TW200403532A - Highly heat-resistant negative-type photosensitive resin composition - Google Patents

Abstract

The present invention discloses a negative-type photosensitive resin composition containing: (A) a photo-polimerizable polyamide having an unsaturated double bond, (B) a photo-polimerizable monomer having an unsaturated double bond, (C ) a photopolymerization initiator and (D) a melamine resin.

Description

200403532 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於電子部件之絕緣材料或半導體裝置中鈍 化膜，緩衝塗層膜，層間絕緣膜等耐熱性凸紋花樣 (relief pattern)之形成所用的負型感光性樹脂組成物。 【先前技術】 習知電子部件之絕緣材料或半導體裝置之鈍化膜，表 面保護膜，層間絕緣膜等，係使用同時具有耐熱性及電特 性，機械特性之聚醯亞胺樹脂。在此聚醯亞胺樹脂中，尤 以負型感光性聚醯亞胺先質組成物形式供作使用之情形， 對其施予塗敷，曝光，顯像，熱醯亞胺化處理等，可容易 地形成耐熱性之凸紋花樣皮膜。此等負型感光性聚醯亞胺 先質組成物，與習知使用非感光型聚醯亞胺之情形比較， 具有可大幅縮短處理步驟之特徵。 然而，使用上述負型感光型聚醯亞胺先質組成物時， 其顯像步驟中，必須大量使用作爲顯像液之呲咯啶酮類或 酮類等之有機溶劑，由於安全性及近年來對環境問題之關 心高漲，故脫有機溶劑化爲所期望。有鑑於此，在最近， 於上述之材料領域，與光蝕刻相同，則有各種以稀薄鹼性 水溶液來顯像之耐熱性感光性樹脂材料被提案。 其中，在鹼性水溶液利用可溶性羥基聚醯胺，例如， 利用聚苯并鸣唑先質之方法近年廣受注目。此等物質，例 如將聚苯并聘D坐先質與驅二曝農（quin〇nediazide)等之 -5- (2) (2)200403532 光活性成分加以混合，以作爲正型感光性材料使用之方法 (曰本特公平卜46862號公報，日本特開招63-96162號 公報等）或在聚苯并噚唑先質之酚性羥基之一部份導入具 有光聚合性不飽和雙鍵之基，使其與具有光聚合性不飽和 雙鍵之單體，光聚合引發劑等加以混合，以作爲負型感光 性材料用之方法（日本特開平2 0 0 2 - 1 2 6 6 5號公報）等爲 周知。 在負型感光性材料中，具有光聚合性不飽和雙鍵等之 樹脂，以光照射聚合之結果，相對於顯像液爲不溶。相對 於此，在正型感光性材料中，因與被混合之光活性成分之 相互作用而對顯像液之溶解性降低之 '樹脂，會因光照射所 致該光活性成分之分解，而相對於顯像液有溶解性。因 此，欲使某種樹脂相對於光照射部及非照射部之間顯像液 的溶解差爲大之負型感光材料來加以使用之情形，與作爲 正型感光性材料使用之情形比較，則負型感光性材料可採 取之處理步驟範圍（Process margin)顯得特別廣，顯像 後凸紋花樣之形成亦容易。又一般而言，就負型感光性材 料一方，與正型感光性材料比較，則在組成物之保存穩定 性較良好。 又，聚苯并鸣唑皮膜與聚醯亞胺皮膜具有相同之熱硬 化膜特性等，因此’以稀薄鹼性水溶液可顯像之負型感光 性聚苯并鸣唑先質，有望作爲有機溶劑顯像型之負型感光 性聚醯亞胺先質之代替材料’而廣受矚目。 一方面使用上述材料之半導體裝置之封裝 -6- (3) (3)200403532 (packaging )方法的變遷亦極顯著。就近年來積體度或 機能之提高與晶片尺寸短小化之觀點言之，使封裝多層配 線化之1頃向顯著，而且在該等構造之形成過程中聚醯亞胺 皮膜或聚苯并鸣唑皮膜在曝曬之條件下，亦比以前增加並 呈多樣化。因此，半導體材料相對於強酸，強鹼等，已被 要求更高之耐藥品性。 又，基於同樣之理由，對半導體裝置之印刷配線基板 之實裝（mount )方法，亦從習知之金屬針（pin )及鉛-錫共晶（eutectic )焊接有關之實裝方法，來進行更高密 度實裝之球狀柵極陣列封裝體BGA( ball grid array)， 晶方尺寸構裝 CSP( chip size package)等，半導體裝置 之聚醯亞胺皮膜或聚苯并鸣唑皮膜，正在改變成直接接觸 焊接***物（S ο 1 d e r b u m p )之方法。所用之焊接，亦於 降低環境負荷之目的，正在轉換成無鉛（lead free)之高 融點焊接，又***物用之焊接，比基板實裝用者，一般更 能使用高融點之物。 總之，半導體裝置之聚醯亞胺皮膜或聚苯并Df唑皮 膜，在焊接***物之圓滑熱處理（reflow )步驟等中，繼 續接觸焊藥，並曝曬於目前爲止沒有之高溫下，且被要求 要有高溫耐焊藥（flux)性。 本發明之課題在於提供在基材上形成於加熱硬化後具 有極高耐熱性，耐藥品性之凸紋花樣之方法，及爲此而使 用之高性能負型感光性樹脂組成物。並提供該方法，或使 用該負型感光性樹脂組成物之半導體裝置之製法。 -7- hiri.'i (4) (4)200403532 【發明內容】 本發明人等爲解決‘上述課題，經專心致志檢討結果， 發現 在藉顯像來形成凸紋花樣後之聚醯胺皮膜加熱至200 °C以上以變換成聚醯亞胺或聚苯并哼唑骨架構造之際，可 同時使其獲得分子間橋聯，或者添加其本身可形成橋聯網 路之化合物（以下稱爲橋聯劑），則可獲得耐熱性及耐藥 品性更爲提高之橋聯聚醯亞胺，或具有橋聯聚苯并Uf唑骨 架構造之皮膜。而且經各種橋聯劑之試驗結果，發現將蜜 胺樹脂添加於本發明所用特定之負型感光性樹脂組成物 中，可於高位準（level )解決前述課題，而完成本發明。 亦即，本發明提供含有以下成分之負型感光性樹脂組 成物。 (I ) ( A )具有光聚合性不飽和雙鍵之下述式（1 ) 所示構造單位之聚醯胺：1 0 0質量份， (B)具有光聚合性不飽和雙鍵之單體：1〜50質量 份， (C )光聚合引發劑：1〜20質量份，及 (D )蜜胺樹脂：5〜30質量份 (5)200403532 〇 Ο Η Ττ II II ι ^ (1) k ι 、 T、N_ (C00Ra) i (〇^ (式中、X爲2〜4僧 -、之方曰5矢基、Y爲2〜4價之芳 香族基。i及j爲〇〜m 正數滿足i十j = 2、k爲2〜 150之整數。Ra爲獨立之下叶广 卜％〔 2 )所示具有光聚合性不 飽和雙鍵之1價有機姑献 二+ g=、或碳數1〜4之飽和脂肪族基。 Rb爲獨JLL之氣原子或卞、、价叶f 述式（3 )所示具有光聚合性不 飽和雙鍵之1價有機基。# 0 诅、便Rb之全莫耳數爲100莫 耳％時、其10莫耳％以上、 上50吴耳％以下係下述式（3) 所不具有光聚合性不飽和雙鍵之1價有機基。 •ch2-200403532 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a heat-resistant relief pattern such as a passivation film, a buffer coating film, an interlayer insulating film in an insulating material of an electronic component or a semiconductor device. The negative photosensitive resin composition used was formed. [Prior art] Conventional insulating materials for electronic parts or passivation films, surface protection films, and interlayer insulating films for semiconductor devices are polyimide resins that have both heat resistance, electrical properties, and mechanical properties. In this polyimide resin, in the case of using a negative photosensitive polyimide precursor composition in particular, it is coated, exposed, developed, thermally imidized, etc. A heat-resistant relief pattern film can be easily formed. These negative photosensitive polyimide precursor compositions have the feature that the processing steps can be greatly shortened as compared with the conventional case where a non-photosensitive polyimide is used. However, when the negative photosensitive polyfluorene imide precursor composition is used, it is necessary to use a large amount of organic solvents such as pyrrolidones or ketones as a developing solution in the development step. Due to safety and recent years, Since the concern for environmental issues has increased, deorganization is expected. In view of this, in the above-mentioned material field, recently, as with photoetching, various heat-resistant and photosensitive resin materials for development using a dilute alkaline aqueous solution have been proposed. Among them, a method using a soluble hydroxypolyamidamine in an alkaline aqueous solution, for example, a method using a polybenzazole precursor is attracting attention in recent years. These substances are, for example, a mixture of a polybenzoic precursor and a 5- (2) (2) 200403532 photoactive component of quinonediazide, etc., for use as a positive photosensitive material. Method (Japanese Patent Publication No. 46862, Japanese Patent Application Publication No. 63-96162, etc.) or introducing a photopolymerizable unsaturated double bond into a part of a phenolic hydroxyl group of a polybenzoxazole precursor. Method for mixing it with a monomer having a photopolymerizable unsaturated double bond, a photopolymerization initiator, etc., as a method for using a negative photosensitive material (Japanese Patent Laid-Open No. 2 0 0 2-1 2 6 6 5 Gazette) is well known. Among the negative-type photosensitive materials, a resin having a photopolymerizable unsaturated double bond or the like is polymerized by light irradiation, and is insoluble in a developing solution. On the other hand, in a positive-type photosensitive material, the 'resin of which the solubility of the developing solution is reduced due to the interaction with the mixed photoactive component will decompose the photoactive component due to light irradiation, and It is soluble in imaging solution. Therefore, in the case where a certain type of resin is used in a negative photosensitive material having a large dissolution difference between a light-irradiated portion and a non-irradiated portion in a developing solution, as compared with a case where it is used as a positive photosensitive material, The range of process margins that can be taken by negative photosensitive materials appears to be particularly wide, and the formation of embossed patterns after development is also easy. In general, the negative photosensitive material has better storage stability in the composition than the positive photosensitive material. In addition, the polybenzoimidazole film has the same thermally cured film characteristics as the polyfluorene imide film, so it is expected to be used as an organic solvent as a negative photosensitive polybenzoxazole precursor that can be developed with a thin alkaline aqueous solution. The development type of the negative photosensitive polyfluorene imide precursor material 'has attracted wide attention. On the one hand, the packaging of semiconductor devices using the above materials, the 6- (3) (3) 200403532 (packaging) method, has also changed significantly. From the viewpoints of the increase in integration or function and the reduction in chip size in recent years, one hectare of packaging multilayer wiring is significant, and polyimide film or polybenzazole is formed during the formation of these structures. The film also increased and diversified under the conditions of exposure. Therefore, semiconductor materials have been required to have higher chemical resistance than strong acids, strong bases, and the like. For the same reason, the mounting method of the printed wiring board of the semiconductor device is also changed from the conventional mounting method related to the metal pin and lead-tin eutectic welding. High-density ball grid array packages (BGA), chip size packages (CSP), etc., polyimide film or polybenzoxazole film for semiconductor devices are changing. Method for forming direct contact with welding bump (S ο 1 derbump). The welding used is also being converted to lead free high-melting point welding for the purpose of reducing the environmental load, and the welding of bumps is generally more capable of using the high-melting point than the substrate mounting user. In short, the polyimide film or polybenzo Dfazole film of semiconductor devices, during the smooth reflow step of the solder bump, etc., continue to contact the flux and be exposed to a high temperature that has not been available so far, and is required Have high temperature flux resistance. An object of the present invention is to provide a method for forming a relief pattern on a base material which has extremely high heat resistance and chemical resistance after heat curing, and a high-performance negative photosensitive resin composition for this purpose. This method is also provided, or a method for manufacturing a semiconductor device using the negative photosensitive resin composition. -7- hiri.'i (4) (4) 200403532 [Summary of the Invention] In order to solve the above-mentioned problems, the inventors have intently reviewed the results and found that the polyamine film is heated after the convex pattern is formed by imaging. When the temperature is above 200 ° C to transform into a polyfluorene or polybenzoxazole skeleton structure, it can be simultaneously obtained intermolecular bridges, or a compound that can form a bridge network (hereinafter referred to as a bridge) can be added at the same time. Agent), a bridged polyfluorene imine with improved heat resistance and chemical resistance, or a film with a bridged polybenzo Ufazole structure can be obtained. Furthermore, through the test results of various bridging agents, it was found that adding the melamine resin to the specific negative photosensitive resin composition used in the present invention can solve the aforementioned problems at a high level and complete the present invention. That is, the present invention provides a negative photosensitive resin composition containing the following components. (I) (A) Polyamine having a structural unit represented by the following formula (1) having a photopolymerizable unsaturated double bond: 100 parts by mass, (B) a monomer having a photopolymerizable unsaturated double bond : 1 to 50 parts by mass, (C) photopolymerization initiator: 1 to 20 parts by mass, and (D) melamine resin: 5 to 30 parts by mass (5) 200403532 〇τ Ττ II II ^ (1) k ι, T, N_ (C00Ra) i (〇 ^ (where X is 2 to 4 monk-, the square is 5 yadyl, Y is 2 to 4 valent aromatic group. i and j are 0 to m positive numbers Satisfy i = j = 2, k is an integer from 2 to 150. Ra is a monovalent organic compound with photopolymerizable unsaturated double bond shown by Ye Guangbo% [2), which is independent from the following + g =, or carbon A saturated aliphatic group of the number 1 to 4. Rb is a gas atom or fluorene alone of JLL, and a valence leaf f is a monovalent organic group having a photopolymerizable unsaturated double bond as shown in the formula (3). # 0 诅 、 便When the total mole number of Rb is 100 mole%, its 10 mole% or more and 50 mole% or less are monovalent organic groups having no photopolymerizable unsaturated double bond in the following formula (3). ch2-

0II +—0—C—C=cI \ Rio (2) 式中、R8爲氫原子或碳數丨〜3之有機基、r9、Riq係 各爲獨立之氫原子或碳數1〜3之有機基、q爲2〜1〇之整 數。0II + —0—C—C = cI \ Rio (2) In the formula, R8 is a hydrogen atom or an organic group with a carbon number of 丨 3, and r9 and Riq are each an independent hydrogen atom or an organic group with a carbon number of 1 to 3. The base and q are integers of 2 to 10.

NIH - OMHC CH2 R4R5 /c\II ^ I OHC 1 ο 3 -9- (6) 200403532 式中、R3爲氫原子或碳數1〜3之有機基 爲獨立之氫原子或碳數1〜3之有機基、m爲 數）。 (II)如上述（I)記載之負型感光性樹月旨 中，（A )具有光聚合性不飽和雙鍵之聚醯胺 式（4 )所示構造單位之聚苯并哼唑先質’ 、R4及R5各 2〜1 0之整 組成物，其 :、具有下述NIH-OMHC CH2 R4R5 / c \ II ^ I OHC 1 ο 3 -9- (6) 200403532 In the formula, R3 is a hydrogen atom or an organic group of carbon number 1 to 3 is an independent hydrogen atom or a carbon number of 1 to 3 Organic group, m is a number). (II) As described in the negative photosensitive tree moon described in (I) above, (A) a polybenzoxazole precursor having a structural unit represented by the polyamine formula (4) having a photopolymerizable unsaturated double bond ', R4 and R5 each have a total composition of 2 to 10, which has:

(式中、乂1爲2價芳香族基、¥1爲4價: 爲2〜150之整數。1及。各爲獨立之氫原 (3 )所示具有光聚合性不飽和雙鍵之1價有 Ri及R2之合計莫耳爲100莫耳°/。時、Ri與R %以上、5 〇莫耳％以下、係下述式（3 )所示 合性不飽和雙鍵的1價有機基。 芳香族基、η 子或下述式 機基。但、 2之1〇莫耳 、具有光聚(In the formula, 乂 1 is a divalent aromatic group, ¥ 1 is a tetravalent: an integer from 2 to 150. 1 and. Are each 1 of a photopolymerizable unsaturated double bond shown by an independent hydrogenogen (3) The sum of the mols with valences of Ri and R2 is 100 mol ° / ° C, a monovalent organic compound having a unsaturated unsaturated double bond represented by the following formula (3) with Ri and R% or more and 50 mol% or less Aromatic group, η-ion or organic group of the following formula. However, 2 of 10 moles, with photopolymerization

但、R3係氫原子或碳數1〜3之有機基、 各自獨立之氫原子或碳數1〜3之有機基、m R4及R5爲 爲2〜10之 •10- (7) 200403532 整數。） (in )如Ji述（I )所記載之負型感光性樹脂組成 物，其中，（a )具有光聚合性不飽和雙鍵之聚醯胺、係 具有下述式（5)所示構造單位之聚醯亞胺先質、However, R3 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, an independent hydrogen atom or an organic group having 1 to 3 carbon atoms, and m R4 and R5 are 2 to 10 • 10- (7) 200403532 integer. ) (In) The negative photosensitive resin composition as described in (I) of Ji, wherein (a) a polyamine having a photopolymerizable unsaturated double bond has a structure represented by the following formula (5) Units of polyimide precursors,

C N—Y2—N C一OR7 0C N—Y2—N C—OR7 0

P …（5) (式中，X2爲4價芳香族基，-COOR6基及-C〇〇R7 基與該等相鄰之-CONH —基互爲鄰位。Y2爲2價芳香族 基、p爲2〜150之整數。R6及R7爲各自獨立、下述式 (2 )所示具有光聚合性不飽和雙鍵之1價有機基、或艘 數1〜4之脂肪族基。 (2)P… (5) (wherein X2 is a tetravalent aromatic group, the -COOR6 group and the -COOR7 group are adjacent to each other and the -CONH-groups adjacent to each other. Y2 is a divalent aromatic group, p is an integer of 2 to 150. R6 and R7 are each independently a monovalent organic group having a photopolymerizable unsaturated double bond represented by the following formula (2), or an aliphatic group having a number of 1 to 4. (2 )

Η 严 〇—c—c=c I \Η yan 〇—c—c = c I \

Rg Rio 但、R8爲氫原子或碳數1〜3之有機基、R9、爲 各自獨立之氫原子或碳數1〜3之有機基、q爲2〜1〇之 整數。） (IV )如上述（〗）〜（m )中任一記載之負型感光 -11 - 200403532Rg Rio, R8 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R9 is a separate hydrogen atom or an organic group having 1 to 3 carbon atoms, and q is an integer of 2 to 10. ) (IV) Negative photosensitivity as described in any of the above (〖) ~ (m) -11-200403532

性樹脂組成物，其中（D )蜜胺樹脂之聚合度爲1 .〇以 上、2.2以下、 (V y如上述（I)〜（III)之任一記載之負型感光 性樹脂組成物，其中，（D )蜜胺樹脂係六甲氧甲基化蜜 胺、 (VI ) —種耐熱性、耐藥品性的凸紋花樣之形成方 法， 其含有下列步驟： (1)使上述（I)〜（v)之任一所記載之負型感光 性樹脂組成物予以塗敷於基材者、 (2 )透過圖案掩罩使活性光線照射、曝光於此塗膜 者、 (3 )使用顯像液來溶解除去塗膜之末曝光部份以形 成凸紋花樣者、 (4 )在200 °C以上溫度下加熱塗膜、使其硬化者、 (VII) —種半導體裝置之製造方法，含有藉由上述 (VI )所記載之凸紋花樣形成方法來形成凸紋花樣者。 (VIII ) —種半導體裝置之製造方法，其含有使用上 述（I )〜（V )之任一所記載負型感光性樹脂組成物。 【實施方式】 實施發明之最佳型態 以下具體說明本發明 本發明之負型感光性樹脂組成物、作爲必需成分則含 -12- (9) (9)(D) The degree of polymerization of (D) the melamine resin is 1.0 or more and 2.2 or less, (V y is the negative photosensitive resin composition according to any one of (I) to (III) above, wherein (D) A melamine resin based hexamethoxymethylated melamine, (VI)-A method for forming a heat-resistant and chemical-resistant relief pattern, comprising the following steps: (1) Making the above (I) ~ ( v) Those who apply the negative photosensitive resin composition according to any one of the above to a substrate, (2) Those who irradiate active light through a pattern mask and expose this coating film, (3) Use a developer Those who dissolve and remove the exposed portion at the end of the coating film to form embossed patterns, (4) Those who heat the coating film at a temperature of 200 ° C or higher to harden it, (VII) A method for manufacturing a semiconductor device, including the method described above (VI) A method for forming a relief pattern as described in (VI) A method for manufacturing a semiconductor device, comprising using the negative photosensitive resin described in any one of (I) to (V) above Composition [Embodiment] The best mode for carrying out the invention The present invention is described in detail below. Ming negative photosensitive resin composition containing as essential components the 12- (9) (9)

200403532 有以下4成分。 A成分：具有光聚合性不飽和雙鍵之聚醯胺。 B成分：具有光聚合性不飽和雙鍵之單體。 C成分：光聚合引發劑。 D成分：蜜胺樹脂。 <A成分> 其中首先就前述化學式（1)所示A成分加, 本發明之負型感光性樹脂組成物中較佳之 係具有光聚合性不飽和雙鍵之聚醯胺、在200 以加熱環化處理、來變換成聚苯并Df唑或聚醯亞 本發明之A成分、尤其是具有下述化學式 構造單位之聚苯并噚唑先質爲有用。 (4) (式中Χι爲2價芳香族基、乂^爲*價芳1 爲2至150之整數。1及R2各爲獨立之氫原子 學式（3 )所示具有光聚合性不飽和雙鍵之1價 但、R!與R2之合計莫耳爲100莫耳％時、Ri與 旲耳％以上、5 0旲耳％以下、係下述式（3 )所 4説明。 A成分、 °C以上施 胺者。 (4 )所示 ,族基。η 或下述化 有機基。 R2 之 10 示、具有 -13- …（3)200403532 do) 光聚合性不飽和雙鍵之1價有機基 0 〇 II ( \ II Λ —-c—n4ch2-4—〇—c—c=c I V An I \ H R3 r5 式中R3爲氫原子或碳數1〜3之有機基，R4及R5各 爲獨立之氫或碳數1〜3之有機基。m爲2〜10之整數。） 在上述化學式（4 )中，Xi所示之2價芳香族基具有 以下之構造。200403532 has the following 4 components. Component A: Polyamine having a photopolymerizable unsaturated double bond. Component B: a monomer having a photopolymerizable unsaturated double bond. Component C: Photopolymerization initiator. Component D: melamine resin. < A component > Among them, the A component represented by the aforementioned chemical formula (1) is added first. The preferred negative photosensitive resin composition of the present invention is a polyamine having a photopolymerizable unsaturated double bond. The cyclization treatment is performed by heating to convert it to polybenzo Dfazole or polyfluorene. The A component of the present invention, especially a polybenzoxazole precursor having a structural unit of the following chemical formula is useful. (4) (where X is a divalent aromatic group, 乂 ^ is * valent aromatic 1 is an integer from 2 to 150. 1 and R2 are each independent hydrogen atomic formula and have photopolymerizable unsaturated as shown in formula (3) When the valence of the double bond is 1, the total moles of R! And R2 are 100 mole%, Ri is more than 50%, and less than 50%, and it is described by the following formula (3): A component, Those who apply amines above ° C. (4), a group group. Η or the following organic group. R2 of 10 shows -13-… (3) 200403532 do) 1-valence of photopolymerizable unsaturated double bond Organic group 0 〇II (\ II Λ —-c—n4ch2-4—〇—c—c = c IV An I \ H R3 r5 where R3 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R4 and R5 Each is an independent hydrogen or an organic group having 1 to 3 carbon atoms. M is an integer of 2 to 10. In the above chemical formula (4), the divalent aromatic group represented by Xi has the following structure.

ch3 -14- (11) (11)200403532 同樣在上述化學式（4 )中，.Yi所示之4價芳香族基 具有以下之構造。ch3 -14- (11) (11) 200403532 Also in the above chemical formula (4), the tetravalent aromatic group represented by .Yi has the following structure.

在本發明中、化學式（4 )所示聚苯并鸣唑先質、係 首先調製含2價芳香族基Xi之芳香族二羧酸或其衍生 物、與含有4價芳香族基Υι之雙（鄰胺苯酚）類之醯胺 縮聚體（原料聚合物）、接著、在其羥基之一部份、可藉 由導入具有光聚合性不飽和雙鍵之基而獲得。 (原料聚合物之調製） 本發明可恰當使用之含有2價芳香族基X!之二羧酸 及其衍生物有例如、酞酸、異酞酸、對酞酸、4，4’-二苯 醚二羧酸酯、3，4’-二苯醚二羧酸酯、3，3’-二苯醚二羧 -15- (12) (12)200403532 酸酯、4，4-聯苯基二羧酸酯、3，4'-聯苯基二羧酸酯、 3 ， 3’-聯苯基二羧酸酯 、4 ， 4’-二苯基酮 (benzophenone)二殘酸酯、3，4’ -二苯基酮二竣酸酯、 3，3’ -二苯基酮二羧酸酯、4，4'-六氟亞異丙基二苯甲酸 酯、4，4’-二羧基二苯基醯胺、1，4-伸苯基二乙酸酯 (phenylene diethanoate ) 、1，1 -雙（4-竣基苯基）-1 一 苯基_2，2，2 -三氟乙烷、雙（4 一羧基苯基）硫化物、雙 (4-羧基苯基）四苯基二矽氧烷、雙（4-羧基苯基）四甲 基二矽氧烷、雙（4-羧基苯基）颯、雙（4-羧基苯基）甲 烷、5—第三丁基異酞酸、5-溴異酞酸、5-氟異酞酸、5-氯 異酞酸、2，2-雙（對羧基苯基）丙烷、4，4’-(對亞苯 基二氧）二苯甲酸酯、2，6 -萘二羧酸酯及該等之酸性氯 化物體、及羥基苯并***等活性酯體等。又該等可單獨或 混合使用。 又，本發明可恰當使用之含有4價芳香族基Υι之雙 (鄰胺苯酣）、有例如3，3-二經基聯苯胺（benzidine)、3 3二氨基_4，4，-二羥基聯苯、3，3’-二羥基-4，4’-二氨基 二苯礪、雙-(3-氨基-4-羥基苯基）甲烷、2，2-雙-(3-氨基-4-羥基苯基）丙烷、2，2-雙-(3-氨基-4-羥基苯 基）六氟丙烷、2，2-雙- (3-羥基-4-氨基苯基）六氟丙烷、 雙-(3-羥基-4-氨基苯基）甲烷、2，2-雙- (3-羥基-4-氨基 苯基）丙烷，3，3，-二羥基-4，4’-二氨基二苯基酮、3，3、 二羥基-4，4，-二氨基二苯基醚、4，^一二羥基-3，3’-二 氨基二苯基醚、3，3，_二羥基-4， 4’ -二氨基聯苯、3，3，- -16- (13) (13)200403532 二氨基-4,4f-二羥基聯苯、2 ’ 5-二羥基，4•二氨基苯、 4，6-二氨基間苯二酚、及其混合物等。 又、爲了提局與基板之密接性目的、亦可與雙_(鄰 胺苯酚）一起、使丨，3_雙-氨基丙基）四甲基二矽氧 烷、1，3 -雙（3 -氨基丙基）四苯基二矽氧烷等之二氨基 矽氧烷類共聚合。 在使用芳香族二羧酸二氯化物或芳香族二羧酸之活性 酯體時、可在適當溶媒中於呲啶等鹼性化合物存在下，使 該等與雙-(鄰胺苯酚）混合、而可得到原料聚合物。 一方面、使用芳香族二羧酸時、適當的縮合劑爲必 要。此等縮合劑可使用公知的脫水縮合劑、例如有二（環 己亞胺）甲烷（dicyclohexylcarbodiimide) 、1-乙氧基羰 基-2 -乙氧基-1 ’ 2 - 一^氣口奎、1 ’ r —'鑛基二氧-二-1，2，3-苯并***（benzotriazole ) 、N，N’ -二琥珀醯亞胺碳酸酯 (disuccinimidylcarbonate)、亜磷酸酯等。其中、在使 用二（環己亞胺）甲烷時、則與1 -羥基-1，2，3 -苯并三 唑共用較佳。 反應溶媒的話、以可完全溶解於生成之原料聚合物較 佳、例如、N -甲基-2 -呲咯啶酮、N，N _二甲基乙醯胺、 N，N-二甲基甲醯胺、二甲基亞颯、四甲基脲、γ-丁內酯 等。 其他、反應溶媒之例有酮類、酯類、內酯類、醚類、 鹵化烴類、烴類、例如、丙酮、甲基乙基酮、甲基異丁基 酮、環己酮、乙酸甲酯、乙酸乙酯、乙酸丙酯、草酸二乙 -17- (14) 200403532 酯、乙二醇二甲醚、二乙二醇二甲醚、四氫呋喃、二氯甲 烷、1，2-二氯乙烷、1，4-二氯丁烷、氯苯、鄰二氯苯、 已烷、庚烷、苯、甲苯、二甲苯等。該等可因應需要、單 獨或混合使用。 將芳香族二羧酸二氯化物做爲原料使用時、因可抑制 其分解去活性、故在上述中、尤其是溶解於二醇醚系等之 無極性溶媒並供與反應使用較佳。 反應完成後、使該反應液投入於、水或水和脂肪族低 級醇之混合液等之、相對於原料聚合物爲劣溶媒之中、使 原料聚合物分散析出、進而重複再沈澱並予以精製之、進 行真空乾燥、以離析出原料聚合物。 爲使精製度更加提高、可使陰陽両離子交換樹脂在適 當有機溶媒下潤漲（swelling )之，並此原料聚合物溶液 通過已充塡之柱（column)等，以除去離子性不純物。 (具有光聚合性不飽和雙鍵基的導A ) 本發明之A成分中、前述化學式（4)所示具有光聚 合性不飽和雙鍵之聚醯胺、係使上述反應所得之原料聚合 物再溶解於有機溶媒等、可得到下述化學式（6 )所示、 與含有光聚合性不飽和雙鍵之異氰酸酯化合物反應而獲 得。In the present invention, the precursor of polybenzoimidazole represented by the chemical formula (4) is prepared by first preparing an aromatic dicarboxylic acid or a derivative thereof containing a divalent aromatic group Xi, and a bis containing a tetravalent aromatic group Υι. (O-aminophenol) amidoamine polycondensate (raw polymer), and then a part of its hydroxyl group can be obtained by introducing a group having a photopolymerizable unsaturated double bond. (Preparation of raw polymer) Dicarboxylic acids and derivatives thereof containing a divalent aromatic group X! Which can be suitably used in the present invention include, for example, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-diphenyl Ether dicarboxylic acid ester, 3,4'-diphenyl ether dicarboxylic acid ester, 3,3'-diphenyl ether dicarboxylic acid-15- (12) (12) 200403532 acid ester, 4,4-biphenyl dicarboxylic acid Carboxylic acid ester, 3,4'-biphenyl dicarboxylic acid ester, 3, 3'-biphenyl dicarboxylic acid ester, 4, 4'-diphenyl ketone (benzophenone) diresidue acid ester, 3, 4 '-Diphenyl ketone diunate, 3,3'-diphenyl ketone dicarboxylate, 4,4'-hexafluoroisopropylidene dibenzoate, 4,4'-dicarboxydi Phenylphosphonium amine, 1,4-phenylene diethanoate, 1,1-bis (4-endylphenyl) -1 monophenyl_2,2,2-trifluoroethane , Bis (4-carboxyphenyl) sulfide, bis (4-carboxyphenyl) tetraphenyldisilazane, bis (4-carboxyphenyl) tetramethyldisilaxane, bis (4-carboxybenzene) Group) hydrazone, bis (4-carboxyphenyl) methane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,2-bis (Correct Phenyl) propane, 4,4 '-(p-phenylene dioxy) dibenzoate, 2,6-naphthalene dicarboxylic acid esters, acidic chlorinated substances thereof, and hydroxybenzotriazole, etc. Active esters, etc. These can be used alone or in combination. In addition, bis (o-aminophenylphenyl) containing a tetravalent aromatic group Υι, which can be suitably used in the present invention, for example, 3,3-diazylbenzidine, 3 3 diamino-4,4, -di Hydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenyl, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4 -Hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (3-hydroxy-4-aminophenyl) hexafluoropropane, bis -(3-hydroxy-4-aminophenyl) methane, 2,2-bis- (3-hydroxy-4-aminophenyl) propane, 3,3, -dihydroxy-4,4'-diaminodiphenyl Ketone, 3,3, dihydroxy-4,4, -diaminodiphenyl ether, 4, ^-dihydroxy-3,3'-diaminodiphenyl ether, 3,3, _dihydroxy-4 , 4'-diaminobiphenyl, 3,3,--16- (13) (13) 200403532 diamino-4,4f-dihydroxybiphenyl, 2 '5-dihydroxy, 4 • diaminobenzene, 4 , 6-diaminoresorcinol, and mixtures thereof. In addition, for the purpose of improving the adhesion between the substrate and the substrate, it can be used together with bis- (o-aminophenol) to make 3, bis-aminopropyl) tetramethyldisilazane, 1,3-bis (3 -Aminopropyl) tetraphenyldisilanes and other diaminosilane copolymers. When using an aromatic dicarboxylic acid dichloride or an active ester of an aromatic dicarboxylic acid, these can be mixed with bis- (o-aminophenol) in the presence of a basic compound such as pyridine in an appropriate solvent, Instead, a base polymer can be obtained. On the one hand, when an aromatic dicarboxylic acid is used, an appropriate condensation agent is necessary. As these condensing agents, well-known dehydrating condensing agents can be used, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2 -ethoxy-1 '2-1-Houkou Kui, 1' r-'mine-based dioxo-di-1,2,3-benzotriazole, N, N'-disuccinimidylcarbonate, phosphonium phosphate and the like. Among them, when bis (cycloheximine) methane is used, it is preferably shared with 1-hydroxy-1,2,3-benzotriazole. In the case of the reaction solvent, it is preferable to dissolve the raw polymer completely, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Phenylamine, dimethylsulfenyl, tetramethylurea, γ-butyrolactone, etc. Examples of other reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl acetate. Ester, ethyl acetate, propyl acetate, diethyl oxalate-17- (14) 200403532 ester, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethyl Alkane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like. These can be used individually or in combination as needed. When an aromatic dicarboxylic acid dichloride is used as a raw material, its decomposition and deactivation can be suppressed. Therefore, it is preferable to use it in a non-polar solvent which is dissolved in a glycol ether system and the like. After the reaction is completed, the reaction solution is poured into water, a mixed solution of water and an aliphatic lower alcohol, etc., and the raw polymer is inferior to the raw polymer. The raw polymer is dispersed and precipitated, and then reprecipitated and refined repeatedly. Then, vacuum drying is performed to isolate the base polymer. In order to further improve the precision system, the cation exchange resin of yin and yang can be swelled under an appropriate organic solvent, and the raw polymer solution is passed through a filled column to remove ionic impurities. (Conductive A having a photopolymerizable unsaturated double bond group) In the component A of the present invention, the polyamine having a photopolymerizable unsaturated double bond represented by the aforementioned chemical formula (4) is a base polymer obtained by the above reaction. It can be obtained by redissolving in an organic solvent, etc. and obtaining the following formula (6) and reacting with an isocyanate compound containing a photopolymerizable unsaturated double bond.

RR

C— o^ch2+C— o ^ ch2 +

·.· (6) -18- (15) (15)200403532 (式中、係氫原子或碳數丨〜3之有機基、Rl2、 Rh係各爲獨立之氫原子或碳數i〜3之有機基、_r爲2〜 1 〇之整數。） 3有上述化學式（6 )所示光聚合性不飽和雙鍵的異 氫酸酯化合物有例如、異氫酸基乙基丙烯酸酯、異氫酸基 丙基丙燃酸酯、異氫酸基丁基丙烯酸酯、異氫酸基戊基丙 嫌酸酯、異氫酸基己基丙烯酸酯、異氫酸基辛基丙烯酸 酯、異氫酸基癸基丙烯酸酯、異氫酸基十八基丙烯酸酯、 異氫酸基乙基甲基丙烯酸酯、異氫酸基丙基甲基丙烯酸 醋、異氫酸基丁基異丁烯酸酯、異氫酸基戊基異丁烯酸 酯、異氫酸基己基異丁烯酸酯、異氫酸基辛基異丁烯酸 酯、異氰酸基癸基異丁烯酸酯、異氫酸基十八基異丁烯酸 酉曰、異氣旨义基乙基巴丑酸醋（crotonate)、異氯酸基丙基 巴丑酸醋、異氫酸基丁基巴豆酸酯、異氫酸基戊基巴豆酸 醋、異氫酸基己基巴豆酸酯等、較佳是使用2_異氫酸基 乙基異丁烯酸酯。 原料聚合物與該異氫酸酯化合物之反應、通常、係在 0〜1 0 0 °c、較佳是在2 0〜7 0 °C之溫度條件下進行、以 三乙胺、呲啶、二甲基氨基呲啶、喂啶 (quinuclidine ) 、1，4 -二氮雜雙環[2、2，2 ]辛院 (diazabicycl〇[2、2，2]octane )等之胺類、或二 丁基錫 二月桂酸鹽、二丁基鍚二乙酸鹽等之錫化合物作爲觸媒使 用時、反應會更容易進行。 -19- (16) (16)200403532 反應所用有機溶媒對異氫酸酯基爲不活性、且可完全 溶解於含有原料聚合物或反應生成物之溶解（d i s s ο 1 v e d ) 成分的溶媒較佳、例如 N -甲基-2 -呲咯啶酮、N，N -二甲 基乙醯胺、N，N-二甲基甲醯胺、二甲基亞颯、γ_丁內酯 等。其他酮類、酯類、內酯類、醚類、鹵化烴類、烴類、 可使用例如丙酮、甲基乙基酮、甲基異丁基酮、環己酮、 乙酸甲酯、乙酸乙酯、乙酸丁酯、草酸二乙酯、乙二醇二 甲醚、二乙二醇二甲醚、四氫呋喃、二氯甲烷、1，2 -二 氯乙院、1 ’ 4_ 一氯丁院、氯苯、鄰二氯苯、已院、庚 烷、苯、甲苯、二甲苯等。該等可因應需要、單獨或混合 使用。 此反應生成物、可就這樣作爲本發明之負型感光性樹 脂組成物之Α成分使用、亦可因應需要、投入於水或水 及脂肪族低級醇之混合液等之、相對於所生成之聚合物成 分爲劣溶媒之中、使分散析出、進而重複再沉澱予以精製 之、乾燥並使用之。 含光聚合性不飽和雙鍵之異氫酸酯化合物之、對原料 聚合物之導入率、相對於原料聚合物之羥基莫耳數、爲 1 〇莫耳％以上、5 0莫耳％以下較佳。亦即、上述式（4 ) 中、Ri及R2之合§十旲耳數爲1〇〇莫耳％時、^與R2之 1 0旲耳％以上、5 0旲耳％以下爲含有光聚合性不飽和雙鍵 之有機基較佳。 該異氫酸酯化合物之導入率相對於原料聚合物之羥基 旲耳數，不足1 0旲耳％時、光聚合時之橋聯密度會過 - 20- (17) 200403532 低、使得光感度降低、造成凸紋花樣之潤漲易於產生、難 以得到實用的凸紋花樣。同樣地、導入率超過5 0莫耳％ 的話、骨架中酚性羥基濃度會過度減少、使得相對於所得 @醯胺聚合物鹼性水溶液顯像液的溶解性會極端低、造成 顯像後末曝光部之殘溶物易於產生、並不符實用。 由於該異氫酸酯化合物活性高、藉由溶解於反應溶液 中之水分、其本身則無法避免一部份被二聚化（dimerization) 反應 。因此 、實 際反 應中該 異氫酸 酯化合 物之裝 入量、有必要比目標之導入率更高一些、則相對於原料聚 合物之羥基莫耳數、以1〇〜80莫耳％較佳。 再者、本發明之A成分、就具有下述式（5)所示構 造單位之聚醯亞胺先質亦爲有用。 ΟII -c、〜〇—if 〇 ：x2. OH ΗII I I ,C—N—Y2—N- 、c—or7II o (5)(6) -18- (15) (15) 200403532 (wherein, the system is a hydrogen atom or an organic group with a carbon number of 3, R12, and Rh are each an independent hydrogen atom or a carbon number of i to 3 The organic group and _r are integers of 2 to 10.) 3 The isohydrogenate compound having a photopolymerizable unsaturated double bond represented by the above-mentioned chemical formula (6) includes, for example, isohydroacid ethylacrylate, isohydroacid Propyl propionate, isohydrobutyl acrylate, isohydropentyl propanoate, isohydro acid hexyl acrylate, isohydro acid octyl acrylate, isohydro acid decyl Acrylate, octadecyl acrylate, methacrylate methacrylate, methacrylate methacrylate, methacrylate methacrylate, methacrylate methacrylate Amyl methacrylate, hexyl methacrylate, octyl methacrylate, octyl methacrylate, decyl methacrylate, octadecyl methacrylate, octadecyl methacrylate Crotonate, isopropyl crotonate, isobutyl crotonate, butyl crotonate, amyl crotonate , Hexyl crotonate, etc., preferably 2-hexyl ethyl methacrylate. The reaction between the base polymer and the isohydrogenate compound is usually carried out at a temperature of 0 to 100 ° C, preferably 20 to 70 ° C, with triethylamine, pyridine, Amines such as dimethylaminopyridine, quinuclidine, 1,4-diazabicyclo [2,2,2] xin (diazabicycl0 [2,2,2] octane), or dibutyltin When tin compounds such as dilaurate and dibutylphosphonium diacetate are used as catalysts, the reaction proceeds more easily. -19- (16) (16) 200403532 The organic solvent used for the reaction is inactive to the isohydrogen ester group and can be completely dissolved in a solvent containing diss ο 1 ved component of the raw polymer or reaction product. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylmethylene, γ-butyrolactone, and the like. Other ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate , Butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1 '4-chlorobutane, chlorobenzene , O-dichlorobenzene, Alcohol, heptane, benzene, toluene, xylene, etc. These can be used individually or in combination as needed. This reaction product can be used as the A component of the negative photosensitive resin composition of the present invention as it is, or it can be put into water or a mixed solution of water and an aliphatic lower alcohol, etc., if necessary, with respect to the produced product. The polymer component is dispersed in a poor solvent, and then re-precipitated, purified, dried, and used. The introduction ratio of the photopolymerizable unsaturated double bond-containing isohydrogenate compound to the base polymer, and the molar number of hydroxyl groups with respect to the base polymer are 10 mol% or more and 50 mol% or less. good. That is, in the above formula (4), when the total number of Ri and R2 is 100 mole%, 10% or more of R2 and 50% or less of R2 are photopolymerized. Organic groups of the unsaturated unsaturated double bond are preferred. The introduction rate of the isohydrogen ester compound is less than 10 旲% relative to the number of hydroxyl groups of the base polymer, and the bridge density during photopolymerization will be too low.-20- (17) 200403532, lowering the light sensitivity 2. The embossed pattern is easy to produce, and it is difficult to obtain a practical embossed pattern. Similarly, if the introduction rate exceeds 50 mol%, the concentration of phenolic hydroxyl groups in the skeleton will be excessively reduced, so that the solubility with respect to the obtained @ 醯 amine polymer alkaline aqueous solution developer will be extremely low, resulting in late development. Residuals in the exposed area are easy to produce and are not practical. Due to the high activity of the isohydrogenate compound, it is impossible to avoid a part of the dimerization reaction due to the water dissolved in the reaction solution. Therefore, in the actual reaction, the content of the isohydrogen ester compound needs to be higher than the target introduction rate, and it is preferably 10 to 80 mol% relative to the number of hydroxyl moles of the raw material polymer. Furthermore, the component A of the present invention is also useful as a polyimide precursor having a structural unit represented by the following formula (5). 〇II -c, ~ 〇—if 〇: x2. OH ΗII I I, C—N—Y2—N-, c—or7II o (5)

P (式中、X2爲4價芳香族基、-COO R6基及- COO R7 基與該等相鄰之-CONH —基互在鄰位。Y2係2價芳香族 基、p爲2〜150之整數。R6與R7爲各自獨立之下述式 (2 )所示具有光聚合性不飽和雙鍵之一價有機基、或碳 數1〜4之飽和脂肪族基。 -21 - (2) 18)200403532P (where X2 is a tetravalent aromatic group, -COO R6 group, and -COO R7 group are adjacent to the adjacent -CONH — groups. Y2 is a divalent aromatic group, and p is 2 to 150. R6 and R7 are each independently a monovalent organic group having a photopolymerizable unsaturated double bond represented by the following formula (2), or a saturated aliphatic group having 1 to 4 carbon atoms. -21-(2) 18) 200403532

Ο II R9 -CH2~~)—〇—c—c—c k I \ r8 ri〇 但、R8爲氫原子或碳數1〜3之有機基、R9、R1G爲 各自獨立之氫原子或碳數1〜3之有機基、q爲2〜10之 整數。） 上述化學式（5 )中，X2所示4價之芳香族基之例有 例如以下之構造。〇 II R9 -CH2 ~~) —〇—c—c—ck I \ r8 ri〇 However, R8 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R9 and R1G are each a separate hydrogen atom or carbon number 1 The organic group of ˜3, and q is an integer of 2˜10. ) In the chemical formula (5), examples of the tetravalent aromatic group represented by X2 include the following structures.

ONSNOONSNO

CH34 丨S3CH34 丨 S3

3 3 F I F CICIC3 3 F I F CICIC

上述化學式（5 )中，Υ2所示2價芳香族基之例有例 如以下之構造。 -22- (19)200403532Examples of the divalent aromatic group represented by Υ2 in the chemical formula (5) include the following structures. -22- (19) 200403532

oo

oneone

OMMSNOOMMSNO

CH3—A—CH3CH3—A—CH3

3 3 F I F C — CIC3 3 F I F C — CIC

2 H c2 H c

0 6 0 00 6 0 0

o 0.o 0.

oo

oo

oo

OHSMMMOOHSMMMO

0-90-9

c — cIc c—cIcc — cIc c—cIc

3 H3 H

3 3 HF I F3 3 HF I F

o oo o

A-AA-A

KK

AA

A ONSMOA ONSMO

oo

AA

AA

CH3-C—-CH3CH3-C—-CH3

AA

AA

AA

A oneA one

AA

3 3 F I F CICIC3 3 F I F CICIC

AA

-23- (20) 200403532-23- (20) 200403532

f~CH2 士 本發明中、化學式（5 )所示聚醯亞胺先質係首先將 含4價芳香族基X2之芳香族四羧酸二酐、與具有光聚合 性不飽和雙鍵之醇類及/或碳數1〜4之飽和脂肪族醇類反 應之、在調整半酸/半酯（half acid/half ester)體後、使 其與含有2價芳香族基Y2之芳香族二胺類之間，藉醯胺 縮聚而獲得。 (半酸/半酯體之調製） 酐有例如、焦蜜石酸酐（pyromellitic anhydride)、二苯 基醚-3，3’，4，4’ -四羧酸二酐、二苯基酮-3，3’，4，4’- 四羧酸二酐、聯苯-3，3 ’，4， 4 ’ -四羧酸二酐、二苯颯_ 3， 3’，4，4、四羧酸二酐、二苯甲烷-3，3’，4，4’ -四羧酸二 酐、2，2 ·雙（3，4 -酞酸酐）丙烷、2，2 -雙（3，4 -酞酸 酐）-1，1，1，3，3，3 -六氟丙烷等。又當然該等可單獨 使用、亦可混合2種以上使用。 本發明可恰當使用之具有光聚合性不飽和雙鍵之醇類' 有例如2-丙烯醯基氧乙醇、1-丙烯醯基氧-3-丙醇、2-丙 烯醯胺乙醇、羥甲基乙烯酮、2-羥乙基乙烯酮、2-羥基-3- -24- (21) (21)200403532 甲氧基丙基丙烯酸酯、2-羥基-3-丁氧基丙基丙烯酸酯、2-羥基-3-苯氧基丙基丙烯酸酯、2-羥基-3-丁基丙基丙烯酸 酯、2-羥基-3-第三丁氧基丙基丙烯酸酯、2-羥基-3-環己 基氧丙基丙烯酸酯、2 -甲基丙烯醯基氧乙醇、1-甲基丙烯 醯基氧-3-丙基醇、2 -甲基丙烯醯胺乙醇、2 -羥基-3-甲氧 基丙基甲基丙烯酸酯、2_羥基-3-丁氧基丙基甲基丙烯酸 酯、2-羥基-3-苯氧基丙基甲基丙烯酸酯、2-羥基一 3-丁 氧基丙基甲基丙烯酸酯、2-羥基一 3-第三丁氧基丙基甲基 丙烯酸酯、2-羥基-3-環己基氧丙基甲基丙烯酸酯等。 上述醇類可與碳數1〜4之飽和脂肪族醇、例如、甲 醇、乙醇、正丙醇、異丙醇、正丁醇、第三丁醇等一部份 混合使用。 前述式（5)所示聚醯亞胺先質中、以6與R7之合計 莫耳爲100%時、R6與R7之70莫耳％以上以來自上述醇 類之具有不飽和雙鍵之有機基較佳、90莫耳％以上更佳、 95莫耳％以上最佳。 將上述本發明恰當之芳香族酸二酐與醇類、於呲啶等 鹼性触媒存在下、藉由適當溶媒中撹拌溶解、混合、來進 行酸酐之酯化反應、可得到所要之半酸/半酯體。 反應溶媒以可將半酸/半酯體、及此與二胺成分之爲 醯胺縮聚生成物之聚醯亞胺先質予以完全溶解者較佳、例 如N-甲基-2-呲咯啶酮、N，N-二甲基乙醯胺、N，N —二 甲基甲醯胺、二甲基亞碾、四甲脲（tetramethyl urea)、 γ-丁內酯等。 -25- (22) (22)200403532 其他、溶媒有酮頻、酯類、內酯類、醚類、鹵化烴 類、烴類、例如、丙酮、甲基乙基酮、甲基異丁基酮、環 己酮、乙酸甲酯、乙酸乙酯、乙酸丙酯、草酸二乙酯、乙 二醇二甲醚、二乙二醇二甲醚、四氫呋喃、二氯甲烷、 1，2 -二氯乙烷、1，4 -二氯丁烷、氯苯、鄰二氯苯、已 烷、庚烷、苯、甲苯、二甲苯等。該等可因應需要、單獨 或混合使用。 (聚醯亞胺先質之調製） 在上述半酸/半酯體溶液中、於冰冷下、將適當的脫 水縮合劑、例如、將二環己基碳二醯亞胺、1 一乙氧基羰 基-2-乙氧基-1，2-二氫喹啉、1，1-羰基二氧-二-1，2，3-苯并***、N，Ν’-二琥珀醯亞胺基碳酸酯）等予以投入混 合、使半酸/半酯體成爲聚酸酐後、將本發明所恰當使用 之含2價芳香族基Υ2之二胺類、使溶解或分散於其他途 徑溶媒之物予以滴定投入、並以醯胺縮聚、而可得到標的 之聚醯亞胺先質。 本發明所恰當使用之、含2價芳香族基 Υ2之二胺 類，有例如對亞苯二胺、間亞苯二胺、4， 4’-二氨基二 苯醚、3， 4’-二氨基二苯醚、3，3’一二氨基二苯醚、4, 4 f -二氨基二苯基硫化物、3，4 ’ -二氨基二苯基硫化物、 3， 3’ -二氨基二苯基硫化物、4，4'-二氨基二苯基颯、 3，4’-二氨基二苯基颯、3，3’-二氨基二苯基礪、4，4’-二 氨基聯苯、3，4’-二氨基聯苯、3，3、二氨基聯苯、4，4 -26- (23) (23)200403532 一二氨基二苯基酮、3，4-二氨基二苯基酮、3，3’-二氨基 二苯基酮、4，4’-二氨基二苯甲烷、3， 4’-二氨基二苯甲 烷、3，3 ’ -二氨基二苯甲烷、1，4 -雙（4 -氨基苯氧基）苯、 1， 3 -雙（4 -氨基苯氧基）苯、1，3 -雙（3 -氨基苯氧 基）苯、雙〔4-(4-氨基苯氧基）苯基〕颯、雙〔4-(3· 氨基苯氧基）苯基〕颯、4，4 -雙（4 -氨基苯氧基）聯苯、 4，4 -雙（3 -氨基苯氧基）聯苯、雙〔4-(4 -氨基苯氧基） 苯基〕醚、雙〔4-(3-氨基苯氧基）苯基〕醚、1 ，4-雙 (4-氨基苯基）苯、1，3-雙（4-氨基苯基）苯、9，10-雙 (4-氨基苯基）蒽、2，2-雙（4-氨基苯基）丙烷、2，2-雙（4-氨基苯基）六氟丙烷、2，2-雙〔4-(4-氨基苯氧 基）苯基〕丙烷、2，2 -雙〔4-(4 -氨基苯氧基）苯基〕 六氟丙烷、1，4-雙（3 -氨基丙基二甲基甲矽烷基 (silyl ))苯、聯鄰甲苯胺碼（（ortho-tolidine sulfone ) ) 、9，9-雙（4-氨基苯基）莽、及該等苯環上 氫原子之一部份、係以甲基、乙基、甲氧基、乙氧基、鹵 素等所取代者、例如3， 3’-二甲基-4，4-二氨基聯苯、 2， 2’ -二甲基-4，4'一 二氨基聯苯、3，3 -二甲基-4，4’一 二氨基二苯甲烷、2，2’-二甲基-4，4’-二氨基二苯甲烷、 3，3 — 二甲氧基-4，4’-二氨基聯苯、3，3’ -二氯-4，4’-二 氨基聯苯、及其混合物等。 又爲了提高與各種基板之密接性目的、可使1，3-雙 (3 -氨基丙基）四甲基二矽氧烷、1，3 -雙（3 -氨基丙 基）四苯基二矽氧烷等之二氨基矽氧烷類共聚合之。 •27- (24) (24)200403532 在反應完成後、可將該反應液中所共存之脫水縮合劑 之吸水析出物因應需要予以濾除。接著、在該反應液、將 水或脂肪族低級醇、或其混合液等之、相對於所得聚合物 成分爲劣溶媒予以投入，使析出聚合物成分、進而重覆再 溶解、再沈澱析出操作而予以精製、進行真空乾燥以離析 出標的物之聚醯亞胺先質成分。 爲使精製度更加提高、則使陰陽離子交換樹脂在適當 有機溶媒潤漲之，使此聚合物溶液通過已充塡之柱、除去 離子性不純物亦可。 <B成分> 其次、就具有光聚合性不飽和雙鍵之單體、B成分加 以説明。 作爲本發明負型感光性樹脂組成物之B成分使用、 具有光聚合性不飽和雙鍵之單體、以光聚合引發劑所致可 聚合之（間位）丙烯基化合物較佳、例如聚乙二醇二丙烯 酸酯，（各乙二醇單位數爲2〜20)、聚乙二醇二甲基丙 烯酸酯（各乙二醇單位數爲 2〜20 )、聚（1，2-丙二 醇）二丙烯酸酯、聚（1，2 _丙二醇）二甲基丙烯酸酯、 新戊四醇（pentaerythritol )二丙烯酸酯、新戊四醇二甲 基丙烯酸酯、甘油二丙烯酸酯、甘油二甲基丙烯酸酯、二 新戊四醇六丙烯酸酯、亞甲基雙丙烯醯胺、N —羥甲基丙 烯醯胺、乙二醇二環氧丙基醚甲基丙烯酸加成物、甘油二 環氧丙基醚丙烯酸加成物、雙酚A二環氧丙基醚丙烯酸 -28- (25) (25)200403532 加成物、雙酚A二環氧丙基醚甲基丙烯酸加成物、N，N，-雙（2 -異丁烯醯基（methacryl〇yl)氧乙基）脲等、但不 限定於該等。又在使用該等時、可因應需要、單獨或混合 2種以上使用。 B成分之添加量、相對於本發明之A成分、以1〜50 質量份較佳。但、本發明之 A成分爲聚苯幷鸣唑先質 時、爲1 0〜50質量份、較佳爲20〜50質量份、更佳爲 30〜45質量份。又、本發明之a成分爲聚醯亞胺先質之 情形、爲1〜5 0質量份、較佳爲1〜2 0質量份、更佳爲1 〜1〇質量份。B成分添加量若爲1質量份以下、則因光聚 合時之橋聯密度過低、光感度降低、造成顯像後凸紋花樣 之潤漲激烈、無法得到實用的凸紋花樣、又添加量在50 質量份以上時、相反的光聚合時之橋聯密度過高、故在曝 光之際、因自基板面之散乱光所致末曝光部之影響變大、 故在末曝光部顯像後残渣易於產生、並不合適。 其次、就光聚合引發劑C成分加以説明。 作爲本發明負型感光性樹脂組成物之C成分使用的 光聚合引發劑、有例如： (a) 二苯基酮、鄰苯甲醯基苯甲酸甲酯、4_苯甲醯 基-V-甲基二苯酮、二苯甲酮、莽酮等之二苯基酮衍生物 (b) 2，2-二乙氧基乙醯苯、2-羥基-2-甲基丙醯苯、 1 -羥基環己基苯酮等之乙醯苯衍生物、 •29- (26) (26)200403532 (c )氧硫U山喔（thioxanthone) 、2 -甲基氧硫d山喔、 2-異丙基氧硫fl山喔、二乙基氧硫ϋ山喔等之氧硫山星衍生物、 (d)苄、苄基二甲基縮酮（ketai)、苄基-β-甲氧基 乙基縮醛等之苄基衍生物、 (e )安息香、安息香甲基醚等之安息香衍生物、 (f) 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 之肟類、 等較佳。又在使用該等時、可單獨或爲2種以上之混 合物亦無妨。 上述光聚合引發劑中、尤其就光感度而言、以（f) 之肟類較佳。C成分之添加量、相對於本發明之A成分、 爲1〜20質量份、較佳爲2〜10質量份、更佳爲4〜8質 量份。此係添加量在1質量份以下時、於曝光之際、只使 光游離基聚合（radical polymerlization)充分進行之游離 基並不供給、使得光感度降低、造成顯像後圖案的潤漲激 烈、難以得到實用的凸紋花樣、相反的添加量在2 0重量 部以上時、在塗膜表面附近之曝光光線吸收會變得過大、 因此曝光光線無法到達基板面附近、造成光橋聯在膜厚方 向不均勻、終無法得到實用的凸紋花樣。 -30- (27) 200403532 <D成分> 其次、就D成分之蜜胺樹脂加以説明。 本發明所用D成分之蜜胺樹脂係指：具有下述化學式 (7)所示構造之單體、或該單體所聚合之聚合體辑該單 體之混合物。D成分係在A成分加熱環化處理之際、同時 與 A成分橋聯、或者其本身爲可形成橋聯網路之化合 物、在用於本發明負型感光性樹脂組成物時、加熱硬化處 理後之聚苯并噚唑皮膜及聚醯亞胺皮膜、顯現習知所無之 優異耐熱性、耐藥品性、高溫耐焊藥（flux )性。f ~ CH2 In the present invention, the polyimide precursor represented by the chemical formula (5) is firstly an aromatic tetracarboxylic dianhydride containing a tetravalent aromatic group X2 and an alcohol having a photopolymerizable unsaturated double bond. For the reaction of saturated and / or saturated aliphatic alcohols having 1 to 4 carbon atoms, after adjusting the half acid / half ester body, it is reacted with an aromatic diamine containing a divalent aromatic group Y2 Classes are obtained by polycondensation of amidine. (Semi-acid / half-ester preparation) Anhydride includes, for example, pyromellitic anhydride, diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride, and diphenyl ketone-3 , 3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic dianhydride, diphenylhydrazone-3, 3 ', 4,4, tetracarboxylic acid Dianhydride, diphenylmethane-3,3 ', 4,4'-tetracarboxylic dianhydride, 2,2 · bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-phthalic anhydride ) -1,1,1,3,3,3-hexafluoropropane and so on. Of course, these can be used alone or in combination of two or more. The alcohols having a photopolymerizable unsaturated double bond that can be suitably used in the present invention include, for example, 2-propenyloxyethanol, 1-propenyloxy-3-propanol, 2-propenylamine ethanol, methylol Ketene, 2-hydroxyethylketene, 2-hydroxy-3--24- (21) (21) 200403532 methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2 -Hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butylpropyl acrylate, 2-hydroxy-3-third butoxypropyl acrylate, 2-hydroxy-3-cyclohexyl Oxypropyl acrylate, 2-methacrylfluorenyloxyethanol, 1-methacrylfluorenyloxy-3-propyl alcohol, 2-methacrylamide ethanol, 2-hydroxy-3-methoxypropyl Methyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methyl Acrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like. The above-mentioned alcohols can be mixed with a saturated aliphatic alcohol having 1 to 4 carbon atoms, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol. Among the polyfluorene imine precursors represented by the above formula (5), when the total mole of 6 and R7 is 100%, and the molar mole of R6 and R7 is more than 70%, organic compounds having unsaturated double bonds derived from the above alcohols are used. The base is preferably, more preferably 90 mol% or more, and most preferably 95 mol% or more. The appropriate aromatic acid dianhydride of the present invention, alcohols, and the presence of a basic catalyst such as pyridine, are mixed and dissolved in a suitable solvent, and mixed to carry out the esterification reaction of the acid anhydride to obtain the desired semiacid / Semi-ester. The reaction solvent is preferably one which can completely dissolve the half acid / half ester body and the polyimide precursor which is a polycondensation product of diamine with diamine component, such as N-methyl-2-pyrrolidine Ketones, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylmethylene, tetramethyl urea, γ-butyrolactone, and the like. -25- (22) (22) 200403532 Others, solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone , Cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethyl Alkane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like. These can be used individually or in combination as needed. (Preparation of polyfluorene imine precursor) In the above-mentioned semi-acid / half-ester solution, under ice cooling, an appropriate dehydrating condensing agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl -2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-bissuccinimide carbonate ), Etc. After mixing and making the semi-acid / half-ester into a polyanhydride, the diamines containing the divalent aromatic group Υ2 suitably used in the present invention and the substances dissolved or dispersed in other routes of the solvent are titrated. And polycondensation with amidine, the target polyimide precursor can be obtained. Diamines containing divalent aromatic fluorene 2 suitably used in the present invention include, for example, p-phenylene diamine, m-phenylene diamine, 4, 4'-diaminodiphenyl ether, 3, 4'-di Amino diphenyl ether, 3,3'-diaminodiphenyl ether, 4, 4 f-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3, 3'-diaminodi Phenyl sulfide, 4,4'-diaminodiphenylphosphonium, 3,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminobiphenyl , 3,4'-diaminobiphenyl, 3,3, diaminobiphenyl, 4,4 -26- (23) (23) 200403532 monodiaminodiphenyl ketone, 3,4-diaminodiphenyl Ketone, 3,3'-diaminodiphenyl ketone, 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-amino Phenoxy) phenyl] fluorene, bis [4- (3 · aminophenoxy) phenyl] fluorene, 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-amino Phenoxy) phenyl] hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone), 9, 9-bis (4-aminophenyl), and a part of the hydrogen atom on these benzene rings, are substituted with methyl, ethyl, methoxy, ethoxy, halogen, etc., such as 3, 3'-dimethyl-4,4-diaminobiphenyl, 2, 2'-dimethyl-4,4'-diaminobiphenyl, 3,3-dimethyl-4,4'-diamino Diphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro -4,4'-diaminobiphenyl, and Mixtures. In order to improve the adhesion with various substrates, 1,3-bis (3-aminopropyl) tetramethyldisilazane and 1,3-bis (3-aminopropyl) tetraphenyldisilazide can be used. Dioxane and other diaminosilane are copolymerized. • 27- (24) (24) 200403532 After the reaction is completed, the water-absorbent precipitates of the dehydration condensation agent coexisting in the reaction solution can be filtered as necessary. Next, in this reaction solution, water, an aliphatic lower alcohol, or a mixed solution thereof is introduced as a poor solvent with respect to the obtained polymer component, and the polymer component is precipitated, and then re-dissolved and re-precipitated. Then, it is purified and vacuum-dried to isolate the polyimide precursor component of the target. In order to further improve the precision system, the anion-cation exchange resin is allowed to swell in an appropriate organic solvent, and the polymer solution may be passed through a packed column to remove ionic impurities. < Component B > Next, the monomer having a photopolymerizable unsaturated double bond and the component B will be described. As the B component of the negative photosensitive resin composition of the present invention, a monomer having a photopolymerizable unsaturated double bond and a polymerizable (meta) propylene-based compound caused by a photopolymerization initiator are preferred, such as polyethylene Diethylene glycol diacrylate (2 to 20 for each ethylene glycol unit), polyethylene dimethacrylate (2 to 20 for each ethylene glycol unit), poly (1,2-propanediol) Acrylate, poly (1,2-propylene glycol) dimethacrylate, pentaerythritol diacrylate, neopentaerythritol dimethacrylate, glycerol diacrylate, glycerol dimethacrylate, Dipentaerythritol hexaacrylate, methylene bisacrylamide, N-hydroxymethacrylamine, ethylene glycol diglycidyl ether methacrylic acid adduct, glycerin diglycidyl ether acrylic acid Adduct, Bisphenol A Diglycidyl Ether Acrylic Acid-28- (25) (25) 200403532 Adduct, Bisphenol A Diglycidyl Ether Methacrylic Acid Adduct, N, N, -Bis (2-methacryloyloxyethyl) urea and the like are not limited thereto. When using these, you can use them alone or in combination of two or more according to your needs. The added amount of the B component is preferably 1 to 50 parts by mass based on the A component of the present invention. However, when the component A of the present invention is a polybenzimidazole precursor, it is 10 to 50 parts by mass, preferably 20 to 50 parts by mass, and more preferably 30 to 45 parts by mass. In the case where the component a of the present invention is a polyimide precursor, it is 1 to 50 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass. If the component B is added in an amount of 1 part by mass or less, the bridge density during photopolymerization is too low, the light sensitivity is reduced, and the embossed pattern after the development is intensely increased. A practical embossed pattern cannot be obtained. When it is 50 parts by mass or more, the bridge density during the opposite photopolymerization is too high. Therefore, during exposure, the influence of the unexposed portion due to the scattered light from the substrate surface becomes large. Therefore, after the unexposed portion is developed, Residues are easy to produce and are not suitable. Next, the photopolymerization initiator C component will be described. Examples of the photopolymerization initiator used as the C component of the negative photosensitive resin composition of the present invention include: (a) diphenyl ketone, methyl o-benzoyl benzoate, 4-benzyl phenyl-V- Diphenyl ketone derivatives such as methyl benzophenone, benzophenone, and manganese (b) 2,2-diethoxyacetanilide, 2-hydroxy-2-methylpropanone, 1- Ethylbenzene derivatives such as hydroxycyclohexyl phenone, • 29- (26) (26) 200403532 (c) thioxanthone, 2-methyloxysulfan d, 2-isopropyl Oxythiofloxacin, diethyloxanthine and other oxanthine derivatives, (d) benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl ketal Benzyl derivatives such as aldehydes, (e) benzoin derivatives such as benzoin, benzoin methyl ether, (f) 1-phenyl1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1 -Phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-benzene -1,2-propanedione-2- (o-benzylidene) oxime, 1,3-diphenylglycerone-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3- Ethoxyglycerone-2- (o Acyl methyl) oxime oxime, etc., and so preferred. When these are used, they may be used alone or as a mixture of two or more. Among the above-mentioned photopolymerization initiators, the oximes of (f) are particularly preferred in terms of photosensitivity. The amount of the component C to be added is 1 to 20 parts by mass, preferably 2 to 10 parts by mass, and more preferably 4 to 8 parts by mass with respect to the component A of the present invention. When the added amount is less than 1 part by mass, only free radicals that sufficiently undergo radical polymerlization are not supplied during exposure, resulting in a decrease in photosensitivity and a sharp increase in the pattern after development. It is difficult to obtain a practical embossed pattern. When the opposite addition amount is more than 20 parts by weight, the exposure light absorption near the surface of the coating film will become too large, so the exposure light cannot reach the vicinity of the substrate surface, resulting in optical bridges in the film thickness The direction is not uniform, and a practical convex pattern cannot be obtained. -30- (27) 200403532 < D component > Next, the melamine resin of the D component will be described. The melamine resin of the D component used in the present invention means a monomer having a structure represented by the following chemical formula (7), or a polymer of the monomer and a mixture of the monomer. The D component is a compound that is bridged with the A component at the same time as the heating and cyclization treatment of the A component, or is a compound that can form a bridge network. When used in the negative photosensitive resin composition of the present invention, it is after heat curing treatment. The polybenzoxazole film and polyimide film exhibit excellent heat resistance, chemical resistance, and high-temperature flux resistance that are not known in the art.

R14\ /Rl5 NR14 \ / Rl5 N

Rl 7 NIR1 \ niri 中 式 示 所 Nly 8 式 述 下 或 子 原 氫 之 立 獨 0 各 爲 9 1 ο -R» 4機 R1有 、 価Rl 7 NIR1 \ niri Chinese formula display Nly 8 formula described below or the original hydrogen stand alone 0 each for 9 1 ο -R »4 machines R1 Yes, 価

Η——C—HΗ——C—H

Z 8 但、取代基r14〜r19全部並非氫原子。又z爲氫原 子或碳數1〜4之脂肪族基，非全爲氫原子。） -31 - (28) (28)200403532 上記式（7)中R14〜R19爲各自獨立、表示氫原子、 經基、甲基、烷氧甲基之任一、全部爲氫原子者、亦即蜜 胺本身、在本發明中並無法期待D成分所應產生之熱橋 聯効果。要期待熱橋聯効果、則Rl 4〜r19之至少2處以 上、係以羥甲基及/或烷氧甲基所取代、此取代程度越 局、則本發明聚醯胺及爲其熱變質（thermal meta morphism )體之聚苯并噚唑或聚醯亞胺之分子間橋聯効率 可提高。 又、將羥甲基所取代者與烷氧甲基所取代者加以比 較、在烷氧甲基所取代者一方自我縮合性較低、因此可提 高本發明負型感光性樹脂組成物之保存穩定性，爲更佳。 此烷氧甲基、具體而言以甲氧甲基、乙氧甲基、正丙 氧甲基、異丙氧甲基、正丁氧甲基、第三丁氧甲基等爲恰 當之例子。 又、此烷氧甲基之取代部位、可爲上述恰當例中任 一’或只有一種之構造亦可，以多數種類混在一起之形式 亦可、若考慮穩定性或橋聯効率、則上述化學式（8 )之 Z、爲更低分子量較佳。因此學式（7)中之R14〜r19均 爲甲氧甲基者、亦即六甲氧甲基蜜胺、作爲本發明之d 成分最佳° 本發明可恰當使用之蜜胺樹脂、聚合度在丨.〇時爲單 體、亦即具有化學式（7)所示基本單位構造本身。又聚 合度在1 . 〇以上者、通常、係在化學式（7 )之環上鍵結 之氮原子之一部份、藉由-CH2-、或者-CH2-〇-CH2-構造、 -32- (29) (29)200403532 與鍵結於鄰接之基本單位構造之環的氮原子相連接、係二 聚物以上多數成分所成聚合體成分與爲基本單位構造本身 之單體成分的混合體。其聚合度、通常係以凝膠滲透色層 分析法 GP C ( gel permeation chromatograph )之峰値面積 比所致加重平均聚合度來表示。 本發明中、可恰當使用之上述蜜胺樹脂、聚合度 (GPC峰値面積比加重平均聚合度）在1.0以上者、僅由 該聚合度之單一成分所構成者即可，爲單體成分與二聚物 以上之多數聚合物成分之混合體亦可、其聚合度（GPC峰 値面積比加重平均聚合度）爲1.0以上、2.2以下較佳。 此係因爲蜜胺樹脂之聚合度越高、在本發明之負型感 光性樹脂組成物中、爲其主成分之聚醯胺的相溶性會降 低、故其本身易於凝集、同時蜜胺樹脂間之自我縮合亦易 於產生。其聚合度在2.2以上時、蜜胺樹脂成分會析出、 使得組成物之保存穩定性降低之傾向變的顯著。 又、D成分之添加量、相對於本發明之聚醯胺A成 分、爲5〜30質量份、較佳爲5〜20質量份、更佳爲8〜 1 5質量份。此係因爲添加量在5質量份以下時、本發明 的各効果、亦即聚苯并噚唑皮膜或聚醯亞胺皮膜之耐熱 性、耐藥品性之提高効果會非常薄弱、而添加量在3 0質 量份以上時、本發明的各効果雖充分、但在感光性樹脂組 成物中、其本身易凝集、同時蜜胺樹脂間之自我縮合亦容 易產生、故蜜胺樹脂成分會析出、組成物之保存穩定性的 降低傾向變得顯著。 -33- (30) (30)200403532 <其他成分> 除了以上4種類成分以外、在本發明之負型感光性樹 脂組成物、可因應需要、添加光感度提高用之増強劑 (intensifier )。此等増強劑有例如米蚩酮（michler’s ketone) 、4，4’ -雙（二乙基氨基）二苯基酮、2， 5-雙 (4-二乙基氨基亞苄基）環戊酮、2，6-雙（4-二甲基氨 基亞苄基）環戊酮、2，6-雙（4-二甲基氨基亞苄基）-4-甲基環戊酮、2，6-雙（4-二甲基氨基亞苄基）-4-甲基環 戊酮、4，4’-雙（二甲基氨基）查耳酮（chalcone) 、4， 4-雙（二乙基氨基）查耳酮、2- (4-二甲基氨基亞桂皮基 (cinnamy lidene ))二氫茚酮、2- (4 -二甲基氨基亞节 基）二氫茚酮、2-(對-4-二甲基氨基聯苯）苯并噻唑、 1，3-雙（4-二甲基氨基亞苄基）丙酮、1，3-雙（4-二甲 基氨基亞苄基）丙酮、3，3-羰基-雙（7-二甲基氨基香豆 素）、3-乙醯基-7-二甲基氨基香豆素、3-乙氧基羰基- 7-二甲基氨基香豆素、3-苄基氧羰基-7-二甲基氨基香豆 素、3-甲氧基羰基-7-二乙基氨基香豆素、3-乙氧基羰基-7-二乙基氨基香豆素、N —苯基-N-乙基乙醇胺、N-苯基 二乙醇胺、N-對芴基二乙醇胺、N —苯基乙醇胺、4-味啉 二苯基酮、4 -二甲基氨基苯甲酸異戊（isoamyl)酯、4 -二 乙基氨基苯甲酸異戊酯、2 -氫硫苯并咪1¾、：I -苯基-5-氫硫 基-1，2，3，4 -四唑、1 -環己基-5 -氫硫基· 1，2，3，4 -四 唑、卜（第三丁基）-5-氫硫基-1，2，3，4-四唑、2 -氫硫 -34- (31) (31)200403532 基苯並噻唑（benzothiazole) 、2-(對二甲基氨基苯乙燦 基）苯並噚唑、2-(對二甲基氨基苯乙烯基）苯並噻唑、 2_(對二甲基氨基苯乙烯基）萘基（1，2-對）噻唑、 (對二甲基氨基苯甲醯基）苯乙烯等。又在使用時、可單 獨或爲2種以上之混合物。其添加量、亦有與其他添加劑 成分兼顧者、相對於聚醯胺成分則以1 5質量份以下較 佳。 又、爲形成負型感光性樹脂組成物之淸漆 (varnish )、可使用稀釋溶劑、此種溶劑成分有例如、 N，N-二甲基甲醯胺、N，N -二甲基乙醯胺、N -甲基-2·呲 咯啶酮、二甲基亞颯、六甲基磷酸胺、呲啶、γ-丁內酯、 a -乙醯基-γ-丁內酯、二乙二醇單甲醚、二乙二醇二甲醚、 丙二醇單甲醚、丙二醇單甲醚乙酸酯、乳酸乙酯、乳酸丁 酯等。在使用時、可單獨或2種以上之混合物亦無妨。 本發明之負型感光性樹脂組成物、可因應所需爲提高 保存時組成物溶液之粘度或光感度之穩定性，可添加阻聚 劑（condensation inhibitor )。此等阻聚劑可使用例如、 氫醌、N —亞硝二苯胺、對第三丁基兒茶酚、啡噻畊 (Phenothiazine ) 、N —苯基萘基胺、乙烯二胺四乙酸酯、 1，2 -環己烷二胺四乙酸酯、乙二醇醚二胺四乙酸酯、2， 6-二-第三丁基對甲基酚、5 —亞硝基-8-羥基喹啉、1 一亞 硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5- ( N —乙基-N —硫丙胺）酚、N —亞硝.基-N-苯基羥胺銨鹽、N-亞硝 基-N-苯基羥胺銨鹽、N —亞硝基-N- ( 1-萘基）羥胺銨鹽、 -35- (32) (32)200403532 雙（4-羥基-3，5 -第三丁基）苯甲烷等、但並不限於此。 其添加量相對於本發明之聚醯胺成分、以5質量份以下較 佳。添加量在5質量份以上時，會阻礙原來應期待之光橋 聯反應本身、有引起光感度降低之虞。 除以上之外、在本發明感光性樹脂組成物、以散亂光 吸收劑或塗膜平滑性賦予劑、矽烷偶合劑爲始、在不阻礙 本發明負型感光性樹脂組成物各特性之範圍、可因應需 要、適當配合各種添加劑。 本發明之負型感光性樹脂組成物之使用例如以下所 示。 首先將該組成物塗敷於適當基材、例如矽晶圓、陶 瓷、鋁基板等。塗敷方法可利用旋轉塗敷法、噴灑塗敷 法、浸漬、印刷、刀塗敷法、滾輪塗敷法等。在80〜120 °C下預先烘烤，於塗膜乾燥後、使用接觸式光刻機 (contact aligner )、鏡面聚光(mirror projection)、分 節器（stepper)等之曝光投影 置、藉由所要之光掩罩來 照射化學線。 化學線可利用 X線、電子線、紫外線、可視光線 等、在本發明中以使用 200〜5 OOnm波長之物較佳。就圖 案之解像度及處理性而言、其光源波長尤其在UV-i線 (3 6 5 n m )較佳、曝光投影 置則以分卽益較佳。 其後、爲提高光感度等之目的、可因應需要以任意溫 度、時間之組合（較佳是溫度40〜120 °C、時間1 〇秒〜 240秒）來進行曝光後烘烤（PEB )或顯像前烘烤均可。 -36- (33) (33)200403532 接著進行顯像、可選擇浸漬法、攪拌（paddle )法、 旋轉噴灑法等方法來進行。 顯像液係、在塗膜爲本發明鹼惶可溶性聚苯并哼唑先 質組成物所成時、可使用氫氧化鈉、碳酸鈉、矽酸鈉、氨 水等之無機鹼類、乙胺、二乙胺、三乙胺、三乙醇胺等有 機胺類、氫氧化四甲基銨、氫氧化四丁基銨等4級銨塩類 等之水溶液、及在該等可因應需要適量添加甲醇、乙醇等 之水溶性有機溶媒或界面活性劑等來使用。 塗膜爲本發明之聚醯亞胺先質組成物所成時、顯像液 可單獨使用其優溶媒、或者優溶媒與劣溶媒予以適宜混合 使用。優溶媒有、N-甲基-2-呲咯啶酮、N-乙醯基一 2-呲 咯啶酮、N，N-二甲基乙醯胺、N，N-二甲基甲醯胺、二 甲基亞颯、γ-丁內酯、α -乙醯基-γ-丁內酯、環戊酮，環己 酮等。劣溶媒則有甲苯、二甲苯、甲醇、乙醇、異丙醇、 丙二醇單甲醚乙酸酯、丙二醇單甲醚及水等可使用。在混 合使用優溶媒及劣溶媒時、其混合比率、可因應使用之聚 醯亞胺先質組成物塗膜之溶解性或使用之顯像方法來加以 調整。 顯像完成後、以淸洗液洗浄、藉除去顯像液、以獲得 負型附有圖案之塗膜。淸洗液可單獨或適宜混合蒸餾水、 甲醇、乙醇、異丙醇、甲苯、二甲苯、丙二醇單甲醚乙酸 酯、丙二醇單甲醚等使用、又可階段性的組合使用。 如此所得聚醯胺之附有圖案之塗膜、加熱至200 °C 以上、進行脫水環化反應、又同時產生橋聯’而可變換成 -37- (34) (34)200403532 富有耐熱性或耐藥品性的聚苯并噚唑皮膜或聚醯亞胺皮 膜。此種加熱環化處理、係使用電爐（hot plate )、惰性 爐（inert )、可設定溫度計畫之升溫式爐等來進 行。在加熱環化之際的氛圍氣體可使用空氣、亦可使用 氮、氬等惰性氣體。 藉含有上述聚醯胺之負型感光性樹脂組成物、可製造 半導體裝置。又使用上述聚苯并噚唑皮膜或聚醯亞胺皮膜 所致凸紋花樣形成方法、可製造半導體裝置。 以下、依實施例詳細說明本發明實施形態之例。 参考例1 (聚苯并噚唑先質PB 0-1之合成） 在容量2升之可分離燒瓶（separable flask)中、將 N，N_ 二甲基乙醯胺（DMAc ) 43 6 g、呲啶 13.45g (〇·17莫耳）、2，2-雙（3-氨基-4-羥苯基）六氟丙烷 (6FAP ) 1 24.5 3 g (0.3 4 莫耳），在室溫（24 t：) 下混合攪拌、溶解之。對此，將由其他途徑之二乙二醇二 甲醚（DMDG) 248 g中，使二苯醚_4，4’-二羰基二氯 (DEDC ) 82.63 g ( 0.28莫耳）溶解之物、藉滴定漏斗 予以滴定。此時、以1 5〜20 °C 水浴下來冷卻可分離燒 瓶。滴定所要時間約20分、反應液溫最高爲3 0 °C。Z 8 However, all of the substituents r14 to r19 are not hydrogen atoms. Z is a hydrogen atom or an aliphatic group having 1 to 4 carbon atoms, and not all of them are hydrogen atoms. ) -31-(28) (28) 200403532 In the above formula (7), R14 to R19 are each independently and represent a hydrogen atom, any of a methyl group, a methyl group, and an alkoxymethyl group, all of which are hydrogen atoms, that is, The melamine itself, in the present invention, cannot expect the thermal bridging effect that the D component should have. To expect the thermal bridging effect, at least two or more of Rl 4 to r19 are replaced by methylol and / or alkoxymethyl. The degree of substitution is more serious. The polyamidamine of the present invention and its thermal deterioration (Thermal meta morphism) The intermolecular bridging efficiency of polybenzoxazole or polyimide can be improved. In addition, when the hydroxymethyl group is substituted with the alkoxymethyl group, the self-condensation property is lower on the alkoxymethyl group, so the storage stability of the negative photosensitive resin composition of the present invention can be improved. Sex is better. Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, an n-butoxymethyl group, and a third butoxymethyl group. In addition, the substitution site of this alkoxymethyl group may be any one of the above-mentioned appropriate examples, or may have only one structure, and may be mixed in the form of a plurality of types. If stability or bridging efficiency is considered, the above chemical formula (8) Z is preferably a lower molecular weight. Therefore, R14 to r19 in the formula (7) are all methoxymethyl, that is, hexamethoxymethylmelamine, which is the best component d in the present invention. The degree of polymerization of the melamine resin that can be properly used in the present invention is between丨 .00 is a monomer, that is, it has the basic unit structure itself represented by chemical formula (7). Those having a polymerization degree of 1.0 or more are usually a part of a nitrogen atom bonded to a ring of the chemical formula (7), a structure of -CH2- or -CH2-〇-CH2-, -32- (29) (29) 200403532 It is a mixture of a polymer component formed by most of the dimer and the monomer component that is connected to the nitrogen atom bonded to the ring of the adjacent basic unit structure and a monomer component that is the basic unit structure itself. The degree of polymerization is usually expressed by the weighted average degree of polymerization due to the peak-to-peak area ratio of the gel permeation chromatograph (GP C). In the present invention, the above-mentioned melamine resin, which can be suitably used, has a degree of polymerization (GPC peak-to-area area ratio increased average degree of polymerization) of 1.0 or more, and can be composed of only a single component of the degree of polymerization. A mixture of a plurality of polymer components of a dimer or more may also be used, and the polymerization degree (GPC peak-to-area area ratio weighted average polymerization degree) is preferably 1.0 or more and 2.2 or less. This is because the higher the degree of polymerization of the melamine resin, the lower the compatibility of the polyamide, which is the main component, in the negative photosensitive resin composition of the present invention, so that it is easy to agglutinate itself, and at the same time between melamine resins. Self-condensation is also easy to produce. When the degree of polymerization is 2.2 or more, the melamine resin component is precipitated, and the tendency of the storage stability of the composition to decrease is significant. The added amount of the D component is 5 to 30 parts by mass, preferably 5 to 20 parts by mass, and more preferably 8 to 15 parts by mass based on the polyamine A component of the present invention. This is because when the added amount is 5 parts by mass or less, each effect of the present invention, that is, the effect of improving the heat resistance and chemical resistance of the polybenzoxazole film or polyimide film is very weak. When 30 parts by mass or more, the effects of the present invention are sufficient, but in the photosensitive resin composition, it is easy to agglomerate, and at the same time, self-condensation between melamine resins is also easy to occur. Therefore, the melamine resin component is precipitated and the composition The reduction tendency of the storage stability of the material becomes remarkable. -33- (30) (30) 200403532 < Other ingredients > In addition to the above four types of ingredients, in the negative photosensitive resin composition of the present invention, it is possible to add an intensifier for light sensitivity improvement according to need. . These strong agents are, for example, michler's ketone, 4,4'-bis (diethylamino) diphenyl ketone, 2,5-bis (4-diethylaminobenzylidene) cyclopentanone , 2,6-bis (4-dimethylaminobenzylidene) cyclopentanone, 2,6-bis (4-dimethylaminobenzylidene) -4-methylcyclopentanone, 2,6- Bis (4-dimethylaminobenzylidene) -4-methylcyclopentanone, 4,4'-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) ) Chalcone, 2- (4-dimethylaminocinene) dihydroindenone, 2- (4-dimethylaminoidene) dihydroindenone, 2- (p- 4-dimethylaminobiphenyl) benzothiazole, 1,3-bis (4-dimethylaminobenzylidene) acetone, 1,3-bis (4-dimethylaminobenzylidene) acetone, 3 , 3-carbonyl-bis (7-dimethylaminocoumarin), 3-ethylamino-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin , 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin Element, N-benzene -N-ethylethanolamine, N-phenyldiethanolamine, N-p-fluorenyldiethanolamine, N-phenylethanolamine, 4-tasteline diphenyl ketone, 4-dimethylaminobenzoic acid isoamyl Ester, 4-diethylaminobenzoic acid isoamyl ester, 2-hydrothiobenzimid 1¾ ,: I-phenyl-5-hydrothio-1,2,3,4-tetrazole, 1-cyclohexyl -5 -Hydroxythio · 1,2,3,4-tetrazole, Bu (third butyl) -5-hydrosulfanyl -1,2,3,4-tetrazole, 2-hydrosulfan-34- (31) (31) 200403532 benzothiazole, 2- (p-dimethylaminophenethenyl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2_ (P-dimethylaminostyryl) naphthyl (1,2-p-) thiazole, (p-dimethylaminobenzyl) styrene and the like. In use, it may be used alone or as a mixture of two or more. The addition amount may be compatible with other additive components, and it is preferably 15 parts by mass or less relative to the polyamide component. In order to form a varnish for a negative photosensitive resin composition, a diluent solvent may be used. Examples of such a solvent include N, N-dimethylformamide and N, N-dimethylacetamidine. Amine, N-methyl-2 · pyrrolidone, dimethylsulfinium, hexamethylamine phosphate, pyridine, γ-butyrolactone, a-ethylamyl-γ-butyrolactone, diethylene glycol Alcohol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and the like. In use, it may be used alone or as a mixture of two or more. According to the negative photosensitive resin composition of the present invention, a polymerization inhibitor (condensation inhibitor) may be added in order to improve the stability of the composition solution or the stability of the light sensitivity during storage. As these polymerization inhibitors, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, Phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetate , 1,2-cyclohexanediamine tetraacetate, glycol ether diamine tetraacetate, 2, 6-di-third-butyl-p-methylphenol, 5-nitroso-8-hydroxyl Quinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-thiopropylamine) phenol, N-nitros .-N-phenylhydroxylamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, -35- (32) ( 32) 200403532 Bis (4-hydroxy-3,5-tert-butyl) benzenemethane and the like, but it is not limited thereto. The added amount is preferably 5 parts by mass or less based on the polyamidoamine component of the present invention. When the added amount is 5 parts by mass or more, the optical bridging reaction itself, which was originally expected, may be hindered, and there is a possibility that the photosensitivity may decrease. In addition to the above, the photosensitive resin composition of the present invention starts with a scattered light absorber, a coating film smoothness-imparting agent, and a silane coupling agent within a range that does not hinder each characteristic of the negative photosensitive resin composition of the present invention. 5. Various additives can be appropriately matched according to needs. Examples of the use of the negative photosensitive resin composition of the present invention are shown below. This composition is first applied to a suitable substrate, such as a silicon wafer, ceramic, aluminum substrate, or the like. The coating method may be a spin coating method, a spray coating method, dipping, printing, a knife coating method, a roller coating method, or the like. Bake in advance at 80 ~ 120 ° C, after the coating film is dried, use an exposure projection set such as a contact aligner, mirror projection, stepper, etc. The light mask to shine the chemical rays. The chemical rays may be X-rays, electron rays, ultraviolet rays, visible rays, etc. In the present invention, it is preferable to use a substance having a wavelength of 200 to 500 nm. In terms of resolution and processability, the wavelength of the light source is better in the UV-i line (3 65 nm), and the projection and projection settings are better in terms of resolution. Thereafter, for the purpose of improving light sensitivity, etc., post-exposure baking (PEB) or a combination of any temperature and time (preferably a temperature of 40 to 120 ° C, a time of 10 seconds to 240 seconds) may be used as required. Baking before development is acceptable. -36- (33) (33) 200403532 Next, development is performed by a method such as dip method, paddle method, and rotary spray method. The developing liquid system, when the coating film is made of the alkali-soluble polybenzoxazole precursor composition of the present invention, inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, ammonia water, ethylamine, Diethylamine, triethylamine, triethanolamine and other organic amines, tetramethylammonium hydroxide, tetrabutylammonium hydroxide and other quaternary ammonium hydrazones and other aqueous solutions, and if necessary, appropriate additions of methanol, ethanol, etc. Water-soluble organic solvent or surfactant. When the coating film is formed of the polyimide precursor composition of the present invention, the developing solution can be used alone as a superior solvent, or the superior solvent and the inferior solvent can be appropriately mixed and used. Preferred solvents are, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide , Dimethyl sulfene, γ-butyrolactone, α-ethylamido-γ-butyrolactone, cyclopentanone, cyclohexanone, and the like. Inferior solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water. When a superior solvent and a poor solvent are used in combination, the mixing ratio can be adjusted according to the solubility of the polyimide precursor composition coating film used or the imaging method used. After the development is completed, wash with a cleaning solution, and then remove the developing solution to obtain a negative patterned coating film. The washing liquid can be used alone or as a mixture of distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and the like, and can be used in combination in stages. The patterned coating film of polyamine obtained in this way can be converted to -37- (34) (34) 200403532 with heat resistance or heating when it is heated to 200 ° C or higher to carry out dehydration cyclization reaction. Chemically resistant polybenzoxazole film or polyimide film. This heating and cyclization treatment is performed using an electric furnace (hot plate), an inert furnace (inert), a temperature-increasing furnace that can set a temperature plan, and the like. For the heating and cyclization, air may be used as the atmosphere, and inert gases such as nitrogen and argon may be used. A semiconductor device can be manufactured by using the negative photosensitive resin composition containing the aforementioned polyamide. Furthermore, a semiconductor device can be manufactured by using the method for forming a relief pattern by the above-mentioned polybenzoxazole film or polyimide film. Hereinafter, examples of embodiments of the present invention will be described in detail according to the examples. Reference Example 1 (Synthesis of Polybenzoxazole Precursor PB 0-1) In a separable flask with a capacity of 2 liters, N, N_dimethylacetamide (DMAc) 43 6 g, Pyridine 13.45 g (0.17 mole), 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) 1 24.5 3 g (0.3 4 mole) at room temperature (24 t :) Mix and dissolve. In this regard, from 248 g of diethylene glycol dimethyl ether (DMDG) from other sources, diphenyl ether_4,4'-dicarbonyldichloride (DEDC) 82.63 g (0.28 mole) is dissolved, and The titration funnel is used for titration. At this time, cool the separable flask in a water bath at 15-20 ° C. The time required for the titration is about 20 minutes, and the maximum temperature of the reaction solution is 30 ° C.

滴下完成後攪拌放置1小時、其後、使反應液在5升 水高速攪拌下滴定、將生成之聚合物分散析出、並予回 收、在適宜水洗、脫水後施予真空乾燥、得到兩末端均具 有氨基之聚苯并哼唑先質。此聚合物之聚苯乙烯換算GPC -38- (35) (35)200403532 重量平均分子量（THF溶媒）爲 1 03 00，殘溶媒率爲 1 3.9 5 % ，收率爲 8 6 · 5 1 % 。 参考例2 (感光性聚苯并鸣唑先質PSP-1之合成） 在参考例1所得PBO-1，藉以下方法導入具有光聚合 性不飽和雙鍵之有機基。 將PB 0-1之乾燥粉體100g放入容量1升之可分離燒 瓶、添加γ-丁內酯（GBL ) 400g、再溶解之、添加二丁基 錫二月桂酸酯〇 · 8 5 g、於油浴下加溫至5 0 °C。對此、將 由其他途徑之GBL 5 lg，溶解有2-異氰酸基乙基甲基丙烯 酸酯16.94 g (0.109莫耳。此係自PBO-1之收率及對該 反應之使用量所算出、相當於PB 0-1之全羥基的35莫耳 % )之物經1 5分予以滴定。 在滴定完成後、於5 0 °C攪伴4小時。在4小時後、 將此反應液滴定於離子交換水4升、使此時析出的聚合體 分離、洗浄後、在5 0 °C施予24小時真空乾燥、以獲得 具有光聚合性不飽和雙鍵之感光性聚苯并鸣唑先質PSP-1 ° 在此反應、異氫酸酯與聚合物末端的胺基繼續呈優勢 反應、亦與聚合物骨架中之羥基反應、藉由聚合物末端部 之脲鍵結、骨架中羥基部分之一部份藉由胺甲酸乙酯鍵結 而成爲甲基丙烯酸酯基被導入之構造。 測定此聚合物之1H-NMR光譜、由來自骨架重複單位 部分之芳香環上氫原子的積分強度之和、與來自導入之甲 •39- (36) 200403532 基丙烯酸基之碳一碳雙鍵前端部分之氫原子2個的積分強 度之比率、可算出相對於骨架全體之甲基丙烯酸酯基之導 入率。在本例之情形、甲基丙烯酸酯基之導入率，、相對於 骨架中全羥基則計算出爲2 8.6 %。亦即、P S P -1、在上述 式（4)中、Ri與R2之合計莫耳爲1〇〇莫耳％時、111與 R2之28.6莫耳％爲上述式（3 )所示具有光聚合性不飽和 雙鍵之一價有機基之化合物。 参考例3 (感光性聚苯并鸣唑先質PSP-2之合成） 在参考例1所得PB 0-1，藉以下方法導入具有光聚合 性不飽和雙鍵之有機基。 將PBO-1乾燥粉體100 g放入容量1升之可分離燒 瓶、添加γ-丁內酯（GBL ) 400g再溶解之、添加二丁基錫 月桂酸酯1 .5 7 g、於油浴中加溫至5 0 °C。在此、將於 其他途徑GBL 94g，有溶解2-異氰酸基乙基甲基丙烯酸酯 31.35g (0.202莫耳。此係自PBO-1之收率及對該反應 之使用量而算出、相當於PBO-1全羥基之65莫耳％ )之 物經3 0分鐘予以滴定。 滴定完成後、在5 0 °C下攪拌四小時。於4小時後、 使此反應液滴定於離子交換水4升、此時將析出之聚合物 分離、洗浄後、於5 0 °C下實施2 4小時真空乾燥、可得 到感光性聚苯并鳄唑先質p s P- 2。 與参考例2相同方式算出之甲基丙烯酸酯基之導入 率、相對於骨架中全羥基爲55.3 %。亦即、P S P_ 2在上 -40 - (37) 200403532 述式（4)中、1^與R2之合計莫耳爲100旲耳％時、 R2之55.3莫耳％爲上述式（3 )所示具有光聚合性不 雙鍵之1價有機基系之化合物。 参考例4 (感光性聚苯并鸣唑先質PSP-3之合成） 藉以下方法將具有光聚合性不飽和雙鍵之有機基 参考例1所得P B 〇 -1。 使PB 0-1之乾燥粉體100g放入容量1升之可分 瓶、添加γ -丁內酯（GBL) 400g再溶解之，添加二 錫月桂酸酯0.24 g、於油浴加溫至50 °C。對此、在 途徑之GBL 15g中，溶解有2-異氰酸基乙基甲基丙 酯4.8 1 g ( 0.031莫耳，此係自PB0-1之收率及對 應之使用量算出、相當於PB 0-1全羥基之10莫耳％ 物經1 0分鐘予以滴定之。將此反應液滴定於離子交 4升、此時析出之聚合物加以分離、洗浄後、於5 0 施24小時真空乾燥、可得到感光性聚苯并鸣唑先質 3 ° 與参考例2相同方式所算出之甲基丙烯酸酯基之 率、相對於骨架中全羥基爲8.3 %。亦即、P S P - 3在 式（4)中、1^與R2之合計莫耳爲100莫耳％時、] R2之8 · 3莫耳％爲上述式（3 )所示具有光聚合性不 雙鍵之1價有機基化合物。 参考例5 (感光性聚醯亞胺先質P S P-4之合成）After the completion of the dropping, it was stirred and left for 1 hour. After that, the reaction solution was titrated under high-speed stirring of 5 liters of water, and the resulting polymer was dispersed and precipitated. Polybenzoxazole precursor of amino group. The polystyrene-equivalent GPC -38- (35) (35) 200403532 of this polymer has a weight average molecular weight (THF solvent) of 1 03 00, a residual solvent ratio of 1 3.9 5%, and a yield of 8 6 · 5 1%. Reference Example 2 (Synthesis of Photosensitive Polybenzopyrazole Precursor PSP-1) In PBO-1 obtained in Reference Example 1, an organic group having a photopolymerizable unsaturated double bond was introduced by the following method. Put 100 g of dry powder of PB 0-1 into a separable flask with a capacity of 1 liter, add 400 g of γ-butyrolactone (GBL), re-dissolve, add dibutyltin dilaurate 0.85 g, and add oil Warm to 50 ° C in the bath. In this regard, GBL 5 lg of other routes, 16.94 g (0.109 mol) of 2-isocyanatoethyl methacrylate dissolved. This is calculated from the yield of PBO-1 and the amount used for the reaction. , Equivalent to 35 mole% of the total hydroxyl groups of PB 0-1) was titrated after 15 minutes. After completion of the titration, stir at 50 ° C for 4 hours. After 4 hours, the reaction solution was titrated to 4 liters of ion-exchanged water, and the polymer precipitated at this time was separated, washed, and vacuum-dried at 50 ° C for 24 hours to obtain a photopolymerizable unsaturated double Photosensitive polybenzopyrazole precursor PSP-1 ° At this reaction, the isohydrogenate continues to dominate the reaction with the amine group at the polymer end, and also reacts with the hydroxyl group in the polymer backbone. The urea bond in the part and the hydroxyl part in the skeleton are bonded by urethane to form a structure in which a methacrylate group is introduced. Measure the 1H-NMR spectrum of this polymer, the sum of the integrated intensity of the hydrogen atom on the aromatic ring from the repeating unit part of the backbone, and the carbon-carbon double bond front end of the acrylic group introduced from 39- (36) 200403532 The ratio of the integral intensity of two partial hydrogen atoms can be used to calculate the introduction rate of methacrylate groups with respect to the entire skeleton. In the case of this example, the introduction rate of the methacrylate group was calculated to be 28.6% with respect to the total hydroxyl group in the skeleton. That is, PSP-1, in the above formula (4), when the total mole of Ri and R2 is 100 mole%, 28.6 mole% of 111 and R2 has photopolymerization as shown in the formula (3). A compound of a monovalent organic group with an unsaturated double bond. Reference Example 3 (Synthesis of Photosensitive Polybenzoxazole Precursor PSP-2) In PB 0-1 obtained in Reference Example 1, an organic group having a photopolymerizable unsaturated double bond was introduced by the following method. Put 100 g of PBO-1 dry powder into a separable flask with a capacity of 1 liter, add 400 g of γ-butyrolactone (GBL) and re-dissolve it, add 1.5 g of dibutyltin laurate, and add in an oil bath. Temperature to 50 ° C. Here, there will be 94 g of GBL in other routes, and 31.35 g (0.202 mole) of 2-isocyanatoethyl methacrylate dissolved. This is calculated from the yield of PBO-1 and the amount used for the reaction. The equivalent of 65 mole% of PBO-1 full hydroxyl group) was titrated over 30 minutes. After the titration is complete, stir at 50 ° C for four hours. After 4 hours, the reaction solution was titrated to 4 liters of ion-exchanged water. At this time, the precipitated polymer was separated, washed, and vacuum-dried at 50 ° C for 24 hours to obtain a photosensitive polybenzoate. Azole precursor ps P-2. The introduction rate of the methacrylate group calculated in the same manner as in Reference Example 2 was 55.3% with respect to the total hydroxyl groups in the skeleton. That is, when PS P_ 2 is in the formula (4) above -40-(37) 200403532, when the total mole of 1 ^ and R2 is 100 mole%, the 55.3 mole% of R2 is the formula (3) above. It is a monovalent organic group compound having a photopolymerizable non-double bond. Reference Example 4 (Synthesis of Photosensitive Polybenzopyrazole Precursor PSP-3) The organic group having a photopolymerizable unsaturated double bond in Reference Example 1 was obtained by the following method: P B 0 -1. Put 100g of dry powder of PB 0-1 in a 1-liter separable bottle, add 400g of γ-butyrolactone (GBL) and dissolve it, add 0.24 g of ditin laurate, and warm to 50 in an oil bath ° C. In this regard, in 15 g of GBL of the route, 4.8 1 g (0.031 mol) of 2-isocyanatoethylmethylpropyl is dissolved, which is calculated from the yield of PB0-1 and the corresponding usage amount, and is equivalent to 10 mol% of PB 0-1 perhydroxy group was titrated in 10 minutes. The reaction solution was titrated to 4 liters of ion exchange, and the polymer precipitated at this time was separated, washed, and vacuumed at 50 for 24 hours. The photosensitive polybenzazole precursor 3 ° can be obtained by drying, and the rate of the methacrylate group calculated in the same manner as in Reference Example 2 is 8.3% with respect to the total hydroxyl group in the skeleton. That is, PSP-3 is in the formula (4) In the case where the total mole of 1 ^ and R2 is 100 mole%, 8 · 3 mole% of R2 is a monovalent organic compound having a photopolymerizable non-double bond represented by the above formula (3) Reference Example 5 (Synthesis of Photosensitive Polyamidine Precursor PS P-4)

Ri與 飽和 導入 離燒 丁基 其他 烯酸 該反 )之 換水 C實 PSP- 導入 上述 h與 飽和 -41 - (38) (38)200403532 在容量5升之可分離燒瓶、投入二苯醚-3，3’，4 ’ 4’ -四羧酸二酐310.22g(1.00莫耳） 、2 -異丁烯醯基氧 乙醇 270.69g (2.08 莫耳）、呲啶 158.2g(2.00 莫 耳）、GB L 1 0 0 0 g、並混合之、在常溫下攪拌放置1 6小 時。對此，將二環己基碳二醯亞胺400.28 g (1·9 4莫 耳）溶解稀釋於GBL400g之物，在冰冷下、經30分左右 予以滴定投入、接著將4，4’-二氨基二苯醚1 8 5.97 g (0.93 莫耳）分散於GBL 650g之物、經60分左右予以 添加。在冰冷狀態下攪拌3小時、其後添加乙醇50g、自 冰冷浴取出，進而攪拌放置1小時。將上述步驟所析出之 固形成分（二環己基脲）予以加壓濾除後、將反應液滴定 投入於40升乙醇、此際將析出之聚合物予以分離、洗 浄，在5 0 °C下進行2 4小時真空乾燥、得到感光性聚乙 醯亞胺先質PSP-4。聚苯乙烯換算之GPC重量平均分子量 (THF 溶媒）爲 22000。 参考例6 (感光性聚醯亞胺先質PS P-5之合成） 將焦蜜石酸酐65.44 g (0.30莫耳）、二苯基酮_3, 3’，4，4’-四羧酸二酐 225.56§(0.70莫耳） 、2 -異丁烯 醯基氧乙醇 270.69g (2.08 莫耳）、呲啶 158.2 gIntroduce ri and saturated butyl and other enoic acid. Invert the water. C Real PSP- Introduce the above h and saturated -41-(38) (38) 200403532 In a separable flask with a capacity of 5 liters, put diphenyl ether-3. 3,4'4'-tetracarboxylic dianhydride 310.22g (1.00 mole), 2-isobutenyloxyethanol 270.69g (2.08 mole), pyridine 158.2g (2.00 mole), GB L 1 0 0 0 g, mix and mix at room temperature for 16 hours. In this regard, 400.28 g (1.94 mol) of dicyclohexylcarbodiimide was dissolved and diluted in 400 g of GBL, and the solution was titrated under ice-cooling for about 30 minutes, and then 4,4'-diamino Diphenyl ether 1 8. 5.97 g (0.93 mol) was dispersed in 650 g of GBL and added after about 60 minutes. After stirring for 3 hours in an ice-cooled state, 50 g of ethanol was added thereto, taken out from the ice-cooled bath, and further stirred for 1 hour. After the solid component (dicyclohexylurea) precipitated in the above step was filtered off under pressure, the reaction solution was titrated into 40 liters of ethanol, and the precipitated polymer was separated and washed at 50 ° C. It was dried under vacuum for 24 hours to obtain a photosensitive polyethyleneimine precursor PSP-4. The polystyrene equivalent GPC weight average molecular weight (THF solvent) was 22,000. Reference Example 6 (Synthesis of photosensitive polyfluorene imine precursor PS P-5) 65.44 g (0.30 mole) of pyromelite anhydride, diphenyl ketone_3, 3 ', 4, 4'-tetracarboxylic acid Dianhydride 225.56§ (0.70 mole), 270.69 g (2.08 mole) of 2-isobutenyloxyethanol, 158.2 g of pyridine

(2.00莫耳）、GBLIOOOg投入於容量5升之可分離燒 瓶、混合之、在常溫下攪拌放置1 6小時。在此、將二環 己基碳二醯亞胺12.66g ( 2.00莫耳）溶解稀釋於GBL 4 00g者、於冰冷下、經30分左右予以滴定投入、接著將 -42- ："·«· ：Γ· (39) (39)200403532(2.00 mol), GBL1000g was put into a separable flask with a capacity of 5 liters, mixed, and left to stir at room temperature for 16 hours. Here, 12.66 g (2.00 mol) of dicyclohexylcarbodiimide was dissolved and diluted in GBL 4 00 g, and the solution was titrated under ice-cooling for about 30 minutes, and then -42-: " · «· : Γ · (39) (39) 200403532

4，4'-二氨基二苯醚185.97 g(0.93莫耳）分散於GBL 6 5 0 g者、經6 0分左右添加°在冰冷狀態下攪拌3小時、 其後添加乙醇5 0 g、自水冷浴取出、在室溫下進而攪梓放 置一小時。將上述步驟所析出之固形成分（一環己基脈） 予以加圧濾除後、將反應液滴定投入於4 0升之乙醇、將 此時析出之聚合物分離、洗浄、於5 0 °C下藉由2 4小時 真空乾燥、獲得感光性聚醯亞胺先質p s p -5 聚苯乙烯換 算GPC重量平均分子量（THF溶媒）爲3 0000。 &lt;實施例1&gt; 在感光性聚苯并鸣唑先質（PSP-1 ) 1〇〇質量份、添 加四乙二醇二甲基丙烯酸酯16質量份、N， 1^’-雙（2-異 丁烯醯基氧乙基）脲16質量份、1-苯基-1，2-丙二酮- 2-(鄰苯甲醯基）肟6質量份、六甲氧甲基化蜜胺樹脂（三 和化學社製、商標名NIKALAC、品號MW-30HM、聚合度 1.0) 10質量份、1-苯基_5_氫硫基d，2，3，4-四唑2質 量份、4，4'-雙（二甲基氨基）二苯基酮1質量份、N-亞 硝基二苯胺0.1質量份、並溶解於N -甲基-2 -呲咯啶酮 (NMP ) 220質量份、得到淸漆形之負型感光性樹脂組成 物。 &lt;實施例2&gt; 在感光性聚苯幷噚唑先質（PSP_1 ) 100質量份、添 加四乙二醇二甲基丙烯酸酯16質量份、N，N，-雙（2 -異 -43 - (40) (40)200403532 丁燒醯基氧乙基）脲16質量份、ι_苯基_1，2 -丙二酮- 2-(鄰苯甲釀基）0亏6質量份、六甲氧甲基化蜜胺樹脂 (二和化學社製、商標名NIKALAC、品號MW-30HM、聚 合度1.0) 10質量份、米蚩酮2質量份、N_亞硝基二苯胺 〇· 1質量份、並溶解於N-甲基-2-呲咯啶酮（NMP ) 220質 量份、以獲得淸漆形之負型感光性樹脂組成物。 &lt;實施例3〜7及比較例1〜3 &gt; 使蜜胺樹脂及其添加量照表1方式使用以外、其他則 與實施例2相同、得到淸漆形之感光性樹脂組成物。 〈比較例4〜8 &gt; 爲本發明A成分、B成分、C成分、各爲具有光聚合 性不飽和雙鍵之聚醯胺、具光聚合性不飽和雙鍵之單體、 光聚合引發劑、及其添加量照表2所用以外、其他則與實 施例2相同、得到淸漆形之負型感光性樹脂組成物。 &lt;實施例8&gt; 在感光性聚醯亞胺先質（PSP-4 ) 1〇〇質量份、添加 四乙二醇二甲基丙烯酸酯4質量份，1，3 -二苯基丙二酮-2-(0 -乙氧基羰基）肟4質量份，六甲氧基甲基化蜜胺 樹脂（三和化學社製、商標名NIKALAC、品號MW-3 0ΗΜ、 聚合度〗·〇) 1〇質量份、卜苯基氫硫基-1，2，3，4_四 唑1質量份，N，N -雙（2 -羥乙基）苯胺4質量份、Ν Α- (41) (41)200403532 亞硝基二苯胺0 · 〇 5質量份、並溶解於N -甲基-2 -呲咯啶酮 (NMP ) 1 〇 5質量份及乳酸乙酯45質量份之混合溶媒、 得到淸漆形負型感光性樹脂組成物。 &lt;貫施例9〜1 3及比較例9〜1 1 &gt; 將蜜胺樹脂與其添加量、照表1方式使用以外、其他 則與實施例8相同、以獲得淸漆形之負型感光性樹脂組成 物。 &lt;比較例1 2〜1 4 &gt; 除了爲本發明A成分、B成分、C成分、各具有光聚 合性不飽和雙鍵之聚醯胺、具光聚合性不飽和雙鍵之單 體、光聚合引發劑、及其添加量照表2方式使用以外、其 他與實施例8相同、得到淸漆状之負型感光性樹脂組成 物0 &lt;實施例14〉185.97 g (0.93 mol) of 4,4'-diaminodiphenyl ether dispersed in GBL 650 g, added after about 60 minutes, and stirred under ice-cooled state for 3 hours, then 50 g of ethanol was added. Take out the water-cooled bath and stir at room temperature for one hour. After the solid component (a cyclohexyl vein) precipitated in the above step was filtered off, the reaction solution was titrated into 40 liters of ethanol, and the polymer precipitated at this time was separated, washed, and borrowed at 50 ° C. GPC weight average molecular weight (THF solvent) in terms of polystyrene-equivalent GPC weight was obtained by vacuum drying for 24 hours to obtain a photosensitive polyfluorene imine precursor psp -5. &lt; Example 1 &gt; 100 parts by mass of a photosensitive polybenzopyrazole precursor (PSP-1), 16 parts by mass of tetraethylene glycol dimethacrylate, and N, 1 ^ '-bis (2 -16 parts by mass of isobutenyloxyethyl) urea, 1 part by mass of 1-phenyl-1,2-propanedione, 6 parts by mass of 2- (o-benzylfluorenyl) oxime, hexamethoxymethylated melamine resin Manufactured by Wako Chemicals Co., Ltd. under the brand name NIKALAC, product number MW-30HM, polymerization degree 1.0) 10 parts by mass, 1-phenyl-5_hydrothio group d, 2, 3, 4-tetrazole 2 parts by mass, 4, 4 1 part by mass of '-bis (dimethylamino) diphenyl ketone, 0.1 part by mass of N-nitroso diphenylamine, and dissolved in 220 parts by mass of N-methyl-2-pyrrolidone (NMP), to obtain Lacquer-shaped negative photosensitive resin composition. &lt; Example 2 &gt; 100 parts by mass of photosensitive polybenzoxazole precursor (PSP_1), 16 parts by mass of tetraethylene glycol dimethacrylate, and N, N, -bis (2-iso-43- (40) (40) 200403532 Butanyloxyethyl) urea 16 parts by mass, ι_phenyl_1,2-propanedione 2- (o-benzoyl) group, 6 parts by mass, hexamethoxy Methylated melamine resin (manufactured by Niwa Chemical Co., Ltd. under the brand name NIKALAC, product number MW-30HM, polymerization degree 1.0) 10 parts by mass, 2 parts by mass of mignonone, and 1 part by mass of N_nitrosodiphenylamine And dissolved in 220 parts by mass of N-methyl-2-pyrrolidone (NMP) to obtain a lacquer-shaped negative photosensitive resin composition. &lt; Examples 3 to 7 and Comparative Examples 1 to 3 &gt; A lacquer-shaped photosensitive resin composition was obtained in the same manner as in Example 2 except that the melamine resin and its addition amount were used in the same manner as in Table 1. <Comparative Examples 4 to 8> Components A, B, and C of the present invention, each of which is a polyamine having a photopolymerizable unsaturated double bond, a monomer having a photopolymerizable unsaturated double bond, and photopolymerization initiation Except for the agents and their addition amounts, as in Table 2, the rest were the same as in Example 2 to obtain a negative photosensitive resin composition in the form of a lacquer. &lt; Example 8 &gt; To 100 parts by mass of photosensitive polyfluorene imine precursor (PSP-4), 4 parts by mass of tetraethylene glycol dimethacrylate, and 1,3-diphenylpropanedione were added. 4 parts by mass of 2- (0-ethoxycarbonyl) oxime, hexamethoxymethylated melamine resin (manufactured by Sanwa Chemical Co., trade name NIKALAC, product number MW-3 0 μM, degree of polymerization 〖· 〇) 1 〇part by mass, 1 part by mass of phenylhydrosulfanyl-1,2,3,4-tetrazole, 4 parts by mass of N, N-bis (2-hydroxyethyl) aniline, ΝΑ- (41) (41 200403532 0.5 parts by mass of nitrosodiphenylamine, and dissolved in a mixed solvent of 105 parts by mass of N-methyl-2-pyrrolidone (NMP) and 45 parts by mass of ethyl lactate to obtain a lacquer Shaped negative photosensitive resin composition. &lt; Examples 9 to 1 3 and Comparative Examples 9 to 1 1 &gt; Except for using melamine resin and its addition amount, as shown in Table 1, the same as in Example 8 to obtain a negative photosensitivity Sexual resin composition. &lt; Comparative Example 1 2 ~ 1 4 &gt; Except for components A, B, and C of the present invention, polyamines each having a photopolymerizable unsaturated double bond, monomers having a photopolymerizable unsaturated double bond, Except that the photopolymerization initiator and its addition amount were used in the same manner as in Table 2, the same procedure as in Example 8 was performed to obtain a negative photosensitive resin composition in the form of a varnish. 0 &lt; Example 14>

在感光性聚醯亞胺先質（PSP-4) 70質量份與感光性 聚醯亞胺先質（PSP-5 ) 30質量份之混合物、添加四乙二 醇二甲基丙烯酸酯4質量份、1，3 -二苯基丙三酮- 2-(0-乙氧基鐵基）肟 4質量份、六甲氧基甲基化蜜胺樹脂 (三和化學公司製、商標名NIKALAC，品號MW-30HM、 聚合度1.0) 10質量份、1-苯基-5-氫硫基_1，2，3，4 -四 口坐1質量份、N，N-雙（2-羥基乙基）苯胺4質量份、N -45- (42) (42)200403532 一亞硝基二苯胺0 · 0 5質量份、並溶解於N -甲基-2 -卩此略D定 酮（Ν Μ P ) 1 〇 5質量份及乳酸乙酯4 5質量份之混合溶媒、 得到淸漆状之負型感光性樹脂姐織物。 &lt;實施例1 5〜1 9、比較例1 5〜1 7&gt; 除了將蜜胺樹脂及其添加量照表1方式使用以外，其 他與實施例1 4相同、得到淸漆状負型感光性樹脂組成 物。 &lt;比較例18〜20&gt; 除了爲本發明Α成分、Β成分、C成分、各具有光聚 合性不飽和雙鍵之聚醯胺、具光聚合性不飽和雙鍵之單 體、光聚合引發劑、及其添加量照表2方式使用以外、其 他與實施例1 4相同、得到淸漆形負型感光性樹脂組成 物。 &lt;比較例2 1 &gt; 除了以爲環氧基系橋聯劑之epolite 3 002 (共榮社化 學製），相對於聚醯胺成分使用1 0質量份來取代蜜胺樹 脂以外，其他與實施例2相同、可得到淸漆状負型感光性 樹脂組成物。 &lt;比較例22&gt; 除了以三烯丙基異三聚氰酸酯、相對於聚醯胺成分使 -46- (43) (43)200403532 用1 〇質量份來取代蜜胺樹脂以外、其他與實施例2相 同、得到淸漆形負型感光性樹脂組成物。 &lt;比較例2 3 &gt; 除了將環氧基系橋聯劑之ep〇lite3 002 (共榮社化學 製）相對於聚醯胺成分使用1 〇質量份以取代蜜胺樹脂以 外、其他與實施例8相同、得到淸漆形之負型感光性樹脂 組成物。 &lt;比較例2 4 &gt; 除了以三烯丙基異三聚氰酸酯、相對於聚醯胺成分使 用1 0質量份以取代蜜胺樹脂以外、其他與實施例8相 同、得到淸漆形負型感光性樹脂組成物。 &lt;比較例2 5 &gt; 除了以環氧系橋聯劑之 ep〇lite3〇〇2 (共榮社化學 製）、相對於聚醯胺成分使用1 0質量份來取代蜜胺樹脂 以外、其他與實施例i 4相同、獲得淸漆形負型感光性樹 脂組成物。 &lt;比較例2 6 &gt; 除了以三嫌丙基異三聚氰酸酯、相對於聚醯胺成分使 用1 0質量份來取代蜜胺樹脂以外、其他與實施例丨4相 同、得到淸漆形負型感光性樹脂組成物。 -47- (44) (44)200403532 表1 蜜胺樹脂 製造者 商標名 品號 聚合度 添加量 (質量份） 實施例1 六甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-30HM 1.0 10 實施例2 六甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-30HM 1.0 10 實施例3 六甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-390 1.0 10 實施例4 甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-100LM 1.3 10 實施例5 甲氧甲基化蜜胺樹脂 三井cytec社 CYMEL 303 1.7 10 實施例6 甲氧基/ 丁氧基混合甲基化 蜜胺樹脂 三井cytec社 CYMEL 235 1.4 10 實施例7 丁氧甲基化蜜胺樹脂 三井cytec社 MYCOAT 506 2.2 10 實施例8 六甲氧甲基化蜜胺樹月旨 三和化學 NIKALAC MW-30HM 1.0 10 實施例9 甲氧甲基化蜜胺樹脂 三井cytec CYMEL 303 1.7 10 實施例10 甲氧基/ 丁氧基混合甲基 化蜜胺樹脂 三井cytec CYMEL 235 1.4 10 實施例11 丁氧甲基化蜜胺樹月旨 三井cytec MYCOAT 506 2.2 10 實施例12 甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW- lOOLM 1.3 10 實施例13 六甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-390 1.0 10 實施例14 六甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-30HM 1.0 10 實施例15 甲氧甲基化蜜胺樹脂 三井cytec CYMEL 303 1.7 10 實施例16 甲氧基/ 丁氧基混合甲基化 蜜胺樹脂 三井cytec CYMEL 235 1.4 10 實施例Π 丁氧甲基化蜜胺樹脂 三井cytec MYCOAT 506 2.2 10 實施例18 甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-100LM 1.3 10 實施例19 六甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-390 1.0 10 比較例1 4fflP J\S\ 身 - - 0 比較例2 甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW- lOOLM 1.3 3 比較例3 甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-100LM 1.3 40 比較例9 Μ J\ &gt;N - — 一 - 0 比較例10 甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW- lOOLM 1.3 3 比較例11 甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-100LM 1.3 40 比較例15 赫 JW\ 參 一 - 一 0 比較例16 甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-100LM 1.3 3 比較例17 甲氧甲基化蜜胺樹脂 三和化學 NIKALAC MW-100LM 1.3 40 ※添加量之値、爲相對於本發明A成分之聚醯胺質量份。 -48- (45) (45)200403532 表2 Α成分(質量份） B成分(質量份） c成分(質量份） 比較例4 PSP-3(10 0) 4 EM (16)BMU(16) PDO⑹ 比較例5 PSP-2(100) 4 EM (16)BMU(16) PDO⑹ 比較例6 PSP-1 (100) 4EM(30)BMU(30) PDO⑹ 比較例7 PSP-l(lOO) 4 EM (16) BMU(16) PDO(0.5) 比較例8 PSP-l(lOO) 4EM(1 6)BMU(1 6) PDO(25) 比較例12 PSP-4(100) 4EM(55) PTO(4) 比較例13 PSP-4 (10 0) 4EM(4) PTO(0.5) 比較例14 PSP-4(100) 4EM(4) PTO(25) 比較例18 PSP-4(70)PSP-5(30) 4EM(55) PTO(4) 比較例19 PSP-4(70)PSP-5(30) 4EM(4) PTO(0.5) 比較例20 PSP-4(70)PSP-5(30) 4EM(4) PTO(35) 4EM··四乙二醇二甲基丙烯酸酯 BMU:N，N’·雙(2-異丁烯醯基氧乙基)脲 PDO:l-苯基-1，2-丙二酮-2-(0-苯甲醯基)月弓 ΡΤΟ:1，3-二苯基丙三酮-2-(0乙氧基羰基)肟 (46) (46)200403532 (聚醯胺塗膜之製作平版印刷（lithography)評價） 將上述實施例、比較例所得淸漆形負型感光性樹脂組 成物、預先以3 -氨基丙基三乙氧基矽烷進行前處理之5 英吋矽晶圓上、使用旋轉塗敷機（東京electron公司製、 型號 Clean Track mark7)來塗敷、於95 °C預先烘烤處 理3分鐘、得到初期膜厚1 0微米的塗膜。 在此塗膜、藉i線分節器曝光機（NIKON製、型號 NSR200 5 i 8A)、透過評價用光掩罩、使曝光量在50〜 5 OOm J/cm2範圍內呈階段性變化並曝光之。曝光完成開始 60秒後、使用電爐、在70 °C於90秒曝光後實施烘焙 (PEB )。 其後關於實施例1〜7、比較例1〜8、比較例2 1〜2 2 組成物之塗膜、則使用 2.3 8 %氫氧化四甲銨水溶液 (Clariant Japan公司製、品號AZ3 00MIF )、經過未曝光 部完全溶解消失爲止之時間乘以1.4時間，並實施攪拌 (paddle )顯像、接著以純水淸洗20秒、得到負型附圖 案塗膜。 又關於實施例8〜1 9、比較例9〜2 0、比較例2 3〜2 6 組成物之塗膜、係使用γ- 丁內酯與二甲苯之 50/50 (ν/ν% )混合溶媒、實施在未曝光部完全溶解消失爲止之 時間乘以1.4倍時間之旋轉噴灑顯像、接著以異丙醇淸洗 2 0秒、得到負型附圖案塗膜。 將所得附圖案塗膜在光學顯微鏡下觀察、來評價無潤 漲的敏銳凸紋花樣所得最低曝光量（感度）、最低曝光量 -50- (47) 200403532 照射時通路孔（v i a h 0 1 e )(矩形顯像丨谷出邰）之解像度 (解像度〇 、顯像後之凝集析出部分或殘渣之有無等。又To a mixture of 70 parts by mass of photosensitive polyimide precursor (PSP-4) and 30 parts by mass of photosensitive polyimide precursor (PSP-5), 4 parts by mass of tetraethylene glycol dimethacrylate was added. 4 parts by mass of 1,3-diphenylglycerone-2- (0-ethoxyferroyl) oxime, hexamethoxymethylated melamine resin (manufactured by Sanwa Chemical Co., trade name NIKALAC, product number MW-30HM, degree of polymerization 1.0) 10 parts by mass, 1 part by mass of 1-phenyl-5-hydrosulfanyl 1,2,3,4-four parts, N, N-bis (2-hydroxyethyl) 4 parts by mass of aniline, N-45- (42) (42) 200403532 mononitrosodiphenylamine 0.5 parts by mass, and dissolved in N-methyl-2-this slightly dione (NMP) A mixed solvent of 105 parts by mass and 45 parts by mass of ethyl lactate was obtained to obtain a negative photosensitive resin fabric in the form of a lacquer. &lt; Example 1 5 to 19, Comparative Example 1 5 to 1 7 &gt; Except that the melamine resin and its addition amount were used in the same manner as in Table 1, the same procedure as in Example 14 was performed to obtain a lacquer-like negative-type photosensitivity. Resin composition. &lt; Comparative Examples 18 to 20 &gt; In addition to the components A, B, and C of the present invention, polyamines each having a photopolymerizable unsaturated double bond, a monomer having a photopolymerizable unsaturated double bond, and photopolymerization initiation Except that the agent and its addition amount were used in the same manner as in Table 2, the same procedure as in Example 14 was performed to obtain a varnish-shaped negative photosensitive resin composition. &lt; Comparative Example 2 1 &gt; Except for epolite 3 002 (manufactured by Kyoeisha Chemical Co., Ltd.), which is an epoxy-based bridging agent, and using 10 parts by mass of polyamine component instead of melamine resin, Example 2 was the same, and a varnish-like negative photosensitive resin composition was obtained. &lt; Comparative Example 22 &gt; Except that triallyl isocyanurate was used instead of -46- (43) (43) 200403532 with respect to the polyamido component to replace melamine resin with 10 parts by mass. Example 2 was the same, and a lacquer-shaped negative photosensitive resin composition was obtained. &lt; Comparative Example 2 3 &gt; Except for using epolite 3 002 (manufactured by Kyoeisha Chemical Co., Ltd.) as an epoxy-based bridging agent in an amount of 10 parts by mass with respect to the polyamidoamine component in place of the melamine resin, other implementation Example 8 was the same, and a negative photosensitive resin composition in the form of a lacquer was obtained. &lt; Comparative Example 2 4 &gt; A lacquer shape was obtained in the same manner as in Example 8 except that triallyl isocyanurate was used in place of melamine resin in an amount of 10 parts by mass relative to the polyamidoamine component. A negative photosensitive resin composition. &lt; Comparative Example 2 5 &gt; Except for using epoxy-based bridging agent ep〇lite 3002 (manufactured by Kyoeisha Chemical Co., Ltd.) and using 10 parts by mass of polyamine component instead of melamine resin, In the same manner as in Example i 4, a lacquer-shaped negative photosensitive resin composition was obtained. &lt; Comparative Example 2 6 &gt; A varnish was obtained in the same manner as in Example 1-4, except that melamine resin was replaced with 10 parts by mass of polymethylamine with respect to trimethylpropyl isocyanurate. Shaped negative photosensitive resin composition. -47- (44) (44) 200403532 Table 1 Addition amount (mass parts) of degree of polymerization of melamine resin manufacturer's brand name Example 1 Hexamethoxymethylated melamine resin Sanwa Chemical NIKALAC MW-30HM 1.0 10 Example 2 Hexamethoxymethylated melamine resin Sanwa Chemical NIKALAC MW-30HM 1.0 10 Example 3 Hexamethoxymethylated melamine resin Sanwa Chemical NIKALAC MW-390 1.0 10 Example 4 Methoxymethylated melamine resin Sanwa And chemical NIKALAC MW-100LM 1.3 10 Example 5 Methoxymethylated melamine resin Mitsui cytec CYMEL 303 1.7 10 Example 6 Methoxy / butoxy mixed methylated melamine resin Mitsui cytec CYMEL 235 1.4 10 Example 7 Butoxymethylated melamine resin Mitsui cytec company MYCOAT 506 2.2 10 Example 8 Hexamethoxymethylated melamine tree purpose Sanwa Chemical NIKALAC MW-30HM 1.0 10 Example 9 Methoxymethylated melamine Resin Mitsui Cytec CYMEL 303 1.7 10 Example 10 Methoxy / butoxy mixed methylated melamine resin Mitsui Cytec CYMEL 235 1.4 10 Example 11 Butoxymethylated melamine tree Mitsui cytec MYCOAT 506 2.2 10 Implementation Example 12 Methoxymethylation Amine resin Sanwa Chemical NIKALAC MW-100LM 1.3 10 Example 13 Hexamethoxymethylated melamine resin Sanwa Chemical NIKALAC MW-390 1.0 10 Example 14 Hexamethoxymethylated melamine resin Sanwa Chemical NIKALAC MW-30HM 1.0 10 Example 15 Methoxylated melamine resin Mitsui cytec CYMEL 303 1.7 10 Example 16 Methoxy / butoxy mixed methylated melamine resin Mitsui cytec CYMEL 235 1.4 10 Example Π Butyl methylated honey Amine resin Mitsui cytec MYCOAT 506 2.2 10 Example 18 Methoxymethylated melamine resin Sanwa Chemical NIKALAC MW-100LM 1.3 10 Example 19 Methoxy hexamethylolated melamine resin Sanwa Chemical NIKALAC MW-390 1.0 10 Comparative example 1 4fflP J \ S \ Body--0 Comparative Example 2 Methoxymethylated Melamine Resin Sanwa Chemical NIKALAC MW- 100LM 1.3 3 Comparative Example 3 Methoxymethylated Melamine Resin Sanwa Chemical NIKALAC MW-100LM 1.3 40 Comparative Example 9 Μ J \ &gt; N----0 Comparative Example 10 Methoxymethylated melamine resin Sanwa Chemical NIKALAC MW- 100LM 1.3 3 Comparative Example 11 Methoxymethylated melamine resin Sanwa Chemical NIKALAC MW -100LM 1.3 40 Comparative Example 15 Hz JW \ Part 1-10 Comparative Example 16 Methoxymethylated Melamine Resin Sanwa Chemical NIKALAC MW-100LM 1.3 3 Comparative Example 17 Methoxymethylated Melamine Resin Sanwa Chemical NIKALAC MW-100LM 1.3 40 ※ The amount of addition , Is the mass part of polyamide based on component A of the present invention. -48- (45) (45) 200403532 Table 2 A component (parts by mass) B component (parts by mass) c component (parts by mass) Comparative Example 4 PSP-3 (10 0) 4 EM (16) BMU (16) PDO⑹ Comparative Example 5 PSP-2 (100) 4 EM (16) BMU (16) PDO⑹ Comparative Example 6 PSP-1 (100) 4EM (30) BMU (30) PDO⑹ Comparative Example 7 PSP-1 (100) 4 EM (16 ) BMU (16) PDO (0.5) Comparative Example 8 PSP-1 (100) 4EM (1 6) BMU (1 6) PDO (25) Comparative Example 12 PSP-4 (100) 4EM (55) PTO (4) Comparison Example 13 PSP-4 (100) 4EM (4) PTO (0.5) Comparative Example 14 PSP-4 (100) 4EM (4) PTO (25) Comparative Example 18 PSP-4 (70) PSP-5 (30) 4EM (55) PTO (4) Comparative Example 19 PSP-4 (70) PSP-5 (30) 4EM (4) PTO (0.5) Comparative Example 20 PSP-4 (70) PSP-5 (30) 4EM (4) PTO (35) 4EM ·· Tetraethylene glycol dimethacrylate BMU: N, N '· bis (2-isobutenyloxyethyl) urea PDO: 1-phenyl-1,2-propanedione-2 -(0-Benzamyl) Moonbow PT0: 1,3-Diphenylglycerone-2- (0ethoxycarbonyl) oxime (46) (46) 200403532 (Polyamide film production Lithography evaluation) The lacquer-shaped negative photosensitive resin composition obtained in the above Examples and Comparative Examples was preliminarily charged with 3-aminopropyltriethoxysilane. The pre-processed 5 inch silicon wafer was coated with a spin coater (manufactured by Tokyo Electron Co., Ltd., Clean Track mark 7), and baked at 95 ° C for 3 minutes to obtain an initial film thickness of 10 microns. Coating film. Here, the film is exposed by an i-line segmentation exposure machine (manufactured by NIKON, model NSR200 5 i 8A), through a photomask for evaluation, and the exposure amount is changed stepwise within the range of 50 to 5 00 m J / cm2 and exposed. . 60 seconds after the completion of the exposure, baking was performed using an electric furnace at 70 ° C for 90 seconds after exposure (PEB). For the coating films of the compositions of Examples 1 to 7, Comparative Examples 1 to 8, and Comparative Examples 1 to 22, a 2.38% tetramethylammonium hydroxide aqueous solution (Clariant Japan, product number AZ3 00MIF) was used. The time until the unexposed part completely dissolves and disappears is multiplied by 1.4, and a paddle image is developed, followed by rinsing with pure water for 20 seconds to obtain a negative patterned coating film. Also about Examples 8 to 19, Comparative Examples 9 to 20, Comparative Examples 2 to 2 6 The coating film of the composition was mixed with 50/50 (ν / ν%) of γ-butyrolactone and xylene The solvent was spray-developed by multiplying the time until the unexposed part completely dissolved and disappeared by 1.4 times, and then rinsed with isopropanol for 20 seconds to obtain a negative patterned coating film. Observe the obtained patterned coating film under an optical microscope to evaluate the minimum exposure amount (sensitivity) and minimum exposure amount of the sharp relief pattern without swelling -50- (47) 200403532 Via holes (viah 0 1 e) during irradiation (Rectangular development 丨 valley out 邰) resolution (resolution 0, the presence or absence of agglomerated or precipitated parts after development, etc.)

將曝光量150mJ/cm2之圖案中顯像前跑能A 計測來算出其變化率（顯像残膜率 永則與嘁像後之膜厚予以 °結果如表3所示。Measure the running energy A before development in a pattern with an exposure amount of 150mJ / cm2 to calculate the change rate (the residual film rate of the image is always equal to the film thickness after image formation). The results are shown in Table 3.

-51 . (48)200403532 表3 感度 (mJ/cm2) 解像度 (μηι) 析出 残渣 顯像残膜率 (%) 實施例1 110 4 〇 〇 82 實施例2 120 4 〇 〇 81 實施例3， 110 3.5 〇 〇 85 實施例4 120 4.5 〇 〇 80 實施例5 120 4.5 〇 〇 82 實施例6 130 4.5 〇 〇 78 實施例7 150 6 〇 〇 72 實施例8 100 5 〇 〇 90 實施例9 110 5 〇 〇 91 實施例10 110 5 〇 〇 90 實施例11 130 7.5 〇 〇 83 實施例12 110 5 〇 〇 92 實施例13 100 4.5 〇 〇 95 實施例14 130 6 〇 〇 90 實施例15 130 6.5 〇 〇 93 實施例16 140 6.5 〇 〇 91 實施例Π 150 7.5 〇 〇 82 實施例18 130 6 〇 〇 90 實施例19 110 5 〇 〇 96 比較例1 120 4 〇 〇 78 比較例2 120 4 〇 〇 80 比較例3 130 12 X X 79 比較例4 500以上 無解像 〇 X 46 比較例5 200 25 〇 X 89 比較例6 130 16 〇 Δ 78 比較例7 450 22 〇 X 51 比較例8 100 18 〇 X 83 比較例9 110 5 〇 〇 90 比較例10 100 5 〇 〇 91 比較例11 110 9 X X 91 比較例12 130 20 〇 X 76 比較例13 460 28 〇 X 49 比較例14 100 18 〇 X 92 比較例15 130 6 〇 〇 93 比較例16 130 6 〇 〇 91 比較例Π 140 12 X X 91 比較例18 160 25 〇 X 72 比較例19 460 30 〇 X 42 比較例20 100 22 〇 X 92 比較例21 150 6 〇 〇 75 比較例22 140 6 〇 〇 81 比較例23 150 7 〇 〇 85 比較例24 150 6.5 〇 〇 90 -52- (49) 200403532 表3 (續上) 感度 (mJ/cm2) 解像度 (μπι) 析出 残渣 顯像残膜率 (%) 比較例25 170 7.5 〇 〇 87 比較例26 160 7 〇 〇 93 析出、残渣之評價指標◦都 专△:些微產生X:激烈產生 -53- (50) (50)200403532 (耐熱性之評價） 將本發明實施例、比較例之各淸漆、與上述平版印刷 評價相同、在5英吋矽晶圓上塗敷、預先烘烤處理後、使 用縱型加工（cure )爐（光洋Lind berg公司製、形號乂？-2 0 0 0 B )、在氮氛圍下、於3 5 0 °C實施2小時加熱硬化處 理、來製作硬化後膜厚5 μηι之聚苯并噚唑皮膜及聚醯亞 胺皮膜。使用切割鋸刀（dicing saw ) ( Disco公司製、 型號DAD-2H/6T)將此皮膜切割成3.0mm寬度、並浸漬 於氟化氫酸水溶液而自矽晶圓上剝離、成爲薄長方形之薄 膜樣品。 將此薄膜樣品之玻璃轉化溫度（Tg )使用熱機械分析 置（島津製作所製、形號TMA-5 0)來測定、成爲聚苯 并噚唑皮膜及聚醯亞胺皮膜的耐熱性指標。測定條件爲試 料長10mm、定負載200g/mm2、測定溫度範圍25°C〜450 °C、昇溫速度10 C/min、氮氛圍。結果如表4所示。 (耐藥品性之評價） 將上述平版印刷評價所得附圖案塗膜、設定成前出之 縱型加工爐、於氮氛圍下、在3 5 0 t實施2小時之加熱 硬化處理、來製作硬化後膜厚5 μιη之附圖案聚苯并鸣唑 皮膜及聚醯亞胺皮膜。將此皮膜在加熱至8 5 °C之抗蝕劑 剝離液（東京應化工業製、品號1 〇5 )予以浸漬1小時。 使其冷却後、水洗、乾燥之、在光學顯微鏡觀察對圖案之 損傷、主要爲對龜裂或皺折等之有無加以評價。 -54- (51) (51)200403532 又、測定藥品浸漬前後之膜厚、以算出其變化率（膜 厚變化率）。結果如表4所示。 (高溫耐焊藥性之評價） 製作與耐藥品性評價相同之附圖案聚苯并嘴D坐及聚醯 亞胺皮膜、將焊藥（日本Alpha metalzu公司製、商標名 Solbond、品號R5003)予以旋轉塗敷（以500旋轉20 秒）。將此、使用網眼皮帶（m e s h b e 11 )式連續煅燒爐 (光洋Lindberg公司製、型號6841-2 OAMC-36)、以模 擬的焊接圓滑熱處理條件、在氮氛圍下、加熱至峰値溫度 3 8 0 °C爲止。 此時、在確保評價客觀性上爲重要者、係昇溫速度、 峰値温度附近之滯留時間、冷却速度等之溫度分佈 (profile )規格、而此係與半導體裝置之評價方法有關， 準照美國半導體業界標準規格之IPC/JEDEC J-STD-020A 之7 · 6項所記載之焊接圓滑熱處理條件之形式、來假設焊 接融點爲高溫的3 1 0 t、而予規格化。 將上述模擬圓滑熱處理後之皮膜浸漬於二甲苯1 〇分 鐘、接著浸漬於2 -丙醇1 〇分鐘，靜置之，除去焊藥、予 以乾燥後、於光學顯微鏡下觀察，來評價圖案之損傷、主 要爲龜裂或皺折之有無。 又、測定一連串處理前後之膜厚、並算出其變化率 (膜厚變化率）。結果如表4所示。 -55- (52)200403532 表4 耐薬品性 (85 °C *60min) 高温耐焊藥性 (380 °C ) Tg α ) 龜裂 膜厚變化率 (% ) 龜裂 膜厚變化率 (%) 實施例1 〇 101 〇 105 388 實施例2 〇 102 〇 105 388 實施例3 〇 100 〇 101 393 實施例4 〇 103 〇 106 386 實施例5 〇 102 〇 107 389 實施例6 〇 101 〇 105 378 實施例7 〇 106 〇 109 368 實施例8 〇 101 〇 105 359 實施例9 〇 102 〇 106 361 實施例10 〇 102 〇 104 366 實施例11 〇 105 〇 107 352 實施例12 〇 102 〇 105 370 實施例13 〇 100 〇 101 372 實施例14 〇 104 〇 106 366 實施例15 〇 106 〇 108 368 實施例16 〇 107 〇 108 369 實施例17 〇 107 〇 110 358 實施例18 〇 102 〇 103 375 實施例19 〇 10T 〇 102 379 比較例1 X 112 X 133 255 比較例2 X 110 X 129 262 比較例3 〇 101 〇 102 397 比較例4 〇 102 〇 106 385 比較例5 〇 103 〇 108 388 比較例6 〇 102 〇 106 388 比較例7 〇 103 〇 106 387 比較例8 〇 102 〇 107 389 比較例9 糸] 0钔 X 121 245 比較例10 X 23※之 X 116 296 比較例11 〇 103 〇 105 372 比較例12 〇 105 〇 105 360 比較例]3 〇 102 〇 104 360 比較例14 〇 104 〇 105 361 比較例15 X 24※之 X 119 25! 比較例16 X 63 X 114 301 比較例17 〇 104 〇 106 382 比較例18 〇 105 〇 106 365 比較例19 〇 102 〇 105 366 比較例20 〇 102 〇 106 365 比較例2] X 110 X 135 261 比較例22 X 112 X 131 260 -56- A ·') 200403532 (53) 表4 (續上） 耐薬品性 (85〇C *60min) 高温耐焊藥性 (380〇C ) 丁 g (t ) 龜裂 膜厚變化率 (°/〇 ) 龜裂 膜厚變化率 (% ) 比較例23 ※玉 0钔 X 120 246 比較例24 X】 0钔 X 119 250 比較例25 X 31扪 X 120 250 比較例26 X 35釣 X 122 252 龜裂評價指標◦:無龜裂X:有龜裂發生 ※1無耐性、完全溶出。X2耐性弱、膜減少激烈。 -57- (54) (54)200403532 比較例1、比較例9、比較例1 5、並不含有爲本發明 要件之蜜胺樹脂、與此比較、在本發明實施例之情形、優 異的平版印刷特性與高度耐熱性、耐藥品性、在極高之位 準上爲並存、故在高精細、且暴露於高溫之半導體裝置的 製造步驟亦爲可充分對應之材料。 在比較例2、比較例1 0、比較例1 6、蜜胺樹脂之添 加量比本發明之恰當範圍爲過少、相反的，比較例3、比 較例1 1、比較例1 7，蜜胺樹脂添加量爲過多。蜜胺樹脂 添加量過少時、耐熱性、耐藥品性不充分、反之過多的 話、耐熱性、耐藥品性雖充分、但顯像後之殘渣發生激 烈、在任何情形均比本發明實施例爲差。 在比較例4〜5、係本發明A成分之聚醯胺、聚苯并 哼唑先質之情形、具有光聚合性不飽和雙鍵之基的導入 率、比本發明之恰當範圍更少、或者更多之情形。 又、在比較例6、比較例1 2，比較例1 8、係爲本發 明B成分之具有光聚合性不飽和雙鍵單體之添加量、比本 發明恰當範圍更多之情形。 再者、比較例 7〜8、比較例1 3〜1 4、比較例1 9〜 20、係本發明C成分之光聚合引發劑添加量、比本發明之 恰當範圍更少、或者過多之情形。其在任何情況、均無法 確保充分的平版印刷特性、故比本發明實施例爲差。 進而、在比較例21〜26、係取代本發明之蜜胺樹 脂、而使用一般橋聯劑之環氧樹脂系橋聯劑或三烯丙基異 三聚氫酸酯之情形、其在任何情況、均完全無法確保耐藥 -58- (55) (55)200403532 品性、高溫耐焊藥性、而比本發明之實施例爲差。 産業上利用可能性 ’ 如上所述、本發明所提供之負型感光性樹脂組成物、 具有鹼性顯像負型、或具有溶劑顯像負型之優異平版印刷 特性、同時將此感光性樹脂組成物塗膜予以加熱硬化所得 聚苯并鸣唑或聚醯亞胺皮膜、具有極高之耐熱性、耐藥品 性、故可充分滿足近年對半導體裝置製造步驟之高度要 求。-51. (48) 200403532 Table 3 Sensitivity (mJ / cm2) Resolution (μηι) Residual residue imaging residual film rate (%) Example 1 110 4 〇82 Example 2 120 4 〇81 Example 3, 110 3.5 〇85 Example 4 120 4.5 〇80 Example 5 120 4.5 〇82 Example 6 130 4.5 〇78 Example 7 150 6 〇72 Example 8 100 5 〇90 Example 9 110 5 〇 〇91 Example 10 110 5 〇90 Example 11 130 7.5 〇83 Example 12 110 5 〇92 Example 13 100 4.5 〇095 Example 14 130 6 〇90 Example 15 130 6.5 〇0093 Example 16 140 6.5 〇91 Example Π 150 7.5 〇82 Example 18 130 6 〇90 Example 19 110 5 〇96 Comparative Example 1 120 4 〇78 Comparative Example 2 120 4 〇80 Comparative Example 3 130 12 XX 79 Comparative Example 4 500 or more without resolution OX 46 Comparative Example 5 200 25 〇X 89 Comparative Example 6 130 16 〇Δ 78 Comparative Example 7 450 22 〇X 51 Comparative Example 8 100 18 〇X 83 Comparative Example 9 110 5 〇90 Comparative Example 10 100 5 〇91 Comparative Example 11 110 9 XX 91 Comparative Example 12 130 20 〇X 76 Comparative Example 13 460 28 〇X 49 Comparative Example 14 100 18 〇X 92 Comparative Example 15 130 6 〇93 Comparative Example 16 130 6 〇91 Comparative Example Π 140 12 XX 91 Comparative Example 18 160 25 OX 72 Comparative Example 19 460 30 OX 42 Comparative Example 20 100 22 OX 92 Comparative Example 21 150 6 〇75 Comparative Example 22 140 6 〇81 Comparative Example 23 150 7 〇85 Comparative Example 24 150 6.5 〇〇90 -52- (49) 200403532 Table 3 (continued) Sensitivity (mJ / cm2) Resolution (μπι) Residual residue imaging residual film rate (%) Comparative Example 25 170 7.5 〇87 Comparative Example 26 160 7 〇 〇93 Evaluation index of precipitation and residues ◦ Both: △: Slightly generated X: Severely generated -53- (50) (50) 200403532 (Evaluation of heat resistance) The paints of Examples and Comparative Examples of the present invention and the above Lithographic evaluation was the same. After coating on a 5-inch silicon wafer, pre-baking, and using a vertical furnace (manufactured by Koyo Lindberg Co., Ltd.?)? -2 0 0 0 B), and heat-cured for 2 hours at 350 ° C. under a nitrogen atmosphere to produce a polybenzoxazole film and a polyimide film with a thickness of 5 μm after curing. This film was cut to a width of 3.0 mm using a dicing saw (manufactured by Disco, model No. DAD-2H / 6T), and immersed in a hydrofluoric acid aqueous solution to peel off the silicon wafer to form a thin rectangular thin film sample. The glass transition temperature (Tg) of this film sample was measured using a thermomechanical analysis device (manufactured by Shimadzu Corporation, shape number TMA-5 0), and it was used as an index of heat resistance of polybenzoxazole film and polyimide film. The measurement conditions were a sample length of 10 mm, a constant load of 200 g / mm2, a measurement temperature range of 25 ° C to 450 ° C, a heating rate of 10 C / min, and a nitrogen atmosphere. The results are shown in Table 4. (Evaluation of Chemical Resistance) The pattern-coated film obtained from the above-mentioned lithographic evaluation was set to a vertical processing furnace which was outputted, and was subjected to a heat-hardening treatment in a nitrogen atmosphere at 350 ° C for 2 hours to produce a cured product. 5 μm thick patterned polybenzazole film and polyimide film. This film was immersed for 1 hour in a resist stripping solution (manufactured by Tokyo Yingka Kogyo Co., Ltd., No. 105) heated to 85 ° C. After cooling, washing with water, drying, and observing the damage to the pattern with an optical microscope, the presence or absence of cracks or wrinkles is mainly evaluated. -54- (51) (51) 200403532 In addition, the film thickness before and after immersion of the drug was measured to calculate the rate of change (film thickness change rate). The results are shown in Table 4. (Evaluation of high-temperature soldering resistance) Production of a patterned polybenzo mouthpiece D seat and polyimide film with the same chemical resistance evaluation, and soldering (manufactured by Alpha Metalzu, Japan, brand name Solbond, product number R5003) Spin coating (rotating at 500 for 20 seconds). This was performed using a mesh belt (meshbe 11) type continuous calciner (manufactured by Koyo Lindberg, model number 6841-2 OAMC-36), under simulated welding smooth heat treatment conditions, and heated to a peak temperature of 3 in a nitrogen atmosphere. Up to 0 ° C. At this time, it is important to ensure the objectivity of the evaluation, and it is a temperature profile specification such as the heating rate, the residence time near the peak temperature, and the cooling rate, which is related to the evaluation method of the semiconductor device. The soldering heat treatment conditions described in IPC / JEDEC J-STD-020A, item 7 · 6 of the semiconductor industry standard specifications are standardized in assuming that the solder melting point is 3 1 0 t at a high temperature. The film after the simulated smooth heat treatment was immersed in xylene for 10 minutes, then immersed in 2-propanol for 10 minutes, left to stand, removed the flux, dried, and observed under an optical microscope to evaluate the pattern damage. , Mainly the existence of cracks or wrinkles. The film thickness before and after a series of treatments was measured, and the change rate (film thickness change rate) was calculated. The results are shown in Table 4. -55- (52) 200403532 Table 4 Anti-jade resistance (85 ° C * 60min) High temperature solder resistance (380 ° C) Tg α) Change rate of cracked film thickness (%) Change rate of cracked film thickness (%) Implementation Example 1 〇101 〇105 388 Example 2 〇102 〇105 388 Example 3 〇100 〇101 393 Example 4 〇103 〇106 386 Example 5 〇102 〇107 389 Example 6 〇101 〇105 378 Example 7 〇106 〇109 368 Example 8 〇101 〇105 359 Example 9 〇102 〇106 361 Example 10 〇102 〇104 366 Example 11 〇105 〇107 352 Example 12 〇102 〇105 370 Example 13 〇100 〇101 372 Example 14 〇104 〇106 366 Example 15 〇106 〇108 368 Example 16 〇107 〇108 369 Example 17 〇107 〇110 358 Example 18 〇102 〇103 375 Example 19 〇10T 〇102 379 Comparative Example 1 X 112 X 133 255 Comparative Example 2 X 110 X 129 262 Comparative Example 3 〇101 〇102 397 Comparative Example 4 〇102 〇106 385 Comparative Example 5 〇103 〇108 388 Comparative Example 6 〇102 〇106 388 Compare Example 7 〇103 〇106 387 Comparative Example 8 〇102 〇107 389 Comparative Example 9 糸] 0 钔 X 121 245 Comparative Example 10 X 23 * X 116 296 Comparative Example 11 〇103 〇105 372 Comparative Example 12 〇105 〇105 360 Comparative Example] 3 〇102 〇104 360 Comparative Example 14 〇104 〇105 361 Comparative Example 15 X 24 * X 119 25! Comparative Example 16 X 63 X 114 301 Comparative Example 17 〇104 〇106 382 Comparative Example 18 〇105 〇106 365 Comparative Example 19 〇102 〇105 366 Comparison Example 20 〇102 〇106 365 Comparative Example 2] X 110 X 135 261 Comparative Example 22 X 112 X 131 260 -56- A · ') 200403532 (53) Table 4 (continued) Durability (85 ° C * 60min ) High-temperature soldering resistance (380 ° C) D g (t) Change rate of cracked film thickness (° / 〇) Change rate of cracked film thickness (%) Comparative Example 23 ※ Jade 0 钔 X 120 246 Comparative Example 24 X] 0 钔 X 119 250 Comparative Example 25 X 31 扪 X 120 250 Comparative Example 26 X 35 Fishing X 122 252 Crack evaluation index ◦: No crack X: Crack occurrence * 1 No resistance and complete dissolution. X2 has weak resistance and drastic film reduction. -57- (54) (54) 200403532 Comparative Example 1, Comparative Example 9, Comparative Example 1 5. Melamine resin which does not contain the essential elements of the present invention, compared with this, in the case of the examples of the present invention, excellent lithography Printing characteristics and high heat resistance and chemical resistance coexist at an extremely high level. Therefore, the manufacturing steps of a semiconductor device that is high-definition and exposed to high temperatures are also adequate materials. In Comparative Example 2, Comparative Example 10, Comparative Example 16, the amount of melamine resin added is less than the proper range of the present invention, and the opposite is the opposite, Comparative Example 3, Comparative Example 1, 1, Comparative Example 17, and Melamine resin The amount added is too much. When the amount of melamine resin is too small, the heat resistance and chemical resistance are insufficient, and if the melamine resin is added too much, the heat resistance and chemical resistance are sufficient, but the residue after development is intense, which is worse than the embodiment of the present invention in any case. . In Comparative Examples 4 to 5, the polyamine and polybenzoxazole precursors of component A of the present invention, the introduction rate of the group having a photopolymerizable unsaturated double bond is less than the proper range of the present invention, Or more situations. In addition, in Comparative Example 6, Comparative Example 12, and Comparative Example 18, the addition amount of the photopolymerizable unsaturated double bond monomer of the component B of the present invention may be more than the proper range of the present invention. In addition, Comparative Examples 7 to 8, Comparative Examples 1 to 3, 4, Comparative Examples 1 to 20, and the addition amount of the photopolymerization initiator of the component C of the present invention may be less than the appropriate range of the present invention or may be excessive. . In any case, it cannot ensure sufficient lithographic characteristics and is inferior to the embodiment of the present invention. Furthermore, in Comparative Examples 21 to 26, in the case of using an epoxy resin-based bridging agent or triallyl isotrihydrohydrogen ester in place of the melamine resin of the present invention and using a general bridging agent, it is in any case It is impossible to ensure the drug resistance-58- (55) (55) 200403532, and the high-temperature soldering resistance is inferior to the embodiment of the present invention. Industrial Applicability 'As mentioned above, the negative-type photosensitive resin composition provided by the present invention has excellent lithographic characteristics with a negative-type alkaline development or a negative-type solvent development. The polybenzoimidazole or polyimide film obtained by heating and hardening the coating film of the composition has extremely high heat resistance and chemical resistance, so it can fully meet the high requirements for semiconductor device manufacturing steps in recent years.

Claims (1)

(1) 200403532 拾、申請專利範圍 1 · 一種負型感光性樹脂組成物，其含有： (A )具有光聚合性不飽和雙鍵之具下述式（1 )所 示構造單位之聚醯胺：1 0 0質量份， (B) 具有光聚合性不飽和雙鍵之單體：1〜50質量 份， (C) 光聚合引發劑：1〜20質量份，及 (D) 蜜胺樹脂：5〜30質量份， 〇 Ο Η Η II II I I …（1)(1) 200403532 Patent application scope 1 · A negative photosensitive resin composition containing: (A) Polyamine having a photopolymerizable unsaturated double bond having a structural unit represented by the following formula (1) : 100 parts by mass, (B) a monomer having a photopolymerizable unsaturated double bond: 1 to 50 parts by mass, (C) a photopolymerization initiator: 1 to 20 parts by mass, and (D) a melamine resin: 5 ~ 30 parts by mass, 〇〇 Η Η II II II… (1) C—X一C一N一Υ—N I I (coora) i (0RB) j (式中、X爲2〜4價之芳香族基、Y爲2〜4價之 芳香族基；i及j爲〇〜2之整數，並滿足i十j=2、k爲2 〜150之整數；RA爲獨立之下述式（2)所示具有光聚合 性不飽和雙鍵之1價有機基、或碳數1〜4之飽和脂肪 族基；Rb爲獨立之氫原子、或下述式（3)所示具有光聚 合性不飽和雙鍵之1價有機基：但、使Rb之全莫耳數爲 i 0 0莫耳％時、其1〇莫耳％以上、5〇莫耳％以下係丁述 式（3)所示具有光聚合性不飽和雙鍵之1價有機基·C—X—C—N—Υ—NII (coora) i (0RB) j (wherein X is an aromatic group having 2 to 4 valence, and Y is an aromatic group having 2 to 4 valence; i and j are 0. An integer of ~ 2 and satisfying i = j = 2, k is an integer of 2 ~ 150; RA is an independent monovalent organic group or a carbon number having a photopolymerizable unsaturated double bond represented by the following formula (2) A saturated aliphatic group of 1 to 4; Rb is an independent hydrogen atom or a monovalent organic group having a photopolymerizable unsaturated double bond represented by the following formula (3): However, the total mole number of Rb is i At 0 mol%, it is 10 mol% or more and 50 mol% or less is a monovalent organic group having a photopolymerizable unsaturated double bond represented by formula (3). -60- (2) 200403532 式中、R8爲氨原子或碳數1〜3之有機基、r9、ri〇 係各爲獨立之氫原子或碳數1〜3之有機基、q爲2〜10 之整數； 0 II C—N I Η-60- (2) 200403532 In the formula, R8 is an ammonia atom or an organic group having 1 to 3 carbon atoms, r9 and ri0 are each an independent hydrogen atom or an organic group having 1 to 3 carbon atoms, and q is 2 to 10 Integer; 0 II C—NI Η (3) 式中、R3爲氫原子或碳數i〜3之有機基、R4及R5 各爲獨立之氫原子或碳數1〜3之有機基、m爲2〜1 Ο 之整數）。 2·如申請專利範圍第i項記載之負型感光性樹脂 組成物：其中，（A )具有光聚合性不飽和雙鍵之聚醯 胺、係具有下述式（4 )所示構造單位之聚苯并曙唑先 質；(3) In the formula, R3 is a hydrogen atom or an organic group having a carbon number of i to 3, R4 and R5 are each an independent hydrogen atom or an organic group having a carbon number of 1 to 3, and m is an integer of 2 to 10). 2. The negative photosensitive resin composition according to item i in the scope of the patent application: wherein (A) polyamine having a photopolymerizable unsaturated double bond is a unit having a structural unit represented by the following formula (4) Polybenzoxazole precursor (4) (式中、Χι爲2價芳香族基、Υι爲4價芳香族 基、η爲2〜150之整數；Rl及R2各爲獨立之氫原子或 -61 - (3) 200403532 下述式（3 )所示、具有光聚合性不飽和雙鍵之1價有 機基；但、Ri及R2之合計莫耳爲1〇〇莫耳％時、Ri與R2 之1 0莫耳％以上、5 0莫耳％以下、係下述式（3 )所 示、具有光聚合性不飽和雙鍵的1價有機基； 〇 II C—N I Η(4) (where, X is a divalent aromatic group, Υ is a tetravalent aromatic group, and η is an integer of 2 to 150; R1 and R2 are each an independent hydrogen atom or -61-(3) 200403532 The following A monovalent organic group having a photopolymerizable unsaturated double bond as shown in formula (3); however, when the total mole of Ri and R2 is 100 mole%, the mole of Ri and R2 is 10 mole% or more, 50 mol% or less, a monovalent organic group represented by the following formula (3) and having a photopolymerizable unsaturated double bond; II C—NI Η (3)(3) 但、R3係氫原子或碳數1〜3之有機基、R4及R5爲 各自獨立之氫原子或碳數1〜3之有機基、m爲2〜10之 整數）。 3.如申請專利範圍第1項記載之負型感光性樹脂組 成物，其中，（A )具有光聚合性不飽和雙鍵之聚醯胺、 係具有下述式（5)所示構造單位之聚醯亞胺先質、However, R3 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R4 and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10). 3. The negative photosensitive resin composition according to item 1 in the scope of the patent application, wherein (A) polyamine having a photopolymerizable unsaturated double bond is a unit having a structural unit represented by the following formula (5) Polyimide precursors, ΟII-c、 ：χ2. R^O—IIο OH HII I I ,C—N—Y2—N- 、c——or7IIo (5) P (式中，X2爲4價芳香族基，-COOR6基及-COOR7 基與該等相鄰之-CONH —基互爲鄰位；Y2爲2價芳香族 基、ρ爲2〜150之整數；R6及R7爲各自獨立之下述式 -62- (4) 200403532 (2 )所示具有光聚合性不飽和雙鍵之1價有機基、％ 碳數1〜4之飽和脂肪族基， Ο 〇〇II-c, ： χ2. R ^ O—IIο OH HII II, C—N—Y2—N-, c—or7IIo (5) P (wherein X2 is a tetravalent aromatic group, -COOR6 group, and- The COOR7 group and the adjacent -CONH — groups are adjacent to each other; Y2 is a divalent aromatic group and ρ is an integer of 2 to 150; R6 and R7 are each independently of the following formula -62- (4) 200403532 (2) a monovalent organic group having a photopolymerizable unsaturated double bond, and a saturated aliphatic group having 1 to 4% carbon number, as shown in FIG. 、II 严 CHri~0—c—…⑵ R8 rio 爲 但、R8爲氫原子或碳數1〜3之有機基、R9、d κι〇 各自獨立之氫原子或碳數1〜3之有機基、q爲2〜l() 整數。） 感光性 以上， 感光性 化蜜胺 4.如申請專利範圍第1、2或3項記載之負型 樹脂組成物，其中（D )蜜胺樹脂之聚合度在1.〇 2 · 2以下者。 5.如申請專利範圍第1、2或3項記載之負型 樹脂組成物，其中（D )蜜胺樹脂係六甲氧甲基 者0 其包 6 · —種耐熱性，耐藥品性之凸紋花樣形成方$ ^ 含下列步驟： 項 (1 ) 將申請專利範圍第1項至第5 I貞ψ 記載之負型感光性樹脂組成物塗敷於基材’ (2) 透過圖案掩罩使活性光線照射，_ &amp; ^ 噪允於此 塗膜， (3 ) 使用顯像液來溶解除去塗膜之未g % @， 以形成凸紋花樣’ (4 ) 在2〇〇 °C以上之溫度加熱塗膜，使之硬化 -63- f：v 〇· (5) 200403532 者。 7 . —種半導體裝置之製造方法，其含有以申請專利範 圍第6項之凸紋花樣形成方法來形成凸紋花樣者。 8.—種半導體裝置之製造方法，其含有使用申請專利 範圍第1項至第5項中任一項所記載之負型感光性樹脂組成 物者。 -64- 200403532 柒、（一）、本案指定代表圖為：無 (二）、本代表圖之元件代表符號簡單說明：無 捌、本案若有化學式時，請揭示最能顯示發明特徵的化學 式： -4-, II rigor CHri ~ 0—c —... ⑵ R8 rio is but R8 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R9 and d κο are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, q is an integer from 2 to l (). ) Above photosensitivity, photosensitized melamine 4. The negative resin composition as described in item 1, 2, or 3 of the patent application scope, wherein (D) the degree of polymerization of the melamine resin is 1.02 · 2 or less . 5. The negative resin composition according to item 1, 2 or 3 in the scope of the patent application, in which (D) the melamine resin is hexamethoxymethyl, and the package includes 6: a kind of convexity of heat resistance and chemical resistance The pattern forming square $ ^ includes the following steps: Item (1) Applying the negative photosensitive resin composition described in the first to the fifth patent scope of the patent application to the substrate '(2) Activate the pattern mask Light irradiation, _ &amp; Noise is allowed to this coating film, (3) Use imaging solution to dissolve and remove the coating film %% @, to form convex patterns' (4) at a temperature above 2000 ° C The coating film is heated to harden -63- f: v 〇 · (5) 200403532. 7. A method for manufacturing a semiconductor device, comprising a method for forming a relief pattern by a relief pattern forming method according to item 6 of the patent application. 8. A method for manufacturing a semiconductor device, comprising using the negative photosensitive resin composition described in any one of claims 1 to 5 of the scope of patent application. -64- 200403532 柒, (1), the designated representative of this case is: No (II), the representative symbols of the elements in this case are simply explained: No, if there is a chemical formula in this case, please reveal the chemical formula that can best show the characteristics of the invention: -4-