TW201140242A - Negative photosensitive resin composition, method for manufacturing cured relief pattern, and semiconductor device - Google Patents

Abstract

The present invention provides a negative photosensitive resin composition that provides a cured film excellent in adhesion to a substrate after low-temperature curing, a method for manufacturing a cured relief pattern, and a semiconductor device. The negative photosensitive resin composition of the present invention comprises: (A) 100 mass parts of a polyimide precursor of a specific structure, (B) 1 to 20 mass parts of a photo-polymerization initiator, and (C) 0.01 to 10 mass parts of a 2-30C monocarboxylic acid compound having one or more functional groups selected from the group consisting of a hydroxyl group, an ether group and an ester group.

Description

201140242 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於形成例如電子零件之絕緣材料、 與半導體裝置中之鈍化膜、緩衝膜及層間絕緣膜等之浮凸 圖案的感光性樹脂組合物、使用其之硬化浮凸圖案之製造 方法、與半導體裝置。 【先前技術】 先前，電子零件之絕緣材料、及半導體裝置之鈍化膜、 表面保護膜、層間絕緣膜等係使用兼具優異之耐熱性、電 氣特性及機械特性之聚醯亞胺樹脂。該聚醯亞胺樹脂之 中以感光性聚酿亞胺前驅物之形式所供給者可藉由該前 驅物之塗佈、曝光、顯影及利用了固化之熱醯亞胺化處理， 而容易地形成耐熱性之浮凸圖案皮膜。此種感光性聚醯亞 胺前驅物與先前之非感光型聚醯亞胺相比，具有能夠大幅 度縮短步驟之特徵。 另一方面，近年來，就積體度及功能之提高、與晶片尺 寸之矮小化之觀點而言，將半導體裝置安裝於印刷配線基 板上之方法亦發生了變化。由先前之利用金屬接腳與鉛-錫 共曰曰焊之安裝方法逐漸轉變為使用能夠實現更高密度之安 裝的 BGA(Ball Grid Array，球柵陣列）、cSP(Chip ScaleBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive pattern for forming an insulating material such as an electronic component, and a relief pattern of a passivation film, a buffer film, and an interlayer insulating film in a semiconductor device. A resin composition, a method for producing a cured embossed pattern using the same, and a semiconductor device. [Prior Art] Conventionally, an insulating material for an electronic component, a passivation film of a semiconductor device, a surface protective film, an interlayer insulating film, and the like are used as a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties. Among the polyimine resins, those supplied as photosensitive polyimide precursors can be easily coated by coating, exposing, developing, and utilizing curing heat imidization treatment. A heat-resistant embossed pattern film is formed. Such a photosensitive polyimide precursor has a characteristic that the step can be greatly shortened compared to the prior non-photosensitive polyimide. On the other hand, in recent years, the method of mounting a semiconductor device on a printed wiring board has also changed from the viewpoint of an increase in the degree of integration and function and a reduction in the size of the wafer. The previous installation method using metal pins and lead-tin co-twisting has gradually changed to BGA (Ball Grid Array) and cSP (Chip Scale) which can achieve higher density mounting.

Package ’晶片尺寸封裝）等聚醯亞胺皮膜直接接觸焊錫凸塊 之、構。於形成此種凸塊結構時，對於該皮膜要求較高之 =熱性與耐化學品性^揭示有藉由於含有聚醯亞胺前驅物 或聚苯并4唑前驅物之組合物中添加熱交聯劑而提高聚醯 153046.doc 201140242 亞胺皮膜或聚苯并θ唑皮膜之耐熱性之方法（參照專利文 獻1)〇 進而，由於半導體裝置之微細化之發展，而逐漸無法忽 視半導體裝置之配線電阻。因此，正在由迄今為止所使用 之金或鋁之配線向電阻更低之銅或銅合金之配線轉變。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開2003-287889號公報 【發明内容】 [發明所欲解決之問題] 然而，發明人認識到：若使用上述專利文獻1中揭示之感 光性樹脂組合物於包含銅或銅合金之基板上形成圖案，則 存在使圖案於250。(：左右之低溫下固化時硬化物與基板之 接著性未達到使用水準之問題；經過銳意研究，結果完成 本發明。 本發明之目的在於提供一種可提供低溫固化後與基板之 接著性優異之硬化膜的負型感光性樹脂組合物、使用該感 光性樹脂組合物形成聚醯亞胺圖案之硬化浮凸圖案之製造 方法、與半導體裝置。 [解決問題之技術手段] 本發明人等發現，藉由使用具有特定結構之化合物，可 獲得一種負型感光性樹脂組合物，其即便於使用銅或銅合 金作為基板之情形時，亦可提供低溫固化後與基板之接著 性優異之硬化膜，從而完成本發明。即，本發明如下所述。 153046.doc • 4 - 201140242 []種負型感光性樹脂組合物，其含有以下之： (A)具有通式⑴所示之結構之聚醯亞胺前驅物⑽質量 份’· [化1]The polyimide film such as Package 'wafer size package is in direct contact with the solder bump. In the formation of such a bump structure, the film is required to have higher heat and chemical resistance, and it is revealed that heat is added by the composition containing the polyimide precursor or the polybenzotetrazole precursor. A method of improving the heat resistance of the amide film or the polybenzopyrazole film by using a compounding agent (refer to Patent Document 1), and further, the semiconductor device is gradually neglected due to the development of the miniaturization of the semiconductor device. Wiring resistance. Therefore, the wiring of gold or aluminum used so far is shifting to the wiring of copper or copper alloy having a lower electric resistance. [Prior Art] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-287889 [Draft of the Invention] [Problems to be Solved by the Invention] However, the inventors have recognized that the use of the above-mentioned Patent Document 1 When the photosensitive resin composition disclosed is patterned on a substrate containing copper or a copper alloy, the pattern is present at 250. (The problem that the adhesion between the cured product and the substrate does not reach the level of use when curing at a low temperature is about to be used; after careful study, the present invention has been completed. It is an object of the present invention to provide an excellent adhesion to a substrate after curing at a low temperature. A negative-type photosensitive resin composition of a cured film, a method of producing a cured embossed pattern of a polyimine pattern using the photosensitive resin composition, and a semiconductor device. [Technical means for solving the problem] The present inventors have found that By using a compound having a specific structure, a negative photosensitive resin composition can be obtained which can provide a cured film excellent in adhesion to a substrate after low-temperature curing even when copper or a copper alloy is used as a substrate. The present invention has been completed. The present invention is as follows. 153046.doc • 4 - 201140242 [A negative photosensitive resin composition containing the following: (A) Polyfluorene having the structure represented by the general formula (1) Imine precursor (10) parts by mass '· [Chemical 1]

{式中，Xl為4價有機基，Υι為2價有機基，η為2〜150之整 數Ri及R2刀別獨立為氫原子、或下述通式⑺： [化2] 0 (ch2-^o-c-c= r3Wherein X1 is a tetravalent organic group, Υι is a divalent organic group, η is an integer of 2 to 150, and Ri and R2 are each independently a hydrogen atom, or the following formula (7): [Chemical 2] 0 (ch2- ^occ= r3

(2) (式中R3 R4及R_5分別獨立為氫原子或碳數1〜3之有機基， 並且m為2〜10之整數）所示之Hf有機基、或碳數卜4之飽和 脂肪族基；其中’ Ri及&兩者不會同時為氫原子卜 (B) 光聚合起始劑i〜2〇質量份、及 (C) 八有1個以上選自由羥基、醚基及酯基所組成之群之 官能基的碳數2〜30之單羧酸化合物 0.01〜10質量份。 [2]如上述[1]之負型感光性樹脂組合物，其中上述（〇 之單㈣化合物為選自由下述通式（3)所示之化合物所組成 153046.doc 201140242 之群中的至少1種單羧酸化合物： [化3](2) (wherein R3 R4 and R_5 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), or a saturated aliphatic group of carbon number 4 Wherein ' Ri and & both are not simultaneously a hydrogen atom (B) photopolymerization initiator i 2 parts by mass, and (C) 8 or more are selected from a hydroxyl group, an ether group and an ester group The functional group of the group consisting of 0.01 to 10 parts by mass of the monocarboxylic acid compound having 2 to 30 carbon atoms. [2] The negative photosensitive resin composition according to the above [1], wherein the above-mentioned (tetra) compound is at least one selected from the group consisting of compounds represented by the following formula (3): 153046.doc 201140242 1 monocarboxylic acid compound: [Chemical 3]

C—ο—Η (3) R7 Ο {式中，Re為氫原子或碳數1~3之有機基’ I為氫原子、碳 數1〜3之烷基4R8，此處r8為下述通式： [化4]C—ο—Η (3) R7 Ο {wherein, Re is a hydrogen atom or an organic group having 1 to 3 carbon atoms. 'I is a hydrogen atom and an alkyl group 4R8 having a carbon number of 1 to 3, where r8 is as follows. Type: [Chemical 4]

(式中，羥基或碳數卜3之烷氧基，j為〇〜5之整數’並且 於存在複數個之情形時相互之間可相同亦可不同）所示 之基，R9為氫原子、碳數1〜3之烷基或碳數丨〜3之烷基羰 [3]如上述Π]或[2]之負型感光性樹脂組合物，其中上述 (C)之單羧酸化合物為選自由下述通 ,,, 〜所不之化合物所 成之群中的至少1種單羧酸化合物： [化5](wherein, a hydroxyl group or a carbon number of alkoxy groups, j is an integer of 〇~5 and may be the same or different from each other in the case where a plurality of them are present), and R9 is a hydrogen atom, An alkyl group having a carbon number of 1 to 3 or an alkylcarbonyl group having a carbon number of 丨3, and the negative photosensitive resin composition of the above [2] or [2], wherein the monocarboxylic acid compound of the above (C) is selected Freely, at least one monocarboxylic acid compound in the group formed by the compound of any of the following: [Chemical 5]

OH (4)OH (4)

Rio — C—C—Ο— Η I IIRio — C—C—Ο—Η I II

Rn〇 {式中Rn〇 {

Rio為氫原子或碳數1〜3之有機基 R11為氣原子、 153046.doc 201140242 碳數1〜3之烷基或r12，此處為下述通式： [化6]Rio is a hydrogen atom or an organic group having 1 to 3 carbon atoms. R11 is a gas atom, 153046.doc 201140242 Alkyl group having 1 to 3 carbon atoms or r12, here is the following formula: [Chem. 6]

(式中’ Z2為羥基或碳數卜3之烷氧基，k為〇〜5之整數，並 且於存在複數個之情形時相互之間可相同亦可不同）所 [4] 如上述[1]至[3]中任一項之負型感光性樹脂組合 物，其中進而含有（D)有機鈦化合物ο ”〜1〇質量份。 有機鈦化合物為選自由鈦螯合化合物 [5] 如上述[4]之負型感光性樹脂組合物，其中上述⑺) 四烷氧基鈦化合 物、及二茂鈦化合物所組成之群中的至少丨種化合物。 [6] —種硬化浮凸圖銮夕制士、+ u ^ ^(wherein Z2 is a hydroxyl group or a carbon number of alkoxy group, k is an integer of 〇~5, and may be the same or different when there are a plurality of cases) [4] as above [1] The negative photosensitive resin composition according to any one of [3], further comprising (D) an organic titanium compound ο" to 1 〇 by mass. The organotitanium compound is selected from the group consisting of titanium chelate compounds [5] as described above [4] The negative photosensitive resin composition of the above-mentioned (7)) tetraalkoxy titanium compound and at least an anthracene compound of the group consisting of a titanocene compound. [6] A hardened relief pattern Bachelor, + u ^ ^

(2)對該感光性樹脂層進行曝光之步(2) Step of exposing the photosensitive resin layer

凸圖案之Convex pattern

凸圓案之步Step of the convex case

法所獲得之硬化浮凸圖案而成。 其係具有藉由如上述[6]之製造 153046.doc 201140242 [發明之效果] 根據本發明，藉由於負型感光性樹脂組合物中調配具有 特定結構之化合物，可獲得—種負型感光性樹脂組合物， 其藉由低溫固化亦可提供固化後與基板之接著優異之硬化 膜進而可提供一種使用該感光性樹脂組合物形成聚酿 亞胺圖案之硬化浮凸圖案之製造方法、與半導體裝置。 【實施方式】 以下對本發明進行具體說明。再者，貫穿本說明書全文， 於通式中以同一符號表示之結構於分子中存在複數個之情 形時相互之間可相同亦可不同。 <負型感光性樹脂組合物> 本發明提供如下之負型感光性樹脂組合物，其含有：（A) 具有下述通式（1)所示之結構之聚醯亞胺前驅物（以下，亦稱 為（A)聚醯亞胺前驅物）1〇〇質量份： [化7] Ο II -C. i? •C—N—γ1—N- O)The hardened embossed pattern obtained by the law. It is manufactured by the above-mentioned [6] 153046.doc 201140242 [Effects of the Invention] According to the present invention, a negative photosensitive property can be obtained by formulating a compound having a specific structure in a negative photosensitive resin composition. A resin composition which can provide a cured film which is excellent after bonding with a substrate by curing at a low temperature, and further provides a method for producing a hardened embossed pattern in which a polyimide resin pattern is formed using the photosensitive resin composition, and a semiconductor Device. [Embodiment] Hereinafter, the present invention will be specifically described. Further, throughout the specification, structures having the same reference numerals in the general formula may be the same or different from each other when there are a plurality of cases in the molecule. <Negative Photosensitive Resin Composition> The present invention provides a negative photosensitive resin composition containing (A) a polyimine precursor having a structure represented by the following formula (1) ( Hereinafter, also referred to as (A) polyimine precursor) 1 part by mass: [Chemical 7] Ο II -C. i? • C-N-γ1 - N- O)

Ri〇—C' II Ο C- II 0 -OR, n {式中’又1為4價有機基，1為2價有機基，n為2〜150之整 數’ Rl及R2分別獨立為氫原子、或下述通式（2): 153046.doc (2) (2)201140242 [化8]Ri〇—C' II Ο C-II 0 -OR, n {wherein 1 is a tetravalent organic group, 1 is a divalent organic group, and n is an integer of 2 to 150'. Rl and R2 are each independently a hydrogen atom. Or the following general formula (2): 153046.doc (2) (2) 201140242 [Chem. 8]

(式中，Rs、R4及Rs分別獨立為氫原子或碳數卜3之有機基， 並且m為2〜10之整數）所示之1價有機基、或碳數卜4之飽和 脂肪族基。其中，心及艮2兩者不會同時為氫原子}、（B)光 聚合起始劑1〜20質量份、及（〇具有1個以上選自由羥基、 醚基及酯基所組成之群之官能基的碳數2〜3 0之單叛酸化合 物（以下，亦稱為（C)單羧酸化合物）〇.〇1〜1〇質量份。即，本 發明之負型感光性樹脂組合物以（A)聚醯亞胺前驅物10〇質 量份、（B)光聚合起始劑1〜20質量份、及（C)單羧酸化合物 0.01-10.質量份作為必需成分。 (A)聚醯亞胺前驅物 就本發明所使用之（A)聚酿亞胺前驅物加以說明。（a)聚 醯亞胺前驅物為本發明之負型感光性樹脂組合物中之樹脂 成分，為具有上述通式（1)所示之結構之聚酿胺。（八）聚酿亞 胺前驅物藉由實施加熱（例如200°C以上）環化處理而轉化為 聚醢亞胺。 上述通式（1)中，就兼具耐熱性與感光特性之方面而言， X!所示之4價有機基較佳為碳數6〜40之有機基，進而較佳為 -COOR^基及_c〇〇R2基與—conh-基相互處於鄰位之芳香族 基、或脂環式脂肪族基。作為X,所示之4價有機基，進而較 佳為舉出下述式（5): 153046.doc 201140242 [化9](wherein, Rs, R4 and Rs are each independently a hydrogen atom or an organic group of carbon number 3, and m is an integer of 2 to 10), or a saturated aliphatic group of carbon number . Wherein, both the heart and the ruthenium 2 are not simultaneously a hydrogen atom}, (B) a photopolymerization initiator: 1 to 20 parts by mass, and (the ruthenium has one or more groups selected from the group consisting of a hydroxyl group, an ether group, and an ester group) a mono-repulsive compound having a carbon number of 2 to 30 (hereinafter, also referred to as (C) monocarboxylic acid compound) having a functional group of 官能. 1 to 1 〇 by mass. That is, the negative photosensitive resin composition of the present invention The material (A) polyimine precursor is 10 parts by mass, (B) photopolymerization initiator 1 to 20 parts by mass, and (C) monocarboxylic acid compound is 0.01 to 10. parts by mass as an essential component. The polyimine precursor is described in the (A) polyaniline precursor used in the present invention. (a) The polyimine precursor is the resin component in the negative photosensitive resin composition of the present invention, It is a polystyrene having a structure represented by the above formula (1). (8) The chitoimine precursor is converted into a polyimine by subjecting to a cyclization treatment by heating (for example, 200 ° C or higher). In the formula (1), the tetravalent organic group represented by X! is preferably an organic group having 6 to 40 carbon atoms in terms of both heat resistance and photosensitivity, and more preferably An aromatic group or an alicyclic aliphatic group in which the -COOR group and the _c〇〇R2 group and the -conh- group are ortho to each other. The tetravalent organic group represented by X is further preferably exemplified The following formula (5): 153046.doc 201140242 [Chemical 9]

' °構’但並不限定於該等。又，X1之結構可為1 種亦可為2種以上之組合。具有上述式（5)所示之結構之 X1基於兼具耐熱性與感光特性方面較佳。 ^述通式（1)中，就兼具耐熱性與感 Υι所示之2價有機基較 之方面而言， 出下述_·· 為讀6〜4〇之芳香族基，例如可舉 J53046.doc 201140242 化10'°Configuration' is not limited to these. Further, the structure of X1 may be one type or a combination of two or more types. X1 having the structure represented by the above formula (5) is preferable in terms of both heat resistance and photosensitivity. In the general formula (1), the divalent organic group having both heat resistance and sensitivity is compared with the following, and the following _·· is an aromatic group of 6 to 4 Å, for example, J53046.doc 201140242 10

所示之結構、及下述式（7): 153046.doc -11 - 201140242The structure shown, and the following formula (7): 153046.doc -11 - 201140242

丁 {式中’ A表示曱基（_CH3)、乙基（-C2H5)、丙基（-C3H7)或 基(-C4H9)} 斤不之結構’但並不限定於該等。又’ Υι之結構可為1In the formula, A represents a thiol group (_CH3), an ethyl group (-C2H5), a propyl group (-C3H7) or a group (-C4H9)}, but is not limited thereto. ’ Υι’s structure can be 1

種’亦可為2種以Λ A 上之組合。具有上述式及所示之結 構之Yi基於兼具耐熱性與感光特性之方面較佳。 關於心及尺2，上述通式（2)中之&較佳 原子或甲基， 153046.doc •12· 201140242 就感光特性之觀點而言，域尺5較佳為 光特性之觀點而言，4 2以上1〇以下，較佳為2以上4以下感 [(A)聚醯亞胺前驅物之製備方法] ⑷聚醮亞胺前驅物中，上述通式⑴所示之結構例如係 藉由如下方法獲得：首先’使含有上述4價有機基&之四幾 酸二野與具有光聚合性不飽和雙鍵之醇類及任意之碳數 1〜4之飽和脂肪族醇類反應，製備部分酿化之四羧酸（以 下’亦稱為酸/酉旨體）後，使其與含有上述2價有機奸之二 胺類進行醯胺聚縮合。 (酸/酯體之製備） 本發明中，作為適於製備⑷聚醯亞胺前驅物之含有*價 有機基&之四㈣：肝，例如可舉出：均笨四甲酸針、二 苯醚-3,3|，4,4·_四甲酸二酐、二苯甲酮_3,3，，4,4，_四甲酸二 針、聯苯-3,3|，4,4’-四甲酸二酐、二苯基職_3,3,,4,4,_四甲酸 二酐、二苯基甲貌_3,3|，4,4._四甲酸二酐、2,2_雙（3,4_鄰苯 二甲酸酐）丙烧、2,2·雙（3,4_鄰苯二f 六氣 丙烧等旦並不限定於該等。又，該等當然可單獨使用， 亦可混合使用2種以上。 本發明t，作為適於製備（A)聚醯亞胺前驅物之具有光聚 合性不飽和雙鍵之醇類’例如可舉出：2_丙稀酿氧基乙醇、 1丙稀醯氧基-3·丙醇、2_丙烯酿胺乙醇、經甲基乙稀基嗣、 2-¾基乙基乙稀基_、丙稀酸2經基_3_甲氧基丙醋、丙稀 酉欠2-羥基-3-丁氧基丙酯、丙烯酸2_羥基_3_苯氧基丙酯、丙 稀酸2·沒基_3·τ氧基丙g旨、丙烯酸2_經基_3_第三丁氧基丙 153046.doc 13 201140242 醋、丙烯酸2-經基-3-環己氧基丙酯、2-甲基丙稀醯氧基乙 醇、1-子基丙烯醯氧基-3-丙醇、2-f基丙烯醯胺乙醇、甲 基丙烯酸2-經基-3-甲氧基丙酯、甲基丙烯酸2-羥基_3_ 丁氧 基丙酯、甲基丙烯酸2-羥基-3-苯氧基丙酯、甲基丙烯酸2_ 羥基-3-丁氧基丙酯、甲基丙烯酸2·羥基_3_第三丁氧基丙 醋、甲基丙稀酸2-經基-3-環己氧基丙醋等。 上述醇類中亦可混合使用一部分碳數丨〜4之飽和脂肪族 醇例如曱醇、乙醇、正丙醇、異丙醇、正丁醇、第三丁 醇等。 將上述適於本發明之四羧醆二酐與上述醇類於吡啶等鹼 性觸媒之存在下，於適當之反應溶劑中，於溫度2〇〜5〇艺下The species ' can also be a combination of two kinds of Λ A . The Yi having the above formula and the structure shown is preferable in terms of both heat resistance and photosensitive characteristics. Regarding the heart and the rule 2, the above-mentioned general formula (2) is preferably an atom or a methyl group, 153046.doc • 12· 201140242. From the viewpoint of photosensitivity, the domain rule 5 is preferably from the viewpoint of optical characteristics. 4 2 or more and 1 or less, preferably 2 or more and 4 or less [(A) Preparation method of polyimine precursor] (4) Polyimine precursor, the structure represented by the above formula (1) is for example Obtained by the following method: first, 'reacting the tetrabasic acid dimer containing the above tetravalent organic group & and the alcohol having a photopolymerizable unsaturated double bond and any saturated aliphatic alcohol having a carbon number of 1 to 4, After preparing a partially brewed tetracarboxylic acid (hereinafter referred to as an acid/deuterium), it is subjected to polycondensation with a guanamine with a diamine having the above-mentioned divalent organic trait. (Preparation of acid/ester body) In the present invention, as the fourth (four)-containing liver which is suitable for the preparation of the (4) polyimine precursor, the liver may be, for example, a stearic tetracarboxylic acid needle or a diphenyl group. Ether-3,3|,4,4·_tetracarboxylic dianhydride, benzophenone _3,3,,4,4,_tetracarboxylic acid two-needle, biphenyl-3,3|,4,4'- Tetracarboxylic acid dianhydride, diphenyl _3,3,,4,4,_tetracarboxylic dianhydride, diphenylmethyl _3,3|, 4,4._tetracarboxylic dianhydride, 2,2_ The bis (3,4-phthalic anhydride)-propene-burning, 2,2·bis (3,4-o-phenylene-f-hexa-propylene-acrylic acid, etc. are not limited to these. Further, these may of course be used alone. Further, two or more kinds may be used in combination. The present invention t, as an alcohol having a photopolymerizable unsaturated double bond which is suitable for preparing the (A) polyimine precursor, may be exemplified by 2 - propylene oxide Ethanol, 1 propylene decyloxy-3·propanol, 2 propylene acrylamide, methyl ethyl hydrazide, 2-3⁄4 ethyl ethyl amide, acrylic acid 2 via _3_A Oxypropyl acetoacetate, acetonitrile oxime 2-hydroxy-3-butoxypropyl ester, 2-hydroxyl-3-phenoxypropyl acrylate, acrylic acid 2· sylylene _3· τ oxy propyl , acrylic 2_经基_3_ Tributoxypropene 153046.doc 13 201140242 vinegar, 2-yl-3-cyclohexyloxypropyl acrylate, 2-methyl propyl decyloxyethanol, 1-phenylpropenyloxy-3-propanol Alcohol, 2-f-based acrylamide ethanol, 2-carbyl-3-methoxypropyl methacrylate, 2-hydroxy-3-phenylbutoxypropyl methacrylate, 2-hydroxy-3-methacrylate Phenoxypropyl ester, 2_hydroxy-3-butoxypropyl methacrylate, 2, hydroxy_3_t-butoxy propyl acrylate, methyl methacrylate 2-carbyl -3- ring Hexyloxypropyl vinegar, etc. A part of a saturated aliphatic alcohol having a carbon number of 丨4 may be used in combination with the above alcohols, for example, decyl alcohol, ethanol, n-propanol, isopropanol, n-butanol, or butanol. The above-mentioned tetracarboxylic phthalic anhydride suitable for the present invention and the above alcohol are in the presence of a basic catalyst such as pyridine in a suitable reaction solvent at a temperature of 2 〇 5 5

應’可獲得所需之酸/酯體。 例如可舉出：N-甲 一甲基甲酿胺、二 作為上述反應溶劑，較佳為完全地溶解酸/酯體、及作為 其與二胺成分之酿胺聚縮合生成物的聚醯亞胺前驅物者， 甲基-2-吡咯烷酮、队冰二甲基乙醯胺、n，nThe desired acid/ester body should be obtained. For example, N-methyl monomethylamine and II are used as the above-mentioned reaction solvent, and it is preferred to completely dissolve the acid/ester and the polycondensate which is a polycondensation product of the amine with the diamine component. Amine precursor, methyl-2-pyrrolidone, team ice dimethyl acetamide, n, n

153046.doc 201140242 (聚醯亞胺前驅物之製備） 於上述酸/酯體（典型的是上述反應溶劑中之溶液）中，於 冰浴冷卻下投入混合適當之脫水縮合劑，例如二環己基碳 二醯亞胺、1-乙氧基羰基-2-乙氧基-1,2-二氫喹啉、1,1-羰 基二氧基-二-1，2,3-苯并***、N，N’-二丁二醯亞胺基碳酸酯 等而使酸/酯體成為聚酸酐後，向其中滴加投入使於本發明 中較好地使用之含有2價有機基丫丨之二胺類溶解或分散於 其他溶劑中而成者，進行醯胺聚縮合，藉此可獲得目標聚 醯亞胺前驅物》 作為於本發明中較好地使用之含有2價有機基Y〗之二胺 類，例如可舉出：對苯二胺、間苯二胺、4,4-二胺基二苯醚、 3,4’-二胺基二笨醚、3,3'-二胺基二苯醚、4,4'-二胺基二苯基 硫醚、3,4'-二胺基二苯基硫醚、3,3，-二胺基二苯基硫醚、 4,4 - 一胺基一求基礙、3，4’-二胺基二苯基硬、3，3’-二胺基二 苯基砜、4,4·-二胺基聯苯、3,4，-二胺基聯苯、3,3，·二胺基聯 本、4,4 - 一胺基二苯曱嗣、3,4’-二胺基二苯曱嗣、3,3’-二胺 基二苯甲酮、4,4·-二胺基二苯基甲烷、3,4'-二胺基二苯基 曱烷、3,3’-二胺基二苯基曱烷、ι，4-雙（4-胺基苯氧基）苯、 1，3-雙（4-胺基苯氧基）苯、ι，3-雙（3-胺基苯氧基）苯、雙[4_(4_ 胺基苯氧基）苯基]砜、雙[4-(3_胺基苯氧基）苯基]砜、4,4-雙（4-胺基苯氧基）聯苯、4,4-雙（3-胺基苯氧基）聯苯、雙 [4-(4-胺基苯氧基）苯基]醚、雙[4-(3-胺基苯氧基）苯基]醚、 1，4-雙（4-胺基笨基）笨、i，3-雙（4-胺基笨基）笨、9，1〇-雙（4-胺基本基）蒽、2,2-雙（4-胺基苯基）丙院、2,2-雙（4-胺基苯基） 153046.doc -15- 201140242 六氟丙烷、2,2-雙[4-(4-胺基苯氧基）苯基）丙烷、2,2-雙[4-(4-胺基苯氧基）苯基）六氟丙烷、1，4-雙（3-胺基丙基二甲基矽烷 基）苯、鄰聯曱苯胺砜、9,9-雙（4-胺基苯基）苐、及該等之苯 環上之氫原子之一部分由曱基、乙基、羥基曱基、羥基乙 基、鹵素等取代者，例如3,3’-二曱基-4,4’-二胺基聯苯、2,2·· 二曱基·4,4·-二胺基聯苯、3,3·-二曱基-4,4·-二胺基二苯基曱 烷、2,2’-二甲基-4,4’-二胺基二苯基曱烷、3，3，-二甲氧基 -4,4- 一胺基聯苯、3,3'-二氣- 4,4' -二胺基聯苯、及其混合物 等，但並不限定於該等。 又’為提高藉由將本發明之負型感光性樹脂組合物塗佈 於基板上而形成於基板上之感光性樹脂層與各種基板之密 接性’而於製備（Α)聚醯亞胺前驅物時，亦可使1,3-雙（3-胺 基丙基）四甲基二矽氧烷、1，3-雙（3-胺基丙基）四苯基二矽氧 烷等二胺基矽氧烷類共聚合。 醯胺聚縮合反應結束後，視需要將該反應液中共存之脫 水縮合劑之吸水副產物過濾分離，其後將水、脂肪族低級 醇或其之渴合液等不良溶劑投入所獲得之聚合物成分中， 使聚合物成分析出，進而反覆進行再溶解、再沈澱析出操 作等’藉此使聚合物純化，進行真空乾燥，而單獨分離出 目標聚酼亞胺前驅物β為提高純化度，亦可使聚合物之溶 液通過填充有以適當之有機溶劑膨潤之陰離子及/或陽離 子交換樹脂之管柱，去除離子性雜質。 (Α)於藉由凝膠滲透層析法並以聚苯乙烯換算重量平均 分子量進行測定之情形時，聚醯亞胺前驅物之分子量較佳 153046.doc • 16 - 201140242 為8,00〇〜150,00〇，更佳為9’〇〇〇〜5〇〇〇〇。重量平均分子量 為8,000以上之情形時機械物性良好，以下之情形時 於顯影液中之分散性良好，浮凸圖案之解析性能良好。作 為凝膠滲透層析法之展開溶劑，推薦四氫。夫喃及N.甲基·2_ 0比略烧網。X，分子量係根據使用料單分散聚苯乙烯所 製成之校準曲線而求得。作為標準單分散聚苯乙烯，推薦 自Βα和電工公司製造之有機溶劑系標準試樣standarD SM-105中選擇。 (B)光聚合起始劑 就本發明所使用之（B)光聚合起始劑加以說明。作為⑺） 光聚η起始劑，可任意地選擇先前用作化用光聚合起 始劑之化合物❶作為可較好地用作（Β)光聚合起始劑之化合 物，例如較佳為舉出：二笨甲酮、鄰苯甲醯苯甲酸甲酯、 4-苯曱酿_4'_甲基二苯基酮、二节基’、第酮等二苯甲嗣衍 生物，2,2’-二乙氧基苯乙酮、2•羥基_2_曱基苯丙酮、卜羥 基％己基笨基酮等苯乙酮衍生物，硫雜蒽酮、2_甲基硫雜 蒽酮、2-異丙基硫雜蒽酮、二乙基硫雜蒽酮等硫雜蒽酮衍 生物，笨偶醯、笨偶醯二甲基縮酮、苯偶醯甲氧基乙基 縮路等苯偶㈣生物，安息香、安息香甲趟等安息香衍生 物，1-苯基-1，2·丁二酮_2_(鄰甲氧基羰基）肟、苯基 丙一嗣2-(鄰甲氧基幾基）躬·、ι_苯基·ι，2_丙二_·2_(鄰乙氧 基羰基）肟、1-苯基-12-丙二酮_2_(鄰苯甲醯）肟、丨，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-(鄰苯曱醯）肟等肟類，Ν_苯基甘胺酸等Ν•芳基甘胺酸 153046.doc -17· 201140242 類，過氣化苯甲醯等過氧化物類，芳香族聯咪唑類等"旦 並不限定於該等。又’於使用該等時，可為1種，亦可為2 種以上之混合物。上述光聚合起始劑之中，尤其是於感光 度方面，更佳為肟類。 (B)光聚合起始劑之調配量相對於（A)聚醯亞胺前驅物 1 00質量份為1〜20質量份，就感光度特性之觀點而言，較佳 為2〜15質量份。藉由相對於（A)聚醯亞胺前驅物1〇〇質量份 調配1質量份以上之（B)光聚合起始劑，而使感光度優異， 藉由調配20質量份以下，而使厚膜硬化性優異。 (C)單羧酸化合物 就本發明所使用之（C)單缓酸化合物加以說明。（C)單缓 酸化合物係分子中僅含有1個羧基，且含有丨個以上選自由 羥基、醚基及酯基所組成之群之官能基的碳數2〜30之羧酸 化合物。藉由使用（C)單敌酸化合物，而即便藉由低溫固 化’亦可獲得固化後之基板（尤其是銅或銅合金）與由（A)聚 醯亞胺前驅物形成之聚醯亞胺樹脂之良好之接著性。 藉由低溫固化亦可獲得良好之接著性之化學機制並不確 定，但推測係由於藉由分子内僅1個之羧基與基板上之例如 銅相互作用，且選自由羥基、醚基及酯基所組成之群之官 能基經由氩鍵等與（A)聚醯亞胺前驅物之羰基或藉由加熱 而環化之聚酿亞胺之羰基相互作用，可將基板與樹脂之距 離保持為固定’藉此使接著性提高。 (C)就提高負型感光性樹脂組合物之固化後之硬化物與 基板（尤其是銅或銅合金）之接著性之觀點而言’單叛酸化合 153046.doc -18 - 201140242 物之碳數為2以上30以下。該碳數較佳為2〜2〇之範圍，更佳 為2〜15之範圍。 作為（C)單羧酸化合物之具體例，可舉出··羥基乙酸、甲 氧基乙酸、乙氧基乙酸、異丙氧基乙酸、乳酸、2_甲氧基 丙酸、2-羥基異丁酸、苯亞甲基乳酸、仁羥基苯基乳酸、4_ I基扁桃酸、3,4-二羥基扁桃酸、4_羥基_3_甲氧基扁桃酸、 2-羥基-3-苯基丙酸、2·甲氧基_2_(1_萘基）丙酸、扁桃酸、 阿卓乳馱、〇-乙醯基扁桃酸、α_甲氧基笨基乙酸、羥基 丁酸、4-經基戊酸、4-甲氧基丁酸及3-甲氧基丙酉复等。其中 就更好地獲得上述接著性之觀點而言，較佳為緩基之α位具 有至少1個選自由經基、鍵基錢基所組成之群之官能基的 碳數2〜30之單羧酸化合物。 進而’就提高接著性之觀點而言，（c)單竣酸化合物更佳 為選自由下述通式(3)所示之化合物所組成之群中的至少】 種單羧酸化合物： [化 12] 0¾ ^C-C-0-Η ⑴ R7 0 {式中’ R6為氫原子或碳數卜3之有機基，r7為氣、浐 數1〜3之烷基或汉8 ,此處r8為下述通式： 反 [化 13] 153046.doc •19· 201140242 (式中，Ζι為羥基或碳數1〜3之烷氧基，j為〇〜5之整數，並且 4於存在複數個之情形時相互之間可相同亦可不同）所示 之基，R9為氫原子、碳數1〜3之烷基或碳數1〜3之烷基羰 基}。 作為上述通式（3)所示之化合物，具體而言，可舉出：羥 基乙酸、曱氧基乙酸、乙氧基乙酸、異丙氧基乙酸、乳酸、 2-甲氧基丙酸、2-羥基異丁酸、4-羥基扁桃酸、3,4_二羥基 扁桃酸、4-羥基-3-曱氧基扁桃酸、扁桃酸、阿卓乳酸、〇_ 乙酿基扁桃酸及α-甲氧基苯基乙酸等。 其中，選自由下述通式（4): [化 14]153046.doc 201140242 (Preparation of Polyimine Precursor) In the above acid/ester body (typically a solution in the above reaction solvent), a suitable dehydrating condensing agent such as dicyclohexyl group is added and mixed under ice cooling. Carboimine, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, After the acid/ester is a polyanhydride, the N/N'-dibutyl quinone imino carbonate is added thereto, and the divalent organic ruthenium containing the divalent organic ruthenium which is preferably used in the present invention is added dropwise thereto. When the amine is dissolved or dispersed in another solvent, the guanamine polycondensation is carried out, whereby the target polyimine precursor can be obtained. As the divalent organic group Y which is preferably used in the present invention. Examples of the amines include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 3,3'-diamino group II. Phenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3,-diaminodiphenyl sulfide, 4,4 - one Amino-based, 3,4'-diaminodiphenyl hard, 3,3'-diamino Diphenyl sulfone, 4,4·-diaminobiphenyl, 3,4,-diaminobiphenyl, 3,3,diamine-based, 4,4-diaminodiphenyl hydrazine, 3,4'-diaminodiphenyl hydrazine, 3,3'-diaminobenzophenone, 4,4.-diaminodiphenylmethane, 3,4'-diaminodiphenyl Decane, 3,3'-diaminodiphenyl decane, iota, 4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, ι , 3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 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) stupid, i,3-bis(4-aminophenyl) stupid, 9 ,1〇-bis(4-amine basic) fluorene, 2,2-bis(4-aminophenyl)propyl, 2,2-bis(4-aminophenyl) 153046.doc -15- 201140242 Hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylhydrazine) Benzo, o-anisidine sulfone, 9,9-bis(4-aminophenyl)anthracene, and one of the hydrogen atoms on the benzene ring are partly composed of a fluorenyl group, an ethyl group, a hydroxy group, or a hydroxy group a substituent such as a group or a halogen, such as 3,3'-dimercapto-4,4'-diaminobiphenyl, 2,2··dimercapto-4,4·-diaminobiphenyl, 3, 3·-Dimercapto-4,4·-diaminodiphenyl decane, 2,2′-dimethyl-4,4′-diaminodiphenyl decane, 3,3,-di Methoxy-4,4-monoaminobiphenyl, 3,3'-dioxa-4,4'-diaminobiphenyl, mixtures thereof and the like, but are not limited thereto. Further, in order to improve the adhesion between the photosensitive resin layer formed on the substrate and the various substrates by applying the negative photosensitive resin composition of the present invention to the substrate, the polyimine precursor is prepared. In the case of a substance, a diamine such as 1,3-bis(3-aminopropyl)tetramethyldioxane or 1,3-bis(3-aminopropyl)tetraphenyldioxane may be used. Alkoxy olefins are copolymerized. After completion of the polycondensation reaction of the guanamine, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid is filtered and separated as necessary, and then a poor solvent such as water, an aliphatic lower alcohol or a thirsty liquid thereof is supplied to the obtained polymerization. In the composition of the component, the polymer is analyzed, and then re-dissolved, reprecipitated and precipitated, etc., thereby purifying the polymer and vacuum drying, separately separating the target polyimine precursor β to improve the purification degree. Alternatively, the solution of the polymer may be passed through a column packed with an anion and/or cation exchange resin swelled with a suitable organic solvent to remove ionic impurities. (Α) When the gel permeation chromatography is carried out and the weight average molecular weight is measured in terms of polystyrene, the molecular weight of the polyimide precursor is preferably 153046.doc • 16 - 201140242 is 8,00〇~ 150,00 〇, more preferably 9' 〇〇〇 ~ 5 〇〇〇〇. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and in the following cases, the dispersibility in the developer is good, and the analytical performance of the embossed pattern is good. As a developing solvent for gel permeation chromatography, tetrahydrogen is recommended. Fu and N. methyl · 2_ 0 than slightly burned net. X, the molecular weight is determined based on a calibration curve prepared by using a monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to select from the standard sample standarD SM-105 of the organic solvent system manufactured by Βα and Electric Works. (B) Photopolymerization initiator The (B) photopolymerization initiator used in the present invention will be described. As the (7)) photopolymerization initiator, the compound previously used as a photopolymerization initiator can be arbitrarily selected as a compound which can be preferably used as a photopolymerization initiator, and is preferably, for example, Out: dimercapto ketone, methyl phthalic acid benzoate, 4-benzoquinone _4'-methyl diphenyl ketone, bis- ketone, ketone and other benzamidine derivatives, 2, 2 Acetophenone derivatives such as '-diethoxyacetophenone, 2•hydroxy-2-indolylpropiophenone, hydroxy%hexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2 - thioxanthone derivatives such as isopropyl thioxanthone and diethyl thioxanthone, styrene, styrene, dimethyl ketal, benzophenone methoxyethyl condensate, etc. (4) Benzoin derivatives such as benzoin, benzoin and formazan, 1-phenyl-1,2·butanedione_2_(o-methoxycarbonyl)anthracene, phenylpropanyl-2-(o-methoxyl-yl) )躬,, ι_phenyl·ι, 2_propyl _·2_(o-ethoxycarbonyl) fluorene, 1-phenyl-12-propanedione 2-(o-benzamide) hydrazine, hydrazine, 3 -diphenylpropanetrione_2-(o-ethoxycarbonyl)anthracene, 1-phenyl-3-ethoxypropanetrione-2-(o-benzene醯) 肟 肟 Ν Ν 苯基 苯基 芳 芳 芳 芳 芳 芳 芳 芳 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 153 Dan is not limited to these. Further, when these are used, one type may be used, or a mixture of two or more types may be used. Among the above photopolymerization initiators, in particular, in terms of sensitivity, it is more preferably an anthracene. (B) The amount of the photopolymerization initiator is from 1 to 20 parts by mass based on 100 parts by mass of the (A) polyimine precursor, and is preferably from 2 to 15 parts by mass in terms of sensitivity characteristics. . By blending 1 part by mass or more of the (B) photopolymerization initiator with respect to 1 part by mass of the (A) polyimine precursor, the sensitivity is excellent, and the thickness is made by blending 20 parts by mass or less. Excellent film hardenability. (C) Monocarboxylic acid compound The (C) mono-acidic acid compound used in the present invention will be described. (C) A carboxylic acid compound having a carbon number of 2 to 30 which contains only one carboxyl group in the molecule and contains at least one functional group selected from the group consisting of a hydroxyl group, an ether group and an ester group. By using (C) a single acid compound, even after curing by low temperature, a cured substrate (especially copper or copper alloy) and a polyimine formed from (A) a polyimide precursor can be obtained. Good adhesion of the resin. The chemical mechanism by which low-temperature curing can also obtain good adhesion is not certain, but it is presumed that since only one carboxyl group in the molecule interacts with, for example, copper on the substrate, and is selected from a hydroxyl group, an ether group, and an ester group. The functional group of the group can be kept fixed to the distance between the substrate and the resin by an argon bond or the like by interacting with the carbonyl group of the (A) polyimine precursor or the carbonyl group of the cyclized carbamide which is cyclized by heating. 'This will improve the adhesion. (C) From the viewpoint of improving the adhesion between the cured product of the negative photosensitive resin composition and the substrate (especially copper or copper alloy), the monocarbonic acid 153046.doc -18 - 201140242 carbon The number is 2 or more and 30 or less. The carbon number is preferably in the range of 2 to 2 Å, more preferably in the range of 2 to 15. Specific examples of the (C) monocarboxylic acid compound include glycolic acid, methoxyacetic acid, ethoxyacetic acid, isopropoxyacetic acid, lactic acid, 2-methoxypropionic acid, and 2-hydroxyiso Butyric acid, benzylidene lactic acid, hydroxyphenyl lactic acid, 4 I-methicillin, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxylated mandelic acid, 2-hydroxy-3-phenyl Propionic acid, 2·methoxy-2-(1_naphthyl)propionic acid, mandelic acid, Azhuo nipple, 〇-acetamidyl mandelic acid, α-methoxy phenyl acetic acid, hydroxybutyric acid, 4- Recovering with valeric acid, 4-methoxybutyric acid and 3-methoxypropanoid. From the viewpoint of better obtaining the above-mentioned adhesion, it is preferred that the α-position of the slow-radical group has at least one carbon number of 2 to 30 selected from the functional group of the group consisting of a trans group and a bond group. Carboxylic acid compound. Further, from the viewpoint of improving the adhesion, the (c) monodecanoic acid compound is more preferably at least one selected from the group consisting of the compounds represented by the following formula (3): 12] 03⁄4 ^CC-0-Η (1) R7 0 {wherein R6 is a hydrogen atom or an organic group of carbon number 3, r7 is a gas, an alkyl group having a number of 1 to 3 or a Han 8, where r8 is the lower (Formula 13) 153046.doc •19· 201140242 (wherein, Ζι is a hydroxyl group or alkoxy group having a carbon number of 1 to 3, j is an integer of 〇~5, and 4 is present in plural cases When they are the same or different from each other, the group represented by R9 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkylcarbonyl group having 1 to 3 carbon atoms}. Specific examples of the compound represented by the above formula (3) include glycolic acid, decyloxyacetic acid, ethoxyacetic acid, isopropoxyacetic acid, lactic acid, 2-methoxypropionic acid, and 2 -hydroxyisobutyric acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-indolyl mandelic acid, mandelic acid, Azhuo lactic acid, 〇_Ethyl mandelic acid and α- Methoxyphenylacetic acid and the like. Wherein, it is selected from the following general formula (4): [Chem. 14]

0H0H

II

Rj〇— C—C—Ο—Η I IIRj〇— C—C—Ο—Η I II

Rn〇 {式中，R1G為氫原子或碳數〗〜3之有機基，Rn為氫原子、 碳數1〜3之烷基或R,2,此處R|2為下述通式： [化 15]Rn〇{ wherein R1G is a hydrogen atom or an organic group having a carbon number of 〜3, and Rn is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or R, 2, where R|2 is a general formula: 15]

(式中，Z2為羥基或碳數卜3之烷氧基，让為〇〜5之整數，並 且Z2於存在複數個之情形時相互之間可相同亦 示之基}。 可不同）所 I53046.doc -20. 201140242 所示之化合物所組成之群中的至少丨種單羧酸化合物於 接著性尤其良好之方面更佳。作為上述通式（4)所示之化合 物，具體而§，可舉出：經基乙酸、乳酸、2_經基異丁酸、 4-羥基扁桃酸、3,4-二羥基扁桃酸、4_羥基_3_甲氧基扁桃 酸、扁桃酸等。 就感光特性之觀點而言，通式（3)中之&及通式（4)中之 R1〇分別為氫原子或碳數1〜3之有機基。又，就感光特性之 觀點而言，通式（3)中之R?為氫原子、碳數卜3之烷基或上 述以，出於與上述I相同之理由，通式（4)中之Rn為氫原 子、奴數1〜3之烷基或上述R〗2。就提高負型感光性樹脂組 合物之固化後之硬化物與基板（尤其是銅或銅合金）之接著 性之觀點而言，通式（3)中之R9為氫原子、碳數丨〜3之烷基 或碳數1〜3之烷基羰基。 (C)單緩酸化合物之調配量相對於（A)聚醯亞胺前驅物 100質量份為0_01〜10質量份，較佳為〇 〇5〜2質量份。於上述 調配S：為0.01質量份以上之情形時，表現出良好之接著 性，另一方面，於上述調配量為10質量份以下之情形時， S使用本發明之負型感光性樹脂組合物於銅或銅合金之基 板上形成感光性樹脂層之情形時，銅或銅合金上之變色抑 制效果優異。 (D)有機鈦化合物 亦可使本發明之負型感光性樹脂組合物中含有（D)有機 欽化合物。藉由含有（D)有機鈦化合物，而即便於以25〇°c 之低溫硬化進行固化之情形時，亦可形成耐化學品性優異 】53046.doc •21 · 201140242 之感光性樹脂層。又，尤其是藉由使負型感光性樹脂組合 物中含有（C)單羧酸化合物與（D)有機鈦化合物兩者，而發 揮除使固化後之感光性樹脂層之基板接著性優異以外，亦 使其耐化學品性優異之效果。 作為可用作（D)有機欽化合物之有機欽化合物，可舉出有 機化學物質經由共價鍵或離子鍵鍵結於鈦原子而成者。 將（D)有機鈦化合物之具體例示於以下之〗)〜νπ): I) 敛螯合化合物：其中’由於具有2個以上之烷氧基的 欽螯合物可獲得負型感光性樹脂組合物之保存穩定性及良 好之圖案，故更佳，具體例為雙（三乙醇胺）二異丙醇鈦、雙 (2,4-戊二酸）二正丁醇鈦、雙（2,4_戊二酸）二異丙醇鈦、雙（四 甲基庚二酸）二異丙醇鈦、雙（乙基乙醯乙酸）二異丙醇鈦等。 II) 四烧氧基鈦化合物：例如為四正丁醇鈦、四乙醇鈦、 四（2-乙基己醇）鈦、四異丁醇鈦、四異丙醇鈦、四甲醇鈦、 四甲氧基丙醇鈦、四甲酚鈦、四正壬醇鈦、四正丙醇鈦、 四硬脂醇鈦、四[雙{2,2-(烯丙氧基曱基）丁醇}]鈦等。 III) 二茂鈦化合物：例如為（五甲基環戊二烯基）三甲醇 鈦、雙（η5-2,4-環戊二烯_丨_基）雙（26_二氟苯基）鈦雙 (η -2,4-環戊二烯-1-基）雙（2 6•二氟_3 (1h_d比咯丨基）苯基） 鈦等。 IV) 單烷氧基鈦化合物：例如為三（二辛基磷酸）異丙醇 鈦、三（十二烷基苯磺酸）異丙醇鈦等。 V) 氧鈦化合物：例如為雙（戊二酸）氧鈦、雙（四曱基庚 二酸）氧鈦、酞菁氧鈦等。 153046.doc -22· 201140242 νι)四乙醯基丙酮酸鈦化合物：例如四乙醯基丙酮酸鈦 等。 νπ)鈦酸醋偶合劑：例如鈦酸異丙基三（十二烧基苯績 醯基）酯等》 其中，就發揮更加良好之耐化學品性之觀點而言，較佳 為（D)有機鈦化合物係選自由上述1}鈦螯合化合物、π)四烷 氧基鈦化合物、及III)二茂鈦化合物所組成之群中的至少工 種化合物》 調配（D)有機鈦化合物之情形之調配量相對於（A)聚醯亞 胺前驅物100質量份較佳為0·05〜10質量份，更佳為〇質 S：伤。於該調配量為0.05質量份以上之情形時，表現出良 好之财熱性及财化學品性，另一方面，於該調配量為1〇質 量份以下之情形時’保存穩定性優異。 (E)其他成分 本發明之負型感光性樹脂組合物亦可進而含有上述 (A)〜(D)成分以外之成分。本發明之負型感光性樹脂組合物 典型的是以使上述各成分及視需要進一步使用之任意成分 溶解於溶劑中而製成清漆狀之負型感光性樹脂組合物之方 式使用，因此（E)其他成分可舉出溶劑。作為溶劑，就對 聚醯亞胺前驅物之溶解性之觀點而言，較佳為使用極性有 機溶劑。具體而吕，可舉出：N，N-二甲基甲醯胺、N-曱基 -2-吡咯烷酮、N-乙基-2-吡咯烷酮、N，N_二甲基乙醯胺、二 曱基亞颯、二乙二醇二曱醚、環戊酮、γ_ 丁内酯、α_乙醯基 -γ-丁内酯、四甲基脲、1，3·二甲基_2_咪唑啉酮、Ν_環己基 153046.doc -23- 201140242 _2_°比略烷酮等’該等可單獨或以2種以上之組合使用。 上述溶劑可根據負型感光性樹脂組合物所需之塗佈膜厚 及黏度而相對於（A)聚醯亞胺前驅物100質量份，以例如 30〜1500質量份之範圍、較佳為100〜1000質量份之範圍使 用0 進而’就提高負型感光性樹脂組合物之保存穩定性之觀 點而言，較佳為含有醇類。可較好地使用之醇類典型的是 分子内具有醇性羥基而不具有烯烴系雙鍵之醇，作為具體 例，可舉出：曱醇'乙醇、正丙醇、異丙醇、正丁醇、異 丁醇、第二丁醇等烷基醇類，乳酸乙酯等乳酸酯類，丙二 醇-1-曱醚、丙二醇_2_甲醚、丙二醇q -***、丙二醇乙 醚、丙二醇小（正丙基）喊、丙二醇-2-(正丙基）&|等丙二g 單烧基⑽類’乙二醇甲⑽、乙二醇乙㈣、乙二醇正丙峻考 單醇類’ 2-羥基異丁酸醋類，乙二醇及丙二醇等二醇類。 該等之中，較佳為乳酸s旨類、丙二醇單院基㈣類、2_㈣ 異丁酸醋類及乙醇，尤其更佳為乳酸乙醋、丙二醇小甲蝴 丙二醇_ ***、及丙二醇·（正丙基）醚 於溶劑含有不具有烯烴系 6〜〜町〜，月叩吁，金邵(wherein Z2 is a hydroxyl group or alkoxy group of a carbon number of 3, which is an integer of 〇~5, and Z2 may be the same as the base when there are a plurality of cases.} may be different) I53046 .doc -20. At least the hydrazine monocarboxylic acid compound of the group consisting of the compounds shown in 201140242 is more preferable in terms of adhesion. Specific examples of the compound represented by the above formula (4) include transacetic acid, lactic acid, 2-hydroxyisobutyric acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, and 4 _hydroxy_3_methoxy mandelic acid, mandelic acid, and the like. From the viewpoint of the photosensitive property, R1 in the formula (3) and R1 in the formula (4) are each a hydrogen atom or an organic group having 1 to 3 carbon atoms. Further, from the viewpoint of the photosensitive property, R? in the formula (3) is a hydrogen atom, an alkyl group of a carbon number of 3 or the above, and for the same reason as the above I, in the formula (4) Rn is a hydrogen atom, an alkyl group having a slave number of 1 to 3 or the above R>2. From the viewpoint of improving the adhesion between the cured product of the negative photosensitive resin composition and the substrate (especially copper or copper alloy), R9 in the general formula (3) is a hydrogen atom and has a carbon number of 丨3. An alkyl group or an alkylcarbonyl group having 1 to 3 carbon atoms. The amount of the (C) mono-acid-lowering compound is from 0 to 10 parts by mass, preferably from 5 to 2 parts by mass, per 100 parts by mass of the (A) polyimine precursor. In the case where the above-mentioned preparation S is 0.01 parts by mass or more, it exhibits good adhesion. On the other hand, when the above-mentioned compounding amount is 10 parts by mass or less, S uses the negative photosensitive resin composition of the present invention. When a photosensitive resin layer is formed on a substrate of copper or a copper alloy, the discoloration suppressing effect on copper or a copper alloy is excellent. (D) Organic Titanium Compound The (D) organic compound can also be contained in the negative photosensitive resin composition of the present invention. By containing the (D) organotitanium compound, it is possible to form a photosensitive resin layer which is excellent in chemical resistance even when it is cured by low-temperature curing at 25 ° C. 】 53046.doc • 21 · 201140242. In addition, in the negative photosensitive resin composition, the (C) monocarboxylic acid compound and the (D) organic titanium compound are contained, and the photosensitive resin layer after curing is excellent in substrate adhesion. It also has an excellent chemical resistance. Examples of the organic compound which can be used as the (D) organic compound are those in which an organic chemical is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the (D) organotitanium compound are shown in the following:) νπ): I) chelating compound: wherein 'a negative photosensitive resin combination can be obtained due to a chelate compound having two or more alkoxy groups More preferably, the storage stability and good pattern of the material are, for example, bis(triethanolamine) titanium diisopropoxide, bis(2,4-glutaric acid) titanium di-n-butoxide, double (2, 4_ Glutaric acid) titanium diisopropoxide, titanium bis(tetramethylpimelate) diisopropylate, bis(ethylacetamidineacetic acid) titanium diisopropylate, and the like. II) Four alkoxy titanium compounds: for example, titanium tetra-n-butoxide, titanium tetraethoxide, titanium tetrakis(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, tetramethyl Titanium oxypropoxide, titanium tetradecoxide, titanium tetra-n-sterol, titanium tetra-n-propoxide, titanium tetrastearyl, tetra-[double {2,2-(allyloxyindenyl)butanol]] titanium Wait. III) Titanocene compound: for example, (pentamethylcyclopentadienyl) trimethyl methoxide, bis(η5-2,4-cyclopentadienyl)-bis(26-difluorophenyl)titanium Bis(η -2,4-cyclopentadien-1-yl)bis(2 6•difluoro_3 (1h-d than fluorenyl)phenyl) titanium or the like. IV) Monoalkoxy titanium compound: for example, tris(dioctylphosphoric acid) isopropoxide titanium, tris(dodecylbenzenesulfonic acid) titanium isopropoxide or the like. V) oxytitanium compound: for example, bis(glutaric acid) oxytitanium, bis(tetradecylpimelic acid) oxytitanium, phthalocyanine oxytitanium or the like. 153046.doc -22· 201140242 νι) Titanium tetradecylpyruvate compound: for example, titanium tetraethylpyruvate or the like. Νπ) Titanium vinegar coupling agent: for example, isopropyl tris(didecyl phthalocyanyl) titanate, etc. Among them, (D) is preferred from the viewpoint of exhibiting more excellent chemical resistance. The organotitanium compound is selected from the group consisting of the above-mentioned 1} titanium chelate compound, π) tetraalkoxy titanium compound, and III) titanocene compound, in the case of formulating (D) organotitanium compound. The amount of the compound is preferably from 0.05 to 10 parts by mass, more preferably from the sputum S: to 100 parts by mass of the (A) polyimine precursor. When the amount is 0.05 parts by mass or more, it exhibits good fuel economy and chemical properties. On the other hand, when the amount is less than 1 part by mass, the storage stability is excellent. (E) Other components The negative photosensitive resin composition of the present invention may further contain components other than the above components (A) to (D). The negative-type photosensitive resin composition of the present invention is typically used in such a manner that the above-mentioned respective components and optional components which are further used as needed are dissolved in a solvent to form a varnish-like negative photosensitive resin composition. Other solvents include solvents. As the solvent, it is preferred to use a polar organic solvent from the viewpoint of solubility of the polyimide precursor. Specific examples include: N,N-dimethylformamide, N-mercapto-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, diterpenes Chiazone, diethylene glycol dioxime ether, cyclopentanone, γ-butyrolactone, α-ethenyl-γ-butyrolactone, tetramethylurea, 1,3·dimethyl-2-imidazoline Ketone, oxime _cyclohexyl 153046.doc -23- 201140242 _2_°bendanone, etc. These may be used singly or in combination of two or more. The solvent may be in the range of, for example, 30 to 1,500 parts by mass, preferably 100%, based on 100 parts by mass of the (A) polyimine precursor, depending on the coating film thickness and viscosity required for the negative photosensitive resin composition. In the range of -1000 parts by mass, 0 is used. Further, from the viewpoint of improving the storage stability of the negative photosensitive resin composition, it is preferred to contain an alcohol. The alcohol which can be preferably used is typically an alcohol having an alcoholic hydroxyl group in the molecule and no olefinic double bond. Specific examples thereof include decyl alcohol, ethanol, n-propanol, isopropanol and n-butylene. Alcohols such as alcohol, isobutanol and second butanol, lactic acid esters such as ethyl lactate, propylene glycol-1-decyl ether, propylene glycol 2-methyl ether, propylene glycol q-ether, propylene glycol diethyl ether, propylene glycol small (positive Propyl), propylene glycol-2-(n-propyl) &|etc., propylene g, mono-alkyl (10), ethylene glycol (10), ethylene glycol (tetra), ethylene glycol, positive propylene test monool - Hydroxyisobutyric acid vinegar, glycols such as ethylene glycol and propylene glycol. Among these, preferred are lactic acid s, propylene glycol single-yard (4), 2-(tetra) isobutyric acid vinegar, and ethanol, and more preferably lactic acid ethyl acetate, propylene glycol small methyl propylene glycol _ ether, and propylene glycol (positive Propyl) ether in a solvent containing no olefins 6~~ Town~, Yue Yu, Jin Shao

中所占之不具有烯烴系雙鍵之醇之含量較佳為5〜5(M %’更佳為10〜30質量。於不具有烯烴系雙鍵之醇之_ 3量為5質置％以上之情开^矣鱼 料時負型感光性樹脂組合物上 存穩疋性變得良好，於5 〇暂县。/The content of the alcohol having no olefinic double bond is preferably 5 to 5 (M %' is more preferably 10 to 30 mass. The amount of the alcohol having no olefinic double bond is 5 mass%. In the above situation, the stability of the negative photosensitive resin composition becomes good when it is opened.

^ ㈣質量/〇以下之情形時，⑷聚S 胺刖驅物之溶解性變得良好。 本發明之負型感光性樹脂组合 J伽、，且0物亦可進而含有上述 153046.doc -24· 201140242 聚醯亞胺前驅物以外之樹脂成分.作為可含有之樹脂成 分，可舉出：聚醯亞胺、聚吟唑、聚吟唑前驅物、酚樹脂、 聚醯胺、環氧樹脂、矽氧烷樹脂、丙烯酸樹脂等。該等樹 脂成分之調配量相對於（A)聚醯亞胺前驅物丨〇〇質量份較佳 為0.01〜20質量份之範圍。 又，為提高感光度，本發明之負型感光性樹脂組合物可 任意地調配增感劑》作為該增感劑，例如可舉出：米其勒 酮、4,4’-雙（二乙基胺基）二苯甲酮、2,5_雙（4，_二乙基胺基 亞苄基）環戊烷、2,6-雙（4，-二乙基胺基亞苄基）環己酮、2,6_ 雙（4-一乙基胺基亞苄基）_4_甲基環己酌、4,4，雙（二甲基胺 基）查耳酮' 4,4'-雙（二乙基胺基）查耳酮、對二甲基胺基苯 亞烯丙基茚酮、對二曱基胺基苯亞甲基茚酮、2_(對二甲基 胺基苯基伸聯苯基）-苯并噻唑、2_(對二甲基胺基苯基伸乙 烯基）苯并噻唑、2-(對二f基胺基苯基伸乙烯基）異萘噻 唑、1,3-雙（4，-二f基胺基亞苄基）丙酮、丨^雙^^二乙基胺 基亞苄基）丙酮、3,3，-羰基-雙（7_二乙基胺基香豆素）、3_乙 醯基-7-二甲基胺基香豆素、3_乙氧基羰基_7_二甲基胺基香 •a素、3-苄氧基羰基-7-二中基胺基香豆素、3_甲氧基羰基 -7·二乙基胺基香豆素、3_乙氧基羰基_7_二乙基胺基香豆 素、N-苯基-Ν’-乙基乙醇胺、N_苯基二乙醇胺、N_對甲苯 基二乙醇胺、N-苯基乙醇胺、4_咪啉基二苯曱酮、二甲基 胺基苯甲酸異戊酯、二乙基胺基苯甲酸異戊酯、2_鲸基苯 并咪唑、1-苯基-5-巯基四唑、2·巯基苯并噻唑、2_(對二曱 基胺基苯乙烯基）苯并，号唑、2_(對二甲基胺基苯乙烯基）笨 153046.doc •25· 201140242 并噻唑、2-(對二甲基胺基苯乙烯基）萘（1，2_d)噻唑' 2(對二 曱基胺基本甲酿）苯乙烯等。該等可單獨或以例如2〜5種之 組合使用。 負型感光性樹脂組合物含有用以提高感光度之增感劑之 情形之調配量相對於（A)聚醯亞胺前驅物1 〇〇質量份較佳為 0.1〜25質量份。 又’為提尚浮凸圖案之解析性，可任意地調配具有光聚 合性不飽和鍵之單體。作為此種單體，較佳為藉由光聚合 起始劑進行自由基聚合反應之（甲基）丙烯酸化合物，並不特 別限定於以下者’但可舉出：以二乙二醇二曱基丙烯酸酯、 四乙二醇二曱基丙稀酸酯為代表之乙二醇或聚乙二醇之單 或二丙烯酸酯及曱基丙烯酸酯，丙二醇或聚丙二醇之單或 二丙烯酸酯及甲基丙烯酸酯，甘油之單、二或三丙稀酸酯 及曱基丙烯酸酯，環己烷二丙烯酸酯及二甲基丙烯酸酯， 1，4-丁二醇之二丙烯酸酯及二甲基丙烯酸酯，i，6_&amp;二醇之 二丙烯酸酯及二甲基丙烯酸酯、新戊二醇之二丙烯酸酯及 二甲基丙烯酸酯，雙酚A之單或二丙烯酸酯及甲基丙烯酸 酯，苯三甲基丙烯酸酯、丙烯酸異冰片酯及曱基丙烯酸酯， 丙烯醯胺及其衍生物，曱基丙烯醯胺及其衍生物，三羥甲 基丙烷三丙烯酸酯及甲基丙烯酸酯，甘油之二或三丙烯酸 酯及曱基丙烯酸酯，季戊四醇之二、三或四丙烯酸酯及曱 基丙烯酸酯，以及該等化合物之環氧乙烷或環氧丙烷加成 物等化合物。 負型感光性樹脂組合物含有用以提高浮凸圖案之解析性 153046.doc •26- 201140242 的具有上述光聚合性不飽和鍵之單體之情形之調配量相對 於（A)聚醯亞胺前驅物1〇〇質量份較佳為1〜質量份。 又’為提高使用本發明之負型感光性樹脂組合物所形成 之膜與基材之接著性’可任意地調配接著助劑。作為接著 助劑，可舉出：γ-胺基丙基二甲氧基矽烷、：^_(0_胺基乙基）_γ_ 胺基丙基曱基二曱氧基矽烷、γ·縮水甘油氧基丙基甲基二 曱氧基石夕烧、γ-毓基丙基曱基二曱氧基矽烷、3_曱基丙稀醯 氧基丙基二曱氧基甲基矽烷、3_甲基丙烯醯氧基丙基三甲 氧基石夕烧、一甲氧基曱基-3-旅咬基丙基石夕烧、二乙氧基_3_ 縮水甘油氧基丙基甲基矽烷、Ν_(3_:乙氧基曱基矽烷基丙 基）丁二醯亞胺、Ν-[3-(三乙氧基矽烷基）丙基]鄰苯二曱醯胺 酸、二苯甲酮-3,3’-雙（Ν-[3-三乙氧基矽烷基]丙基醯 胺）-4’4’-二曱酸、苯-Μ·雙（Ν_[3_三乙氧基矽烷基]丙基醯 胺）-2,5-二甲酸、3-(三乙氧基矽烷基）丙基丁二酸酐、Ν_苯 基胺基丙基三甲氧基矽烷等矽烷偶合劑、及鋁三（乙基乙醯 乙酸）、三（乙醯丙酮）鋁、乙基乙醯乙酸二異丙氧基鋁等鋁 系接著助劑等。 該等接著助劑之中，就接著力之觀點而言，更佳為使用 矽烷偶合劑。負型感光性樹脂組合物含有接著助劑之情形 之調配量相對於（Α)聚醯亞胺前驅物1 〇〇質量份較佳為 0.5〜25質量份之範圍。 又，尤其是為提高在含有溶劑之溶液狀態下保存時之負 型感光性樹脂組合物之黏度及感光度之穩定性，可任意地 調配熱聚合抑制劑。作為熱聚合抑制劑，可舉出：對苯二 153046.doc -27· 201140242 紛、Ν·亞硝基二苯基胺、對第三丁基鄰苯二酚、酚噻畊、 Ν-苯基萘基胺、乙二胺四乙酸、丨^ —環己二胺四乙酸、乙二 醇醚二胺四乙酸、2,6-二-第三丁基_對曱基苯酚、5·亞硝基 -8-羥基喹啉、1-亞硝基萘酚、2_亞硝基萘酚、2亞硝 基-5-(Ν-乙基·Ν-項丙基胺基）苯酚、Ν_亞硝基_Ν_苯基羥基 胺敍鹽、Ν-亞硝基-N(l-萘基）羥基胺銨鹽等。 調配至負型感光性樹脂組合物中之情形之熱聚合抑制劑 之調配量相對於（Α)聚醯亞胺前驅物1〇〇質量份較佳為 0.005~12質量份之範圍。 又，可任意地調配交聯劑。交聯劑可為在對使用本發明 之負型感光性樹脂組合物所形成之浮凸圖案進行加熱硬化 時’可使（Α)聚醯亞胺前驅物交聯或交聯劑自身可形成交聯 網絡之交聯劑。交聯劑可進一步強化由負型感光性樹脂組 合物形成之硬化膜之耐熱性及耐化學品性。作為交聯劑， 可較好地使用胺基樹脂及其衍生物，其中，可較好地使用 脲樹脂、乙内醯脲樹脂、羥基伸乙脲樹脂、三聚氰胺樹脂、 苯代三聚氰胺樹脂、及該等之衍生物。特佳為烷氧基曱基 化脲化合物及烷氧基曱基化三聚氰胺化合物，例如可舉出 ΜΧ-290(曰本Carbide公司製造）、UFR-65(日本Cytec公司製 造）、及MW-3 90(日本Carbide公司製造）。 為兼顧耐熱性及耐化學品性以外之各種性能，負型感光 性樹脂組合物含有交聯劑之情形之調配量相對於（A)聚醯 亞胺前驅物100質量份較佳為0.5〜20質量份，更佳為2〜1〇質 量份。於該調配量為0.5質量份以上之情形時，表現出良好 153046.doc •28- 201140242 之耐熱性及耐化學品性，另一方面，於該調配量為20質量 份以下之情形時’保存穩定性優異。 又’於使用包含例如銅或銅合金之基板之情形時，為抑 制基板變色，可任意地調配唑化合物。作為唑化合物，可 舉出：1H-二0坐、5-甲基_1H_***、5_乙基·1H•***、4 5_ 二甲基-1H-二唑、5-苯基-1H_***、4_第三丁基_5_苯基·1H_ ***、5-羥基苯基-1Η·***、苯基***、對乙氧基苯基三 唑、5-苯基-1-(2-二甲基胺基乙基）***、5_苄基·1Η***、 羥基苯基二°坐、1，5-二曱基***、4,5_二乙基-1Η-三嗤、1Η-本并二°坐、2-(5 -甲基_2-經基苯基）苯并三唾、2-[2-經基-3,5_ 雙（α，α-二曱基苄基）苯基]_苯并***、2_(3,5_二第三丁基-2_ 羥基苯基）苯并***、2-(3-第三丁基-5-甲基-2-羥基苯基）-本并二°坐、2-(3,5-二-第三戊基_2_經基苯基）苯并三唾'2_(2，_ 經基-5-苐二辛基苯基）苯并三。坐、經基苯基苯并三唾、曱 笨基二0坐、5 -曱基-1H-苯并三唾、4-曱基-1H-笨并三嗤、4-羧基-1H-苯并***、5·羧基·1H_苯并***、ιΗ四唑、5甲 基-1H-四唑、5-苯基-1H-四唑、5-胺基-1H-四唑、i_曱基_1H_ 四唾等。特佳為舉出：甲苯基***、5_甲基_1H_苯并***、 及4-甲基-1H-苯并***。又，該等唑化合物可使用1種，亦 可以2種以上之混合物使用。 負型感光性樹脂組合物含有上述嗤化合物之情形之調配 量相對於（A)聚醯亞胺前驅物100質量份較佳為〇卜2〇質量 份’就感光度特性之觀點而言，更佳為〇.5〜5質量份。。坐化 合物相對於（Α)聚醯亞胺前驅物1〇〇質量份之調配量為〇」質 153046.doc •29- 201140242 量份以上之情形時，在將本發明之負型感光性樹脂組合物 形成於銅或銅合金之上之情形時，可抑制銅或銅合金表面 之變色’另一方面’於20質量份以下之情形時，感光度優 異。 又’為抑制銅上之變色’可任意地調配受阻酚化合物。 作為受阻酚化合物，可舉出：2,6-二-第三丁基-4-曱基苯 齡、2,5 - — 第二丁基-對本二紛、丙酸十八炫基-3-(3，5 -二-第三丁基-4-羥基苯基）酯、丙酸異辛基-3-(3,5-二-第三丁基 -4-羥基苯基）酯、4,4'-亞曱基雙（2、6-二-第三丁基苯酚）、 4,4·-硫-雙（3-甲基-6-第三丁基苯酚）、4,4'-亞丁基-雙（3-曱基 -6-第三丁基苯酚）、三乙二醇-雙[3_(3_第三丁基_5•曱基_4_ 羥基苯基）丙酸酯]、1,6-己二醇-雙[3-(3,5-二-第三丁基-4-羥基苯基）丙酸酯]、2,2-硫-二伸乙基雙[3_(3,5_二-第三丁基 -4-羥基苯基）丙酸酯]、n，N'-六亞曱基雙（3,5-二-第三丁基 -4-羥基-苯丙醯胺）、2,2'-亞曱基-雙（4-甲基-6-第三丁基苯 酚）、2,2’-亞曱基·雙（4-乙基-6-第三丁基苯酚）、季戊四醇基 -四[3-(3,5-二-第三丁基_4_羥基苯基）丙酸酯]、異三聚氰酸 二-(3,5-二-第三丁基·4·羥基苄基）酯、13,5_三曱基_2,4,6_ 三（3,5-二-第三丁基-4·羥基苄基）苯、13 5_三（3_羥基_2 6_ 二曱基-4-異丙基苄基;三畊_2,46_(1H3h，5H)s 酮、1’3,5-三（4-第三丁基-3-羥基-2,6-二甲基苄基）-l,3,5-三 畊-2,4,6-(1Η，3Η，5Η)-三酮、ι，3,5-三（4-第二丁基-3-羥基 -2,6-二曱基苄基）_13,5_ 三畊 _2,4,6 (1h，3h，5h) ^_、 1，3,5-二[4-(1·乙基丙基）_3_羥基·2 6二甲基苄基]_13 5三 153046.doc •30· 201140242 畊-2,4,6-(111，311，511)-三酮、1，3,5-三[4-三乙基甲基-3-羥基 -2,6-二甲基苄基]-1，3,5-三畊·2,4,6·(1Η，3Η，5Η)-三酮、 1，3,5-三（3-經基-2,6-二甲基-4-苯基苄基）-ΐ，3,5-三 畊-2,4,6-(111，31511)-三酮、1，3,5-三（4-第三丁基-3-經基 -2,5，6-三甲基苄基）-1，3,5·三畊·2,4,6-(1Η，3Η，5Η)-2_、 1，3,5-三（4·第三丁基-5-乙基-3-羥基-2,6-二曱基苄 基）-1，3,5-三&quot;井-2,4,6-(111，311，511)-三酮、1，3,5-三（4-第三丁 基-6-乙基-3-經基-2-曱基节基）-1，3,5-三 畊-2,4,6-(111，311，5只)-三酮、1,3,5-三（4-第三丁基-6-乙基-3-羥基-2,5-二甲基苄基）-l，3,5-三畊-2,4,6-(1Η，3Η，5Η)-三 酮、1，3,5_三（4-第三丁基-5 ’ 6-二乙基-3-羥基-2-曱基苄 基）-1,3,5-三畊 _2,4,6-(1Η，3Η，5Η)-三酮、l，3,5-三（4·第三丁 基-3-羥基-2-甲基苄基）_ι，3,5 -三畊·2,4,6-(1ϋ,3Η,5Η)·三 酮、1，3,5-三（4-第三丁基_3_羥基_2,5_二曱基苄基卜^^三 畊-2,4,6-(1Η，3Η，5Η)-三酮、1，3,5_ 三（4_ 第三丁基 _5_ 乙基 _3· 羥基-2-甲基苄基）-l，3,5-三畊-2,4,6-(lH,3H，5H)-三酮等，但 並不限定於該等。該等之中，特佳為135三（4第三丁基·3_ 羥基-2,6-二甲基苄基）_1，3,5_三畊_2,4,6_(111，311，511)_三酮等。 文阻盼化合物之調配量相對於（A)聚醯亞胺前驅物1〇〇質 ΐ伤較佳為0.1〜20質量份，就感光度特性之觀點而言，更 佳為0.5〜10質量份。受阻酚化合物相對於（a)聚醯亞胺前驅 物100質里伤之調配量為〇,丨質量份以上之情形時，在將本 發月之負型感光性樹脂組合物形成於例如銅或銅合金之上 之隋形時’可防止銅或鋼合金之變色·腐蝕，另一方面， 153046.doc •31 - 201140242 於20質量份以下之情形時，感光度優異。 〈硬化浮凸圖案之製造方法&gt; 本發明又提供一種硬化浮凸圖案之製造方法，其包括： (1)藉由將上述本發明之負型感光性樹脂組合物塗佈於基板 上而於遠基板上形成感光性樹脂層之步驟、（2)對該感光性 樹脂層進行曝光之步驟、（3)使該曝光後之感光性樹脂層顯 ’sv而形成浮凸圖案之步驟、及（4)藉由加熱處理該浮凸圖案 而形成硬化浮凸圖案之步驟。以下，就各步驟之典型態樣 加以說明。 (1)藉由將負型感光性樹脂組合物塗佈於基板上而於該基 板上形成感光性樹脂層之步驟 於本步驟中，將本發明之負型感光性樹脂組合物塗佈於 基材上，視需要使其後乾燥而形成感光性樹脂層。作為塗 佈方法可使用先刖用於感光性樹脂組合物之塗佈之方 法，例如利用旋轉塗佈機、棒式塗佈機、到刀塗佈機、簾 幕式塗佈機、網版印刷機等進行塗佈之方法，利用喷霧塗 佈機進行喷霧塗佈之方法等。 可視需要使包含負型感光性樹脂組合物之塗膜乾燥，作 為乾燥方法，係使用風乾、利用烘箱或加熱板之加熱乾燥、 真空乾燥等方法。又，塗膜之乾燥期望於不會引起負型感 光性樹脂組合物中之聚醯亞胺前驅物之醯亞胺化之條 件下進行。具體而言，於進行風乾或加熱乾燥之情形時， 可於20 C〜140 c以1分鐘〜1小時之條件進行乾燥。藉由以上 操作可於基板上形成感光性樹脂層。 153046.doc •32- 201140242 (2)對感光性樹脂層進行曝光之步驟 於本步驟中，使用接觸式曝光機、鏡面投影曝光機、步 進曝光機等曝光裝置，經由具有圖案之光罩（ph〇t〇mask)或 掩模（reticle) ’或直接利用紫外線光源等對上述形成之感光 性樹脂層進行曝光。 其後’為提高感光度等，亦可視需要藉由任意之溫度及 時間之組合實施曝光後烘烤（PEB)及/或顯影前烘烤。烘烤 條件之範圍較佳為溫度為40〜1201、時間為1〇秒〜240秒， 但只要不損及本發明之負型感光性樹脂組合物之各種特 性’則並不限定於此範圍。 (3)使曝光後之感光性樹脂層顯影而形成浮凸圖案之步驟 於本步驟中，顯影去除曝光後之感光性樹脂層中之未曝 光。卩作為使曝光（照射）後之感光性樹脂層顯影之顯影方 法，可自先前已知之光阻之顯影方法，例如旋轉喷霧法、 覆液法、伴有超音波處理之浸潰法等中選擇任意之方法並 使用。又，顯影之後，為調整浮凸圖案之形狀等，亦可視 需要藉由任意之溫度及時間之組合實施顯影後烘烤。 人作為用於顯影之顯影液’較佳為針對負型感光性樹脂組 一 良/谷劑、或5亥良溶劑與不良溶劑之組合。作為良溶 劑較佳為N-甲基_2_n比洛烧酮、N_環己基_2·η比洛烧嗣、N，N_ 盔胺、環戊酮、環己酮、γ•丁内酉旨、α_乙醯基_丫_ 内®曰等’作為不良溶劑’較佳為甲苯、二甲苯、甲醇、 =異丙醇、乳酸乙酷、丙二醇甲謎乙酸醋及水等。於 t °使用良洛劑與不良溶劑之情形時時’較佳為根據負型 153046.doc •33- 201140242 感光性樹脂組合物中之聚合物之溶解性而調整不良溶劑相 對於良溶劑之比例。又，亦可將各溶劑組合使用2種以上、 例如數種。 (4)藉由加熱處理浮凸圖案而形成硬化浮凸圖案之步驟 於本步驟中，加熱藉由上述顯影所獲得之浮凸圖案而使 感光成分消散，並且使（A)聚醯亞胺前驅物醯亞胺化，藉此 轉變為包含聚酿亞胺之硬化浮凸㈣。作為加熱硬化之方 法’可選擇利用加熱板之方法、使用烘箱之方法、使用可 設定溫度程式之升溫式烘箱之方法等各種方法。加熱例如 可於2001〜4GGt以30分鐘〜5小時之條件進行。加熱硬化時 之環境氣體可使用空氣，亦可使用氮氣、氬氣等惰性氣體。 &lt;半導體裝置&gt; 本發明又提供-種半導體裝置，其具有藉由上述本發明 之硬化浮凸圖案之製造方法所獲得之硬化浮凸圖案。本發 明亦提供一種半導體裝置’其包括作為半導體元件之基 材、及藉由上述硬化浮凸圖案製造方法於該基材上形成之 聚醯亞胺之硬化浮凸圖案。λ，本發明可應用於使用半導 體元件作為基板、包含上述硬化浮凸圖案之製造方法作為 步驟之一部分的半導體裝置之製造方法。本發明之半導體 裝置可藉由如下方法獲得：將利用上述硬化浮凸圖案製造 方法所獲得之硬化浮凸圖案形成為表面保護膜、層間絕緣 膜、再配線用絕緣膜、覆晶裝置用保護膜、或具有凸塊結 構之半導體裝置之保護膜等，與公知之半導體裝置之製造 方法加以組合。 153046.doc -34 - 201140242 本發明之負型感光性樹脂組合物除應用於如上所述之半 導體裝置以外，亦可用於多層電路之層間絕緣、可撓性銅 猪板之保護層、阻焊膜、及液晶配向膜等用途。 [實施例] 以下，藉由實施例更加具體地說明本發明，本發明並不 限定於此。於實施例、比較例、及製造例中，根據以下方 法測定及評價負型感光性樹脂組合物之物性。 (1) 重量平均分子量 利用凝膠滲透層析法法（標準聚苯乙烯換算）測定各聚醯 亞胺前驅物之重量平均分子量（Mw)e測定中使用之管柱為 日。和電工公司製造之商標名為Sh〇dex 805M/806M者串聯， 標準單分散聚苯乙烯選擇昭和電工股份有限公司製造之 Shodex STANDARD SM· 105,展開溶劑為N•甲基_2_吡咯烷 酮’檢測器係使用昭和電工製造之商標名者。 (2) 接著性試驗 將負型感光性樹脂組合物旋轉塗佈於銅基板上，進行乾 燥而使17 μηι厚之塗膜形成為感光性樹脂層後，使用升溫程 式式固化爐（VF-2000型，日本，K〇y〇Lindberg公司製造）， 於氮氣環境下於200°C加熱處理（固化口小時，接著K25〇&lt;t 加熱處理（固化）2小時，藉此獲得1〇 μιη厚之聚醯亞胺塗膜。 膜厚測定係使用Tencor Ρ_丨5型表面輪廓儀（KLA_Tenc〇r公 司製迈）進行。對於固化後之膜，依據JIS κ 56〇〇_5_6標準之 父又切割法，基於以下基準評價金屬材料（銅基板）/耐熱性 樹脂（聚醯亞胺塗膜）間之接著特性。 153046.doc •35- 201140242 「最良」：接著於基板之聚醯亞胺塗膜之格子數為100者。 「良」：接著於基板之聚醯亞胺塗膜之格子數為80〜99者。 「稍良」：接著於基板之聚醯亞胺塗膜之格子數為50〜79 者。 「稍微不良」：接著於基板之聚醢亞胺塗膜之格子數為 20〜49者。 「不良」：接著於基板之聚醯亞胺塗膜之格子數未滿20 者。 (3)耐化學品性試驗 旋轉塗佈於附有6英吋氮化膜之矽晶圓（Kyodo International公司製造）上’進行乾燥而使17 μηι厚之塗膜形 成為感光性樹脂層。使用附有測試圖案之掩模，藉由ghi線 步進曝光機（Prisma-ghi，Ultratech公司製造），以 200 mJ/cm2 對該塗膜照射能量而進行曝光。其次，使用環戊酮以顯影 機（D-SPIN636型，日本，大日本網屏製造公司製造）對形成 於晶圓上之塗膜進行喷霧顯影，利用丙二醇曱醚乙酸酯進 行沖洗’顯影去除未曝光部’獲得聚醯亞胺前驅物之浮凸 圖案。使用升溫程式式固化爐（VF_2〇〇〇型，日本，K〇y〇^ (4) When the mass is less than 〇, (4) the solubility of the poly-S amine oxime drive becomes good. The negative photosensitive resin composition of the present invention may further contain a resin component other than the above-mentioned 153046.doc -24·201140242 polyimine precursor. The resin component which can be contained may be as follows: Polyimine, polycarbazole, polycarbazole precursor, phenol resin, polyamide, epoxy resin, decyl oxide resin, acrylic resin, and the like. The blending amount of the resin component is preferably in the range of 0.01 to 20 parts by mass based on the mass fraction of the (A) polyimine precursor. Further, in order to increase the sensitivity, the negative photosensitive resin composition of the present invention can optionally be formulated with a sensitizer as the sensitizer, and examples thereof include: mireconone, 4, 4'-double (two Aminophenone)benzophenone, 2,5-bis(4,2-diethylaminobenzylidene)cyclopentane, 2,6-bis(4,2-diethylaminobenzylidene) ring Hexanone, 2,6-bis(4-ethylethylaminobenzylidene)_4_methylcyclohexyl, 4,4,bis(dimethylamino)chalcone 4,4'-double ( Diethylamino)chalcone, p-dimethylaminobenzylidene fluorenone, p-didecylaminobenzylidene ketone, 2-(p-dimethylaminophenyl phenylene )-benzothiazole, 2_(p-dimethylaminophenyl-vinyl)benzothiazole, 2-(p-di-f-aminophenylphenyl-vinyl)isophthalazol, 1,3-double (4,- Di-f-aminoaminobenzylidene)acetone, hydrazine bis-diethylaminobenzylidene)acetone, 3,3,-carbonyl-bis(7-diethylaminocoumarin), 3_ Ethyl 7-dimethylamino coumarin, 3-ethoxycarbonyl _7-dimethylamino sylvestrein, 3-benzyloxycarbonyl-7-di-diamine coumarin Prime, 3_A Carbocarbonyl-7·diethylamino coumarin, 3-ethoxycarbonyl _7-diethylamino coumarin, N-phenyl-fluorene-ethylethanolamine, N-phenyldiethanolamine , N_p-tolyldiethanolamine, N-phenylethanolamine, 4_ morpholinyldibenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2 whale Benzimidazole, 1-phenyl-5-mercaptotetrazole, 2·mercaptobenzothiazole, 2-(p-didecylaminostyryl)benzo, azole, 2-(p-dimethylaminobenzene) Vinyl) stupid 153046.doc •25· 201140242 thiazole, 2-(p-dimethylaminostyryl)naphthalene (1,2_d)thiazole ' 2 (p-didecylamine basic), styrene and the like. These may be used singly or in combination of, for example, 2 to 5 types. The amount of the negative photosensitive resin composition containing the sensitizer for improving the sensitivity is preferably 0.1 to 25 parts by mass based on 1 part by mass of the (A) polyimine precursor. Further, in order to improve the resolution of the embossed pattern, a monomer having a photopolymerizable unsaturated bond can be arbitrarily formulated. The (meth)acrylic compound which is preferably subjected to radical polymerization by a photopolymerization initiator is not particularly limited to the following ones, but may be exemplified by diethylene glycol difluorenyl. Acrylate, tetraethylene glycol dimercapto acrylate as a representative of ethylene glycol or polyethylene glycol mono or diacrylate and mercapto acrylate, propylene glycol or polypropylene glycol mono or diacrylate and methyl Acrylate, glycerol mono-, di- or tri- acrylate and mercapto acrylate, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylate and dimethacrylate , i, 6_&amp; diol diacrylate and dimethacrylate, neopentyl glycol diacrylate and dimethacrylate, bisphenol A mono or diacrylate and methacrylate, benzene Methacrylate, isobornyl acrylate and mercapto acrylate, acrylamide and its derivatives, mercapto acrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerin Or triacrylate and mercapto acrylate, Di-, tri- or tetra-acrylates and decyl acrylates of pentaerythritol, and compounds such as ethylene oxide or propylene oxide adducts of such compounds. The negative photosensitive resin composition contains a compounding amount of the monomer having the above photopolymerizable unsaturated bond to improve the resolution of the embossed pattern 153046.doc •26-201140242 with respect to (A) polyimine The precursor is preferably 1 part by mass based on 1 part by mass. Further, the adhesion aid can be arbitrarily adjusted to improve the adhesion between the film formed by using the negative photosensitive resin composition of the present invention and the substrate. Examples of the subsequent auxiliary agent include γ-aminopropyl dimethoxydecane, :(0-aminoethyl)_γ-aminopropyldecyldimethoxy decane, and γ-glycidyloxygen. Propyl propyl dimethyl oxalate, γ-mercaptopropyl decyl decyloxy decane, 3-mercaptopropyl methoxy propyl dimethoxy methoxy decane, 3- methacryl醯 丙基 methoxy methoxy methoxy ethoxylate, monomethoxy fluorenyl-3-bucking propyl sulfonium, diethoxy _3 _ glycidoxypropyl methyl decane, Ν _ (3 _: ethoxy Base hydrazinoalkyl propyl) butyl quinone imine, Ν-[3-(triethoxy decyl) propyl] phthalic acid, benzophenone-3, 3'-double ( Ν-[3-triethoxydecyl]propyl decylamine)-4'4'-dicapric acid, Benzene-indole bis(indole-[3-triethoxydecyl]propyl decylamine)- a decane coupling agent such as 2,5-dicarboxylic acid, 3-(triethoxydecyl)propyl succinic anhydride, hydrazine-phenylaminopropyltrimethoxydecane, and aluminum tris(ethylacetamidineacetic acid) An aluminum-based adhesion aid such as aluminum (acetonitrile) aluminum or ethyl acetoacetate diisopropoxy aluminum. Among these secondary auxiliaries, a decane coupling agent is more preferably used from the viewpoint of adhesion. The amount of the negative photosensitive resin composition containing the auxiliary agent is preferably in the range of 0.5 to 25 parts by mass based on 1 part by mass of the (by) polyimine precursor. Further, in particular, in order to improve the stability of the viscosity and sensitivity of the negative photosensitive resin composition when stored in a solvent-containing solution, the thermal polymerization inhibitor can be arbitrarily formulated. Examples of the thermal polymerization inhibitor include: p-phenylene 153046.doc -27· 201140242, quinone nitroso-diphenylamine, p-tert-butyl catechol, phenol thiophene, hydrazine-phenyl Naphthylamine, ethylenediaminetetraacetic acid, 丨^-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-t-butyl-p-nonylphenol, 5·nitroso -8-hydroxyquinoline, 1-nitros naphthol, 2-nitroso naphthol, 2 nitroso-5-(anthracene-ethyl·anthracene-propylamino) phenol, hydrazine _ nitrous oxide The group is a hydrazine, a hydrazine-nitroso-N(l-naphthyl)hydroxylamine ammonium salt, and the like. The amount of the thermal polymerization inhibitor to be blended in the negative photosensitive resin composition is preferably in the range of 0.005 to 12 parts by mass based on 1 part by mass of the (fluorene) polyimide precursor. Further, the crosslinking agent can be optionally formulated. The crosslinking agent may be such that when the embossed pattern formed using the negative photosensitive resin composition of the present invention is heat-hardened, the poly(imine) precursor precursor may be crosslinked or the crosslinking agent itself may be formed. Crosslinker of the network. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed of the negative photosensitive resin composition. As the crosslinking agent, an amine-based resin and a derivative thereof can be preferably used, and among them, a urea resin, an intramethylene urea resin, a hydroxyethyl urethane resin, a melamine resin, a benzoguanamine resin, and the like can be preferably used. And other derivatives. Particularly preferred are alkoxythiolated urea compounds and alkoxylated melamine compounds, and examples thereof include ΜΧ-290 (manufactured by Car本Carbide), UFR-65 (manufactured by Cytec, Japan), and MW-3. 90 (manufactured by Japan Carbide Corporation). In order to achieve various properties other than heat resistance and chemical resistance, the amount of the negative photosensitive resin composition containing a crosslinking agent is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the (A) polyimine precursor. The mass fraction is more preferably 2 to 1 part by mass. When the amount is 0.5 parts by mass or more, the heat resistance and chemical resistance of 153046.doc • 28 to 201140242 are exhibited, and on the other hand, when the amount is 20 parts by mass or less, the storage is saved. Excellent stability. Further, in the case of using a substrate containing, for example, copper or a copper alloy, the azole compound can be optionally formulated to suppress discoloration of the substrate. The azole compound may, for example, be 1H-dioxan, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4 5 dimethyl-1H-diazole or 5-phenyl- 1H_triazole, 4_t-butyl_5_phenyl·1H_triazole, 5-hydroxyphenyl-1Η·triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl -1-(2-dimethylaminoethyl)triazole, 5-benzyl-1-lanazole, hydroxyphenyl diazepine, 1,5-dimercaptotriazole, 4,5-diethyl -1Η-三嗤, 1Η-本本二°坐, 2-(5-methyl_2-phenylphenyl)benzotrisene, 2-[2-radio-3,5_bis(α,α -didecylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5- Methyl-2-hydroxyphenyl)-iso-2°, 2-(3,5-di-p-pentyl-2-bromophenyl)benzotrisole 2_(2,_---- 5-decanedioctylphenyl)benzotrien. Sodium, phenylphenyl benzotrisene, sulfhydryl quinone, 5-mercapto-1H-benzotrisene, 4-mercapto-1H-stuppytrimidine, 4-carboxy-1H-benzo Triazole, 5·carboxyl·1H_benzotriazole, ιΗtetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, i_曱Base_1H_ Four saliva and so on. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Further, these azole compounds may be used alone or in combination of two or more. The amount of the negative photosensitive resin composition containing the above-mentioned ruthenium compound is preferably 2 parts by mass relative to 100 parts by mass of the (A) polyimine precursor, from the viewpoint of sensitivity characteristics. Jia Wei 〇. 5~5 parts by mass. . When the compounding amount of the compound is 1 part by mass relative to the (Α) polyimine precursor, the negative photosensitive resin of the present invention is combined when the amount of the compound is 153046.doc •29-201140242 or more. When the material is formed on a copper or a copper alloy, the discoloration of the surface of the copper or copper alloy can be suppressed. On the other hand, when the content is 20 parts by mass or less, the sensitivity is excellent. Further, the hindered phenol compound can be optionally formulated to suppress discoloration on copper. The hindered phenol compound may, for example, be 2,6-di-t-butyl-4-mercaptophenylene, 2,5--second butyl-p-di-bis-, leucoyl-3-propionate-3- (3,5-di-t-butyl-4-hydroxyphenyl) ester, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4, 4'-arylene di(2,6-di-tert-butylphenol), 4,4·-sulfo-bis(3-methyl-6-tert-butylphenol), 4,4'-Adenine Base-bis(3-mercapto-6-tert-butylphenol), triethylene glycol-bis[3_(3_t-butyl-5(indolyl)-4-hydroxyphenyl)propionate], 1 , 6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-sulfan-di-extension ethyl bis[3_(3, 5_Di-t-butyl-4-hydroxyphenyl)propionate], n,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-phenylpropanamide ), 2,2'-arylene-bis(4-methyl-6-tert-butylphenol), 2,2'-fluorenylene, bis(4-ethyl-6-tert-butylphenol ), pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-yl-hydroxyphenyl)propionate], di-(3,5-di-t-butyl) · 4·hydroxybenzyl) ester, 13,5_trimethyl 2,4,6_ three ( 3,5-di-t-butyl-4.hydroxybenzyl)benzene, 13 5_tris(3_hydroxy_2 6_didecyl-4-isopropylbenzyl; three tillage _2,46_(1H3h , 5H)s ketone, 1'3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-l,3,5-three tillage-2,4,6 -(1Η,3Η,5Η)-trione, ι,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimercaptobenzyl)_13,5_ three tillage_2,4 ,6 (1h,3h,5h) ^_, 1,3,5-bis[4-(1·ethylpropyl)_3_hydroxy·2 6 dimethylbenzyl]_13 5三153046.doc •30 · 201140242 Tillage-2,4,6-(111,311,511)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl ]-1,3,5-three tillage·2,4,6·(1Η,3Η,5Η)-trione, 1,3,5-tris(3-carbyl-2,6-dimethyl-4 -phenylbenzyl)-indole, 3,5-trinol-2,4,6-(111,31511)-trione, 1,3,5-tris(4-tert-butyl-3-yl) -2,5,6-trimethylbenzyl)-1,3,5·three tillage·2,4,6-(1Η,3Η,5Η)-2_, 1,3,5-three (4· Tributyl-5-ethyl-3-hydroxy-2,6-dimercaptobenzyl)-1,3,5-tri" well-2,4,6-(111,311,511)-three Ketone, 1,3,5-tris(4-tert-butyl-6-ethyl-3-mercapto-2-indenyl)-1 3,5-three tillage-2,4,6-(111,311,5)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2 ,5-dimethylbenzyl)-l,3,5-three tillage-2,4,6-(1Η,3Η,5Η)-trione, 1,3,5_tri(4-tert-butyl -5 '6-Diethyl-3-hydroxy-2-mercaptobenzyl)-1,3,5-three tillage_2,4,6-(1Η,3Η,5Η)-trione, l,3 ,5-tris(4·t-butyl-3-hydroxy-2-methylbenzyl)_ι,3,5-three tillage·2,4,6-(1ϋ,3Η,5Η)·trione, 1 ,3,5-tris(4-tert-butyl_3_hydroxy-2,5-didecylbenzyl bromide ^3,4,6-(1Η,3Η,5Η)-trione, 1,3,5_ tris(4_t-butyl_5_ethyl_3.hydroxy-2-methylbenzyl)-l,3,5-three tillage-2,4,6-(lH,3H,5H )-trione or the like, but is not limited thereto. Among these, particularly preferred is 135 tris(4th butyl-3-hydroxy-6,6-dimethylbenzyl)_1,3,5_three tillage_2,4,6_(111,311,511 ) _ triketone and the like. The compounding amount of the compound is preferably 0.1 to 20 parts by mass relative to the (A) polyimine precursor 1 enamel, and more preferably 0.5 to 10 parts by mass in terms of sensitivity characteristics. . When the amount of the hindered phenol compound is less than or equal to or greater than the mass fraction of the (a) polyimine precursor, the negative photosensitive resin composition of the present month is formed, for example, of copper or When the copper alloy is on the top of the copper alloy, it prevents the discoloration and corrosion of copper or steel alloy. On the other hand, 153046.doc •31 - 201140242 is excellent in sensitivity under 20 parts by mass or less. <Method for Producing Hardened Emboss Pattern> The present invention further provides a method for producing a cured embossed pattern, comprising: (1) applying the negative photosensitive resin composition of the present invention to a substrate a step of forming a photosensitive resin layer on the far substrate, (2) a step of exposing the photosensitive resin layer, (3) a step of forming the exposed photosensitive resin layer to form a embossed pattern, and ( 4) a step of forming a hardened relief pattern by heat-treating the relief pattern. The following is a description of typical aspects of each step. (1) A step of forming a photosensitive resin layer on the substrate by applying a negative photosensitive resin composition onto a substrate. In this step, the negative photosensitive resin composition of the present invention is applied to a substrate. On the material, it is post-dried as needed to form a photosensitive resin layer. As the coating method, a method of applying the coating to the photosensitive resin composition may be used, for example, by a spin coater, a bar coater, a knife coater, a curtain coater, or screen printing. A method of coating by a machine or the like, a method of spray coating by a spray coater, or the like. The coating film containing the negative photosensitive resin composition may be dried as needed, and as a drying method, air drying, heating drying by an oven or a hot plate, vacuum drying or the like may be used. Further, the drying of the coating film is desirably carried out under conditions which do not cause hydrazine imidization of the polyimide precursor in the negative photosensitive resin composition. Specifically, in the case of air drying or heat drying, drying can be carried out at 20 C to 140 c for 1 minute to 1 hour. By the above operation, a photosensitive resin layer can be formed on the substrate. 153046.doc •32- 201140242 (2) Step of exposing the photosensitive resin layer In this step, an exposure device such as a contact exposure machine, a mirror projection exposure machine, or a stepper is used, and a patterned mask is used ( The photosensitive resin layer formed as described above is exposed directly to the ph〇t〇mask or reticle. Thereafter, in order to increase the sensitivity and the like, post-exposure bake (PEB) and/or pre-development baking may be carried out by any combination of temperature and time. The baking condition is preferably in the range of 40 to 1201, and the time is from 1 to 240 seconds. However, the present invention is not limited to such a range as long as the various characteristics of the negative photosensitive resin composition of the present invention are not impaired. (3) Step of developing the photosensitive resin layer after exposure to form a relief pattern In this step, development is performed to remove unexposed light in the photosensitive resin layer after exposure.显影 As a developing method for developing a photosensitive resin layer after exposure (irradiation), it can be developed from a previously known photoresist development method, such as a rotary spray method, a liquid coating method, a dipping method with ultrasonic treatment, or the like. Choose any method and use it. Further, after development, in order to adjust the shape of the embossed pattern or the like, it is also possible to carry out post-development baking by any combination of temperature and time. The developer as the developing solution for development is preferably a combination of a negative photosensitive resin group, a good solvent, or a solvent and a poor solvent. As a good solvent, N-methyl-2_n ratio cyprofenone, N_cyclohexyl-2·η piroxicam, N,N_helium amine, cyclopentanone, cyclohexanone, γ•丁内酉, α_Ethyl hydrazine 丫 内 内 内 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为When using a good agent and a poor solvent at t °, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition of negative type 153046.doc • 33- 201140242 . Further, two or more kinds, for example, several kinds may be used in combination with each solvent. (4) a step of forming a hardened embossed pattern by heat-treating the embossed pattern. In this step, the embossed pattern obtained by the above development is heated to dissipate the photosensitive component, and the (A) polyimine precursor is made. The substance is imidized, thereby being converted into a hardened embossing comprising tetramine (IV). As a method of heat hardening, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature-increasing oven capable of setting a temperature program can be selected. The heating can be carried out, for example, at a temperature of from 30 to 5 hours at 2001 to 4 GGt. The ambient gas during heat hardening may be air or an inert gas such as nitrogen or argon. &lt;Semiconductor device&gt; The present invention further provides a semiconductor device having a hardened relief pattern obtained by the above-described method for producing a cured embossed pattern of the present invention. The present invention also provides a semiconductor device which includes a substrate as a semiconductor element and a hardened relief pattern of a polyimide which is formed on the substrate by the above-described method for producing a cured relief pattern. λ, the present invention is applicable to a method of manufacturing a semiconductor device using a semiconductor device as a substrate and a manufacturing method including the above-described hardened embossed pattern as a part of the steps. The semiconductor device of the present invention can be obtained by forming a cured embossed pattern obtained by the above-described method for producing a cured embossed pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, and a protective film for a flip chip device. A protective film or the like of a semiconductor device having a bump structure is combined with a known method of manufacturing a semiconductor device. 153046.doc -34 - 201140242 The negative photosensitive resin composition of the present invention can be used for interlayer insulation of a multilayer circuit, a protective layer of a flexible copper pig board, and a solder resist film, in addition to the semiconductor device as described above. And liquid crystal alignment film and other uses. [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the negative photosensitive resin composition were measured and evaluated by the following methods. (1) Weight average molecular weight The column used for the measurement of the weight average molecular weight (Mw) of each of the polyimine precursors was measured by gel permeation chromatography (standard polystyrene conversion). It is connected in series with the brand name Sh〇dex 805M/806M manufactured by the company, and the standard monodisperse polystyrene is selected from Shodex STANDARD SM·105 manufactured by Showa Denko Co., Ltd., and the solvent is N•methyl_2_pyrrolidone. The device uses the trademark name manufactured by Showa Denko. (2) In the following test, the negative photosensitive resin composition was spin-coated on a copper substrate, dried, and a coating film of 17 μm thick was formed into a photosensitive resin layer, and then a temperature-increasing curing oven (VF-2000) was used. Type, manufactured by K〇y〇Lindberg Co., Ltd., Japan, heated at 200 ° C under a nitrogen atmosphere (curing port is small, followed by K25 〇 &lt; t heat treatment (curing) for 2 hours, thereby obtaining 1 〇 μιη thick The film thickness measurement was carried out using a Tencor Ρ_丨5 surface profiler (manufactured by KLA_Tenc〇r Co., Ltd.). For the cured film, it was cut according to the father of the JIS κ 56〇〇_5_6 standard. The method was used to evaluate the adhesion characteristics between a metal material (copper substrate) and a heat-resistant resin (polyimine coating film) based on the following criteria: 153046.doc • 35- 201140242 "Best": a polyimide film coated on a substrate The number of grids is 100. "Good": The number of grids of the polyimide film coated on the substrate is 80 to 99. "Slightly good": The number of lattices of the polyimide film applied to the substrate is 50. ~79. "Slightly bad": then gathered on the substrate The number of lattices of the imide coating film is 20 to 49. "Poor": The number of lattices of the polyimide film coated on the substrate is less than 20. (3) Chemical resistance test is spin-coated on the attached 6 The ruthenium nitride film (manufactured by Kyodo International Co., Ltd.) was dried to form a coating film of 17 μm thick to form a photosensitive resin layer. Using a mask with a test pattern, stepwise exposure by ghi line (Prisma-ghi, manufactured by Ultratech), exposed the coating film at 200 mJ/cm2 for exposure. Secondly, using a cyclopentanone as a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Manufacturing Co., Ltd., Japan) Spray-developing the coating film formed on the wafer, and performing rinsing with propylene glycol oxime ether acetate to remove the unexposed portion to obtain a embossed pattern of the polyimide precursor. VF_2 type, Japan, K〇y〇

Lindberg公司製造），於氮氣環境下於2〇〇&lt;&gt;c將形成有浮凸圖 案之晶圓加熱處理i小時，接著於25〇t加熱處理2小時，藉 此於附有氮化膜之矽晶圓上獲得1〇 μπι厚之聚醯亞胺之硬 化浮凸圖案。 將所獲得之聚醯亞胺圖案於包含氫氧化鉀丨wt%、3-甲氧 基甲土 1 丁醇39 wt%、二曱基亞硬60 wt%之溶液中於 153046.doc -36 - 201140242 100°C浸潰1小時。水洗及風乾之後，藉由膜厚測定與光學 顯微鏡下之觀察而進行聚醯亞胺塗膜之評價。關於浸潰後 之塗膜’將塗膜之膜厚變化相對於浸潰前為土 1 %以内且未 產生龜裂之情形評價為「最良」，將塗膜之膜厚變化為±3% 以内且未產生龜裂之情形評價為「良」，將膜厚變化超過 士 3。/。或產生龜裂之情形評價為「不良」。 〈製造例1&gt; (作為（A)聚醯亞胺前驅物之聚合物A之合成） 將4,4·-氧雙鄰笨二曱酸二酐（〇DpA)1551 g放入2升容量 之可分離式燒瓶中，放入甲基丙烯酸2-羥基乙酯 (HEMA)131.2 g與γ-丁内酯400 ml，於室溫下進行攪拌，一 面攪拌一面添加吡啶81.5 g，獲得反應混合物。反應之發熱 結束後，放置冷卻至室溫，放置丨6小時。 其次’於冰浴冷卻下，一面攪拌將二環己基碳二醯亞胺 (DCC)206.3 g溶解於γ-丁内酯180 ml中而成之溶液，一面花 費40分鐘添加反應混合物，一面攪拌一面花費6〇分鐘添加 使4,4’-二胺基二苯醚（DadPE)93.0 g懸浮於γ·丁内酯350 ml 中而成者。進而於室溫下攪拌2小時後，添加乙醇3〇…並 攪拌1小時，其次添加γ-丁内酯4〇〇 m卜藉由過濾而取出反 應混合物中生成之沈澱物，獲得反應液。 將所獲得之反應液添加至3升乙醇中’生成包含粗聚合物 之沈澱物。將生成之粗聚合物過濾分離，溶解於四氫吱味 1.5升中而獲得粗聚合物溶液。將所獲得之粗聚合物溶液滴 加至28升水中使聚合物沈澱，過濾分離所獲得之沈澱物 後’進行真空乾燥而獲得粉末狀之聚合物（聚合物A)。利用 153046.doc -37- 201140242 凝膠滲透層析法（標準聚苯乙烯換算）測定聚合物A之分子 量’結果重量平均分子量（Mw)為20000。 〈製造例2&gt; (作為（A)聚醯亞胺前驅物之聚合物b之合成） 除使用3,3’，4,4，-聯苯四羧酸二酐147.1 g代替製造例}之 4,4·-氧雙鄰苯二甲酸二酐155.i g以外，與上述製造例1中記 載之方法同樣地進行反應，獲得聚合物B ^利用凝膠滲透層 析法（標準聚苯乙烯換算）測定聚合物B之分子量，結果重量 平均分子量（Mw)為22,000。 〈實施例1 &gt; 使用聚合物A、B並利用以下之方法製備負型感光性樹脂 組合物’進行所製備之組合物之評價.將作為聚醯亞胺前 驅物之聚合物A 50 g及B 50 g((A)聚醯亞胺前驅物）與丨·苯 基-1，2-丙二酮-2-(0-乙氧基羰基）_肟（（B)光聚合起始劑）4 g、扁桃酸（（C)單羧酸化合物）〇 2 g、苯并***〇 15 g、135_ 三（4-第三丁基_3_羥基_2,6_二甲基苄基Η),%三 p井-2,4,6-(lH，3H，5H)-5 _1.5 g、N-苯基二乙醇胺 1〇 g、甲 氧基甲基化腺樹脂（MX-2 90)4 g、四乙二醇二甲基丙烯酸酯 8 g、N-[3-(三乙氧基矽烷基）丙基]鄰苯二甲醯胺酸15 g、 及2·亞硝基-1-萘酚0.05 g一併溶解於包含义曱基吡咯烷 酮（以下稱為NMP)80 g與乳酸乙酯2〇 g之混合溶劑中。藉由 添加少量之該混合溶劑而將所獲得之溶液之黏度調整為約 3 5泊，製成負型感光性樹脂組合物。 根據下述方法評價該組合物，結果即便於低溫固化之情 形時，接著性之評價亦成為丨〇〇，為「最良」，耐化學品性 153046.doc •38· 201140242 之評價為「良」。 &lt;實施例2、3&gt; 將實施例1之作為本發 之調配量變更為表1所示 明中之（C)單羧酸化合物的扁桃酸 之組成内容’製備負型感光性樹脂 組合物’分別進行與實施例！同樣之評價。於任一情形時， 均以與實施例1同樣之方法進行評價，其評價結果與實施例 1相同。 &lt;實施例4&gt; 將貫施例1之作為本發明中之（C)單緩酸化合物的扁桃酸 之調配1變更為表^示之組成内容，製備負型感光性樹脂 組合物，進仃與實施例1同樣之評價。評價接著性之結果成 為8〇’為「良」。&lt;化學品性之評價結果與實施织相同。 &lt;實施例5&gt; 將實施例1之作為本發明中之（c)單叛酸化合物的爲桃酸 =配讀更為表1所示之組成内容，製備負型感光性樹脂 組σ物，進行與實施例1同樣之評價。評價結果與實施例1 相同。 &lt;實施例6&gt; 根據表1所不之組成内容使用2_羥基異丁酸代替實施例【 之作為本發明中之（C)單羧酸化合物的扁桃酸，製備負型感 ^樹知、·且合物，進行與實施例1同樣之評價。評價結果與 實施例1相同。 &lt;實施例7&gt; 柜據表1所示之组成内容使用乳酸代替實施例1之作為本 153046.doc -39- 201140242 發明中之（c)單㈣化合物的爲桃酸，製備負型感光性樹脂 、卫。物’進行與實施例1同樣之評價°評價接著性之結果成 為85，為「良」。耐化學品性之評價結果與實施例丨相同。 &lt;實施例8&gt; 根據表1所示之組成内容使用曱氧基笨基乙酸代替實施 ，之作為本發明令之（c)單羧酸化合物的扁桃酸，製備負 ，感光性樹脂組合物’進行與實施例1|§]樣之評價。評價接 =性之結果成為6G，為「稍良」。魏學品性之評價結果與 貫施例1相同。 &lt;實施例9&gt; 除於實施例i之組成中進而添加作為⑼有機欽化合物之 雙(乙基乙醯乙酸)二異丙醇鈦(D1)〇」g以外以與實施分&quot; 相同之方式製備負型感光性樹脂組合物。進行耐化學品性 評價之結果為’膜之膜厚變化為±1%以内，亦未觀察到龜 裂，為「最良」。接著性之評價結果與實施例丨相同。 &lt;實施例10&gt; 除於實施例k組成中進而添加作為（D)有機鈦化合物之 四正丙醇鈦（02)0·! g以外，以與實施例〗相同之方式製備負 型感光性樹脂組合物。進行耐化學品性評價之尹 膜 之膜厚變化為±1%以内，亦未觀察到龜裂，為/最良接 著性之評價結果與實施例1相同。 &lt;實施例11&gt; 除於實施例1之組成中進而添加作為（D)有機鈦化合物之 雙（η5-2,4-環戊二稀-i-基）雙（2,6_二氟_3 (ih•料小基）苯 153046.doc -40· 201140242 基）欽（D3)0.1 g以外，以與實施例丨相同之方式製備負型感 光性樹脂組合物。進行耐化學品性評價之結果為，膜之膜 厚變化為±1%以内，亦未觀察到龜裂，為「最良」。接著性 之評價結果與實施例〗相同。 &lt;實施例12&gt; 除使用聚合物A 1〇〇 g作為本發明中之聚醯亞胺前驅 物代替聚合物A 5 〇 g及聚合物B 5 〇 g以外，以與實施例9相 同之方式製備負型感光性樹脂組合物，進行與實施例1同樣 之砰彳貝。s平價結果與實施例9相同。 &lt;比較例1 &gt; 除自實施例1之組成中剔除扁桃酸以外，以與實施例1相 同之方式製備負型感光性樹脂組合物，進行與實施例1同樣 之》平彳貝&quot;依據上述方法塗佈於矽晶圓及銅基板上，並進行 乾燥、曝光、顯影及加熱處理，藉此獲得之聚醯亞胺塗膜 之耐化學品性之評價為「良」，但因不含本發明之(C)單羧 酸化合物，故接著性成為4〇，為「猶微不良」。 &lt;比較例2&gt; 除於比較例1之組成中添加作為（D)有機鈦化合物之雙 (乙基乙酿乙酸）二異丙醇鈦（Dl)O.l g以夕卜，以與比較例α 同之方式製備負型感光性樹脂組合物，進行與實施例1同樣 之評價H述方法塗佈於秒晶圓及銅基板，並進行乾 燥、曝光、顯影及加熱處理，藉此獲得之聚醯亞胺塗膜之 耐化學品性之評價為「最良」，但因不含本發明之⑹單叛 酸化合物，故接著性成為0，為「不良 153046.doc •41 · 201140242 【I ί 1比較例2 1 〇 〇 〇 〇 〇 〇 〇 0 不良 1 ft良1 1比較例1 1 〇 〇 〇 〇 〇 〇 〇 40 稍微不良 實施例12 〇 〇 〇 〇 〇 〇 〇 〇 〇 100 最良 1最良1 1實施例丨1 I (N 〇 〇 〇 〇 〇 〇 〇 O -Ofii Ξ龈 最良 實施例10 (N 〇 〇 〇 〇 〇 5 〇 100 最良 最良 實施例9 1 (N 〇 〇 〇 〇 〇 〇 〇 100 最良 1奸1 實施例8 〇 〇 〇 (N d 〇 〇 〇 60 稍良 實施例7 〇 〇 &lt;N 〇 〇 〇 〇 〇 00 ^ I實施例6 1 〇 &lt;N 〇 〇 〇 〇 〇 〇 100 最良 1實施例5 1 〇 〇 〇 〇 〇 〇 〇 100 最良 實施例4 〇 〇 〇 〇 〇 〇 〇 § ^ I實施例3 1 (N 〇 〇 〇 〇 〇 〇 100 最良 I實施例2 1 S 〇 〇 〇 〇 〇 〇 〇 100 最良 1實施例1 I 〇 (N 〇 〇 〇 〇 〇 〇 〇 100 最良 聚合物A 聚合物B 扁桃酸 2-羥基異丁酸 乳酸 甲氣基笨基乙酸 5 S g 接著性 耐化學品性 153046.doc -42- 201140242 [產業上之可利用性] 本發明之負型感光性樹脂組合物可較好地利用於對於例 如半導體裝置、多層配線基板等電氣•電子材料之製造有 用的感光性材料之領域。 153046.doc 43-(manufactured by Lindberg Co., Ltd.), the wafer having the embossed pattern is heat-treated for 1 hour under a nitrogen atmosphere at a temperature of 2 Å, followed by heat treatment at 25 Torr for 2 hours, thereby attaching a nitride film. A hardened relief pattern of 1 μm thick polyimine is obtained on the wafer. The obtained polyimine imine pattern is contained in a solution containing potassium hydroxide 丨 wt%, 3-methoxymethane 1 butanol 39 wt%, and dimercapto hard 60 wt% at 153046.doc -36 - 201140242 100 ° C immersion for 1 hour. After washing with water and air drying, the polyimide film was evaluated by film thickness measurement and observation under an optical microscope. The coating film after the immersion was evaluated as "best" in the case where the film thickness of the coating film was changed to within 1% of the soil before the immersion and no crack occurred, and the film thickness of the coating film was changed to within ±3%. The case where no crack occurred was evaluated as "good", and the film thickness was changed to more than ±3. /. Or the case of cracking is evaluated as "poor". <Production Example 1&gt; (Synthesis of Polymer A as (A) Polyimine Precursor) 2,4·-oxybis-succinic acid dianhydride (〇DpA) 1551 g was placed in a capacity of 2 liters. In a separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were placed, and the mixture was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat of the reaction was completed, the mixture was allowed to cool to room temperature, and left to stand for 6 hours. Next, while stirring in an ice bath, 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone, and the reaction mixture was added for 40 minutes while stirring. It took 6 minutes to add 93.0 g of 4,4'-diaminodiphenyl ether (DadPE) suspended in 350 ml of γ-butyrolactone. Further, the mixture was stirred at room temperature for 2 hours, and ethanol (3 Torr) was added thereto, and the mixture was stirred for 1 hour, and then γ-butyrolactone was added, and the precipitate formed in the reaction mixture was taken out by filtration to obtain a reaction liquid. The obtained reaction liquid was added to 3 liters of ethanol to produce a precipitate containing a crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 liters of tetrahydroanthracene to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and vacuum-dried to obtain a powdery polymer (Polymer A). The molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion) using 153046.doc -37-201140242, and the weight average molecular weight (Mw) was 20,000. <Production Example 2> (Synthesis of Polymer b as (A) Polyimine Precursor) In addition to the use of 3,3',4,4,-biphenyltetracarboxylic dianhydride 147.1 g instead of the production example} In the same manner as the method described in the above Production Example 1, the reaction was carried out in the same manner as in the above-mentioned Production Example 1, and the polymer B was obtained by gel permeation chromatography (standard polystyrene conversion). The molecular weight of the polymer B was measured, and as a result, the weight average molecular weight (Mw) was 22,000. <Example 1 &gt; Preparation of the prepared composition by using the polymers A and B and preparing the negative photosensitive resin composition by the following method. The polymer A 50 g as a polyimide precursor was used. B 50 g ((A) Polyimine precursor) and 丨Phenyl-1,2-propanedione-2-(0-ethoxycarbonyl)-indole ((B) photopolymerization initiator) 4 g, mandelic acid ((C) monocarboxylic acid compound) 〇 2 g, benzotriazolium 15 g, 135_ tris(4-tert-butyl_3_hydroxy-2,6-dimethylbenzyl hydrazine ),%三普 well-2,4,6-(lH,3H,5H)-5 _1.5 g, N-phenyldiethanolamine 1〇g, methoxymethylated gland resin (MX-2 90 4 g, tetraethylene glycol dimethacrylate 8 g, N-[3-(triethoxydecyl)propyl]phthalic acid 15 g, and 2·nitroso-1 - Naphthol 0.05 g was dissolved in a mixed solvent containing 80 g of anthraquinone pyrrolidone (hereinafter referred to as NMP) and 2 g of ethyl lactate. The negative photosensitive resin composition was prepared by adjusting the viscosity of the obtained solution to about 35 poise by adding a small amount of the mixed solvent. The composition was evaluated according to the following method, and as a result, even in the case of low-temperature curing, the evaluation of the adhesion was 丨〇〇, which was "best", and the chemical resistance 153046.doc •38·201140242 was evaluated as "good". . &lt;Examples 2 and 3&gt; The composition of the present invention was changed to the composition of the mandelic acid of the (C) monocarboxylic acid compound shown in Table 1 to prepare the negative photosensitive resin composition. 'Performed separately with the embodiment! The same evaluation. In either case, the evaluation was carried out in the same manner as in Example 1, and the evaluation results were the same as in Example 1. &lt;Example 4&gt; The preparation of the mandelic acid of the (C) mono-acidic acid compound in the present invention was changed to the composition of the composition, and a negative photosensitive resin composition was prepared. The same evaluation as in Example 1 was carried out. The result of evaluating the adhesion was 8〇' as "good". &lt;Chemical property evaluation results are the same as those of the implementation. &lt;Example 5&gt; The negative photosensitive resin group σ product was prepared by using the composition of the (c) mono-retensive compound of the present invention as the peach acid = reading in Table 1 as shown in Table 1. The same evaluation as in Example 1 was carried out. The evaluation results were the same as in Example 1. &lt;Example 6&gt; According to the composition of Table 1, 2-hydroxyisobutyric acid was used instead of the mandelic acid of the (C) monocarboxylic acid compound of the present invention, and a negative-type feeling was prepared. The same evaluation as in Example 1 was carried out. The evaluation results were the same as in the first embodiment. &lt;Example 7&gt; Cabinet According to the composition shown in Table 1, lactic acid was used instead of the compound of (c) the mono(tetra) compound of the present invention as 153046.doc-39-201140242, and the negative photosensitive property was prepared. Resin, Wei. The product was subjected to the same evaluation as in Example 1. The result of evaluation of the adhesiveness was 85, which was "good". The evaluation results of the chemical resistance were the same as those of the examples. &lt;Example 8&gt; According to the composition shown in Table 1, a non-oxyl stearic acid was used instead of the mandelic acid of the (c) monocarboxylic acid compound of the present invention, and a negative photosensitive resin composition was prepared. Evaluation was performed as in Example 1|§. The result of the evaluation is 6G, which is "slightly good". The evaluation results of Wei Xuepin's character are the same as those of the first example. &lt;Example 9&gt; In addition to the addition of the bis(ethylacetylacetic acid) titanium diisopropylate (D1) 〇"g as the (9) organic compound, the composition of the example i is the same as the implementation point &quot; A negative photosensitive resin composition was prepared in the manner. As a result of the evaluation of the chemical resistance, the change in the film thickness of the film was within ±1%, and no crack was observed, which was the "best". The evaluation result of the subsequent nature is the same as that of the example. &lt;Example 10&gt; Negative photosensitiveness was prepared in the same manner as in the Example except that the composition of Example k was further added with titanium tetra-n-propoxide (02) 0·! g as the (D) organotitanium compound. Resin composition. The film thickness change of the Yin film which was evaluated for chemical resistance was within ±1%, and no crack was observed, and the evaluation result of /best adhesion was the same as in Example 1. &lt;Example 11&gt; In addition to the composition of Example 1, bis(η5-2,4-cyclopenta-i-yl)bis(2,6-difluoro) was further added as the (D) organotitanium compound. A negative photosensitive resin composition was prepared in the same manner as in Example 311 except that benzene 153046.doc -40·201140242 dimethyl phthalate (D3) was 0.1 g. As a result of the evaluation of the chemical resistance, the film thickness of the film was changed to within ±1%, and no crack was observed, which was the "best". The evaluation result of the subsequent nature is the same as that of the embodiment. &lt;Example 12&gt; In the same manner as in Example 9, except that the polymer A 1 〇〇 g was used as the polyimide precursor in the present invention in place of the polymer A 5 〇g and the polymer B 5 〇g The negative photosensitive resin composition was prepared, and the same mussels as in Example 1 were prepared. The s parity result is the same as in the ninth embodiment. &lt;Comparative Example 1&gt; A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the mandelic acid was removed from the composition of Example 1, and the same "flat mussel" as in Example 1 was carried out. According to the above method, it is applied to a ruthenium wafer and a copper substrate, and dried, exposed, developed, and heat-treated, whereby the chemical resistance of the polyimide film obtained by the polyimide film is evaluated as "good", but Since the (C) monocarboxylic acid compound of the present invention is contained, the adhesiveness becomes 4 Å, which is "substantially bad". &lt;Comparative Example 2&gt; In addition to the composition of Comparative Example 1, bis(ethylethanoacetic acid) titanium diisopropylate (Dl)Og was added as the (D) organotitanium compound, in comparison with Comparative Example α. The negative photosensitive resin composition was prepared in the same manner, and the same method as in Example 1 was carried out. The method described in H was applied to a second wafer and a copper substrate, followed by drying, exposure, development, and heat treatment. The evaluation of the chemical resistance of the imine coating film is "best", but since it does not contain the (6) single tickic acid compound of the present invention, the adhesion becomes 0, which is "bad 153046.doc •41 · 201140242 [I ί 1 comparison Example 2 1 〇〇〇〇〇〇〇0 Poor 1 ft good 1 1 Comparative Example 1 1 〇〇〇〇〇〇〇 40 Slightly poor Example 12 〇〇〇〇〇〇〇〇〇100 Best 1 Best 1 1 Implementation Example 1 I (N 〇〇〇〇〇〇〇 O -Ofii Ξ龈 Best Practice 10 (N 〇〇〇〇〇 5 〇 100 Best Best Practice 9 1 (N 〇〇〇〇〇〇〇 100 Best 1)奸1 Example 8 〇〇〇(N d 〇〇〇60 slightly better Example 7 〇〇&lt;N 〇〇〇〇〇00 ^ I Example 6 1 〇&lt;N 〇〇〇〇〇〇100 Best 1 Example 5 1 〇〇〇〇〇〇〇100 Best Practice 4 〇〇 〇〇〇〇〇§ ^ I Example 3 1 (N 〇〇〇〇〇〇 100 Best I Example 2 1 S 〇〇〇〇〇〇〇 100 Best 1 Example 1 I 〇 (N 〇〇〇〇〇 〇〇100 Best Polymer A Polymer B Mandelic Acid 2-Hydroxyisobutyrate Lactic Acid Methyl Phenyl Acetate 5 S g Subsequent Chemical Resistance 153046.doc -42- 201140242 [Industrial Availability] The negative photosensitive resin composition of the invention can be preferably used in the field of photosensitive materials useful for the production of electrical and electronic materials such as semiconductor devices and multilayer wiring boards. 153046.doc 43-

Claims (1)

201140242 七、申請專利範圍： 1. 一種負型感光性樹脂組合物，其含有以下 之物： (A)具有下述通式⑴所示之結構之聚酿亞胺前驅物 100質量份： [化1] 〇 II -c、 OH w ιι i 7 ,C— Ri〇—C〆 II 〇 S 一0R2 o (1) {式中’Xi為4價有機基，Yi為2價有機基 ，η為2〜150之 整數’ R,及R2分別獨立為氫原子、或下述通式（2): [化2] •命 (2) (式中，R3UR5分別獨立為氫原子或碳數卜3之有機 基，並且&quot;為2〜1〇之整數）所示之】價有機基、或碳數卜4 之飽和脂肪族基；其中，R叫兩者不會同時為氫原子卜 (B) 光聚合起始劑丨〜“質量份、 (C) 具有1個以上選自由敍| 之官垂基、驗基及醋基所組成之群 之^基的碳數2〜3G之單幾酸化合物 2.:請求項〗之負型感光性樹腊組合物，其 酸化合物為選自由下述通式 ）之早羧 .^ 所不之化合物所組成之雜 中的至少1種單羧酸化合物： 战之群 153046.doc 201140242 [化3]201140242 VII. Patent Application Range: 1. A negative photosensitive resin composition containing the following: (A) 100 parts by mass of a polyanilin precursor having a structure represented by the following formula (1): 1] 〇II -c, OH w ιι i 7 , C— Ri〇—C〆II 〇S — 0R2 o (1) {wherein 'Xi is a tetravalent organic group, Yi is a divalent organic group, and η is 2 The integers of ~150, R and R2, are each independently a hydrogen atom, or the following formula (2): [Chemical 2] • Life (2) (wherein, R3UR5 is independently a hydrogen atom or a carbon number. a base, and &quot; is an integer of 2 to 1 )), a valence organic group, or a saturated aliphatic group of carbon number 4; wherein R is not a hydrogen atom at the same time (B) photopolymerization Starting agent 丨 “ "" parts by mass, (C) having one or more mono-acid compounds having a carbon number of 2 to 3 G selected from the group consisting of ruthenium, hydrazine, and vine groups. The negative photosensitive bark composition of the present invention, wherein the acid compound is at least one monocarboxylic acid compound selected from the group consisting of compounds of the early carboxylic acid of the following formula: Group 153046.doc 201140242 [Chemical 3] {式中，R6為氫原子或碳數1〜3之有機基，R7為氫原子、 碳數1〜3之烧基或Re，此處R_8為下述通式： [化4]In the formula, R6 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R7 is a hydrogen atom or a carbon group having 1 to 3 carbon atoms or Re, where R_8 is a general formula: [Chemical 4] (式中，冗丨為羥基或碳數1〜3之烷氧基，j為〇〜5之整數，益 且Z丨於存在複數個之情形時相互之間可相同亦可不同）所 示之基，R9為氫原子、碳數1〜3之烧基或碳數1〜3之烧基 羰基}。 3.如請求項1或2之負型感光性樹脂組合物，其中上述（c)之 單叛酸化合物為選自由下述通式（4)所示之化合物所組成 之群中的至少1種單羧酸化合物： [化5] OH I Rio-中一C—Ο— Η Rn〇 {式中’ Rio為風原子或碳數1〜3之有機基，Rn為氫原子、 碳數1〜3之烧基或Ri2,此處R12為下述通式： 153046.doc 201140242 [化6](wherein, the redundancy is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and j is an integer of 〇~5, and Z is the same or different when there are a plurality of cases) Further, R9 is a hydrogen atom, a carbon group having 1 to 3 carbon atoms or a carbonyl group having 1 to 3 carbon atoms}. 3. The negative photosensitive resin composition according to claim 1 or 2, wherein the mono-retensive acid compound of the above (c) is at least one selected from the group consisting of compounds represented by the following general formula (4) Monocarboxylic acid compound: [Chemical 5] OH I Rio-中一 C—Ο—Η Rn〇{wherein Rio is a wind atom or an organic group having 1 to 3 carbon atoms, Rn is a hydrogen atom, and carbon number is 1 to 3 The base or Ri2, where R12 is of the formula: 153046.doc 201140242 [Chem. 6] (式中，Z2為經基或碳數μ之絲基，❻㈠之 且Ζ2於存在複數個之情料相互之間可相同亦可不所 不之基}。 4. 5. 6. 如請求項1至3中任一項之負型感光性樹脂組合物，立中 進而含有（D)有機鈦化合物〇〇5〜1〇質量份。 如請求項4之負型感光性樹脂組合物’其中上述⑼有機欽 化合物為選自由欽螯合化合物、四院氧基鈦化合物、及 二茂鈦化合物所組成之群中的至少丨種化合物。 一種硬化浮凸圖案之製造方法，纟包括^下之步驟： ⑴藉由將如請求項⑴中任—項之負型感光性樹脂 組合物塗佈於基板上而於該基板上形成感光性樹脂層之 步驟、 (2) 對該感光性樹脂層進行曝光之步驟、 (3) 使該曝光後之感光性樹脂層顯影而形成浮凸圖案 之步驟、及 (4) 藉由加熱處理該浮凸圖案而形成硬化浮凸圖案之 步驟。 7. —種半導體裝置，其係具有藉由如請求項6之製造方法所 獲得之硬化浮凸圖案而成。 153046.doc 201140242 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式 o=-ccno °- R1 Η ,0—Ν—Υ,—Ν- Ο Η(wherein, Z2 is a mercapto group or a carbon number μ, and ❻(1) and Ζ2 may be the same or may be the same in the presence of a plurality of materials}. 4. 5. 6. The negative photosensitive resin composition of any one of the above-mentioned items (3) further contains (D) an organic titanium compound 〇〇 5 to 1 part by mass. The negative photosensitive resin composition of claim 4 is the above (9) The organic compound is at least a compound selected from the group consisting of a chelate compound, a tetrakidoxy titanium compound, and a titanocene compound. A method for producing a hardened embossed pattern includes the following steps: (1) a step of forming a photosensitive resin layer on the substrate by applying a negative photosensitive resin composition according to any one of the items (1) to a substrate, and (2) exposing the photosensitive resin layer a step of (3) developing the exposed photosensitive resin layer to form a relief pattern, and (4) a step of forming the cured relief pattern by heat-treating the relief pattern. , which has the manufacture by claim 6 The hardened embossed pattern obtained by the method is formed. 153046.doc 201140242 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If the case has In the chemical formula, please reveal the chemical formula that best shows the characteristics of the invention o=-ccno °- R1 Η , 0—Ν—Υ, —Ν- Ο Η —(-ch2^o-c-c=&lt; r3 R4 Rs (1 ) (2) 153046.doc • 1·—(-ch2^o-c-c=&lt; r3 R4 Rs (1 ) (2) 153046.doc • 1·