0.11 0.02 優優 [Table 2] [Table 2] (A) Polyimide precursor (B)Organic dyes (B) Organic dye (mass part) (C)Organic solvent (D) Photopolymerization initiator UV transmittance of pre-baked film (a) UV transmittance of polyimide film (b) Δ(b-a) Determination of UV transmittance Film elongation Example 1 A-1 B-1 3 C-1 - 0.15 0.15 0.00 Excellent Excellent Example 2 A-2 B-1 3 C-1 - 0.17 0.18 0.01 Excellent Excellent Example 3 A-3 B-1 3 C-1 - 0.18 0.20 0.02 Excellent Excellent Example 4 A-4 B-1 3 C-1 - 0.14 0.14 0.00 Excellent Excellent Example 5 A-5 B-1 3 C-1 - 0.20 0.21 0.01 Excellent Excellent Example 6 A-6 B-1 3 C-1 - 0.15 0.16 0.01 Excellent Excellent Example 7 A-7 B-1 3 C-1 - 0.21 0.22 0.01 Excellent Excellent Example 8 A-8 B-1 3 C-1 - 0.16 0.16 0.00 Excellent Excellent Example 9 A-1/A-2 B-1 3 C-1 - 0.16 0.17 0.01 Excellent Excellent Example 10 A-1/A-5 B-1 3 C-1 - 0.18 0.20 0.02 Excellent Excellent Example 11 A-1 B-1 0.1 C-1 - 0.40 0.40 0.00 good Excellent Example 12 A-1 B-1 0.5 C-1 - 0.35 0.33 -0.02 good Excellent Example 13 A-1 B-1 1 C-1 - 0.28 0.29 0.01 Excellent Excellent Example 14 A-1 B-1 2 C-1 - 0.22 0.21 -0.01 Excellent Excellent Example 15 A-1 B-1 4 C-1 - 0.11 0.10 -0.01 Excellent Excellent Example 16 A-1 B-1 5 C-1 - 0.08 0.09 0.01 Excellent Excellent Example 17 A-1 B-1 10 C-1 - 0.06 0.06 0.00 Excellent Excellent Example 18 A-1 B-1 20 C-1 - 0.04 0.05 0.01 Excellent Excellent Example 19 A-1 B-1 30 C-1 - 0.02 0.02 0.00 Excellent good Example 20 A-1 B-2 3 C-1 - 0.10 0.13 0.03 Excellent Excellent Example 21 A-1 B-3 3 C-1 - 0.13 0.20 0.06 Excellent Excellent Example 22 A-1 B-4 3 C-1 - 0.16 0.14 -0.02 Excellent Excellent Example 23 A-1 B-5 1 C-1 - 0.18 0.21 0.03 Excellent Excellent Example 24 A-1 B-6 3 C-1 - 0.30 0.31 0.01 Excellent Excellent Example 25 A-1 B-7 10 C-1 - 0.09 0.11 0.02 Excellent Excellent

[表3] [表3] (A)聚醯亞胺前驅物 (B)有機染料或(b)顏料 (B)有機染料(質量份) (C)有機溶劑 (D)光聚合起始劑預烘烤膜之UV透過率(a) 聚醯亞胺膜之UV透過率(b) Δ(b－a) UV透過率之判定膜伸長率實施例26 A-1 B-8 3 C-1 - 0.32 0.35 0.03 優優實施例27 A-1 B-9 3 C-1 - 0.21 0.27 0.06 優優實施例28 A-1 B-10 3 C-1 - 0.28 0.31 0.03 優優實施例29 A-1 B-11 3 C-1 - 0.15 0.18 0.03 優優實施例30 A-1 B-1 3 C-2 - 0.15 0.16 0.01 優優實施例31 A-1 B-1 3 C-3 - 0.14 0.15 0.01 優優實施例32 A-1 B-1 3 C-4 - 0.16 0.15 -0.01 優優實施例33 A-1 B-1 3 C-5 - 0.15 0.15 0.00 優優實施例34 A-1 B-1 3 C-1 D-1 0.17 0.17 0.00 優優實施例35 A-1 B-1 3 C-1 D-2 0.16 0.17 0.01 優優實施例36 A-1 B-1 3 C-1 D-3 0.18 0.19 0.01 優優比較例1 A-1 - - C-1 - 0.96 0.95 -0.01 不可優比較例2 A-2 - - C-1 - 0.94 0.94 0.00 不可優比較例3 A-9 - - C-1 - 0.92 0.93 0.01 不可不可比較例4 A-1 b-11 3 C-1 - 0.22 0.95 0.73 不可良比較例5 A-1 b-12 3 C-1 - 0.15 0.76 0.61 不可優比較例6 A-1 b-13 3 C-1 - 0.09 0.55 0.46 不可良比較例7 A-1 b-14 3 C-1 - 0.06 0.89 0.83 不可優比較例8 A-1 b-15 3 C-1 - 0.11 0.12 0.01 優不可比較例9 A-1 b-16 3 C-1 - 0.15 0.15 0.00 優不可比較例10 A-1 b-17 3 C-1 - 0.12 0.15 0.03 優不可比較例11 A-1 b-18 3 C-1 - 0.21 0.19 -0.02 優不可比較例12 A-1 B-1 3 C-6 - 無法評估(不溶於溶劑) 無法評估(不溶於溶劑) 無法評估無法評估(不溶於溶劑) 無法評估(不溶於溶劑) 比較例13 A-1 B-1 3 C-7 - 無法評估(不溶於溶劑) 無法評估(不溶於溶劑) 無法評估無法評估(不溶於溶劑) 無法評估(不溶於溶劑) [table 3] [table 3] (A) Polyimide precursor (B)Organic dye or (b)Pigment (B) Organic dye (mass part) (C)Organic solvent (D) Photopolymerization initiator UV transmittance of pre-baked film (a) UV transmittance of polyimide film (b) Δ(b-a) Determination of UV transmittance Film elongation Example 26 A-1 B-8 3 C-1 - 0.32 0.35 0.03 Excellent Excellent Example 27 A-1 B-9 3 C-1 - 0.21 0.27 0.06 Excellent Excellent Example 28 A-1 B-10 3 C-1 - 0.28 0.31 0.03 Excellent Excellent Example 29 A-1 B-11 3 C-1 - 0.15 0.18 0.03 Excellent Excellent Example 30 A-1 B-1 3 C-2 - 0.15 0.16 0.01 Excellent Excellent Example 31 A-1 B-1 3 C-3 - 0.14 0.15 0.01 Excellent Excellent Example 32 A-1 B-1 3 C-4 - 0.16 0.15 -0.01 Excellent Excellent Example 33 A-1 B-1 3 C-5 - 0.15 0.15 0.00 Excellent Excellent Example 34 A-1 B-1 3 C-1 D-1 0.17 0.17 0.00 Excellent Excellent Example 35 A-1 B-1 3 C-1 D-2 0.16 0.17 0.01 Excellent Excellent Example 36 A-1 B-1 3 C-1 D-3 0.18 0.19 0.01 Excellent Excellent Comparative example 1 A-1 - - C-1 - 0.96 0.95 -0.01 No Excellent Comparative example 2 A-2 - - C-1 - 0.94 0.94 0.00 No Excellent Comparative example 3 A-9 - - C-1 - 0.92 0.93 0.01 No No Comparative example 4 A-1 b-11 3 C-1 - 0.22 0.95 0.73 No good Comparative example 5 A-1 b-12 3 C-1 - 0.15 0.76 0.61 No Excellent Comparative example 6 A-1 b-13 3 C-1 - 0.09 0.55 0.46 No good Comparative example 7 A-1 b-14 3 C-1 - 0.06 0.89 0.83 No Excellent Comparative example 8 A-1 b-15 3 C-1 - 0.11 0.12 0.01 Excellent No Comparative example 9 A-1 b-16 3 C-1 - 0.15 0.15 0.00 Excellent No Comparative example 10 A-1 b-17 3 C-1 - 0.12 0.15 0.03 Excellent No Comparative example 11 A-1 b-18 3 C-1 - 0.21 0.19 -0.02 Excellent No Comparative example 12 A-1 B-1 3 C-6 - Unable to evaluate (insoluble in solvents) Unable to evaluate (insoluble in solvents) Unable to evaluate Unable to evaluate (insoluble in solvents) Unable to evaluate (insoluble in solvents) Comparative example 13 A-1 B-1 3 C-7 - Unable to evaluate (insoluble in solvents) Unable to evaluate (insoluble in solvents) Unable to evaluate Unable to evaluate (insoluble in solvents) Unable to evaluate (insoluble in solvents)

如上述表所示，可確認實施例均可獲得於固化步驟前後均具有良好之著色程度(低透過率)且保持充分之膜伸長率之聚醯亞胺膜(硬化浮凸圖案)。As shown in the above table, it can be confirmed that in all the examples, a polyimide film (hardened relief pattern) with a good degree of coloration (low transmittance) and sufficient film elongation maintained before and after the curing step can be obtained.

以上對本實施方式進行了說明，但本發明並不僅限定於本實施方式。本發明可於不脫離其主旨之範圍內適當進行變更。 [產業上之可利用性] The present embodiment has been described above, but the present invention is not limited only to this embodiment. The present invention can be appropriately modified within the scope that does not deviate from the gist of the invention. [Industrial availability]

本發明例如可於可用於製造半導體裝置、及多層佈線基板等電子材料之感光性材料領域中適宜地利用。例如，本發明於產業上可用作電子零件之絕緣材料、及半導體裝置中之鈍化膜、緩衝塗膜、層間絕緣膜等中使用之樹脂組合物，又，本發明於產業上亦可用作使用該樹脂組合物之聚醯亞胺之製造方法、硬化浮凸圖案之製造方法、及半導體裝置。此種本發明除了應用於半導體裝置以外，還可適宜地應用於多層電路之層間絕緣膜、撓性覆銅板之覆蓋塗膜、防焊膜、液晶配向膜等用途。又，就獲得適於使用532 nm之雷射(綠色雷射)之樹脂之觀點而言，本發明亦較為有用。The present invention can be suitably used in the field of photosensitive materials that can be used for manufacturing electronic materials such as semiconductor devices and multilayer wiring substrates, for example. For example, the present invention can be used industrially as an insulating material for electronic components and a resin composition used in passivation films, buffer coating films, interlayer insulating films, etc. in semiconductor devices. In addition, the present invention can also be used industrially as a resin composition. A method for producing polyimide using the resin composition, a method for producing a hardened relief pattern, and a semiconductor device. In addition to being applied to semiconductor devices, the present invention can be suitably applied to interlayer insulating films for multilayer circuits, cover coating films for flexible copper-clad laminates, solder resists, liquid crystal alignment films, and the like. Furthermore, the present invention is also useful from the viewpoint of obtaining a resin suitable for use with 532 nm laser (green laser).

Claims

一種樹脂組合物，其包含以下成分： (A)下述通式(A1)所表示之聚醯亞胺前驅物： [化1] {式中，X為四價有機基，Y為二價有機基，R ₁及R ₂為氫原子、下述通式(R _h)： [化2] (式中，R ₃、R ₄及R ₅為氫原子或碳數1～3之有機基，p為選自2～10之整數)所表示之一價有機基、或碳數1～4之飽和脂肪族基；其中，R ₁及R ₂並不同時為氫原子}； (B)有機染料；及 (C)有機溶劑；且旋轉塗佈上述樹脂組合物後，於110℃下歷經240秒進行乾燥而獲得之預烘烤膜於532 nm下之以10 μm膜厚換算之UV透過率(a)為40%以下，於230℃下將上述預烘烤膜歷經2小時於氮氣氛圍下加熱而獲得之聚醯亞胺膜於532 nm下之以10 μm膜厚換算之UV透過率(b)為40%以下。 A resin composition containing the following components: (A) A polyimide precursor represented by the following general formula (A1): [Chemical 1] {In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are hydrogen atoms, and the following general formula (R _h ): [Chemical 2] (In the formula, R ₃ , R ₄ and R ₅ are hydrogen atoms or organic groups with 1 to 3 carbon atoms, and p is an integer selected from 2 to 10), or a monovalent organic group with 1 to 4 carbon atoms. Saturated aliphatic group; wherein, R ₁ and R ₂ are not hydrogen atoms at the same time}; (B) organic dye; and (C) organic solvent; and after spin-coating the above resin composition, at 110°C for 240 seconds The prebaked film obtained by drying has a UV transmittance (a) of 10 μm film thickness at 532 nm of less than 40%. The prebaked film is heated at 230°C for 2 hours in a nitrogen atmosphere. The UV transmittance (b) of the obtained polyimide film at 532 nm based on the film thickness of 10 μm is less than 40%.

如請求項1之樹脂組合物，其中UV透過率之差Δ(b－a)滿足-10%≦Δ(b－a)≦10%之關係。For example, in the resin composition of claim 1, the difference in UV transmittance Δ(b-a) satisfies the relationship of -10%≦Δ(b-a)≦10%.

如請求項1之樹脂組合物，其中於上述通式(A1)中，上述X包含下述式(2)所表示之結構： [化3] 。 The resin composition of claim 1, wherein in the general formula (A1), the X includes a structure represented by the following formula (2): [Chemical 3] .

如請求項1之樹脂組合物，其中於上述通式(A1)中，上述Y包含下述式(8)： [化4] 及/或下述式(9)： [化5] 所表示之結構。 The resin composition of claim 1, wherein in the above general formula (A1), the above Y includes the following formula (8): [Chemical 4] And/or the following formula (9): [Chemistry 5] the structure represented.

如請求項1之樹脂組合物，其中上述(B)成分之含量相對於(A)成分100質量份為0.5～30質量份。The resin composition of claim 1, wherein the content of the component (B) is 0.5 to 30 parts by mass relative to 100 parts by mass of the component (A).

如請求項1之樹脂組合物，其中上述樹脂組合物包含相對於上述(A)成分100質量份為1～50質量份之(D)光聚合起始劑。The resin composition according to claim 1, wherein the resin composition contains 1 to 50 parts by mass of the (D) photopolymerization initiator relative to 100 parts by mass of the component (A).

如請求項1之樹脂組合物，其中上述(B)成分包含吖𠯤系染料衍生物、及蒽系染料衍生物之至少一者。The resin composition of claim 1, wherein the component (B) includes at least one of an azine-based dye derivative and an anthracene-based dye derivative.

如請求項1之樹脂組合物，其中上述(C)成分包含選自由N-甲基-2-吡咯啶酮(NMP)、γ-丁內酯(GBL)、二甲基亞碸(DMSO)、3-甲氧基-N,N-二甲基丙醯胺、及乳酸乙酯所組成之群中之至少1者。The resin composition of claim 1, wherein the component (C) is selected from the group consisting of N-methyl-2-pyrrolidinone (NMP), γ-butyrolactone (GBL), dimethylsulfoxide (DMSO), At least one of the group consisting of 3-methoxy-N,N-dimethylpropylamide and ethyl lactate.

如請求項1之樹脂組合物，其進而包含以下成分： (D)光聚合起始劑，且上述(D)成分為肟類。 The resin composition of claim 1 further includes the following components: (D) photopolymerization initiator, and The above-mentioned component (D) is an oxime.

一種硬化浮凸圖案之製造方法，其包括如下步驟： (1)藉由將如請求項1至9中任一項之樹脂組合物塗佈於基板，而形成樹脂組合物膜； (2)藉由對上述樹脂組合物膜進行曝光及顯影之步驟、或雷射照射上述樹脂組合物膜之步驟，而形成浮凸圖案；及 (3)對上述浮凸圖案加熱，而形成硬化浮凸圖案。 A method of manufacturing a hardened relief pattern, which includes the following steps: (1) Forming a resin composition film by coating the resin composition according to any one of claims 1 to 9 on a substrate; (2) Forming a relief pattern through the steps of exposing and developing the above-mentioned resin composition film, or the step of irradiating the above-mentioned resin composition film with laser; and (3) The above-mentioned embossed pattern is heated to form a hardened embossed pattern.

如請求項10之硬化浮凸圖案之製造方法，其中上述基板由銅或銅合金形成。The method of manufacturing a hardened relief pattern according to claim 10, wherein the substrate is formed of copper or copper alloy.

一種半導體裝置，其具有由如請求項1至9中任一項之樹脂組合物獲得之硬化浮凸圖案作為絕緣層。A semiconductor device having as an insulating layer a hardened relief pattern obtained from the resin composition of any one of claims 1 to 9.

一種聚醯亞胺之製造方法，其使用包含以下成分之樹脂組合物： (A)下述通式(A1)所表示之聚醯亞胺前驅物： [化6] {式中，X為四價有機基，Y為二價有機基，R ₁及R ₂為氫原子、下述通式(R _h)： [化7] (式中，R ₃、R ₄及R ₅為氫原子或碳數1～3之有機基，p為選自2～10之整數)所表示之一價有機基、或碳數1～4之飽和脂肪族基；其中，R ₁及R ₂並不同時為氫原子}； (B)有機染料；及 (C)有機溶劑；且旋轉塗佈上述樹脂組合物後，於110℃下歷經240秒進行乾燥而獲得之預烘烤膜於532 nm下之以10 μm膜厚換算之UV透過率(a)為40%以下，於230℃下將上述預烘烤膜歷經2小時於氮氣氛圍下加熱而獲得之上述聚醯亞胺膜於532 nm下之以10 μm膜厚換算之UV透過率(b)為40%以下。 A method for producing polyimide, which uses a resin composition containing the following components: (A) A polyimide precursor represented by the following general formula (A1): [Chemical 6] {In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are hydrogen atoms, and the following general formula (R _h ): [Chemical 7] (In the formula, R ₃ , R ₄ and R ₅ are hydrogen atoms or organic groups with 1 to 3 carbon atoms, and p is an integer selected from 2 to 10), or a monovalent organic group with 1 to 4 carbon atoms. Saturated aliphatic group; wherein, R ₁ and R ₂ are not hydrogen atoms at the same time}; (B) organic dye; and (C) organic solvent; and after spin-coating the above resin composition, at 110°C for 240 seconds The prebaked film obtained by drying has a UV transmittance (a) of 10 μm film thickness at 532 nm of less than 40%. The prebaked film is heated at 230°C for 2 hours in a nitrogen atmosphere. The UV transmittance (b) of the obtained polyimide film at 532 nm calculated from a film thickness of 10 μm is less than 40%.

如請求項13之聚醯亞胺之製造方法，其中UV透過率之差Δ(b－a)滿足-10%≦Δ(b－a)≦10%之關係。For example, in the method of manufacturing polyimide of claim 13, the difference in UV transmittance Δ(b-a) satisfies the relationship of -10%≦Δ(b-a)≦10%.