TW201011469A - Photosensitive resin composition - Google Patents

Abstract

Disclosed is a photosensitive resin composition which is characterized by comprising: (a) 100 parts by mass of a polyamide having a structure represented by general formula (1) [wherein each substituent and others are as defined in the scope of claims]; and (b) 1 to 100 parts by mass of a diazoquinone compound represented by general formula (2) [wherein each substituent and others are as defined in the scope of claims].

Description

201011469 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種具有優異之光敏度與解析性之正型感 光性樹脂組合物、及使用該組合物之高耐熱性凸紋圖案之 製造方法。 【先前技術】 先前，作為半導體元件之表面保護膜、層間絕緣膜，使 用有兼具優異之耐熱性與電氣特性、機械特性等之聚醯亞 胺樹脂。該聚醯亞胺樹脂通常係藉由塗佈非感光性聚醯亞 胺前驅物或者感光性聚醯亞胺前驅物組合物後，進行酿亞 胺化處理而形成。於必須將該聚醯亞胺樹脂圖案化之情形 時，通常使用感光性聚醯亞胺前驅物組合物。其理由係： 若為感光性聚醯亞胺前驅物組合物，則將其塗佈後，利用 活性光線進行成像曝光，接著實施顯影、熱醯亞胺化等處 理，藉此可簡單地形成聚醯亞胺圖案，與使用非感光性聚 酿亞胺之情況相比，可大幅度地縮短步驟。 然而，在使用該感光性聚醯亞胺前驅物組合物進行圖案 化時，於顯影步驟中，必須大量使用沁甲基_2_吡咯啶蜩 等有機溶劑作為顯影液。但是，會有對工廠中之作業環境 及其他製程產生影響等之問題，因而強烈要求用以不使用 有機溶劑來進行顯影之對策或技術開發。因此，最近以 來，對於與光阻劑同樣地可以稀鹼性水溶液進行顯影之耐 熱性感光性樹脂材料，而提出了各種提案（以下，參照專 利文獻1、2)。 140314.doc 201011469 其中，近年來受到注目之方法係，將水性鹼可溶性羥基 聚醯胺、例如聚苯并呤唑（以下亦稱為「pBO」）前驅物與 重氮萘醌（以下亦稱為「DNQ」）等光活性成分（以下亦稱為 「P A C」）加以》昆合而使用。 [專利文獻1]日本專利特公平01_046862號公報 [專利文獻2]曰本專利特開昭63_〇96162號公報 [專利文獻3]曰本專利特開平〇7_281441號公報 [專利文獻4]曰本專利特開2〇〇〇 275833號公報 [專利文獻5]曰本專利特表2〇〇7_525545號公報 [專利文獻6]曰本專利特開2004-117999號公報 [專利文獻7]曰本專利特開2008-58548號公報 【發明内容】 [發明所欲解決之問題] 然而，於藉由至今為止所揭示之方法而獲得之感光性鹼 性顯影系統中，仍有較多問題。 原來，於使用DNQ之感光性樹脂組合物之情形時，藉由 於鹼可溶性聚合物中添加DNQ，而表現出使組合物之鹼溶 解性降低之（溶解抑止）能力，並且未曝光部之顯影液耐性 產生。另一方面，對於曝光部而言，將DNQ更換為茚甲 酸，溶解抑止能力消失而溶解於顯影液中。 利用該曝光部、未曝光部之鹼溶解性之差來進行圖案 化，為了獲得高靈敏度且高殘膜率之圖案化性能，較為重 要的疋選定可充分獲取兩者之溶解性之差的。 即，必須使用如下高靈敏度之PAC: |^添加pAc驗溶 140314.doc 201011469 解性極度下降，—古& ^ 影液耐性，另-方面，於曝=部中具有充分之驗性顯 進行分解，而表現出充分少量光亦會有效地 為了解以述_’於上述專利文獻3 用具有立體性體積大之其沾h此 便 光部之顯影液耐:基的_來作為母核，以提高未曝 2而，關於該等PAC’若為了高靈敏度化而提高卿導[Technical Field] The present invention relates to a positive photosensitive resin composition having excellent photosensitivity and resolution, and a method for producing a highly heat-resistant embossed pattern using the same . [Prior Art] As the surface protective film or interlayer insulating film of the semiconductor element, a polyimide resin having excellent heat resistance, electrical properties, mechanical properties and the like is used. The polyimine resin is usually formed by coating a non-photosensitive polyimide precursor or a photosensitive polyimide precursor composition and then subjecting it to amination treatment. In the case where the polyimine resin must be patterned, a photosensitive polyimide intermediate composition is usually used. The reason for this is that, in the case of a photosensitive polyimide intermediate composition, after application, it is imagewise exposed by active light, and then subjected to development, heat kiln imidization or the like, whereby the polymerization can be easily formed. The quinone imine pattern can significantly shorten the steps compared to the case of using non-photosensitive styrene. However, when patterning is carried out using the photosensitive polyimide intermediate composition, an organic solvent such as fluorenylmethyl-2-pyrrolidinium must be used in a large amount as a developing solution in the developing step. However, there are problems such as the influence on the working environment and other processes in the factory. Therefore, countermeasures or technology development for developing without using an organic solvent are strongly demanded. Therefore, various proposals have been made for heat-resistant photosensitive resin materials which can be developed in a dilute alkaline aqueous solution in the same manner as the photoresist (hereinafter, see Patent Documents 1 and 2). 140314.doc 201011469 Among them, in recent years, attention has been paid to the method of water-based alkali-soluble hydroxypolyamine, such as polybenzoxazole (hereinafter also referred to as "pBO") precursor and diazonaphthoquinone (hereinafter also referred to as Photoactive components (hereinafter also referred to as "PAC") such as "DNQ" are used in combination. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. 2004-117999 (Patent Document 7) JP-A-2008-58548 SUMMARY OF INVENTION [Problems to be Solved by the Invention] However, there are still many problems in the photosensitive alkaline developing system obtained by the method disclosed so far. In the case of using the photosensitive resin composition of DNQ, the ability to reduce the alkali solubility of the composition (dissolution inhibition) by the addition of DNQ to the alkali-soluble polymer, and the developer of the unexposed portion Patience is produced. On the other hand, in the exposed portion, DNQ was replaced with phthalic acid, and the dissolution inhibiting ability disappeared and dissolved in the developing solution. Patterning is performed by the difference in alkali solubility between the exposed portion and the unexposed portion, and in order to obtain patterning performance with high sensitivity and high residual film ratio, it is possible to sufficiently obtain the difference in solubility between the two. That is, the following high-sensitivity PAC must be used: |^ Adding pAc to dissolve 140314.doc 201011469 Extremely decisive, - Gu & ^ Shadow liquid tolerance, and other aspects, with sufficient testability in the exposure section Decomposition, while exhibiting a sufficiently small amount of light, is effective for understanding that the above-mentioned Patent Document 3 uses a developer having a solid volume and a large volume of the developing portion of the light-receiving portion as a mother core. In order to improve the non-exposure 2, if the PAC' is improved for high sensitivity,

則對製成感綠樹脂M合物時所使狀有機溶劑的 :解性變低’而析出性成為問題。即，於對將驗可溶性聚 口物及獸溶解於有機溶财而製成感光性㈣組合物者 進打室溫、冷藏或者冷料存的期間，PAC額體形式析 出’而實際上無法使用該感光性樹脂組合物。因此，必須 降低DNQ導入率，而實質上無法達成高靈敏度化。進而存 在如下問題.此種複雜結構之母核於合成時必需多階段之 反應等製造步驟繁雜’且因生成大量副產物而難以進行品 質管理等。 另方面，如專利文獻2、5、6、7中之較小結構之母核 的PAC，存在靈敏度較低之問題。 士上所述還未出使用以高水準滿足靈敏度等之微影 性能與析出等之穩定性的PAC之感光性樹脂組合物。 本發明所欲解決之課題係提供一種感光性樹脂組合物、 使用其之高耐熱性凸紋圖案之製造方法以及具有該硬化凸 紋圖案之半導體裝置，上述感光性樹脂組合物表現出高靈 敏度、即於低曝光量區域中之圖案化下顯影後之圖案膜減 140314.doc 201011469 少量亦較小，且優異之解析度，並且難以引起PAC之析 出。 [解決問題之技術手段] 本發明者們著眼於PAC ,為了開發表現高靈敏度且高解 析度之圖案化性能並且難以弓丨起pAC析出的感光性樹脂組 合物，而進行了努力研究。結果發現，若使用具有特定結 構之PAC ’則可滿足上述特性，從而完成了本發明。 即’本發明如以下所述。 [1]一種感光性樹脂組合物，其特徵在於含有： U)具有以下述通式（1)所表示之結構之聚醯胺1〇〇質量 份： [化1] •HN—X, 一 NHC〇_ (l) (〇H)q ΥιCo— (COOR)m (式中，Xl為具有2個以上碳原子之2〜4價有機基，Yl為具 有2個以上碳原子之2〜6價有機基，P及q分別獨立為0〜4之 整數，R為氫原子或碳數為Μ。之有機基，爪為〇〜2之整 數’η為2〜1_之整數’其中，m、P及q不同時為〇,且於 ?與4均為0之情形時，R為具有酚性羥基之基广以及 (b)以下述通式（2)所表示之重氮酿化合物卜_質量份： 140314.doc 201011469 [化2]In the case where the green resin M compound is formed, the solubility of the organic solvent is lowered, and the precipitation property is a problem. In other words, during the period in which the photosensitive (4) composition is dissolved in the organic solvent, and the photosensitive (4) composition is allowed to enter the room temperature, refrigerated or cold storage, the PAC form precipitates and is practically unusable. This photosensitive resin composition. Therefore, it is necessary to reduce the DNQ introduction rate, and it is substantially impossible to achieve high sensitivity. Further, there is a problem that the mother core of such a complicated structure is complicated in manufacturing steps such as a reaction in a multi-stage reaction at the time of synthesis, and it is difficult to perform quality management or the like due to generation of a large amount of by-products. On the other hand, the PAC of the mother core of the smaller structure as in Patent Documents 2, 5, 6, and 7 has a problem of low sensitivity. In the above, a photosensitive resin composition of PAC which satisfies the stability of lithographic performance such as sensitivity and precipitation, etc., at a high level has not been used. An object of the present invention is to provide a photosensitive resin composition, a method for producing a high heat-resistant embossed pattern using the same, and a semiconductor device having the cured embossed pattern, wherein the photosensitive resin composition exhibits high sensitivity. That is, the pattern film after patterning in the low exposure amount region is reduced by 140314.doc 201011469, the amount is small, and the resolution is excellent, and it is difficult to cause precipitation of PAC. [Means for Solving the Problem] The inventors of the present invention have focused on PAC, and have conducted efforts to develop a photosensitive resin composition that exhibits high sensitivity and high resolution of patterning performance and is difficult to extract pAC. As a result, it has been found that the above characteristics can be satisfied by using a PAC' having a specific structure, thereby completing the present invention. That is, the present invention is as follows. [1] A photosensitive resin composition comprising: U) 1 part by mass of polyamine having a structure represented by the following formula (1): [Chemical Formula 1] • HN—X, an NHC 〇_ (l) (〇H)q ΥιCo—(COOR)m (wherein X1 is a 2~4-valent organic group having 2 or more carbon atoms, and Y1 is a 2~6-valent organic having 2 or more carbon atoms; The base, P and q are each independently an integer of 0 to 4, R is a hydrogen atom or the carbon number is Μ. The organic group, the claw is an integer of 〇~2 'η is an integer of 2 to 1_ where m, P And q is not 不同 at the same time, and when both ? and 4 are 0, R is a broad base having a phenolic hydroxyl group; and (b) is a diazo brewing compound represented by the following general formula (2). : 140314.doc 201011469 [Chemical 2]

(2) {式中，乙丨、Z2及Z3分別獨立為碳數為卜⑺之丨價有機基， 刀別獨立為〇〜4之整數，e為〇〜5之整數，複數個q内之 任一個為由以下： [化3](2) In the formula, 丨, Z2 and Z3 are independent of the 碳 有机 organic base with carbon number (b), the knives are independent of 〇~4, and e is an integer of 〇~5, a plurality of q Any one is as follows: [Chemical 3]

所表示之2個基之任一個，其餘為氫原子}。 上述（b)重氮醌Any one of the two bases indicated, the remainder being a hydrogen atom}. Above (b) diazonium

[2]如上述[1]之感光性樹脂組合物，其中 化合物為以下述式（3)所表示之化合物： [化4][2] The photosensitive resin composition of the above [1], wherein the compound is a compound represented by the following formula (3): [Chemical 4]

{式中，複數個Q内之任一個為由以下 140314.doc 201011469 [化5]In the formula, any one of the plurality of Qs is determined by the following 140314.doc 201011469 [Chemical 5]

所表不之2個基之任—個，其餘為氫原子}。 [3]士上述[1]或[2]之感光性樹脂組合物，其中上述⑷聚 醯胺具有以下述通式（4)所表示之重複單元： [化6]The two bases are not listed, and the rest are hydrogen atoms}. [3] The photosensitive resin composition of the above [1] or [2] wherein the (4) polyamine has a repeating unit represented by the following formula (4): [Chem. 6]

OH 即一子2— NHC〇~Y2—CO OH (4) {式中，又2為4價芳香族基，¥2為2價芳香族基並且福 2~1 〇〇〇之整數}。 [4]-種硬化凸紋圖案之製造方法，其包括以下步驟： 將如上述[1 ]〜[3]中任—項之感光性樹脂組合物塗佈於基 板上之步驟；OH is a sub- 2 - NHC 〇 ~ Y2 - CO OH (4) { wherein, 2 is a tetravalent aromatic group, and ¥ 2 is a divalent aromatic group and an integer of 2 to 1 }. [4] A method for producing a hardened relief pattern, comprising the steps of: applying a photosensitive resin composition according to any one of the above [1] to [3] to a substrate;

經由光罩以光化射線進行曝光或直接 或者離子束之步驟； 照射光線、電子束 將曝光部或照射部溶出或除去之步驟； 加熱所獲得之凸紋圖案之步驟。 [5] —種半導體裝置 之硬化凸紋圖案。 其具有藉由上述[4]之方法而獲得 I40314.doc -8 - 201011469 [發明之效果] 根據本發明，可提供一種感光性樹脂組合物、使用其之 高耐熱性凸紋圖案之製造方法以及具有該硬化凸紋圖案之 半導體裝置，上述感光性樹脂組合物係表現出高靈敏度、 即於低曝光量區域之圖案化下顯影後之圖案膜減少量亦較 小，且優異之解析度，並且難以引起PAC之析出。 【實施方式】 以下，對構成本發明之感光性樹脂組合物之各成分加以 具體說明。 (a)聚醯胺 (a)聚醯胺具有以下述通式（1)所表示之結構： [化7] (1) (〇H>P (OH)q HN—Xj—NHCO—Yj—C( (C00R)ma step of exposing or directly or ion beaming with actinic rays through a mask; a step of irradiating light, an electron beam to dissolve or remove the exposed portion or the irradiating portion; and a step of heating the obtained relief pattern. [5] A hardened relief pattern of a semiconductor device. It is obtained by the method of the above [4]. I40314.doc -8 - 201011469 [Effects of the Invention] According to the present invention, a photosensitive resin composition, a method for producing a high heat-resistant embossed pattern using the same, and a method for producing the same In the semiconductor device having the hardened relief pattern, the photosensitive resin composition exhibits high sensitivity, that is, the amount of pattern film reduction after patterning in a low exposure amount region is small, and excellent resolution, and It is difficult to cause the precipitation of PAC. [Embodiment] Hereinafter, each component constituting the photosensitive resin composition of the present invention will be specifically described. (a) Polyamine (a) Polyamine has a structure represented by the following formula (1): (Chemical Formula 7) (1) (〇H>P (OH)q HN-Xj-NHCO-Yj-C ( (C00R)m

{式中，X!為具有2個以上碳原子之2〜4價有貞基，γι為具 有2個以上碳原子之2〜6價有機基’ p及q分別獨立為〇〜4之 整數，R為氫原子或碳數為_之有機基，^之整 數’η為2〜1000之整數’其中，m'Mq不同時為〇,且於 P與q均為0之情形時，R為具有酚性羥基之基}。 ⑷聚醯胺係將具有Xl(〇H)p之結構之二胺、與具有 Yi(〇H)q(CO〇R)m2結構之二綾酸進行聚縮合而獲得。& 較好的疋具有2個以上且3G個以下碳原子之2〜4價有機基。 140314.doc 201011469 30個以下碳原子之2〜6價有機 ’更好的是2〜100之範圍，最 Υι較好的是具有2個以上且 基。η較好的是2〜2〇〇之範圍 好的是3〜50之範圍。 將⑷聚酿胺以則〜彻。c進行加熱後脫水閉環而轉變 成稱為聚酿亞㈣聚苯并料之耐熱性樹脂。 作為上述具有Xl(0H)p(其中，？為〇〜4之整數）之結構之 二胺，例如可舉出芳香族二胺、矽二胺、羥基二胺。其 中，作為芳香族二胺，例如可舉出：間苯二胺、對苯二 胺2,4 f笨一胺、3,3'-二胺基二苯基㈣、3,4,_二胺基二 苯基醚、4,4，-二胺基二苯基醚、3,3,_二胺基二苯基砜、 4.4- 一胺基二苯基砜、3 4，_二胺基二苯基砜、3,3，_二胺基 二苯基甲烷、4,4'-二胺基二苯基甲烷、3,4,_二胺基二苯基 曱烷、4,4’-二胺基二苯硫醚、3,31_二胺基二苯基酮、4,4，_ 一胺基二苯基酮、3,4’-二胺基二苯基酮、2,2，_雙（4_胺基苯 基）丙烧、2,2'-雙（4-胺基苯基）六氟丙烧、uk%胺基苯 氧基）苯、1,3-雙（4-胺基苯氧基）苯、丨，4_雙（4-胺基苯氧基） 笨、4-甲基-2,4-雙（4-胺基苯基）-1_戊稀、4-曱基-2,4-雙（4-胺基苯基）-2-戊烯、l，4-雙（α，α_二甲基_4_胺基苄基）苯、亞 胺基二對苯二胺、1，5-二胺基萘、2,6-二胺基萘、4-甲基- 2.4- 雙（4-胺基苯基）戊烧、5(或6)-胺基-1-(4-胺基苯基）-1，3,3-三甲基茚滿、雙（對胺基苯基）氧化膦、4,4'-二胺基偶 氮苯、4,4·-二胺基二苯基脲、4,4’-雙（4-胺基苯氧基）聯 苯、2,2-雙[4-(4-胺基苯氧基）苯基]丙烷、2,2-雙[4-(4-胺基 苯氧基）苯基]六氟丙烷、2,2-雙[4-(3-胺基苯氧基）苯基]二 140314.doc •10· 201011469 苯甲酮、4,4|-雙（4-胺基苯氧基）二笨基颯、4,4,_雙[4_(α，α_ 二甲基-4-胺基节基）苯氧基]二苯甲酮、4,4，_雙[4(α，α二曱 基-4-¾基节基）苯氧基]二苯基碾、4,4,_二胺基聯苯、4,4,_ 二胺基二苯甲酮、苯基茚滿二胺、3,3，_二甲氧基_4,4,_二胺 基聯苯、3,3’-二曱基-4,4’-二胺基聯苯、鄰节苯胺砜、2,2_ 雙（4-胺基苯氧基苯基）丙烷、雙（4_胺基苯氧基苯基）礙、雙 (4-胺基苯氧基苯基）硫醚、丨，4_(4胺基苯氧基苯基）苯、 1，3-(4-胺基笨氧基笨基）苯、9,9_雙（4胺基苯基）蒽、99_雙 (4-胺基苯基）第、4,4，_二（3_胺基苯氧基）二苯基砜、4,4,_二 胺基苯f醯苯胺等、以及該等芳香族二胺之芳香核之氫原 子被選自氣原子、氟原子、漠原子、甲基、甲氧基、氰 基、苯基所組成群t之至少一種取代基所取代的化合物。 又，為了提高與基材之接著性，可選擇矽二胺，作為此 例，可舉出：雙（4_胺基苯基）二甲基矽烷、雙（4_胺基苯基） 四曱基石夕乳烧、雙（對胺基苯基）四曱基二碎氧烧、雙（γ-胺 基丙基）四甲基二矽氧烷、L4-雙（γ_胺基丙基二曱基矽烷 基）笨、雙（4·胺基丁基）四曱基二矽氧烷、雙（γ_胺基丙基） 四苯基二矽氧烷等。 又’為了提高聚醯胺之鹼溶解性，較好的是使用羥基二 胺’作為此例，可舉出：3,3，_二羥基聯苯胺、3,3,二胺基_ 4,4'_二羥基聯苯、4,4'-二胺基-3,3，-二羥基聯笨、3,3，-二胺 基-4,4'-二羥基二笨基砜、4,4,二胺基_3,3,·二羥基二苯基 颯、雙（3-胺基-4-羥基笨基;)曱烷、2,2_雙（3_胺基_4_羥基笨 基）丙烷、2,2-雙（3-胺基羥基苯基）六氟丙烷、2,2·雙（4_ 140314.doc 201011469 胺基_3_羥基苯基）六氟丙烷、雙（4-胺基-3-羥基苯基）甲 烷2,2_雙（4_胺基-3-羥基苯基）丙烷、4,4，-二胺基_3,3，-二 羥基二苯甲鲖、3,3，-二胺基-4,4，-二羥基二苯曱酮、4,4，-二 胺土 ’ ~~經基二苯基喊、3,3'-二胺基-4,4'-二經基二笨 基醚、1，4-二胺基_2,5_二羥基苯、丨，3_二胺基-2,4_二羥基 苯、1,3-二胺基_4,6_二羥基苯等。 該等二胺可單獨使用，或者亦可混合使用。 其中’作為特別好之例，X!為選自下述之基： [化8]In the formula, X! is a fluorenyl group having 2 to 4 valences having 2 or more carbon atoms, and γι is a 2 to 6 valent organic group having 2 or more carbon atoms, and p and q are each independently an integer of 〇4. R is a hydrogen atom or an organic group having a carbon number of _, and an integer 'η is an integer from 2 to 1000' wherein m'Mq is not 〇 at the same time, and when both P and q are 0, R is Phenolic hydroxyl group}. (4) Polyamine is obtained by polycondensing a diamine having a structure of X1(〇H)p with a diernic acid having a structure of Yi(〇H)q(CO〇R)m2. & A preferred fluorene has 2 to 4 valent organic groups of 2 or more and 3 G or less carbon atoms. 140314.doc 201011469 30 to 30 carbon atoms of 2 to 6 organic ‘better is 2 to 100 range, and most preferably ι has more than 2 bases. η is preferably in the range of 2 to 2 . It is preferably in the range of 3 to 50. (4) Polyamide can be used. c is heated and then dehydrated and closed to a heat resistant resin called poly (tetra) polybenzoate. Examples of the diamine having a structure of X1(0H)p (wherein ? is an integer of 〇~4) include aromatic diamine, decanediamine, and hydroxydiamine. In addition, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine 2,4 f-p-monoamine, 3,3'-diaminodiphenyl (tetra), and 3,4,-diamine. Diphenyl ether, 4,4,-diaminodiphenyl ether, 3,3,-diaminodiphenyl sulfone, 4.4-monoaminodiphenyl sulfone, 3 4, _diamine Phenyl sulfone, 3,3,-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4,-diaminodiphenyl decane, 4,4'-di Aminodiphenyl sulfide, 3,31-diaminodiphenyl ketone, 4,4,-aminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2,_ Bis(4-aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, uk% aminophenoxy)benzene, 1,3-bis(4-amine Benzophenoxy)benzene, anthracene, 4_bis(4-aminophenoxy) stupid, 4-methyl-2,4-bis(4-aminophenyl)-1-pentyl, 4-anthracene Base-2,4-bis(4-aminophenyl)-2-pentene, 1,4-bis(α,α-dimethyl-4-indobenzyl)benzene, iminodi-p-phenylene Diamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2.4-bis(4-aminophenyl)pentane, 5 (or 6)-amino-1 -(4-aminophenyl)-1,3,3-three Base ruthenium, bis(p-aminophenyl)phosphine oxide, 4,4'-diaminoazobenzene, 4,4.-diaminodiphenylurea, 4,4'-bis(4-amine Phenyloxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl] Hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]di 140314.doc •10· 201011469 benzophenone, 4,4|-bis(4-aminophenoxy) ) 2,4,_bis[4_(α,α_dimethyl-4-amino)phenoxy]benzophenone, 4,4,_bis[4(α,α Dimercapto-4-3⁄4 base group) phenoxy]diphenyl milling, 4,4,-diaminobiphenyl, 4,4,-diaminobenzophenone, phenylindane diamine , 3,3,_dimethoxy_4,4,-diaminobiphenyl, 3,3'-dimercapto-4,4'-diaminobiphenyl, o-aniline sulfone, 2,2_ Bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl) thio, bis(4-aminophenoxyphenyl) sulfide, hydrazine, 4-(4 amino group Phenoxyphenyl)benzene, 1,3-(4-aminophenyloxyphenyl)benzene, 9,9-bis(4-aminophenyl)anthracene, 99-bis(4-aminophenyl) 4,4,_di(3_aminophenoxy) Diphenyl sulfone, 4,4,-diaminobenzene fluorenyl aniline, and the hydrogen atom of the aromatic nucleus of the aromatic diamine are selected from the group consisting of a gas atom, a fluorine atom, a desert atom, a methyl group, and a methoxy group. A compound substituted with at least one substituent of the group t consisting of a group, a cyano group and a phenyl group. Further, in order to improve the adhesion to the substrate, decyl diamine may be selected, and as an example, bis(4-aminophenyl)dimethyl decane and bis(4-aminophenyl)tetraindole may be mentioned. Keshixi milk-fired, bis(p-aminophenyl)tetradecyl dihydrogenate, bis(γ-aminopropyl)tetramethyldioxane, L4-bis(γ-aminopropyldiazine (Alkyl)alkyl, bis(4.aminobutyl)tetradecyldioxane, bis(γ-aminopropyl)tetraphenyldioxane, and the like. Further, in order to increase the solubility of the base of polyamine, it is preferred to use a hydroxydiamine as an example, which may be exemplified by 3,3,-dihydroxybenzidine, 3,3,diamine-4,4. '_Dihydroxybiphenyl, 4,4'-diamino-3,3,-dihydroxy phenyl, 3,3,-diamino-4,4'-dihydroxydi-phenyl sulfone, 4,4 , diamino-3,3,-dihydroxydiphenylanthracene, bis(3-amino-4-hydroxyphenyl) decane, 2,2-bis(3-amino-4_hydroxyphenyl) Propane, 2,2-bis(3-aminohydroxyphenyl)hexafluoropropane, 2,2.bis (4-140314.doc 201011469 Amino-3-hydroxyphenyl) hexafluoropropane, bis(4-amine Benzyl-3-hydroxyphenyl)methane 2,2-bis(4-amino-3-hydroxyphenyl)propane, 4,4,-diamino-3,3,-dihydroxybenzophenone, 3 ,3,-diamino-4,4,-dihydroxydibenzophenone, 4,4,-diamine soil~~~-based diphenyl sulfonate, 3,3'-diamino-4,4 '-Di-based diphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, anthracene, 3-diamino-2,4-dihydroxybenzene, 1,3-diamine 4,6-dihydroxybenzene and the like. These diamines may be used singly or in combination. Among them, as a particularly good example, X! is selected from the following: [Chem. 8]

作為以上述通式（1)中之YjOH^COOf^d式中，q為〇 之整數，並且m為0~2之整數}所表示之2價基，可舉出. 自以下之基： [化9]The divalent group represented by the formula YjOH^COOf^d in the above formula (1), q is an integer of 〇, and m is an integer of 0 to 2, and is exemplified by the following: 9]

140314.doc •12· 201011469140314.doc •12· 201011469

NHCO. ~0~ -(〇~ {式中，A係選自-CH2-、-O-、-S-、 、-C(CF3)2-f};由以下所表示之基： [化 10]NHCO. ~0~ -(〇~ { where A is selected from -CH2-, -O-, -S-, and -C(CF3)2-f}; the base represented by: ]

COOR {式中，R與上述通式（1)之R相同};或者以下 [化 11]COOR {wherein, R is the same as R of the above formula (1)}; or the following [Chem. 11]

ROOC COORROOC COOR

{式中，R與上述通式（1)之R相同，X3為-(：112-、-0-、-8-、-S02-、-CO-、-NHCO-、-C(CF3)2-、單鍵或者由以下所 表示之基： [化 12]Wherein R is the same as R of the above formula (1), and X3 is -(: 112-, -0-, -8-, -S02-, -CO-, -NHCO-, -C(CF3)2 -, single key or base represented by: [Chem. 12]

OHOH

II

-CONH-X»—NHCO-OH (式中，X4為選自以下之基： 140314.doc -13- 201011469 [化 13]-CONH-X»—NHCO-OH (wherein X4 is a base selected from the group consisting of: 140314.doc -13- 201011469 [Chem. 13]

上述通式（1)中，尺表 ㈣為氫原子之料時Ί原子或碳數為1〜2G之有機基， 獲得之感光性^物之籍聚酿胺之驗溶解性提昇，但印 、°物之穩mpAc之溶解抑止能力下 有機基之P有汉令氣原子較好的是50%以下。又，於尺為 有機基之情形時’因所獲得之感光性組合物之穩定㈣ PAC之讀抑止能力提昇而較好，但驗溶解性下降。 β因此 <乍為有機基，較好的是具有紛性經基之基，特別 是於上述通式⑴中ρ與q均為〇之情形時，有機基必須為具 有紛性輕基之f料具㈣㈣基之較佳有機基之例， 可舉出3-羥基苄基、3,5-二羥基苄基等。 作為本發明中所使用之（a)聚醯胺，特別是就優異之鹼溶 解性、及基於其之厚膜下之優異的圖案化特性方面而言， 特別好的是具有以下述通式（4)所表示之重複單元之結構： [化 14] (4)In the above formula (1), when the ruler (4) is a hydrogen atom, the ruthenium atom or the organic group having a carbon number of 1 to 2 G, the solubility of the obtained photosensitive material is improved, but the printing is improved. ° The stability of the stable mpAc of the substance is less than 50% of the organic atomic P. Further, when the ruler is an organic base, it is preferable because the stability of the photosensitive composition obtained (4) the PAC read inhibition ability is improved, but the solubility is lowered. β is therefore an organic group, preferably having a heterogeneous radical group, especially in the case where ρ and q are both fluorene in the above formula (1), the organic group must be a fragrant light base. Examples of the preferred organic group of the material of the material (4) and (4) include a 3-hydroxybenzyl group, a 3,5-dihydroxybenzyl group and the like. The (a) polydecylamine used in the present invention is particularly preferably in the form of the following formula (in terms of excellent alkali solubility and excellent patterning properties under a thick film thereof). 4) Structure of the repeating unit represented: [Chem. 14] (4)

OHOH

I HN-X2_NHCO-Y2—CO- 140314.doc •14· 201011469 {式中，X2為4價芳香族基’ ¥2為2價芳香族基，並且n為 2〜1000之整數}。 其中，作為X2，較佳之基係可舉出由以下： [化 15]I HN-X2_NHCO-Y2—CO- 140314.doc •14· 201011469 {wherein, X2 is a tetravalent aromatic group'. ¥2 is a divalent aromatic group, and n is an integer of 2 to 1000}. Among them, as X2, a preferred base system is exemplified by the following: [Chem. 15]

所表示之基，並且作為I，較佳之基係可分別舉出以下： ❹ [化16] ~ρ η〇>-〇^. ο 通式（4)中，η較好的是2〜2〇〇之範圍，更好的是2〜1〇〇之 範圍，最好的是3〜50之範圍。 • 於具有以上述通式（1)或（4)所表示之重複單元之聚醯胺 (以下，有時僅稱為（a)聚醯胺）中，亦可以特定有機基將其 末端基封端。 ~ 作為此種封端基，例如可舉出：如曰本專利特開平〇5_ 197153號公報中記載之具有不飽和鍵之基、鄰苯二甲酸 酐、琥珀酸酐、2-丁烯·ΐ_基琥珀酸酐、衣康酸酐、環己 基-1，2-二曱酸酐、4-甲基環己基-υ-二曱酸酐、外_3,6_環 氧-1，2,3,6-四氫鄰苯二曱酸酐等，於以該等進行封端之产 形時，期待加熱硬化後之塗膜之機械物性（特別是伸^ 140314.doc •15· 201011469 率）、或硬化凸紋圖案形狀變得良好。作為此種封端基t 之較佳例，可舉出下述基： [化 17]The base represented, and as I, a preferred base system can be exemplified as follows: ❹ [Chemical 16] ~ρ η〇>-〇^. ο In the general formula (4), η is preferably 2 to 2 The range of 〇〇 is better, the range is 2~1〇〇, and the best is the range of 3~50. • In the case of a polydecylamine having a repeating unit represented by the above formula (1) or (4) (hereinafter sometimes referred to simply as (a) polydecylamine), the terminal group may be bonded to a specific organic group. end. As such a capping group, for example, a group having an unsaturated bond, phthalic anhydride, succinic anhydride, 2-butene·ΐ as described in Japanese Laid-Open Patent Publication No. Hei No. Hei-5-197153 Succinic anhydride, itaconic anhydride, cyclohexyl-1,2-diphthalic anhydride, 4-methylcyclohexyl-indole-diphthalic anhydride, external _3,6-epoxy-1,2,3,6-tetra Hydrogen phthalic anhydride or the like is expected to have mechanical properties (especially the rate of 140314.doc •15·201011469) or hardened relief pattern of the coating film after heat curing. The shape is getting good. As a preferable example of such a terminal group t, the following groups are mentioned: [Chem. 17]

本發明中所使用之（a)聚醯胺之藉由凝膠滲透層析法（以 下，亦記作「GPC」）所測定的聚苯乙烯換算重量平均分子 量，較好的是3,000〜50,000，更好的是6,000〜30,000。就 硬化凸紋圖案之物性之觀點而言，重量平均分子量較好的 是3,000以上。又，就解析性之觀點而言，較好的是50,000 以下。作為GPC之展開溶劑，推薦四氫呋喃（以下，亦記作 「THF」）、N-甲基-2-吡咯啶酮（以下，亦記作「NMP」）。 又，分子量係根據使用標準單分散聚苯乙烯而製作之校準 曲線來求出。作為標準單分散聚苯乙烯，推薦選自昭和電 工公司製造之有機溶劑系標準試料之STANDARD SM-105 ° (b)重氮醌化合物 本發明之感光性樹脂組合物中，較為重要的是含有以下 140314.doc -16- 201011469 述通式（2)所表示之重氮醌化合物： [化 18]The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (hereinafter also referred to as "GPC") of (a) polyguanamine used in the present invention is preferably 3,000 to 50,000. Better is 6,000~30,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the hardened relief pattern. Further, from the viewpoint of analyticity, it is preferably 50,000 or less. As a developing solvent for GPC, tetrahydrofuran (hereinafter also referred to as "THF") and N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP") are recommended. Further, the molecular weight was determined from a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, STANDARD SM-105 ° (b) diazonium compound selected from the organic solvent standard sample manufactured by Showa Denko Co., Ltd. is recommended. In the photosensitive resin composition of the present invention, it is important to contain the following 140314.doc -16- 201011469 The diazonium compound represented by the general formula (2): [Chem. 18]

(2) 1~10之1價有機基，(2) 1 to 10% of the organic group,

a及b为別獨立為〇〜4之整數，c為〇〜$之整數，複數個q内之 任一個為由以下： [化 19]a and b are integers independently of 〇~4, c is an integer of 〇~$, and any one of the plural q is the following: [Chem. 19]

所表示之2個基之任一個’其餘為氫原子}。 其中，較好的是以下述式所表示之化合物： [化 20]Any one of the two bases indicated is 'the rest is a hydrogen atom}. Among them, preferred are compounds represented by the following formula: [Chem. 20]

{式中，Z!、Z2、a、b及Q與·上述通式（2)中分別定義者相 同} 〇 進而’就製造之簡便性方面而言，最好的是以下述式所 表示之結構： 140314.doc • 17- (3) 201011469 [化 21]In the formula, Z!, Z2, a, b, and Q are the same as those defined in the above formula (2). Further, in terms of ease of manufacture, it is preferably represented by the following formula. Structure: 140314.doc • 17- (3) 201011469 [Chem. 21]

{式中’ Q與上述通式（2)中定義者相同）。 該等（b)重氮醌化合物可單獨使用，或者亦可混合使 用。又，至於（b)重氮醌化合物相對於聚醯胺之調配 量，係相對於（a)聚醯胺100質量份而為hWO質量份，若調 配量未滿1質量份，則樹脂之光圖案化性變得不良，反 之，若超過100質量份，則加熱硬化後所形成之膜之拉伸 伸長率顯著下降。 Ο)重氮醌化合物之調配量相對於（a)聚醯胺1〇〇質量份， 更好的疋3〜50質量份’尤其好的是$〜質量份。 (b)重氮醌化合物可藉由將上述通式（2)之卩全為氫原子之 酚系化合物作為原料，對其羥基進行醌二疊氮磺酸酯化而 製造。 在進行醌二疊氮磺酸醋化時，可使用具有丨’孓萘醌二疊 氮結構之各種磺酸衍生物，較好的是使用丨，2_萘醌二疊氮_ 4-磺醯函或者i’2-萘醌二#氮_5_磺_。料構成磺醯齒 部分之齒素原有氣原子或漠原子，通常較好的是氣原 子’因此，作為醋化劑，較好的是i，2_蔡酿二疊氮·4_石黃酿 氣或者1，2-蔡酿二疊氣-5-績酿氣。又，該等酯化劑可單獨 使用，或者亦可混合使用。 該反應通常係於脫*化氫劑存在下進行。作為脫齒化氮 140314.doc -18- 201011469 劑’可舉出：通常可與齒化氫形成鹽之鹼性化合物，例如 碳酸鈉、碳酸氫鈉等無機鹼類，乙基胺、乙醇胺、二乙基 胺、二乙醇胺、三乙基胺、三乙醇胺、N，N_二甲基苯胺、 N，N-二乙基苯胺、吼啶等胺類等。 • 脫_化氫劑可單獨使用，或者混合複數種使用，亦可分 階段添加複數種而使用。 酉日化反應通常係於溶劑中進行。作為反應溶劑，可使 攀 用一氧戊環、1，4-一”亏院、四氫吱喃、二乙喊等喊類， 乙二醇二甲醚、二乙二醇二¥醚等乙二醇二甲醚類，r丁 内酯、δ-内酯等内酯類，N_甲基_2_吡咯啶酮等醯胺類，丙 酮、甲基乙基酮等脂肪族酮類等，但並不限定於該等。 (C)其他成分 於本發明之感光性樹脂組合物中，視需要亦可添加染 料、界面活性劑、用以提高與基板之密著性之接著助劑、 溶解促進劑、交聯劑。 • 對上述添加劑加以更具體之敍述，作為染料，例如可舉 出甲基紫、結晶紫、孔雀綠等。 • 作為染料之添加量，相對於（a)聚醯胺100質量份，較好 的是0.1〜30質量份。 又，作為界面活性劑，可舉出：例如包含聚丙二醇或聚 氧乙烯月桂键等$二醇類或該等之衍生物之非離子系界面 活性劑·，例wFlu〇rad(註冊商標，商品名，住友3M公司製 造）、Megafac(註冊商標，商品名，大日本油墨化學工業 (Dainippon Ink and Chemicals)公司製造）或者Lu—呵註 140314.doc •19- 201011469 冊商標，商品名，旭硝子公司製造）等氟系界面活性劑； 例如ΚΡ341(商品名，信越化學工業公司製造）、dbe(商品 名，Chisso公司製造）、GLANOL(商品名，共榮社化學公 司製造）等有機矽氧烷界面活性劑。 作為於感光性樹脂組合物中含有界面活性劑時之含量， 相對於（a)聚醯胺100質量份，較好的是〇 〇1〜1〇質量份。{wherein 'Q is the same as defined in the above formula (2)). These (b) diazonium compounds may be used singly or in combination. Further, the amount of the (b) diazonium compound to the polyamine is hWO parts by mass based on 100 parts by mass of the (a) polyamine, and the light of the resin is less than 1 part by mass. The patterning property is deteriorated. On the other hand, when it exceeds 100 parts by mass, the tensile elongation of the film formed by heat curing is remarkably lowered. The amount of the diazonium compound to be compounded is preferably from 3 to 50 parts by mass, more preferably from 10,000 parts by mass, based on 1 part by mass of the (a) polyamine. (b) The diazonium compound can be produced by subjecting a phenolic compound having a hydrogen atom of the above formula (2) as a raw material to a quinonediazide sulfonate of a hydroxyl group. In the acetalization of quinonediazide sulfonate, various sulfonic acid derivatives having a quinone naphthoquinonediazide structure may be used, preferably hydrazine, 2-naphthoquinonediazide-4-sulfonate Letter or i'2-naphthoquinone #N nitrogen_5_sulfon_. The material constitutes the original gas atom or the desert atom of the tooth of the sulphur tooth, and is usually preferably a gas atom. Therefore, as a acetating agent, it is preferred that i, 2_Cello diazide·4_石黄Brewing gas or 1,2-Caidian two stacks of gas -5 - brewing gas. Further, the esterifying agents may be used singly or in combination. This reaction is usually carried out in the presence of a dehydrogenating agent. As the de-agitating nitrogen 140314.doc -18-201011469 agent, a basic compound which can form a salt with hydrogenated hydrogen, such as an inorganic base such as sodium carbonate or sodium hydrogencarbonate, ethylamine, ethanolamine or the like, may be mentioned. An amine such as ethylamine, diethanolamine, triethylamine, triethanolamine, N,N-dimethylaniline, N,N-diethylaniline or acridine. • The dehydrogenating agent may be used singly or in combination of a plurality of types, or may be added in multiple stages. The daily reaction is usually carried out in a solvent. As a reaction solvent, it can be used to climb monooxylan, 1,4-one "defective", tetrahydrofuran, and two screams, such as ethylene glycol dimethyl ether, diethylene glycol diacetate, etc. Glycol dimethyl ether, lactones such as r butyrolactone and δ-lactone, guanamines such as N-methyl-2-pyrrolidinone, aliphatic ketones such as acetone and methyl ethyl ketone, etc. (C) Other components In the photosensitive resin composition of the present invention, a dye, a surfactant, a bonding aid for improving the adhesion to the substrate, and a dissolution may be added as needed. Promoter and cross-linking agent. The above-mentioned additives are more specifically described. Examples of the dye include methyl violet, crystal violet, malachite green, etc. • As the amount of dye added, relative to (a) polyamine 100 parts by mass, preferably 0.1 to 30 parts by mass. Further, examples of the surfactant include a non-ionic system including a glycol such as polypropylene glycol or a polyoxyethylene laurel bond or a derivative thereof. Surfactant ·, for example, wFlu〇rad (registered trademark, trade name, manufactured by Sumitomo 3M), Megafac (registered trademark, business Product name, manufactured by Dainippon Ink and Chemicals, or Lu-Im. 140314.doc • 19-201011469 Trademark, trade name, manufactured by Asahi Glass Co., Ltd.) Fluoride-based surfactant; for example, ΚΡ341 (trade name) An organic oxoxane surfactant such as dbe (trade name, manufactured by Chisso Co., Ltd.) or GLANOL (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), which is manufactured by Shin-Etsu Chemical Co., Ltd., and contains an interface activity in a photosensitive resin composition. The content of the agent is preferably from 1 to 1 part by mass based on 100 parts by mass of the (a) polyamine.

又’作為接著助劑，例如可舉出烷基咪唑啉、丁酸、烷 基酸、聚羥基苯乙烯、聚乙烯甲醚、第三丁基酚醛清漆、 環氧矽烷、環氧聚合物等、以及各種矽烷偶合劑。 作為石夕烧偶合劑之具體的較佳例，例如可舉出：冰苯 基-3-胺基丙基三烷氧基矽烷、3_巯基丙基三烷氧基矽烷、 2-(二烷氧基矽烷基乙基）吡啶、3甲基丙烯醯氧基丙基三 烷氧基矽烷、3-甲基丙烯醯氧基丙基二烷氧基烷基矽烷、Further, examples of the auxiliary agent include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, third butyl novolac, epoxy decane, and epoxy polymer. And various decane coupling agents. Specific preferred examples of the zebra calcining agent include, for example, ice phenyl-3-aminopropyltrialkoxydecane, 3-mercaptopropyltrialkoxydecane, and 2-(dioxane). Oxidylalkylethyl)pyridine, 3-methacryloxypropyltrialkoxydecane, 3-methylpropenyloxypropyldialkoxyalkylnonane,

3-縮水甘油氧基丙基三烷氧基矽烷、％縮水甘油氧基丙基 二烷氧基烷基矽烷、3-胺基丙基三烷氧基矽烷、％胺基丙 基二烷氧基烷基矽烷、該等之酸酐或酸二酐之反應物、將 3-胺基丙基三烷氧基矽烷或3_胺基丙基二烷氧基烷基矽烷 之胺基變換成胺基甲酸酯基或脲基者等。再者，作為此時 之烧基T舉出甲基、乙基、丁基等，作為酸肝可舉出 馬來酸酐、鄰苯二甲酸酐等，作為H可舉出均苯四 3,3’，4,4’-二苯甲酮四甲酸二酐、4,4，_氧基二鄰 甲酸二酐 本甲酸肝等，作為胺基▼酸醋基，可舉出第三丁氧基 幾基胺基等，作為脲基，可舉出苯基胺基麟胺基等。 作為3有接著助劑時之含量，相對於（a)聚醯胺質量 I403l4.doc -20- 201011469 份’較好的是〇 ^30質量份。 又，作為溶解促進劑，較好的是具有酚性羥基之化合 物例如可舉出：雙酚、MtrisPC、MtetraPC等直鏈狀酚 化 口物，TrisP-HAP、TrisP-PHBA、TrisP-PA等非直鏈狀 酚化σ物（均為本州化學工業公司製造）；二苯基甲烷之 , 2 5個酚取代體、3,3-二笨基丙烷之1〜5個酚取代體；2,2_ 雙（3胺基-4-經基笨基）六氟丙院與5_降蒱烯_2,3_二甲酸酐 φ 之1比2之反應物、雙（3·胺基-4-羥基苯基）颯與1，2_環己基 二甲酸酐之1比2之反應物等。 作為含有溶解促進劑時之含量，相對於（a)聚醯胺1〇〇質 量份’較好的是〇·1〜30質量份。 作為交聯劑，可舉出：^又孓四（對羥基苯基）乙烷、四 縮水甘油醚、甘油三縮水甘油醚、鄰第二丁基苯基縮水甘 油醚、1，6-雙（2,3-環氧丙氧基）萘、二甘油聚縮水甘油醚、 聚乙二醇縮水甘油醚等環氧化合物；乙醯丙酮鋁（ΠΙ)鹽、 • 乙醯丙酮鈦（IV)鹽、乙醯丙酮鉻（m)鹽、乙醯丙酮鎂（π) 鹽、乙醯丙酮鎳（II)鹽、三氟乙醯丙酮鋁（ΙΠ)鹽、三氟乙 酿丙酮鈦（IV)鹽、三氟乙醯丙酮鉻（III)鹽、三氟乙醯丙酮 鎂（II)鹽、三氟乙醯丙酮鎳（Π)鹽等金屬螯合劑；NIKALAC MW-3 0MH、MW-100LH(商品名，三和化學工業（sanwa Chemical Industries)公司製造）、Cymel 300 > Cymel 303(商品名，Mitsui-Cytec公司製造）等三聚氰胺樹脂系交 聯劑；NIKALAC BL-60(商品名，三和化學工業公司製 造）、Cymel 1123、Micoat 102、Micoat 105(商品名， 140314.doc -21· 2010114693-glycidoxypropyl trialkoxydecane, % glycidoxypropyl dialkoxyalkyl decane, 3-aminopropyl trialkoxy decane, % aminopropyl propyl dialkoxy a reaction of an alkyl decane, such an anhydride or an acid dianhydride, converting an amine group of 3-aminopropyltrialkoxydecane or 3-aminopropyldialkoxyalkylnonane to an amine group A An acid ester group or a urea group or the like. Further, as the base T in this case, a methyl group, an ethyl group, a butyl group or the like may be mentioned, and as the acid liver, maleic anhydride, phthalic anhydride or the like may be mentioned, and H may be exemplified as H3. , 4,4'-benzophenonetetracarboxylic dianhydride, 4,4,-oxydi-orthocarboxylic acid dianhydride, formic acid liver, etc., as the amino-based acid vinegar group, a third butoxy group An amine group or the like is exemplified as the ureido group. The content of 3 as a binder is preferably 〇30 parts by mass relative to (a) the mass of the polyamine. I403l4.doc -20-201011469 parts. Further, as the dissolution promoter, a compound having a phenolic hydroxyl group is preferably a linear phenolated oral substance such as bisphenol, MtrisPC or MtetraPC, or a non-trisP-HAP, TrisP-PHBA or TrisP-PA. Linear phenolated σ (all manufactured by Honshu Chemical Industry Co., Ltd.); diphenylmethane, 25 phenolic substituents, 1 to 5 phenolic substituents of 3,3-diphenylpropane; 2,2_ Reaction of bis(3amino-4-pyridyl)hexafluoropropane with hexamidine-2,3-dicarboxylic anhydride φ of 1 to 2, bis(3·amino-4-hydroxyl) a reaction of phenyl) hydrazine with 1, 2 - cyclohexyl dicarboxylic anhydride of 1 to 2, and the like. The content in the case where the dissolution promoter is contained is preferably from 1 to 30 parts by mass based on the mass fraction of (a) polyamine. Examples of the crosslinking agent include tetrakis(p-hydroxyphenyl)ethane, tetraglycidyl ether, glycerol triglycidyl ether, o-t-butylphenyl glycidyl ether, and 1,6-bis ( Epoxy compounds such as 2,3-epoxypropoxy)naphthalene, diglycerin polyglycidyl ether, polyethylene glycol glycidyl ether; acetoacetate aluminum (ruthenium) salt, • titanium acetylacetonate (IV) salt, Ethyl acetonate chromium (m) salt, acetoacetone magnesium (π) salt, acetamidine acetone nickel (II) salt, trifluoroacetic acid aluminum (ruthenium) salt, trifluoroethylene acetone (IV) salt, three Metal chelating agent such as fluoroacetic acid acetone chromium (III) salt, trifluoroacetic acid magnesium (II) salt, trifluoroacetone acetone nickel (ruthenium) salt; NIKALAC MW-3 0MH, MW-100LH (trade name, three And melamine resin-based cross-linking agent such as Cymel 300 > Cymel 303 (trade name, manufactured by Mitsui-Cytec Co., Ltd.); NIKALAC BL-60 (trade name, manufactured by Sanwa Chemical Industry Co., Ltd.) ), Cymel 1123, Micoat 102, Micoat 105 (trade name, 140314.doc -21· 201011469)

Mitsui-Cytec公司製造）等苯胍畊系交聯劑；1^〖/〇>八(：]^：^-270、MX-280、MX-290(商品名，三和化學工業公司製造） 專腺樹脂系樹脂。 作為交聯劑之添加量’相對於（a)聚醯胺丨〇〇質量份，較 好的是0.1〜30質量份。 (D)溶劑Benzene cultivating cross-linking agent manufactured by Mitsui-Cytec Co., Ltd.; 1^ 〖/〇> 八(:]^:^-270, MX-280, MX-290 (trade name, manufactured by Sanwa Chemical Industry Co., Ltd.) The specific amount of the crosslinking agent is preferably 0.1 to 30 parts by mass based on the mass part of the (a) polyamidoxime. (D) Solvent

本發明中’亦可將該等成分溶解於溶劑中而製成清漆 狀，從而用作感光性樹脂組合物之溶液。作為此種溶劑， 可單獨或混合使用：N-曱基-2-吡咯啶酮、γ_ 丁内酯、N，N_ 二曱基乙醯胺、二甲基亞砜、二乙二醇二曱醚、二乙二醇 一***、一乙一醇二丁醚、丙二醇單甲醚、二丙二醇單甲 鍵、丙二醇單甲醚乙酸酯、乳酸甲酯、乳酸乙酯、乳酸丁 自日1,3 丁一醇乙酸甲酯、Μ _丁二醇·3_單甲醚、丙酮酸 曱S旨、丙胸酸乙酉旨、 T氧基丙馱甲酯等。該等溶劑中， 就對光阻劑等之影孿舫小古；工_ ± 寻（元響較}方面而吕，較好的是非醯胺系溶 劑，作為具體之更佳例，舉In the present invention, the components may be dissolved in a solvent to form a varnish, and used as a solution of the photosensitive resin composition. As such a solvent, it can be used singly or in combination: N-mercapto-2-pyrrolidone, γ-butyrolactone, N,N-dimercaptoacetamide, dimethyl sulfoxide, diethylene glycol dioxime ether , diethylene glycol monoethyl ether, monoethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl bond, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, lactate Ding, 1, 3 Monool methyl acetate, Μ-butanediol·3_monomethyl ether, pyruvate strontium S, thymidine, T-oxypropyl methacrylate, and the like. Among these solvents, the effect on the photoresist, etc. is small; the work_± 寻(元响比} aspect, and the non-amined solvent is preferred, as a more specific example,

J卒γ- 丁内酯、環戊酮、環己 嗣、異佛爾綱等。 為於感光性樹脂組合物中含有溶劑時之含量相對; ⑷聚醯胺⑽質量份，較好的是5〇〜1〇〇〇質量份。 〈硬化凸紋圖案以及半導體裝置之製造方法&gt; 凸咬圖幸：：感光性樹脂組合物塗佈於基板上來製造硬4 凸紋圖案之方法加以具體說明。 輥塗機之輥塗， 陶瓷基板、鋁基 首先藉由使用旋塗機之旋塗或者使用 將感光性樹脂組合物塗佈於例如硬晶圓、 140314.doc •22· 201011469 :等基板上’而獲得附有樹脂媒之基板。使用烘箱或加熱 板，以50〜14(TC將其進行乾燥而除去溶劑。 ^著，使用接觸式對準機或步進機，經由光罩進行光化 射線之曝光，或直接照射光線、電子束或者離子束。 然後’以顯影液將曝光部或照射部溶出或除去，接著， ^好^進行淋洗液之淋洗，藉此而獲得所需之凸紋圖 影方法，可為喷霧、授摔、浸潰、超音波等方 式。淋洗液可使用蒸餾水、去離子水等。 用以對由感純樹脂組合物所形成之樹脂 顯影液為溶解除去聚酿胺者，且必須為溶解有驗性化合物 =:溶液。溶解於顯影液中之驗性化合物可為無機驗 性化合物、有機鹼性化合物之任一者。 2為職機驗性化合物，例如可舉出：氫氧_、Μ 、虱氧化鉀、磷酸氫二銨、磷酸氫二鉀、磷酸氛二 =、石夕酸鐘、石夕酸納、简、碳酸鐘、碳酸納、碳酸 鉀、硼酸鋰、硼酸鈉、硼酸鉀、氨等。 又’料該有機驗性化合物，例如可舉出：氫氧化四甲 基銨、氫氧化四乙基錄、氫氧化三曱基經基乙基錢、甲某 胺、二甲基胺、三甲基胺、單乙基胺、二乙基胺、三乙i :、正丙基胺、二正丙基胺、異丙基胺、二異丙基胺、甲 基胺、二甲基乙醇胺、乙醇胺、三乙醇胺等。 進而：視需要可於上述驗性水溶液令添加適量甲醇、乙 醇丙醇、乙二醇等水溶性右娘、、贫漸丨W 穩定劑、樹脂之溶解抑止劑等劑、界面活性劑、保存 140314.doc -23- 201011469 最後，對所獲得之凸紋圖案進行加熱處理，而可形成具 有聚苯并嘮唑結構及/或聚醯亞胺結構之硬化凸紋圖案。 作為用以進行加熱處理之加熱裝置，可使用洪箱爐、加 熱板、立式爐、輸送帶式爐、壓力烘箱等，作為加熱方 法，推薦利用熱風、紅外線、電磁感應之加熱。温度較好 的是200〜450°C，更好的是250〜400°C。加熱時間較好的是 15分鐘〜8小時，更好的是1小時〜4小時。環境氣體較好的 是於氮氣、氬氣等惰性氣體中。 半導體裝置可藉由將硬化凸紋圖案作為表面保護膜、層 間絕緣膜 '再配線用絕緣膜、倒裝晶片裝置用保護膜、或 者具有凸塊結構之裝置之保護膜，並與公知之半導體震置 之製造方法組合而製造。 藉由上述製造方法而製作之硬化凸紋圖案不僅用於半導 體用途，而且亦用作多層電路之層間絕緣膜或可撓性銅箱 板之保護層、阻焊膜或液晶配向膜等。 [實施例] 根據參考例、實施例、比較例對本發明加以更具體之說 明。 &lt;聚醯胺之合成&gt; [參考例1] 於容量為2升之可分離式燒瓶中’於室溫（25。〇下將2,2-雙（3-胺基-4-羥基苯基）六氟丙烷197.8 g(〇.54 mol)、吡咬 71.2 g(〇.9 mol)、N，N-二甲基乙酿胺（以下，亦記作 「DMAc」）692 g進行混合攪拌，使二胺溶解。於其中， 140314.doc • 24· 4 201011469 自滴液漏斗滴加另外使5-降福烯-2,3-二甲酸針29.6 g(0.18 mol)溶解於二 乙二醇二甲醚（以下，亦記作 DMDGj )88 g中而成者。滴加所需之時間為4〇分鐘，反應液溫最大為 28°C。 '商加結束後，藉由熱水浴加溫至50。〇並攪拌1 8小時後， 進行反應液之IR光譜（infrared spectr〇sc〇py，紅外線光譜） 之測定，確認到表現出1385 em·1及1772 cm·1之醯亞胺基的 特性吸收。J γ-butyrolactone, cyclopentanone, cyclohexanthene, isophora and so on. The content in the case where the solvent is contained in the photosensitive resin composition is relatively large; (4) The polyamine (10) parts by mass is preferably 5 Å to 1 Å by mass. <Method for Producing Hardened Relief Pattern and Semiconductor Device> For example, a method of producing a hard 4 relief pattern by applying a photosensitive resin composition onto a substrate will be specifically described. The roll coating of the roll coater, the ceramic substrate, and the aluminum base are first applied by spin coating using a spin coater or by using a photosensitive resin composition on, for example, a hard wafer, 140314.doc •22·201011469: A substrate with a resin medium is obtained. Use an oven or a hot plate to remove the solvent at 50~14 (TC). Using a contact aligner or stepper, expose the actinic ray through the reticle, or directly illuminate the light, electrons Beam or ion beam. Then 'dissolve or remove the exposed portion or the irradiated portion with a developing solution, and then, rinse the eluent to obtain the desired embossing method, which can be a spray , such as dropping, dipping, ultrasonic, etc. The eluent can be distilled water, deionized water, etc. It is used to dissolve the resin developing solution formed by the sensible resin composition to remove the polyamine, and must be The test compound dissolved in the developer may be any one of an inorganic compound and an organic basic compound. 2 For the test compound, for example, hydrogen oxygen _ , Μ, 虱 虱 虱 、, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid arsenal =, oligo acid clock, sodium silicate, simple, carbonic acid clock, sodium carbonate, potassium carbonate, lithium borate, sodium borate, boric acid Potassium, ammonia, etc. For example, tetramethylammonium hydroxide, tetraethyl hydride, trimethyl hydrazide, ethyl methylamine, methylamine, dimethylamine, trimethylamine, monoethylamine, Diethylamine, triethyl i:, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methylamine, dimethylethanolamine, ethanolamine, triethanolamine, etc. It is necessary to add an appropriate amount of methanol, ethanol propanol, ethylene glycol, etc., such as water-soluble right mother, depleted W stabilizer, resin dissolution inhibitor, etc., surfactant, and storage in the above-mentioned aqueous solution. 140314.doc - 23- 201011469 Finally, the obtained relief pattern is heat-treated to form a hardened relief pattern having a polybenzoxazole structure and/or a polyimide structure. As a heating device for performing heat treatment, It can be used as a heating method, such as a hot box furnace, a heating plate, a vertical furnace, a conveyor belt furnace, a pressure oven, etc., and it is recommended to use hot air, infrared, electromagnetic induction heating. The temperature is preferably 200 to 450 ° C, better. It is 250 to 400 ° C. The heating time is preferably 15 minutes. 8 hours, more preferably 1 hour to 4 hours. The ambient gas is preferably in an inert gas such as nitrogen or argon. The semiconductor device can be rewired by using a hardened relief pattern as a surface protective film and an interlayer insulating film. A protective film made of an insulating film, a protective film for a flip chip device, or a device having a bump structure is produced in combination with a known method of mounting a semiconductor device. The hardened relief pattern produced by the above manufacturing method is not only It is used for semiconductor applications, and is also used as an interlayer insulating film of a multilayer circuit or a protective layer of a flexible copper box, a solder resist film, a liquid crystal alignment film, etc. [Embodiment] The present invention is based on Reference Examples, Examples, and Comparative Examples. More specifically, &lt;Synthesis of Polyamide&gt; [Reference Example 1] In room temperature (25) in a separable flask having a capacity of 2 liters. 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 197.8 g (〇.54 mol), 71.2 g (〇.9 mol), N,N-dimethyl Ethylamine (hereinafter also referred to as "DMAc") 692 g was mixed and stirred to dissolve the diamine. Among them, 140314.doc • 24· 4 201011469 29.6 g (0.18 mol) of 5-norfos-2,3-dicarboxylic acid needle was dissolved in diethylene glycol dimethyl ether by dropping from a dropping funnel (hereinafter, Also known as DMDGj) 88 g. The time required for the dropwise addition was 4 minutes, and the temperature of the reaction liquid was at most 28 °C. After the end of the business, warm up to 50 by hot water bath. After stirring for 18 hours, the IR spectrum of the reaction mixture (infrared spectr〇sc〇py, infrared spectrum) was measured, and it was confirmed that the characteristic absorption of the imino group of 1385 em·1 and 1772 cm·1 was exhibited.

然後，藉由水浴將其冷卻至8。〇，於其中，自滴液漏斗 滴加另外使4,4·-二苯基醚二甲醯氣132 8 g(〇 45 m〇1)溶解 於DMDG 398 g中而成者。滴加所需之時間為8〇分鐘，反 應液溫最大為12。(：。 自滴加結束至3小時後，於高速攪拌下將上述反應液滴 加於12 L之水中，使聚合物分散析出，並回收該聚合物， 適當進行水洗、脫水後，實施真空乾燥而獲得聚醯胺（p_ 1)。 以上述方式合成之聚醯胺（P—i)之藉由Gpc所測定的重量 平均分子量’以聚苯乙烯換算計為8,9〇〇。 [參考例2] 於容量為2升之可分離式燒瓶中，於乾燥氮氣流下使2,2_ 雙（3-胺基-4-羥基苯基）六氟丙烷293 〇 g(〇8瓜〇1)與。比啶 253.1 g(3.2 mol)溶解於丙酮2.0升中，並冷卻至_15。〇。以 反應液之溫度不超過吖之方式’於其中滴加溶解於丙酮 500⑹中之㉟苯三甲酸酐醯氣370.6 g(176㈣）。滴加結 140314.doc -25- 201011469 束後，於〇°C下反應4小時。 以蒸發器將該溶液濃縮後’投入至石油趟5升中，而獲 得酸Sf (6FA)。於容莖為3升之可分離式燒瓶中，混合該酸 酐（6FA)357.2 g(0.5 mol)、3_ 羥基苄醇 136.6 g(i.i m〇l)、 NMP 1.25升、》比咬87·0 g(l.l mol)後，於室溫下授拌！6小 時來進行酯化。其後’加入1-羥基·1，2,3-苯并三咬148.64 g(l.l mol) ’於冰浴冷卻下滴加使二環己基碳二醯亞胺 (DCC)227.0 g(l.l mol)溶解於NMP 230 g中而成者，從而 製成二羧酸衍生物。 然後’於該反應液中加入使4,4’-二胺基二苯基趟lio.i g(0.55 mol)溶解於NMP 0.35升中而成者，於室溫下攪拌反 應3小時。 其後’加入5-降宿烯_2,3_二甲酸酐32.8 g(〇.2 mol)，進 而於室溫下反應4小時。過濾該反應液而除去不溶成分 後，投入至水/曱醇=10/1之溶液中，藉由過濾來收集沈澱 物並進行減壓乾燥，而獲得Gpc分子量為9,400(聚苯乙烯 換算）之聚醯胺（P-2)。 &lt;重氮醌化合物之合成&gt; [參考例3] 於附設有攪拌機、滴液漏斗以及溫度計之1升的可分離 式燒版中’使用作為聚經基化合物的以f述結構式： 140314.doc 201011469 [化 22]Then, it was cooled to 8 by a water bath. In the above, a solution of 4,4·-diphenyl ether dimethyl hydrazine 13 8 g (〇 45 m〇1) was dissolved in DMDG 398 g from the dropping funnel. The time required for the addition is 8 minutes and the reaction temperature is at most 12. (: After the completion of the dropwise addition to 3 hours, the above reaction liquid was added to 12 L of water under high-speed stirring to disperse the polymer, and the polymer was recovered, washed with water, dehydrated, and vacuum dried. The polyamine (p-1) was obtained. The weight average molecular weight measured by Gpc of the polyamine (P-i) synthesized in the above manner was 8,9 Å in terms of polystyrene. [Reference Example 2] In a separable flask having a capacity of 2 liters, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 293 〇g (〇8 〇 〇 1) was mixed under a dry nitrogen stream. 253.1 g (3.2 mol) of pyridine is dissolved in 2.0 liters of acetone, and cooled to _15. 〇. 35 benzenetricarboxylic anhydride hydrazine dissolved in acetone 500 (6) is added dropwise thereto in such a manner that the temperature of the reaction liquid does not exceed 吖370.6 g (176 (4)). Adding the knot 140314.doc -25- 201011469 After the bundle, react at 〇 ° C for 4 hours. Concentrate the solution with an evaporator and then put it into 5 liters of petroleum hydrazine to obtain acid Sf ( 6FA). In a separable flask of 3 liters, the anhydride (6FA) was mixed with 357.2 g (0.5 mol) and 3-hydroxybenzyl alcohol 136.6 g ( Ii m〇l), NMP 1.25 liters, "bite 87. 0 g (ll mol), then mix at room temperature! 6 hours for esterification. Then add '1-hydroxy·1,2,3 - Benzene three bites 148.64 g (ll mol) 'added under ice cooling to dicyclohexylcarbodiimide (DCC) 227.0 g (ll mol) dissolved in NMP 230 g a dicarboxylic acid derivative. Then, a solution of 4,4'-diaminodiphenylphosphonium.ig (0.55 mol) dissolved in NMP 0.35 liter was added to the reaction mixture, and the reaction was stirred at room temperature. 3 hours. Thereafter, 32.8 g (〇. 2 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added, and further reacted at room temperature for 4 hours. The reaction solution was filtered to remove insoluble components, and then poured into In a solution of water/sterol = 10/1, the precipitate was collected by filtration and dried under reduced pressure to obtain a polydecylamine (P-2) having a Gpc molecular weight of 9,400 (in terms of polystyrene). Synthesis of a nitrogen hydrazine compound &gt; [Reference Example 3] In a separable burn-in plate to which 1 liter of a stirrer, a dropping funnel, and a thermometer are attached, 'the structural formula is used as a poly-based compound: 140314.doc 201011469 [化22]

-OH CHj 所表示之化合物（旭有機材工業公司製造，商品名：mMC_ BZ)15.0 g(0.05 mol) ’將相當於其〇H基之9〇则1%之量的 1，2-萘醌一疊氮-4-磺醯氣24.2 g(〇.09 m〇l)攪拌溶解於丙酮 • 197.4 g令後’於恆溫槽中將燒瓶調整為3(TC。於其中，以 固定速度以30分鐘滴加用丙酮47 8 g將三乙基胺9 % g稀釋 而成者。此時，反應液係使用冰水浴而將溫度控制在 20〜30 C之範圍。滴加結束後，進而於2〇。〇下攪拌放置3〇 分鐘後，一次性投入濃度為36質量％之鹽酸水溶液36 g， 接著，以冰水浴將反應液冷卻，對析出之固形物進行抽氣 過濾。將此時所獲得之濾液於攪拌下以1小時滴加至濃度 為0.5質量％之鹽酸水溶液5升中，使目標物析出，進行抽 氣過濾後加以回收。將所獲得之濾餅狀回收物再次分散於 離子交換水3升令，進行攪拌、清洗、過濾回收，且重複3 •次該水洗操作。最後，於40°C下將所獲得之濾餅狀物真空 •乾燥48小時，而獲得感光性重氮萘醌化合物 [參考例4] 除了於參考例3中使1，2-萘醌二疊氮-4-確醯氣成為25.5 g(0.095 mol)以外’進行相同之操作，而獲得感光性重氮 萘醌化合物（Q-2)。 140314.doc -27- 201011469 [參考例5] 除了於參考例3中使1，2-萘醌二疊氮-4-磺醯氯成為丨’2萘 醌二疊氮-5-磺醯氯24_2 g(0.09 mol)以外，進行相同之操 作，而獲得感光性重氮萘醌化合物（Q·3)。 [參考例6] 於附設有攪拌機、滴液漏斗以及溫度計之1升的可分離 式燒瓶中，使用作為聚羥基化合物的以下述，结構式： [化 23]-OH CHj Compound (manufactured by Asahi Organic Materials Co., Ltd., trade name: mMC_BZ) 15.0 g (0.05 mol) '1,2-naphthoquinone equivalent to 9% of its 〇H group One azide-4-sulfonium gas 24.2 g (〇.09 m〇l) was stirred and dissolved in acetone • After 197.4 g, the flask was adjusted to 3 (TC in a constant temperature bath), at a fixed speed for 30 minutes. The solution was diluted with 47 8 g of acetone to triethylamine 9 % g. At this time, the reaction liquid was controlled in an ice water bath to control the temperature in the range of 20 to 30 C. After the completion of the dropwise addition, further 2 〇 After stirring for 3 minutes, the mixture was poured into 36 g of a 36% by mass aqueous hydrochloric acid solution, and then the reaction liquid was cooled in an ice water bath, and the precipitated solid matter was subjected to suction filtration. The filtrate was added dropwise to 5 liters of a hydrochloric acid aqueous solution having a concentration of 0.5% by mass for 1 hour, and the target product was precipitated, and subjected to suction filtration to be recovered. The obtained cake-like recovered product was again dispersed in ion-exchanged water. 3 liters, stir, wash, filter and recycle, and repeat 3 times of this washing operation. Finally, The obtained filter cake was vacuum-dried at 40 ° C for 48 hours to obtain a photosensitive diazonaphthoquinone compound [Reference Example 4] except that 1,2-naphthoquinonediazide was used in Reference Example 3 4-According to the fact that the helium gas becomes 25.5 g (0.095 mol), the same operation is carried out to obtain the photosensitive diazonaphthoquinone compound (Q-2). 140314.doc -27- 201011469 [Reference Example 5] Except for the reference example 3, except that 1,2-naphthoquinonediazide-4-sulfonyl chloride was changed to 丨'2 naphthoquinonediazide-5-sulfonyl chloride 24_2 g (0.09 mol), and the same operation was carried out to obtain photosensitivity. The diazonaphthoquinone compound (Q·3). [Reference Example 6] In a separable flask equipped with a stirrer, a dropping funnel, and a thermometer, the following formula was used as a polyhydroxy compound. twenty three]

所表示之化合物（本州化學工業公司製造，商品名：丁士1&gt;-PA)30 g(0.0707 mol)’將相當於其〇H基之76 7 m〇i%之量 的1，2-萘醌二疊氮_4_磺醯氣43.69 g(〇.163 m〇i)攪拌溶解於 丙酮300 g中後，於恆溫槽中將燒瓶調整為3〇它。然後，將 三乙基胺2L0 g溶解於丙酮18 g中，投入滴液漏斗後，以 3、〇分鐘將其滴加於燒瓶t。滴加結束後，進而連續授摔3〇 分鐘’接著’滴加鹽酸’進―步授拌騎鐘而使反應結 束…、後’進仃過濾而將三乙基胺鹽酸鹽除去。一面攪 拌，一面將此處所獲得之渡液滴加於混合授拌有純水购 140314.doc -28- 201011469 g與鹽酸30 g之3升的燒杯中而獲得析出物。對該析出物進 行水洗、過濾之後，於40°C、減壓下乾燥48小時，而獲得 感光性重氮萘醌化合物（Q-4)。 [參考例7] 除了於參考例6中使1，2-萘酿二疊氮-4-磺醯氣成為53.19 g(0.198 mol)以外，進行相同之操作，而獲得感光性重氮 萘醌化合物（Q-5)。 [參考例8] 除了於參考例6中使1，2-萘醌二疊氮_4_磺醯氣成為12_萘 酉昆二疊氮-5-續醯氣43.69 g(0.163 mol)以外，進行相同之操 作，而獲得感光性重氮萘醌化合物（Q-6)。 [參考例9] 於附設有攪拌機、滴液漏斗以及溫度計之1升的可分離 式燒瓶中，使用作為聚羥基化合物的以下述結構式： [化 24]The compound represented by the company (manufactured by Honshu Chemical Industry Co., Ltd., trade name: Dingshi 1&gt;-PA) 30 g (0.0707 mol) '1,2-naphthalene equivalent to 76 7 m〇i% of its 〇H group After the hydrazine diazide_4_sulfonate gas 43.69 g (〇.163 m〇i) was stirred and dissolved in 300 g of acetone, the flask was adjusted to 3 Torr in a thermostat. Then, triethylamine 2L0 g was dissolved in 18 g of acetone, placed in a dropping funnel, and then added dropwise to the flask t in 3 minutes. After the completion of the dropwise addition, the continuous dropping was carried out for 3 minutes, and then the dropwise addition of hydrochloric acid was carried out to carry out the reaction of the cycle clock, and the reaction was carried out, and the triethylamine hydrochloride was removed by filtration. While stirring, the precipitate obtained here was added to a beaker which was mixed with pure water and purchased in a 3 liter beaker of pure water of 140314.doc -28-201011469 g and 30 g of hydrochloric acid to obtain a precipitate. The precipitate was washed with water and filtered, and then dried at 40 ° C for 48 hours under reduced pressure to obtain a photosensitive diazonaphthoquinone compound (Q-4). [Reference Example 7] A photosensitive diazonaphthoquinone compound was obtained by performing the same operation except that the 1,2-naphthalene diazide-4-sulfonium gas was changed to 53.19 g (0.198 mol) in Reference Example 6. (Q-5). [Reference Example 8] Except that in the Reference Example 6, 1,2-naphthoquinonediazide_4_sulfonium gas was changed to 12_naphthoquinonediazide-5-continued helium gas of 43.69 g (0.163 mol), The same operation was carried out to obtain a photosensitive diazonaphthoquinone compound (Q-6). [Reference Example 9] In a 1 liter separable flask equipped with a stirrer, a dropping funnel, and a thermometer, the following structural formula was used as a polyhydroxy compound: [Chem. 24]

所表示之化合物（本州化學工業公司製造，商品名：Bisp_ AP)29.36 g(0.100 mol)，將相當於其 〇H 基之 9〇 m〇1% 之量 的1，2-萘醌一疊氮-4-磺醯氯48.36 g(〇.180 m〇i)攪拌溶解於 丙酮300 g中後，於恆溫槽中將燒瓶調整為3〇&lt;^。然後將 三乙基胺19.1 g溶解於丙酮18 g中，投入滴液漏斗後以 140314.doc -29- 201011469 30分鐘將其滴加於燒瓶中。滴加結束後，進而連續擾拌3〇 分鐘，接著，滴加鹽酸，進一步攪拌30分鐘而使反應結 束。然後，進行過濾而將三乙基胺鹽酸鹽除去。一面攪 拌’ 一面將此處所獲得之濾液滴加於混合攪拌有純水丨64〇 g與鹽酸30 g之3公升的燒杯中而獲得析出物。對該析出物 進行水洗、過濾後，於40。(：、減壓下乾燥48小時，而獲得 感光性重氮萘醌化合物（Q-7)。 [參考例10] 於附設有攪拌機、滴液漏斗以及溫度計之1升的可分離 式燒瓶中’使用作為聚幾基化合物的以下述結構式： [化 25]The compound represented by the company (manufactured by Honshu Chemical Industry Co., Ltd., trade name: Bisp_AP) 29.36 g (0.100 mol), which is equivalent to 9〇m〇1% of its 〇H group, 1,2-naphthoquinone azide After -4-sulfonyl chloride 48.36 g (〇.180 m〇i) was stirred and dissolved in 300 g of acetone, the flask was adjusted to 3 Torr in a constant temperature bath. Then, 19.1 g of triethylamine was dissolved in 18 g of acetone, placed in a dropping funnel, and added dropwise to the flask at 140314.doc -29-201011469 for 30 minutes. After the completion of the dropwise addition, the mixture was further stirred for 3 minutes, and then hydrochloric acid was added dropwise thereto, and the mixture was further stirred for 30 minutes to complete the reaction. Then, filtration was carried out to remove triethylamine hydrochloride. The precipitate obtained here was added to a beaker which was mixed and stirred with a pure water 丨 64 〇 g and 30 g of hydrochloric acid in a 3 liter agitator to obtain a precipitate. The precipitate was washed with water and filtered, and then dried at 40. (:, drying under reduced pressure for 48 hours to obtain a photosensitive diazonaphthoquinone compound (Q-7). [Reference Example 10] In a 1 liter separable flask equipped with a stirrer, a dropping funnel, and a thermometer' The following structural formula is used as a polybasic compound: [Chem. 25]

所表示之化合物（本州化學工業公司製造，商品名：ph_ CC-AP)15.32 g(0.050 mol) ’ 將相當於其 oh基之90 mol%之 量的1，2-萘醌二疊氮-4-磺醯氣36.27 g(0.135 mol)攪拌溶解 於丙酮300 g中後，於恆溫槽中將燒瓶調整為3(rc ^然後， 將二乙基胺14.3 g溶解於丙酮丨8 g中，投入滴液漏斗後， 以30分鐘將其滴加於燒瓶中。滴加結束後，進而連續攪拌 30分鐘，接著，滴加鹽酸，進—步攪拌3〇分鐘而使反應結 束。然後，進行過濾而將三乙基胺鹽酸鹽除去。一面攪 摔，一面將此處所獲得之濾液滴加於混合攪拌有純水164〇 140314.doc -30- 201011469 g與鹽酸30 g之3升的燒杯中而獲得析出物。對該析出物進 行水洗、過濾後，於40°C、減壓下乾燥48小時，而獲得感 光性重氮萘醌化合物（Q-8)。 &lt;感光性樹脂組合物之製備及其評價&gt; [實施例1〜4及比較例1〜5 ]The compound represented (manufactured by Honshu Chemical Industry Co., Ltd., trade name: ph_CC-AP) 15.32 g (0.050 mol) '1,2-naphthoquinonediazide-4 which is equivalent to 90 mol% of its oh group - 36.27 g (0.135 mol) of sulfonium gas was dissolved in 300 g of acetone, and the flask was adjusted to 3 (rc ^ in a thermostat, then 14.3 g of diethylamine was dissolved in 8 g of acetone oxime, and dropped into a drop. After the liquid funnel, the mixture was added dropwise to the flask over 30 minutes. After the completion of the dropwise addition, the mixture was further stirred for 30 minutes, and then hydrochloric acid was added dropwise thereto, and the mixture was stirred for 3 minutes to complete the reaction. Then, filtration was carried out. The triethylamine hydrochloride was removed, and the filtrate obtained here was added to a beaker which was mixed with pure water 164〇140314.doc -30-201011469 g and 30 g of hydrochloric acid in a 3 liter beaker. The precipitate was washed with water and filtered, and then dried at 40 ° C for 48 hours under reduced pressure to obtain a photosensitive diazonaphthoquinone compound (Q-8). &lt;Preparation of photosensitive resin composition and Evaluation> [Examples 1 to 4 and Comparative Examples 1 to 5]

根據下述表1之組合，將上述各參考例中所獲得之聚醯 胺（P-1、2)100質量份、重氮酿化合物（q_i〜8)2〇質量份溶 解於GBL 200質量份中後，以〇.2 μιη之過濾器進行過濾而 製備感光性樹脂組合物’並對其圖案化特性、清漆析出穩 定性進行評價。 (1)圖案化特性評價 藉由東京電子（Tokyo Electron)公司製造之旋塗機（clean Track Mark-8)，將上述感光性樹脂組合物旋塗於6英吋之 石夕ββ圓上’利用加熱板於12〇。〇下預烘烤18〇秒’而形成 11.7 μηι之塗膜。膜厚係藉由Dainipp0n screen MFG公司製 造之膜厚測定裝置（Lambda Ace)而測定。 對於該塗膜，使用具有丨線（365 nm)之曝光波長的尼康 (Nikon)公司製造之步進機（NSR2〇〇5i8A)，通過附有測試 圖案之光罩，使曝光量階段性變化來進行曝光。 使用AZ Electronic Materials公司製造之鹼性顯影液 (AZ300MIF顯影液，2·38重量％之氫氧化四甲基銨水溶 液），於23°C之條件下，調整顯糾間對其進行顯影以使 顯影後膜厚成為9.4吨’而形成正型圖案。感光性樹脂組 a物之靈敏度及解析度示於下述表1。 140314.doc -31 - 201011469 再者，以下述方式對感光性樹脂組合物之靈敏度及解析 度進行評價。 [靈敏度（mj/cm2)】 於上述顯影時間中，可完全溶解除去塗膜之曝光部之最 小曝光量。 [解析度（μηι)] 上述曝光量下之最小解析圖案尺寸。 (2)析出穩定性評價 將所製備之感光性樹脂組合物進行過濾，並且於室溫 及-20 C下將其放置丨週後，目測觀察於清漆中是否見到固 形物之析出。表1中，於未見到析出之情形時以「〇」表 示，於見到析出之情形時以「X」表示。 [表1] 表1According to the combination of the following Table 1, 100 parts by mass of the polydecylamine (P-1, 2) obtained in each of the above Reference Examples, and 2 parts by mass of the diazonium compound (q_i to 8) were dissolved in 200 parts by mass of GBL. After that, the photosensitive resin composition was prepared by filtration using a filter of 〇.2 μηη, and the patterning property and the varnish precipitation stability were evaluated. (1) Evaluation of Patterning Characteristics The above-mentioned photosensitive resin composition was spin-coated on a 6-inch 夕石βββ circle by a spin coater (Clean Track Mark-8) manufactured by Tokyo Electron Co., Ltd. Heat the plate at 12 inches. The undercoat was pre-baked for 18 sec seconds to form a 11.7 μηι coating film. The film thickness was measured by a film thickness measuring device (Lambda Ace) manufactured by Dainipp0n screen MFG. For the coating film, a stepping machine (NSR2〇〇5i8A) manufactured by Nikon Co., Ltd. having an exposure wavelength of 丨 (365 nm) was used, and the exposure amount was changed stepwise by a photomask attached with a test pattern. Exposure. Using an alkaline developer (AZ300MIF developer, 2.38% by weight aqueous solution of tetramethylammonium hydroxide) manufactured by AZ Electronic Materials, at 23 ° C, the development was adjusted to develop the image to develop The film thickness became 9.4 tons' to form a positive pattern. The sensitivity and resolution of the photosensitive resin group a are shown in Table 1 below. 140314.doc -31 - 201011469 Further, the sensitivity and resolution of the photosensitive resin composition were evaluated in the following manner. [Sensitivity (mj/cm2)] In the above development time, the minimum exposure amount of the exposed portion of the coating film can be completely dissolved. [Resolution (μηι)] The minimum resolution pattern size under the above exposure amount. (2) Evaluation of precipitation stability The prepared photosensitive resin composition was filtered, and after standing at room temperature and -20 C for a week, it was visually observed whether or not solid matter was observed in the varnish. In Table 1, when no precipitation is observed, it is represented by "〇", and when it is seen, it is represented by "X". [Table 1] Table 1

梱·據表1可知’藉由使用本發明之感光性樹脂組合物， Μ適當之顯影時間可形成高靈敏度、高解析度之圖案，且 '亦不會析出。與此相對，不含滿足本發明之要件之重氮醌 化合物的比較例1〜5之組合物，其靈敏度、解析度均差， 1403l4.doc 201011469 且比較例2之組合物發生了析出。 [產業上之可利用性] 本發明之感光性樹脂組合物可較佳地用於形成半導體元 件等之表面保護膜、層間絕緣膜等。According to Table 1, it can be seen that by using the photosensitive resin composition of the present invention, a pattern having high sensitivity and high resolution can be formed with an appropriate development time, and 'no precipitation is formed. On the other hand, the compositions of Comparative Examples 1 to 5 which did not contain the diazonium compound satisfying the requirements of the present invention were inferior in sensitivity and resolution, and the composition of Comparative Example 2 was precipitated in 1403l4.doc 201011469. [Industrial Applicability] The photosensitive resin composition of the present invention can be preferably used for forming a surface protective film such as a semiconductor element, an interlayer insulating film, or the like.

140314.doc -33-140314.doc -33-

Claims (1)

201011469 七、申請專利範園： 1. 一種感光性樹脂組合物，其特徵在於含有： ⑷具有以下述通式⑴所表示之結構之聚酿胺⑽質量 份： ' [化1] jOH)p (〇H)q --HN 一 Xl—NHC0_ 十丨〜c〇___ ⑴ _ (COOR)m {式中，Xl為具有2個以上碳原子之2〜4價有機基，A為 具有2個以上碳原子之2〜6價有機基，…分別獨立為 〇〜4之整數’ R為氫原子或碳數為丨〜2〇之有機基，訊為 0〜2之整數，_〜_之整數，其中，瓜、p及^不同時 為0，且於15與〇1均為〇之情形時，R為具有酚性羥基之 基};以及 (b)以下述通式（2)所表示之重氮醌化合物卜丨⑼質量 份： [化2]201011469 VII. Application for a patent garden: 1. A photosensitive resin composition comprising: (4) a polystyrene having a structure represented by the following formula (1): (10 parts by mass): '[Chemical 1] jOH)p ( 〇H)q -HN -Xl-NHC0_ 十丨~c〇___ (1) _ (COOR)m {wherein, Xl is a 2~4 valence organic group having 2 or more carbon atoms, and A is 2 or more 2 to 6 valence organic groups of carbon atoms, ... are each independently an integer of 〇~4' R is a hydrogen atom or an organic group having a carbon number of 丨~2〇, an integer of 0 to 2, an integer of _~_, Wherein, melon, p and ^ are not 0 at the same time, and when both 15 and 〇1 are 〇, R is a group having a phenolic hydroxyl group; and (b) is represented by the following formula (2) Nitrogen bismuth compound diterpenoid (9) parts by mass: [Chemical 2] {式中，A、Z2及&amp;分別獨立為碳數為卜“之i價有機 基’ a及b分別獨立為〇〜4之整數，（；為〇〜5之整數，複數 個Q内之任一個為由以下： 140314.doc 201011469 [化3]In the formula, A, Z2 and &amp; independently are carbon numbers for the "i-valent organic groups' a and b are each an integer of 〇~4, (; is an integer of 〇~5, a plurality of Qs Any one is as follows: 140314.doc 201011469 [化3] Ο 所表示之2個基之任2 The two bases represented 合物為以下述式（3)所表示之化合物·· [化4]The compound is a compound represented by the following formula (3). {式中，複數個Q内之任一個為由以下 [化5]In the formula, any one of the plurality of Qs is as follows [Chemical 5] 所表示之2個基之任一個’其餘為氫原子}。 3·如請求項以感光性樹脂組合物’其中上述⑷聚酿胺具 有以下述通式（4)所表示之重複單元： 140314.doc (4) 201011469 [化6] _册〜子2 — NHCO—Y2—CO· 〇H η {式中’ Χ2為4價芳香族基’ 丫2為2價芳香族基，並 2〜1000之整數為 4. -種硬化凸紋圖案之製造方法，其包括以下步驟： 將如4求項1至3中任一項之感光性樹脂組合物塗佈於 基板上之步驟； ' 經由光罩以光化射線進行曝光或直接照射光線、電子 束或者離子束之步驟； 將曝光部或照射部溶出或除去之步驟； 加熱所獲得之凸紋圖案之步驟。 5 -種半導體裝置，其具有藉由如請求項4之方法而獲得 之硬化凸紋圖案。 140314.doc 201011469 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無） 140314.doc -2-Any one of the two bases indicated is 'the rest is a hydrogen atom}. 3. The request item is a photosensitive resin composition, wherein the above (4) polyamin has a repeating unit represented by the following formula (4): 140314.doc (4) 201011469 [Chem. 6] _ book~ sub 2 - NHCO —Y2—CO· 〇H η {wherein Χ2 is a tetravalent aromatic group' 丫2 is a divalent aromatic group, and an integer of 2 to 1000 is 4. A method for producing a hardened relief pattern, which includes The following steps: a step of applying a photosensitive resin composition according to any one of items 1 to 3 to a substrate; 'exposing or directly irradiating light, an electron beam or an ion beam with actinic rays through a photomask a step of eluting or removing the exposed portion or the irradiated portion; and a step of heating the obtained relief pattern. A semiconductor device having a hardened relief pattern obtained by the method of claim 4. 140314.doc 201011469 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 140314.doc -2-