TW200910007A

TW200910007A - Photosensitive resin composition, photosensitive element, method of forming resist pattern, and process for producing printed wiring board

Info

Publication number: TW200910007A
Application number: TW097117345A
Authority: TW
Inventors: Kuniaki Sato; Toshizumi Yoshino; Masaya Ookawa; Takahiro Hidaka; Hideyasu Tsuiki
Original assignee: Hitachi Chemical Co Ltd
Priority date: 2007-05-11
Filing date: 2008-05-09
Publication date: 2009-03-01
Also published as: CN101675388B; KR101139561B1; JP4985767B2; CN102621810A; CN102621810B; TWI398728B; JPWO2008140016A1; WO2008140016A1; CN101675388A; KR20100009548A

Abstract

A photosensitive resin composition comprising (A) an acid-modified vinyl-containing epoxy resin, (B) a photopolymerization initiator containing a compound having an oxime ester bond and (C) a sensitizer containing any of coumarin compounds of the following general formula (1).

Description

200910007 九、發明說明【發明所屬之技術領域】本發明係關於感光性樹脂組成物、感光性元件、光阻圖形之形成方法及印刷配線板之製造方法。【先前技術】以往，印刷配線板製造中之永久遮罩光阻係以熱或紫外線硬化型之光阻油墨用網版印刷之方法所製成。近年、伴隨電子裝置高集積化，在印刷配線板有要求配線圖型或絕緣圖型之高精細化必要。但是，使用以往之網版印刷的光阻形成法在印刷時會產生滲露、下垂等，所以在形成高精細光阻像係爲困難。因此、爲形成高精細光阻像，開發出藉由光微影術之光阻像形成法。具體上，使乾膜型之感光性光阻熱壓著於基材上，或使液狀之感光性光阻淋幕塗佈或噴霧塗佈於基材上，使紫外線等活性光線介著負像掩模進行照射後，藉由顯像進行光阻像之形成。乾膜型之感光性光阻之情況，對基材熱壓著時，捲入空氣而易產生氣泡，因此有產生密著性降低或光阻像混亂，而光阻性能降低之疑慮。另外，液狀之感光性光阻有溶劑顯像型與鹼顯像型，但由作業環境安全'地球環境安全之觀點來看，鹼顯像型成爲主流。如此之鹼顯像型之感光性光阻（感光性樹脂組成物）已知有下述專利文獻1及2所示般者。又，以提升塗膜之耐熱性、耐藥品性、電特性爲目的，對塗膜更進行 -5- 200910007 紫外線曝光或加熱，亦進行促進交聯反應者。而，光阻圖形之形成方法方面，可舉例如不使用遮罩圖型，直接描畫光阻圖形，亦即直接描畫曝光法受到注目。根據此直接描畫曝光法，可高生產性且以高解像度形成光阻圖形。接著，近年、發射波長405nm之雷射光，以長壽命高輸出之氮化鎵系藍色雷射光源可實用地利用作爲光源，直接描畫曝光法中，藉由利用如此短波長之雷射光，期待以往製造困難之高密度光阻圖形之形成成爲可能。如此直接描畫曝光法方面，可舉例如由Ball Semiconductor公司戶斤提案 Texas Instruments公司提倡之應用 DLP ( Digital Light Processing)系統之方法，適用此方法之曝光装置的實用化已經開始。進而，使用上述般藍色雷射等雷射作爲活性光線經由直接描畫曝光法以使光阻圖形形成之感光性樹脂組成物到如今也提出數種（如，專利文獻3、4作參照）。 [專利文獻1]特開昭6 1 -243 8 69號公報 [專利文獻2]特開平1 - 1 4 1 904號公報 [專利文獻3]特開20〇2-296764號公報 [專利文獻4]特開20〇4-45 5 96號公報【發明內容】 [發明所欲解決之課題] 然而，上述專利文獻3及4所記載之感光性樹脂組成物，使用直接描畫曝光法時等，在使用波長405nm附近 200910007 之曝光光的光阻圖形形成時之感度可更改善。本發明爲有鑑於上述先前技術之課題而成，以提供使用波長370nm〜450nm之範圍內之曝光光，於形成光阻圖形時之感度優的感光性樹脂組成物、使用其之感光性元件、光阻圖形之形成方法及印刷配線板之製造方法爲目的。 [爲解決課題之手段] 爲達成上述目的，本發明係提供含有（A)含乙烯基之酸改性環氧樹酯、（B )含具有肟酯鍵結之化合物的光聚合起始劑、（C)含下述一般式（1)所表示之香豆素化合物之增感劑的感光性樹脂組成物。[Technical Field] The present invention relates to a photosensitive resin composition, a photosensitive element, a method for forming a photoresist pattern, and a method for producing a printed wiring board. [Prior Art] Conventionally, a permanent mask resist in the manufacture of a printed wiring board has been produced by a screen printing method using a heat or ultraviolet curable photoresist. In recent years, with the high integration of electronic devices, it is necessary to have a high definition of a wiring pattern or an insulation pattern on a printed wiring board. However, the photoresist formation method using the conventional screen printing causes bleeding, sagging, and the like during printing, so that it is difficult to form a high-definition photoresist image system. Therefore, in order to form a high-definition photoresist image, a photo-resist image formation method by photolithography has been developed. Specifically, the dry film type photosensitive photoresist is heat-pressed on the substrate, or the liquid photosensitive photoresist is coated or spray coated on the substrate to make the active light such as ultraviolet rays negative. After irradiation like a mask, formation of a photoresist image is performed by development. In the case of the photosensitive film of the dry film type, when the substrate is heat-pressed, air is trapped and air bubbles are easily generated, so that there is a concern that the adhesion is lowered or the photoresist image is disordered, and the photoresist performance is lowered. In addition, the liquid photosensitive photoresist has a solvent development type and an alkali development type, but the alkali development type is the mainstream from the viewpoint of the safety of the working environment. A photosensitive resist (photosensitive resin composition) of the above-described alkali-developing type is known as described in Patent Documents 1 and 2 below. In addition, for the purpose of improving the heat resistance, chemical resistance, and electrical properties of the coating film, the coating film is further exposed to ultraviolet light or heated, and the crosslinking reaction is also promoted. Further, as for the method of forming the photoresist pattern, for example, the photoresist pattern can be directly drawn without using a mask pattern, that is, the direct drawing exposure method is attracting attention. According to this direct drawing exposure method, it is possible to form a photoresist pattern with high productivity and high resolution. Next, in recent years, a laser beam having a wavelength of 405 nm is emitted, and a gallium nitride-based blue laser light source having a long life and a high output can be practically used as a light source. In the direct exposure method, it is expected to use such a short-wavelength laser light. The formation of high-density photoresist patterns that have been difficult to manufacture in the past has become possible. As for the direct exposure method, for example, a method of applying a DLP (Digital Light Processing) system promoted by Texas Semiconductor is proposed by the company of the semiconductor, and the practical use of the exposure apparatus using the method has begun. Further, a photosensitive resin composition using a laser such as the above-described blue laser as the active light to form a resist pattern by a direct drawing exposure method has been proposed (for example, refer to Patent Documents 3 and 4). [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. H20-296764 (Patent Document 4) [Problems to be Solved by the Invention] However, the photosensitive resin composition described in Patent Documents 3 and 4 is used when a direct drawing exposure method is used. The sensitivity of the photoresist pattern of the exposure light of 200910007 near the wavelength of 405 nm can be further improved. The present invention has been made in view of the above-described problems of the prior art, and provides a photosensitive resin composition excellent in sensitivity when forming a photoresist pattern using exposure light in a wavelength range of 370 nm to 450 nm, and a photosensitive element using the same. A method of forming a photoresist pattern and a method of manufacturing a printed wiring board are aimed. [Means for Solving the Problems] In order to achieve the above object, the present invention provides a photopolymerization initiator containing (A) a vinyl group-containing acid-modified epoxy resin, (B) a compound having a oxime ester-bonded compound, (C) A photosensitive resin composition containing a sensitizer of the coumarin compound represented by the following general formula (1).

〔式（1)中，Z1表示鹵原子、碳數1〜20之烷基、碳數 3〜10之環院基、碳數6〜14之芳基、胺基、碳數1〜1〇之烷基胺基、碳數1〜2 〇之二烷基胺基、锍基、碳數1〜 1 0之烷基锍基、烯丙基、碳數1〜2 0之羥基烷基、羧基、烷基之碳數係1〜1 〇之羧基烷基、烷基之碳數係〗〜1 0 之醯基、碳數1〜20之烷氧基、碳數1〜20之烷氧基羰基、或、含雜環之基’ Z2表示鹵原子、碳數1〜20之烷基、碳數3〜10之環烷基、碳數6〜14之芳基、胺基、碳數 1〜1 0之烷基胺基、碳數1〜20之二烷基胺基、锍基、碳 200910007 數1〜1 〇之烷基巯基、烯丙基、碳數1〜2 0之羥基院基之碳數係1〜10之醯基、碳數1〜20之院氧基環之基、或、下述一般式（2)所表示之基，s爲0 整數。又，式（2)中之Ζ1及s與式（1)中之Ζ1 義相同。又’式（1)中之Ζ1及s與式（2)中之可各自相同或相異。進而，式（1)或式（2)中，以上時，複數存在之Ζ1可各自相同或相異、任二相鍵結形成環。〕 mi 烷基、、含雜〜4之及s定 Z1及s s爲2 者可互[In the formula (1), Z1 represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, a ring-membered group having a carbon number of 3 to 10, an aryl group having 6 to 14 carbon atoms, an amine group, and a carbon number of 1 to 1%. An alkylamino group, a dialkylamino group having 1 to 2 carbon atoms, a fluorenyl group, an alkyl fluorenyl group having 1 to 10 carbon atoms, an allyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, The carbon number of the alkyl group is a carboxyalkyl group of 1 to 1 fluorene, a carbon number of the alkyl group is a fluorenyl group of 1 to 10, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, Or a heterocyclic group-containing Z' represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amine group, and a carbon number of 1 to 1 0. Alkylamino group, carbon number 1 to 20 dialkylamino group, fluorenyl group, carbon 200910007 number 1 to 1 fluorene alkyl fluorenyl group, allyl group, carbon number 1 to 2 0 hydroxy group And a base represented by the following general formula (2), wherein s is an integer of 0. Further, Ζ1 and s in the formula (2) are the same as Ζ1 in the formula (1). Further, Ζ1 and s in the formula (1) and the formula (2) may be the same or different from each other. Further, in the above formula (1) or (2), in the above, the plural Ζ1 may be the same or different, and any two-phase bond may form a ring. 〕 mi alkyl, 含～ 4 and s Z1 and s s are 2

根據該感光性樹脂組成物，藉由含有（A )含之酸改性環氧樹酯、及、（B )含具有肟酯鍵結之的光聚合起始劑、與（C )上述一般式（1 )所表示豆素化合物之增感劑，在使用波長3 70nm〜45 0nm 內之曝光光的光阻圖形之形成、尤其係，使用波長之雷射光的直接描畫曝光法的光阻圖形之形成以優及解像度進行。進而，根據具有上述構成之本發明之感光性樹物，可形成在耐熱性、耐濕熱性、密著性、機械特特性優異之高性能的硬化膜，可適用於印刷配線板度多層板及半導體封裝等之製造。乙烯基化合物之含香之範圍 405nm 異感度脂組成性、電、高密 200910007 又，本發明之感光性樹脂組成物以更含（D )具有硫醇基之化合物爲佳。藉由含上述（D )具有硫醇基之化合物，可充分抑制感光性樹脂組成物經時膠體化，提高經日安定性。又，本發明之感光性樹脂組成物中，上述具肟酯鍵結之化合物以含下述一般式（3 )或（4 )所表示之化合物之至少一種者爲佳。According to the photosensitive resin composition, the (A)-containing acid-modified epoxy resin, and (B) the photopolymerization initiator having a oxime ester-bonded bond, and (C) the above general formula (1) The sensitizer of the soy compound represented by the formation of a photoresist pattern of exposure light having a wavelength of from 3 to 70 nm to 45 nm, in particular, a photoresist pattern of a direct drawing exposure method using a laser light of a wavelength The formation is performed with excellent resolution. Further, according to the photosensitive tree of the present invention having the above-described configuration, it is possible to form a high-performance cured film excellent in heat resistance, moist heat resistance, adhesion, and mechanical characteristics, and is applicable to a printed wiring board multilayer board and Manufacturing of semiconductor packages and the like. The range of the fragrant compound of the vinyl compound is 405 nm. The sensibility of the fat is constitutive, electrically, and dense. Further, the photosensitive resin composition of the present invention preferably contains (D) a compound having a thiol group. By containing the above compound (D) having a thiol group, it is possible to sufficiently suppress the gelation of the photosensitive resin composition over time and improve the stability over time. Further, in the photosensitive resin composition of the present invention, the oxime ester-bonded compound is preferably at least one of the compounds represented by the following general formula (3) or (4).

(R4)m3 〔式（3)中，Ri表示碳數2〜12之取代或未取代之鏈烷醯基、雙鍵係不與羰基共軛之碳數4〜6之取代或未取代之鏈烯醯基、取代或未取代之苯甲醯基、碳數2〜6々而 <取代或未取代之烷氧基羰基、或、取代或未取代之苯氧基羰基，R2、R3及R4各自獨立，表示鹵原子、碳數^丨^之取代或未取代之烷基、取代或未取代之環戊基、取代或未取代之環己基、取代或未取代之苯基、取代或未取代之苄基、取代或未取代之苯甲醯基、碳數2〜12之取代戌未代之鏈烷醯基、碳數2〜12之取代或未取代之烷氧基羰基、或、取代或未取代之苯氧基羰基，表 η 4之整齡 200910007 ，m2及m3各自獨立，表示〇〜5之整數。又，以爲2以上時，複數存在之R2可各自相同或相異，1112爲2以上時，複數存在之R3可各自相同或相異，m3爲2以上時，複數存在之R4可各自相同或相異。] [化4](R4)m3 [In the formula (3), Ri represents a substituted or unsubstituted alkane fluorenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted chain having a carbon number of 4 to 6 which is not conjugated to a carbonyl group. An fluorenyl group, a substituted or unsubstituted benzinyl group, a carbon number of 2 to 6 Å and a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted phenoxycarbonyl group, R2, R3 and R4 Each independently represents a halogen atom, a substituted or unsubstituted alkyl group having a carbon number, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted group. a benzyl group, a substituted or unsubstituted benzyl group, a substituted carbon of 2 to 12, an alkane fluorenyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, or a substituted or The unsubstituted phenoxycarbonyl group, the whole age of the table η 4 200910007, m2 and m3 are each independently, and represent an integer of 〇~5. Further, when it is 2 or more, R2 in the plural number may be the same or different, and when 1112 is 2 or more, R3 in the plural may be the same or different, and when m3 is 2 or more, R4 in the plural may be the same or in phase. different. ] [Chemical 4]

〔式（4 )中，R5表示取代或未取代之苯基、碳數丨〜6 之取代或未取代之烷基、取代或未取代之苯基、碳數丨〜 2 0之取代或未取代之烷基、碳數5〜8之取代或未取代之環烷基 '碳數2〜20之取代或未取代之鏈烷醯基、或、取代或未取代之苯甲醯基，R6表示碳數2〜12之取代或未取代之鏈烷醯基、雙鍵係不與羰基共軛之碳數4〜6之取代或未取代之鏈烯醯基、取代或未取代之苯甲醯基 '碳數 2〜6之取代或未取代之烷氧基羰基、或、取代或未取代之本氧基羰基，R7表示氫原子、鹵原子、碳數1〜12之取代或未取代之烷基、取代或未取代之環戊基、取代或未取代之環己基、取代或未取代之苯基、取代或未取代之苄基取代或未取代之苯甲醯基、碳數2〜12之取代或未取代之鏈烷醯基、碳數2〜1 2之取代或未取代之烷氧基羰基或、取代或未取代之苯氧基羰基，R8、R9及各自獨 -10- 200910007 丛，表不鹵原子、碳數1〜1 2之取代或未取代之烷基、取代或未取代之環戊基、取代或未取代之環己基、取代或未取代之苯基、取代或未取代之苄基、取代或未取代之苯甲酿基、碳數2〜12之取代或未取代之鏈烷醯基、碳數2〜 1 2之取代或未取代之院氧基簾基、或、取代或未取代之本氧基羰基’ m4及m5各自獨立，表示〇〜3之整數，m6 表示0〜5之整數。又，m4爲2以上時，複數存在之R8 可各自相同或相異’ m5爲2以上時，複數存在之R9可各自相同或相異，m6爲2以上時，複數存在之R1()可各自相同或相異。〕作爲（B)光聚合起始劑，藉由含有上述一般式（3) 或（4 )所表示之具肟酯鍵結之化合物，感光性樹脂組成物可令使用波長3 70nm〜45 0nm之範圍內之曝光光的光阻圖形之形成、尤其係，使用波長40 5nm之雷射光的直接描畫曝光法之光阻圖形之形成以更優異感度及解像度進行〇又，本發明之感光性樹脂組成物中、上述（A )含乙烯基之酸改性環氧樹酯以下述一般式（5)所表示之酚醛型環氧樹脂、下述一般式（6)所表示之雙酚型環氧樹脂、及、下述一般式（7 )所表示之水楊醛型環氧樹脂所成群選出之至少1種之環氧樹脂（a)與含乙烯基單羧酸（b )進行反應所得之樹脂爲佳。 -11 - 200910007 [化5] Ο—Υ1 ο—Υ1 ο—Υ1[In the formula (4), R5 represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkyl group having a carbon number of 丨~6, a substituted or unsubstituted phenyl group, a substituted or unsubstituted carbon number 丨~2 0 An alkyl group, a substituted or unsubstituted cycloalkyl group having 5 to 8 carbon atoms, a substituted or unsubstituted alkane group having 2 to 20 carbon atoms, or a substituted or unsubstituted benzamidine group, and R6 represents carbon a substituted or unsubstituted alkane fluorenyl group of 2 to 12, a double bond of a substituted or unsubstituted olefinic fluorenyl group having a carbon number of 4 to 6 which is not conjugated to a carbonyl group, or a substituted or unsubstituted benzamyl group a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted oxycarbonyl group, and R 7 represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl substituted or unsubstituted benzamyl group, a carbon number 2 to 12 substitution or Unsubstituted alkane fluorenyl group, substituted or unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, substituted or unsubstituted phenoxycarbonyl group, R8, R9 and From -10-200910007, a non-halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted group a phenyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted alkane fluorenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted carbon number of 2 to 12 The oxyl group, or the substituted or unsubstituted oxycarbonyl group 'm4 and m5' are each independently, and represent an integer of 〇~3, and m6 represents an integer of 0 to 5. Further, when m4 is 2 or more, R8 in the plural number may be the same or different. When m5 is 2 or more, R9 in the plural may be the same or different, and when m6 is 2 or more, R1() in the plural may be used. Same or different. As the (B) photopolymerization initiator, the photosensitive resin composition can be used at a wavelength of from 3 70 nm to 45 nm by containing a compound having a oxime ester bond represented by the above general formula (3) or (4). The formation of the photoresist pattern of the exposure light in the range, in particular, the formation of the photoresist pattern using the direct drawing exposure method using the laser light having a wavelength of 40 5 nm, which is performed with more excellent sensitivity and resolution, and the photosensitive resin composition of the present invention The phenolic epoxy resin represented by the following general formula (5) and the bisphenol epoxy resin represented by the following general formula (6), the (A) vinyl-containing acid-modified epoxy resin And a resin obtained by reacting at least one epoxy resin (a) selected from the group of salicylaldehyde type epoxy resins represented by the following general formula (7) with a vinyl group-containing monocarboxylic acid (b) It is better. -11 - 200910007 [化5] Ο—Υ1 ο—Υ1 ο—Υ1

〔式（5)中，R11表示氫原子或甲基，Υ1表示氫原子或縮水甘油基（但，氫原子/縮水甘油基（莫耳比）爲〇/ 100〜30/70) ，nl表示1以上之整數。又，複數存在之 R11及Y1可各自相同或相異。〕 [化6][In the formula (5), R11 represents a hydrogen atom or a methyl group, and Υ1 represents a hydrogen atom or a glycidyl group (however, the hydrogen atom/glycidyl group (mole ratio) is 〇/100 to 30/70), and nl represents 1 The above integer. Further, R11 and Y1 in the plural may be the same or different. 〕 [Chemistry 6]

〔式（6)中，R12表示氫原子或甲基，Y2表示氫原子或縮水甘油基（但，氫原子/縮水甘油基（莫耳比）爲〇 / 100〜30/70) ，n2表示1以上之整數。又，複數存在之 R12及Y2可各自相同或相異。〕 -12 - 200910007 [化7〕[In the formula (6), R12 represents a hydrogen atom or a methyl group, and Y2 represents a hydrogen atom or a glycidyl group (however, a hydrogen atom/glycidyl group (mole ratio) is 〇/100 to 30/70), and n2 represents 1 The above integer. Further, R12 and Y2 in the plural may be the same or different. 〕 -12 - 200910007 [化7]

〔式（7)中，Y3表示氫原子或縮水甘油基（但，氫原子 /縮水甘油基（莫耳比）爲〇 / 1 〇〇〜3 0 / 70 ) ，η3表示 1以上之整數。又，複數存在之R11及Υ3可各自相同或相異。〕藉由使用相關（A )含乙烯基之酸改性環氧樹酯，感光性樹脂組成物可令使用波長3 7 0 n m〜4 5 0 n m之範圍內之曝光光的光阻圖形之形成、尤其係，使用波長40 5 nm之雷射光的直接描畫曝光法之光阻圖形之形成以更優異感度及解像度進行。又，本發明係提供具備支持體、於該支持體上所形成之上述本發明之感光性樹脂組成物所成之感光性樹脂組成物層的感光性元件。根據該感光性元件，藉由具備上述本發明之感光性樹脂組成物所成之感光性樹脂組成物層，可令使用波長 370nm〜450nm之範圍內之曝光光的光阻圖形之形成、尤其係，使用波長405 nm之雷射光的直接描畫曝光法之光阻圖形之形成以優異感度及解像度進行。 -13- 200910007 又，本發明係提供包含使上述本發明之感光性樹脂組成物所成之感光性樹脂組成物層於基板上層合之層合步驟、於上述感光性樹脂組成物層使活性光線以圖像狀進行照射，使曝光部光硬化之曝光步驟、使上述感光性樹脂組成物層之未曝光部經顯像除去之顯像步驟的光阻圖形之形成方法。在此，上述曝光步驟以經由波長4 0 5 n m之雷射光使上述感光性樹脂組成物層直接描畫曝光，令曝光部光硬化之步驟爲佳。根據該光阻圖形之形成方法，因使用經直接描畫曝光法的光阻圖形形成時之感度優異的上述本發明之感光性樹脂組成物，可有效率形成解像度優異光阻圖形。又，該方法形成之光阻圖形成爲耐熱性、耐濕熱性、密著性、機械特性、電特性優異的高性能硬化膜。本發明進而提供一種印刷配線板之製造方法，其係使經上述本發明之光阻圖形之形成方法形成有光阻圖形之電路形成用基板進行蝕刻或鑛敷。根據該印刷配線板之製造方法，因經由上述本發明之光阻圖形之形成方法形成光阻圖形，可實現配線之高密度化。 [發明效果] 根據本發明’可提供一種感光性樹脂組成物，其於使用波長3 70nm〜4 5 0nm之範圍內之曝光光的光阻圖形形成 -14- 200910007 時、尤其係，使用波長405nm之雷射光的直接描晝曝光法之光阻圖形形成時之感度優異、及使用其之感光性元件、光阻圖形之形成方法及印刷配線板之製造方法。又，根據本發明之感光性樹脂組成物及感光性元件，在以波長 40 5nm之藍色雷射光爲光源之直接描畫曝光法中，可形成以往製造困難的高密度光阻圖形，且可得到耐熱性、耐濕熱性（剪斷接著性）、密著性、機械特性、電特性優異之高性能硬化膜。因此、本發明之感光性樹脂組成物及感光性元件適用於印刷配線板、高密度多層板及半導體封裝等之製造。 [實施發明之最佳形態] 以下、依狀況參考圖式詳細說明本發明之較佳實施形態。又，圖式中’相同或相當部分以同一符號表示，省略重複之說明。又，本發明中（甲基）丙烯酸係指丙烯酸及對應其之甲基丙烯酸’（甲基）丙烯酸酯係指丙烯酸酯及對應其之甲基丙烯酸酯。本發明之感光性樹脂組成物係含有（A )含乙烯基之酸改性環氧樹酯（以下’依情況稱「（ A )成分」）、（ B )含具有肟酯鍵結之化合物的光聚合起始劑（以下，依情況稱「（ B )成分」）、（c )上述一般式（1)所表示之含香豆素化合物之增感劑（以下，依情況稱「（ C )成分」）’較佳爲更含有（D)具有硫醇基之化合物（以下 ’依情況稱「（ D )成分」）。以下、詳細說明有關各成 -15- 200910007 分。本發明所用之（A)含乙烯基之酸改性環氧樹酯方面 ’雖可使用將環氧樹脂以含乙烯基單羧酸改性之樹脂，較 “爲使用τι至少1種選自下述一般式（5)所表示之酸醒型環氧樹脂、下述一般式（6)所表示之雙酚A型環氧樹月曰或雙 F型環氧樹脂、及、下述一般式（？）所表示之水楊醒型環氧樹脂所成群之環氧樹脂（a)、與含乙儲基單羧酸（b )進行反應所得之樹脂。 [化8]In the formula (7), Y3 represents a hydrogen atom or a glycidyl group (however, the hydrogen atom/glycidyl group (mole ratio) is 〇 / 1 〇〇〜 3 0 / 70 ), and η 3 represents an integer of 1 or more. Further, R11 and Υ3 in the plural may be the same or different. 〕 By using the related (A) vinyl-containing acid-modified epoxy resin, the photosensitive resin composition can form a photoresist pattern using exposure light in a wavelength range of 370 nm to 4500 nm. In particular, the formation of a photoresist pattern using a direct drawing exposure method using laser light having a wavelength of 40 5 nm is performed with more excellent sensitivity and resolution. Furthermore, the present invention provides a photosensitive element comprising a support and a photosensitive resin composition layer of the photosensitive resin composition of the present invention formed on the support. According to the photosensitive element, the photosensitive resin composition layer formed of the photosensitive resin composition of the present invention can form a photoresist pattern using exposure light in a wavelength range of 370 nm to 450 nm, in particular, The formation of a photoresist pattern using a direct drawing exposure method using laser light having a wavelength of 405 nm is performed with excellent sensitivity and resolution. Further, the present invention provides a laminating step of laminating a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention on a substrate, and an active ray in the photosensitive resin composition layer. A method of forming a photoresist pattern by irradiation in an image form, an exposure step of photocuring the exposed portion, and a developing step of removing the unexposed portion of the photosensitive resin composition layer by development. Here, in the above-mentioned exposure step, the photosensitive resin composition layer is directly drawn and exposed by laser light having a wavelength of 4 0 5 nm, and the step of photohardening the exposed portion is preferable. According to the method for forming a photoresist pattern, the photosensitive resin composition of the present invention having excellent sensitivity when formed by using a resist pattern by direct drawing exposure can efficiently form a photoresist pattern having excellent resolution. Further, the photoresist pattern formed by this method is a high-performance cured film excellent in heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties. Further, the present invention provides a method of producing a printed wiring board which is subjected to etching or mineralization by a circuit for forming a circuit on which a photoresist pattern is formed by the method for forming a photoresist pattern of the present invention. According to the method for producing a printed wiring board, the photoresist pattern can be formed by the above-described method for forming a photoresist pattern of the present invention, whereby the wiring can be made denser. [Effect of the Invention] According to the present invention, it is possible to provide a photosensitive resin composition which is formed by using a photoresist pattern of exposure light in a range of from 3 to 70 nm to 450 nm, and in particular, a wavelength of 405 nm is used. The photosensitive light-sensitive pattern of the direct scanning exposure method of the laser light is excellent in sensitivity, a photosensitive element using the same, a method of forming a photoresist pattern, and a method of manufacturing a printed wiring board. Further, according to the photosensitive resin composition and the photosensitive element of the present invention, in the direct drawing exposure method using blue laser light having a wavelength of 40 5 nm as a light source, a high-density photoresist pattern which is difficult to manufacture in the past can be formed and obtained. A high-performance cured film excellent in heat resistance, heat and humidity resistance (shear adhesion), adhesion, mechanical properties, and electrical properties. Therefore, the photosensitive resin composition and the photosensitive element of the present invention are suitable for use in the production of printed wiring boards, high-density multilayer boards, and semiconductor packages. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding portions are denoted by the same reference numerals, and the description thereof will be omitted. Further, in the present invention, (meth)acrylic acid means acrylic acid and methacrylic acid corresponding to methacrylate means acrylate and methacrylate corresponding thereto. The photosensitive resin composition of the present invention contains (A) a vinyl-containing acid-modified epoxy resin (hereinafter referred to as "(A) component)", and (B) a compound having an oxime ester-bonded compound. Photopolymerization initiator (hereinafter, referred to as "(B) component"), (c) a coumarin-containing sensitizer represented by the above general formula (1) (hereinafter, referred to as "(C) The component ") is preferably further contained (D) a compound having a thiol group (hereinafter referred to as "(D) component"). The following is a detailed description of each -15-200910007 points. (A) For the vinyl group-containing acid-modified epoxy resin used in the present invention, it is possible to use a resin modified with a vinyl group-containing monocarboxylic acid, and at least one selected from the group consisting of τι The acid-awake type epoxy resin represented by the general formula (5), the bisphenol A type epoxy resin or the double F type epoxy resin represented by the following general formula (6), and the following general formula ( ?) The epoxy resin (a) in the group represented by the water-yang epoxy resin and the resin obtained by reacting the ethyl group-containing monocarboxylic acid (b).

〔式（5)中’ Rii表示氫原子或甲基，γ1爲氫原子或縮水甘油基（但，氫原子/縮水甘油基（莫耳比）爲〇 / 100〜30/70) ，ni表示以上之整數。又，複數存在之 R11及Y1可各自相同或相異。〕 -16 - 200910007 [化9][In the formula (5), ' Rii represents a hydrogen atom or a methyl group, and γ1 is a hydrogen atom or a glycidyl group (however, a hydrogen atom/glycidyl group (mole ratio) is 〇/100 to 30/70), and ni represents the above. The integer. Further, R11 and Y1 in the plural may be the same or different. 〕 -16 - 200910007 [Chemistry 9]

-Ο η2 表示氫原子或耳比）爲〇/ ’複數存在之〔式（6)中’ R”表示氫原子或甲基’ γ2 縮水甘油基 100〜30/ 70 )，n2表示！以上之整數。又 R12及Y2可各自相同或相異。 [化 10]- Ο η2 represents a hydrogen atom or an ear ratio) is 〇 / 'the plural is present [in the formula (6), 'R' represents a hydrogen atom or a methyl 'γ2 glycidyl group 100~30/70), and n2 represents an integer above R12 and Y2 may each be the same or different. [10]

〔式（7)中Y表示氫原子或縮水甘油基（但，氫原子 /縮水甘油基（吴耳比）爲〇/1〇〇〜3〇/7〇) ，d表示以上之整j又，複數存在之R11及γ3可各自相同或相異。〕本發明所用之（A )含乙烯基之酸改性環氧樹酯除上 -17- 200910007 述環氧樹脂（a)與含乙烯基單羧酸（b)之反應生成物（以下、稱「反應性生成物（A ’）」）外’亦可使用於該反應生成物（A’）加成上含飽和或不飽和基之多元酸酐（c )之加成反應生成物。在此，於加成反應生成物合成時’ 在最初之反應，藉由環氧樹脂（a)之環氧基與含乙烯基單羧酸（b)之羧基之加成反應形成羥基，在接下來的反應，推測生成之羥基（亦包含環氧樹脂（a )中原來具有之羥基）與含飽和或不飽和基之多元酸酐（c)之酸酐基進行半酯反應者。上述一般式（5)所表示之酚醛型環氧樹脂方面，可舉例如苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂。此等酚醛型環氧樹脂各自可以公知之方法使苯酚醛樹脂、甲酣酵樹脂與表氯醇進行反應而得到。又，上述一般式（6 )所表示之化合物中、γ2係縮水甘油基的雙酣A型環氧樹脂或雙酣F型環氧樹脂可經由如’下述一般式（8)所表示之雙酚A型環氧樹脂或雙酌 F型環氧樹脂之羥基與表氯醇進行反應而得。 -18 - 200910007 [化 11][In the formula (7), Y represents a hydrogen atom or a glycidyl group (however, the hydrogen atom/glycidyl group (Wer's ratio) is 〇/1〇〇~3〇/7〇), and d represents the above R11 and γ3 in the plural may be the same or different. 〕 (A) a vinyl-containing acid-modified epoxy resin used in the present invention, except for the reaction product of the epoxy resin (a) and the vinyl-containing monocarboxylic acid (b) of -17-200910007 (hereinafter, referred to as The "reactive product (A ')") can also be used as an addition reaction product of the polybasic acid anhydride (c) containing a saturated or unsaturated group in the reaction product (A'). Here, when the addition reaction product is synthesized, the initial reaction is carried out by the addition reaction of the epoxy group of the epoxy resin (a) with the carboxyl group of the vinyl group-containing monocarboxylic acid (b) to form a hydroxyl group. The reaction to be carried out is presumed to be a half ester reaction of the resulting hydroxyl group (which also contains the hydroxyl group originally contained in the epoxy resin (a)) and the acid anhydride group of the polybasic acid anhydride (c) having a saturated or unsaturated group. The phenolic epoxy resin represented by the above general formula (5) may, for example, be a phenol novolak type epoxy resin or a cresol novolac type epoxy resin. Each of the phenolic epoxy resins can be obtained by reacting a phenol resin, a formazan resin and epichlorohydrin by a known method. Further, among the compounds represented by the above general formula (6), a bis 2 A glycidyl group-containing bismuth A type epoxy resin or a big fluorene F type epoxy resin may be via a double represented by the following general formula (8). The hydroxyl group of the phenol A type epoxy resin or the double type F epoxy resin is obtained by reacting with epichlorohydrin. -18 - 200910007 [化11]

〔式（8)中’R12表示氫原子或甲基，n2表示1以上之整數。又’複數存在之R12可各自相同或相異。〕爲促進羥基與表氯醇之反應，以在反應溫度5 〇〜1 2 〇 C ’驗金屬氫氧化物存在下，在二甲基甲醯胺、二甲基乙醯胺、二甲基亞颯等極性有機溶劑中進行反應爲佳。反應溫度未達5 0 °C則反應變慢，反應溫度超過1 2 0 t：，則產生多量副反應，故不佳。上述一般式（7)所表示之水楊醛型環氧樹脂方面，可舉例如具體上可舉例 FAE-25 00、EPPN-501H、EPPN_ 5 02H (以上、日本化藥（股）製、商品名）等。又，含乙烯基單羧酸（b)方面，可舉例如，丙燦酸、丙烯酸之二聚物、甲基丙烯酸、/3-糠基丙烯酸、卢-苯乙烯基丙烯酸、桂皮酸、巴豆酸、〇；-氰桂皮酸等，又，可舉例含羥基之丙烯酸酯與飽和或不飽和二元酸酐之反應生成物的半酯化合物、含乙烯基之單縮水甘油醚或含乙烯 -19- 200910007 基之單縮水甘油酯與飽和或不飽和二元酸酐亦即半酯化合物。此等半酯化合物係藉由使酸酯、含乙烯基之單縮水甘油醚或含乙烯基酯與飽和或不飽和二元酸酐以等莫耳比進行等含乙烯基單羧酸（b )可1種單獨或2種〇含乙烯基單羧酸（b ) —例，即上述半所用之含羥基之丙烯酸酯、含乙烯基之單縮乙烯基之單縮水甘油酯方面，可舉例如羥基、羥基乙基甲基丙烯酸酯、羥基丙基丙烯酸甲基丙烯酸酯、羥基丁基丙烯酸酯、羥基丁酯、聚乙二醇單丙烯酸酯、聚乙二醇單甲基羥甲基丙烷二丙烯酸酯、三羥甲基丙烷二甲季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯四醇五丙烯酸酯、季戊四醇五甲基丙烯酸酯烯酸酯、縮水甘油甲基丙烯酸酯等。上述半酯化合物合成所用之飽和或不飽面，可舉例如琥拍酸酐、馬來酸酐、四氫(苯二甲酸酐、甲基四氫苯二甲酸酐、乙基四氫六氫苯二甲酸酐、甲基六氫苯二甲酸酐、乙酸酐、衣康酸酐等。環氧樹脂（a)與含乙烯基單羧酸（b) 相對於環氧樹脂（a )之環氧基1當量，含 (b)成爲0.6〜1.05當量之比例進行反應之反應生成物含羥基之丙烯之單縮水甘油反應而得。此以上組合使用酯化合物合成水甘油醚、含乙基丙烯酸酯酯、羥基丙基基甲基丙烯酸丙烯酸酯、三基丙烯酸酯、酸酯、二季戊、縮水甘油丙和二元酸酐方二甲酸酐、苯苯二甲酸酐、基六氫苯二甲之反應中，以乙烯基單羧酸爲佳，以成爲 -20- 200910007 0.8〜1.05當量之比例進行反應更佳，以成爲〇.9〜n.o當量之比例進行反應特別佳。環氧樹脂（a )與含乙烯基單羧酸（b )以溶於有機溶劑以進行反應爲佳。有機溶劑方面，可舉例如乙基甲基酮、環己酮等酮類、甲苯、二甲苯、四甲基苯等芳香族烴類、甲基溶纖劑、丁基溶纖劑、甲基卡必醇、丁基卡必醇、丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二乙基醚、三乙二醇單乙基醚等乙二醇醚類、乙酸乙酯、乙酸丁酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯等酯類、辛烷、癸烷等脂肪族烴類、石油醚、石腦油、氫化石腦油、溶煤石油精等石油系溶劑等。進而，爲促進反應以使用觸媒爲佳。可使用之觸媒方面，可舉例如三乙基胺、苄基甲基胺、甲基三乙基氯化銨、苄基三甲基氯化銨、苄基三甲基溴化銨、苄基三甲基甲基碘化銨、三苯基膦等。觸媒之使用量相對於環氧樹脂（ a)與含乙烯基單羧酸（b )合計100質量份，較佳爲0.1 〜1 0質量份。又，以防止反應中的聚合爲目的，以使用聚合防止劑爲佳。聚合防止劑方面，可舉例如對苯二酚、甲基對苯二酚、對苯二酚單甲基醚、兒茶酚、焦掊酚等。聚合防止劑之使用量相對於環氧樹脂（a )與含乙烯基單羧酸（b )合計1 0 0質量份’較佳爲0 · 01〜1質量份。又，反應溫度較佳爲60〜150°C ，更佳爲80〜120°C。又，因應需要，可倂用含乙烯基單羧酸（b)與p-羥 -21 - 200910007 基苯乙醇等苯酌系化合物、偏苯三甲酸酐、均苯四甲酸酐、二苯甲酮四羧酸酐、聯苯基四羧酸酐等多元酸g干。又’本發明中、（A )含乙烯基之酸改性環氧樹酯方面’亦可使用使上述之反應生成物（A，）與含飽和或不飽和基之多元酸酐（c )反應而得到之樹脂。含飽和或不飽和基之多元酸酑（C)方面，可舉例如琥珀酸酐、馬來酸酐、四氫苯二甲酸酐、苯二甲酸酐、甲基四氫苯二甲酸酐、乙基四氫苯二甲酸酐、六氫苯二甲酸酐、甲基六氫苯二甲酸酐、乙基六氫苯二甲酸酐、衣康酸酐等。反應生成物（A，）與含飽和或不飽和基之多元酸酐（ c)之反應中、對於反應生成物（A，）中之羥基1當量，使含飽和或不飽和基之多元酸酐（C) 0」〜；[.0當量反應 ’可調整含乙烯基之酸改性環氧樹酯（A )之酸價。 (A )含乙烯基之酸改性環氧樹酯之酸價以3 〇〜 150mgKOH/g爲佳，50〜120mgKOH/g更佳。酸價未達 3 0mgKOH/g，則感光性樹脂組成物對稀鹼溶液之溶解性有降低傾向’超過l5〇mgKOH/g，則得到之硬化膜的電特性有降低傾向。反應生成物（A，）與含飽和或不飽和基之多元酸酐（ c)之反應溫度以60〜1201爲佳。又’因應需要，環氧樹脂（a )方面，亦可一部份倂用如氫化雙酚A型環氧樹脂。進而，（A )含乙烯基之酸改性環氧樹酯方面’亦可一部份倂用苯乙烯一馬來酸酐共 -22- 200910007 聚合物之羥基乙基丙烯酸酯改性物或苯乙烯-馬來酸酐共聚合物之羥基乙基丙烯酸酯改性物等苯乙烯一馬來酸系樹脂。感光性樹脂組成物中、（A )成分之含有量以感光性樹脂組成物之固形分全量爲基準，以1 〇〜60質量％爲佳，20〜40質量％更佳，20〜30質量％特別佳。此含有量未達1 0質量％，則耐熱性有劣化傾向，超過6 0質量％，則硬化性有劣化傾向。本發明所用之（B )光聚合起始劑所含之具肟酯鍵結之化合物方面，以使用下述一般式（3)或（4)所表示之化合物爲佳。 [化 12][In the formula (8), 'R12 represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or more. Further, R12 may be the same or different. In order to promote the reaction of a hydroxyl group with epichlorohydrin, in the presence of a metal hydroxide at a reaction temperature of 5 〇~1 2 〇C, in the presence of a metal hydroxide, in dimethylformamide, dimethylacetamide, dimethyl It is preferred to carry out the reaction in a polar organic solvent such as hydrazine. When the reaction temperature is less than 50 °C, the reaction becomes slow, and when the reaction temperature exceeds 120 k:, a large amount of side reaction occurs, which is not preferable. In the case of the salicylaldehyde type epoxy resin represented by the above general formula (7), for example, FAE-25 00, EPPN-501H, and EPPN_ 5 02H (above, Nippon Kayaku Co., Ltd., trade name) can be specifically exemplified. )Wait. Further, examples of the vinyl group-containing monocarboxylic acid (b) include a propionic acid, a dimer of acrylic acid, methacrylic acid, /3-mercaptoacrylic acid, lutynylacrylic acid, cinnamic acid, and crotonic acid. , hydrazine; - cyanuric acid, etc., and, for example, a half ester compound of a reaction product of a hydroxyl group-containing acrylate with a saturated or unsaturated dibasic acid anhydride, a vinyl-containing monoglycidyl ether or a vinyl-containing-19-200910007 The monoglycidyl ester is a saturated or unsaturated dibasic acid anhydride, that is, a half ester compound. These semi-ester compounds are obtained by reacting an acid ester, a vinyl-containing monoglycidyl ether or a vinyl-containing ester with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio, and the like, and a vinyl-containing monocarboxylic acid (b). One type or two kinds of oxime-containing vinyl monocarboxylic acids (b), for example, a hydroxyl group-containing acrylate used in the above half, a vinyl group-containing monovinyl group monoglycidyl ester, and examples thereof include a hydroxyl group. Hydroxyethyl methacrylate, hydroxypropyl acrylate methacrylate, hydroxybutyl acrylate, hydroxybutyl ester, polyethylene glycol monoacrylate, polyethylene glycol monomethyl hydroxymethyl propane diacrylate, Trimethylolpropane dimethoxypentaerythritol triacrylate, pentaerythritol trimethyl propylene tetraol pentoxide, pentaerythritol pentamethacrylate acrylate, glycidyl methacrylate, and the like. The saturated or unsaturated surface used for the synthesis of the above-mentioned half ester compound may, for example, be a succinic anhydride, maleic anhydride, tetrahydro (phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrohexahydrophthalate). An acid anhydride, methyl hexahydrophthalic anhydride, acetic anhydride, itaconic anhydride, etc. The epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) are equivalent to 1 equivalent of the epoxy group (a). (b) a monoglycidyl reaction of a hydroxy group-containing propylene obtained by reacting a reaction product of (b) in a ratio of from 0.6 to 1.05 equivalents. The above combination of an ester compound is used to synthesize a glyceryl ether, an ethyl acrylate-containing ester, and a hydroxypropyl group. In the reaction of methacrylic acid acrylate, tribasic acrylate, acid ester, dipentaerythritol, glycidol and dibasic anhydride dicarboxylic anhydride, phthalic anhydride, hexahydrobenzaldehyde, The carboxylic acid is preferably carried out in a ratio of from -20 to 200910007 in an amount of from 0.8 to 1.05 equivalents, and is preferably reacted in a ratio of from 9.9 to no equivalent. Epoxy resin (a) and vinyl-containing monocarboxylic acid (b) to dissolve in organic solvents The reaction is preferably carried out, and examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, and A. Glycol ethers such as carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, Esters such as butyl acetate, butyl cellosolve acetate, carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ether, naphtha, hydrogenated naphtha, and petroleum-soluble petroleum spirit. Further, a solvent or the like is used. In order to promote the reaction, a catalyst is preferably used. Examples of the catalyst which can be used include triethylamine, benzylmethylamine, methyltriethylammonium chloride, and benzyltrimethyl. Ammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine, etc. The amount of catalyst used is relative to epoxy resin (a) and vinyl-containing monocarboxylic acid. The total amount of the acid (b) is 100 parts by mass, preferably 0.1 to 10 parts by mass. Further, in order to prevent polymerization during the reaction, polymerization prevention is used. The polymerization inhibitor may, for example, be hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol or the like. The amount of the polymerization inhibitor is relative to the ring. The total amount of the oxygen resin (a) and the vinyl group-containing monocarboxylic acid (b) is preferably 0. 01 to 1 part by mass. Further, the reaction temperature is preferably 60 to 150 ° C, more preferably 80. ～120° C. Further, if necessary, a benzene-based compound such as a vinyl monocarboxylic acid (b) and p-hydroxy-21 - 200910007 phenyl phenylethanol, trimellitic anhydride, and pyromellitic anhydride may be used. A polybasic acid such as benzophenone tetracarboxylic anhydride or biphenyltetracarboxylic anhydride is dried. In the present invention, (A) a vinyl-containing acid-modified epoxy resin may also be used to form the above reaction. a resin obtained by reacting the substance (A,) with a polybasic acid anhydride (c) containing a saturated or unsaturated group. Examples of the polybasic acid cerium (C) having a saturated or unsaturated group include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and ethyltetrahydrogen. Phthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, ethyl hexahydrophthalic anhydride, itaconic anhydride, and the like. In the reaction of the reaction product (A,) with a polybasic acid anhydride (c) containing a saturated or unsaturated group, for a hydroxyl group in the reaction product (A,), an equivalent amount of a polybasic acid anhydride containing a saturated or unsaturated group (C) 0"~; [.0 equivalent reaction' can adjust the acid value of the vinyl-containing acid-modified epoxy resin (A). (A) The acid value of the vinyl-containing acid-modified epoxy resin is preferably from 3 〇 to 150 mgKOH/g, more preferably from 50 to 120 mgKOH/g. When the acid value is less than 30 mgKOH/g, the solubility of the photosensitive resin composition in the dilute alkali solution tends to decrease. When it exceeds 15 〇 mgKOH/g, the electrical properties of the cured film obtained tend to decrease. The reaction temperature of the reaction product (A,) and the polybasic acid anhydride (c) containing a saturated or unsaturated group is preferably 60 to 1201. Further, as needed, epoxy resin (a) may also be partially used as a hydrogenated bisphenol A type epoxy resin. Further, (A) the vinyl-containing acid-modified epoxy resin may also be partially used for styrene-maleic anhydride total -22-200910007 polymer hydroxyethyl acrylate modification or styrene a styrene-maleic acid resin such as a hydroxyethyl acrylate modified product of a maleic anhydride copolymer. The content of the component (A) in the photosensitive resin composition is preferably from 1 〇 to 60% by mass, more preferably from 20 to 40% by mass, even more preferably from 20 to 30% by mass based on the total amount of the solid content of the photosensitive resin composition. Especially good. When the content is less than 10% by mass, the heat resistance tends to be deteriorated, and when it exceeds 60% by mass, the curability tends to deteriorate. In the case of the compound having a oxime ester bond contained in the (B) photopolymerization initiator used in the present invention, it is preferred to use a compound represented by the following general formula (3) or (4). [化 12]

上述一般式（3)中’ R1表示碳數2〜I2之取代或未取代之鏈烷醯基' 雙鍵係不與羰基共軛之碳數4〜6之取代或未取代之鏈烯醯基、取代或未取代之苯甲醯基、碳數 2〜6之取代或未取代之烷氧基羰基、或、取代或未取代之苯氧基羰基。在此’鏈烷醯基具有1個以上之取代基時 ’該取代基以鹵原子或氰基爲佳。苯甲醯基具有1個 -23- 200910007 之取代基時，該取代基以碳數i〜6之烷基'鹵原子或氰基爲佳。苯氧基羰基具有丨個以上之取代基時，該取代基以碳數1〜6之烷基或鹵原子爲佳。又，上述一般式（3)中，R2、R3& R4各自獨立，表示鹵原子、碳數1〜丨2之取代或未取代之烷基、取代或未取代之環戊基、取代或未取代之環己基、取代或未取代之苯基、取代或未取代之苄基、取代或未取代之苯甲醯基、碳數2〜12之取代或未取代之鏈烷醯基、碳數2〜12之取代或未取代之烷氧基羰基、或、取代或未取代之苯氧基羯基。在此’烷氧基羰基具有1個以上之取代基時，該取代基以羥基或烷氧基爲佳。又’上述一般式（3)中，ml表示〇〜4之整數，m2 及m3各自獨立，表示〇〜5之整數。又’ 爲2以上時 ’—般式（3)中複數存在之R2可各自相同或相異，m2 爲2以上時’ 一般式（3)中複數存在之R3可各自相同或相異’ m3爲2以上時，一般式（3 )中複數存在之R4可各自相同或相異。 [化 13]In the above general formula (3), 'R1 represents a substituted or unsubstituted alkanealkyl group of a carbon number of 2 to 12, and the double bond is a substituted or unsubstituted alkene group having 4 to 6 carbon atoms which is not conjugated to a carbonyl group. a substituted or unsubstituted benzinyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted phenoxycarbonyl group. When the 'alkolylene group has one or more substituents', the substituent is preferably a halogen atom or a cyano group. When the benzamidine group has a substituent of -23 to 200910007, the substituent is preferably an alkyl group having a carbon number of i to 6 or a cyano group. When the phenoxycarbonyl group has at least one substituent, the substituent is preferably an alkyl group having 1 to 6 carbon atoms or a halogen atom. Further, in the above general formula (3), R2, R3 and R4 are each independently and represent a halogen atom, a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted group. a cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted benzamyl group, a substituted or unsubstituted alkane group having 2 to 12 carbon atoms, a carbon number of 2~ A substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted phenoxyfluorenyl group. When the 'alkoxycarbonyl group has one or more substituents, the substituent is preferably a hydroxyl group or an alkoxy group. Further, in the above general formula (3), ml represents an integer of 〇4, and m2 and m3 are each independent, and represent an integer of 〇~5. When 'more than 2', the R2 in the plural form in (3) may be the same or different, and when m2 is 2 or more, the R3 in the plural in the general formula (3) may be the same or different 'm3 When 2 or more, R4 in the plural form in the general formula (3) may be the same or different. [Chem. 13]

上述一般式（4)中，R5表示取代或未取代之苯基 -24- 200910007 碳數1〜6之取代或未取代之烷基、取代或未取代之苯基、碳數1〜20之取代或未取代之烷基、碳數5〜8之取代或未取代之環烷基、碳數2〜20之取代或未取代之鏈烷醯基 '或、取代或未取代之苯甲醯基。在此，烷基具有1個以上之取代基時，該取代基以羥基或烷氧基爲佳。苯甲醯基具有1個以上之取代基時，該取代基以碳數爲1〜6之院基或苯基爲佳。又’上述一般式（4)中’ R6表示碳數2〜12之取代或未取代之鏈烷醯基、雙鍵係不與羰基共軛之碳數4〜6 之取代或未取代之鏈烯醯基、取代或未取代之苯甲醯基、碳數2〜6之取代或未取代之烷氧基羰基、或、取代或未取代之本氧基羰基。在此，鏈烷醯基具有丨個以上之取代基時’該取代基以鹵原子或氰基爲佳。苯甲醯基具有】個以上之取代基時’該取代基以㈣卜6之烷基、鹵原子或氰基爲佳。苯氧基_具有1{@以上之取代基時，該取代基以碳數1〜6之烷基或鹵原子爲佳。又’上述-般式（4)巾’ f表示氫原子、鹵原子、碳數1〜η之取代或未取代之烷基、取代或未取代之環戊基、取代或未取代之環己基、取代或未取代之苯或未取代之节S、取代或未取代之¥甲酸基、碳數2 1 之取代或未取代之鏈烷醯基、碳數2〜 2 12 以之取代或主之烷氧基羰基、或、取代或未取代之苯一In the above general formula (4), R5 represents a substituted or unsubstituted phenyl-24-200910007 substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, and a carbon number of 1 to 20 in substitution. Or an unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group having 5 to 8 carbon atoms, a substituted or unsubstituted alkanealkyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted benzamyl group. Here, when the alkyl group has one or more substituents, the substituent is preferably a hydroxyl group or an alkoxy group. When the benzamidine group has one or more substituents, the substituent is preferably a group having a carbon number of 1 to 6 or a phenyl group. Further, in the above general formula (4), 'R6 represents a substituted or unsubstituted alkane fluorenyl group having 2 to 12 carbon atoms, and a double or a substituted or unsubstituted olefin having 4 to 6 carbon atoms which is not conjugated to a carbonyl group. An anthracenyl group, a substituted or unsubstituted benzamidine group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted peroxycarbonyl group. Here, when the alkanethio group has more than one substituent, the substituent is preferably a halogen atom or a cyano group. When the benzamidine group has more than one substituent, the substituent is preferably an alkyl group, a halogen atom or a cyano group of (4). When the phenoxy group has a substituent of 1 {@ or more, the substituent is preferably an alkyl group having 1 to 6 carbon atoms or a halogen atom. Further, the above-mentioned general formula (4) towel 'f' represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having a carbon number of 1 to η, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, Substituted or unsubstituted benzene or unsubstituted agglomerate S, substituted or unsubstituted carboxylic acid group, substituted or unsubstituted alkane fluorenyl group having 2 to 2 carbon atoms, substituted or predominantly alkane Oxycarbonyl, or substituted or unsubstituted benzene

Λ 牛、鸯每基，β 8 _ Q 及R1各自獨立，表示鹵原子、碳數丨〜12之' 代之烷基、取代或未取代之環戊基取代或未取未取代之環己 -25- 200910007 基、取代或未取代之苯基、取代或未取代之苄基、取代或未取代之苯甲醯基、碳數2〜1 2之取代或未取代之鏈烷醯基、碳數2〜12之取代或未取代之烷氧基羰基、或、取代或未取代之苯氧基羰基。在此，烷氧基羰基具有1個以上之取代基時’該取代基以羥基或烷氧基爲佳。又，上述一般式（4)中，m4及m5各自獨立，表不 0〜3之整數’ m6表示〇〜5之整數。又，m4爲2以上時，複數存在之r8可各自相同或相異，m5爲2以上時’複數存在之R9可各自相同或相異，m6爲2以上時’複數存在之R1Q可各自相同或相異。又，作爲本發明所用之（B )光聚合起始劑所含之具肟酯鍵結之化合物’更具體上，可舉例如下述式（9 )所表示之1,2-辛烷二酮-1-〔4-(苯硫基）苯基〕-2-(〇-苯甲醯基肟）（商品名：OXE-01 、 Ciba Specialty Chemicals公司製）、1-〔 9 -乙基-6- (2 -甲基苯甲醯基）· 9H -昨唑-3-基〕乙酮1-(〇_乙酸基肟）（商品名：〇乂£- 02、Ciba Specialty Chemicals 公司製）、卜苯基 _1，2-丙二酮-2-〔 0-(乙氧基羰基）目弓〕（商品名：Quantacure-PDO、日本化藥公司製）等。 -26- 200910007 [化 14]Λ 牛, 鸯 per base, β 8 _ Q and R1 are each independently, indicating a halogen atom, a carbon number of 丨~12, an alkyl group, a substituted or unsubstituted cyclopentyl group or an unsubstituted unsubstituted ring. 25- 200910007 phenyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted benzinyl, substituted or unsubstituted alkane fluorenyl group having 2 to 12 carbon atoms, carbon number a substituted or unsubstituted alkoxycarbonyl group of 2 to 12, or a substituted or unsubstituted phenoxycarbonyl group. Here, when the alkoxycarbonyl group has one or more substituents, the substituent is preferably a hydroxyl group or an alkoxy group. Further, in the above general formula (4), m4 and m5 are each independent, and the integer "m6" of 0 to 3 represents an integer of 〇5. Further, when m4 is 2 or more, r8 in the plural number may be the same or different, and when m5 is 2 or more, R9 in the plural may be the same or different, and when m6 is 2 or more, the plural R1Q may be the same or Different. Further, as the compound of the (B) photopolymerization initiator used in the present invention, the oxime ester-bonded compound is more specifically, for example, 1,2-octanedione represented by the following formula (9). 1-[4-(phenylthio)phenyl]-2-(indolyl-benzhydrylhydrazine) (trade name: OXE-01, manufactured by Ciba Specialty Chemicals Co., Ltd.), 1-[9-ethyl-6- (2-Methylbenzylidene)·9H-n-oxazol-3-yl]ethanone 1-(anthracene-acetoxy) (trade name: -£- 02, manufactured by Ciba Specialty Chemicals), benzene Base_1,2-propanedione-2-[0-(ethoxycarbonyl)methylglycan] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.). -26- 200910007 [Chem. 14]

又’本發明之感光性樹脂組成物中，（B )成分方面 ’可倂用上述具肟酯鍵結之化合物以外之光聚合起始劑。具肟酯鍵結之化合物以外之光聚合起始劑方面，可舉例如苯偶因、苯偶因甲基醚、苯偶因異丙基醚等苯偶因類、乙醯苯、2,2-二甲氧基-2-苯基乙醯苯、2,2-二乙氧基- 2-苯基乙醯苯、1，1-二氯乙醯苯、丨_羥基環己基苯基酮、2_ 节基-2-二甲基胺基嗎啉代苯基）_丁酮-u-甲基_ 1- 〔 4-(甲基硫基）苯基〕-2_嗎咻基-丙酮·丨、N,N_二甲基fe：基乙酸本等方香族酮類、2 -甲基蒽廳、2 -乙基意酿、 2- tert-丁基蒽醌、丨_氯蒽醌、2_戊基蒽醌、2_胺基蒽醌等葱醒類、乙酸苯二甲基縮酮、苄基二甲基縮酮等縮酮類、 —苯甲酮、甲基二苯甲酮、4,4，_二氯二苯甲酮、4_苯甲醯基-4’-甲基二苯硫等二苯甲酮類、9_苯基吖啶、丨，7_雙（ 9，9 ’ -卩丫 d定基）庚院等吖啶衍生物、2，4,5 _三芳基咪唑二聚物或其衍生物、2,4,6_三甲基苯甲醯基二苯基膦氧化物等。此等可1種單獨或2種以上組合使用。 -27- 200910007 感光性樹脂組成物中、（B )成分之含有量以感光性樹脂組成物之固形分全量爲基準，0.5〜20質量％爲佳，2 〜10質量％更佳，2〜5質量％特別佳。此含有量未達0.5 質量％，曝光部於顯像中有變易溶出之傾向，超過20質量％則所得硬化膜之耐熱性有降低之傾向。本發明之感光性樹脂組成物所用之（C )增感劑係含下述一般式（1)所表示之香豆素化合物者。Further, in the photosensitive resin composition of the present invention, the photopolymerization initiator other than the compound having the above oxime ester-bonded can be used as the component (B). Examples of the photopolymerization initiator other than the compound having a oxime ester bond include benzoin such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2, 2 -dimethoxy-2-phenylethyl benzene, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetamidine, hydrazine-hydroxycyclohexyl phenyl ketone, 2_gangyl-2-dimethylaminomorpholinophenyl)butanone-u-methyl_ 1-[4-(methylthio)phenyl]-2-mercapto-acetone·丨, N,N-dimethyl fe: acetonitrile, aryl ketone, 2-methyl fluorene, 2-ethyl aryl, 2-tert-butyl hydrazine, hydrazine chlorohydrazine, 2 _ pentyl hydrazine, 2_amino hydrazine and other onions, benzoyl ketal acetate, benzyl dimethyl ketal and other ketals, benzophenone, methyl benzophenone, 4 , 4,_dichlorobenzophenone, 4-benzoic acid-4'-methyldiphenylsulfide, benzophenone, 9-phenyl acridine, anthracene, 7_bis (9,9' -卩丫d定) Ginger et al. acridine derivative, 2,4,5-triaryl imidazolium dimer or its derivative, 2,4,6-trimethylbenzimidyl diphenylphosphine oxide Wait. These may be used alone or in combination of two or more. -27- 200910007 The content of the component (B) in the photosensitive resin composition is preferably 0.5 to 20% by mass, more preferably 2 to 10% by mass, more preferably 2 to 5, based on the total solid content of the photosensitive resin composition. The quality % is particularly good. When the content is less than 0.5% by mass, the exposed portion tends to be easily eluted during development, and when it exceeds 20% by mass, the heat resistance of the obtained cured film tends to be lowered. The (C) sensitizer used in the photosensitive resin composition of the present invention contains the coumarin compound represented by the following general formula (1).

上述一般式（1)中，Z1表示鹵原子、碳數1〜20之烷基、碳數3〜10之環烷基、碳數6〜14之芳基、胺基、碳數1〜10之烷基胺基、碳數1〜20之二烷基胺基、锍基、碳數1〜10之烷基酼基、烯丙基、碳數1〜20之羥基烷基、羧基、烷基之碳數係1〜10之羧基烷基、烷基之碳數係1〜10之醯基、碳數1〜20之烷氧基、碳數1〜20之烷氧基羰基、或、含雜環之基，Z2表示鹵原子、碳數1〜20 之烷基、碳數3〜10之環烷基、碳數6〜14之芳基、胺基、碳數1〜10之烷基胺基、碳數1〜20之二烷基胺基、锍基、碳數1〜10之烷基锍基、烯丙基、碳數1〜20之羥基烷基、烷基之碳數係1〜10之醯基、碳數1〜20之烷氧基、含雜環之基、或、下述一般式（2)所表示之基，s爲0 -28- 200910007 〜4之整數。又’式（2)中之Z1及s與式（1)中之z1 及S同義。又，式（1)中之2!及S與式（2)中之Z1及 S可各自相同或相異。進而，式（1)或式（2)中，5爲2 以上時’複數存在之Z1可各自相同或相異 '任二者可互相鍵結形成環。 [化 16]In the above general formula (1), Z1 represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amine group, and a carbon number of 1 to 10; Alkylamino group, dialkylamino group having 1 to 20 carbon atoms, fluorenyl group, alkyl fluorenyl group having 1 to 10 carbon atoms, allyl group, hydroxyalkyl group having 1 to 20 carbon atoms, carboxyl group, alkyl group a carboxyalkyl group having a carbon number of 1 to 10, a carbon number of the alkyl group of 1 to 10, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, or a heterocyclic ring And Z2 represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amine group, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 1 to 20 carbon atoms, a mercapto group, an alkyl fluorenyl group having 1 to 10 carbon atoms, an allyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, and a carbon number of the alkyl group of 1 to 10 A mercapto group, an alkoxy group having 1 to 20 carbon atoms, a heterocyclic group-containing group, or a group represented by the following general formula (2), and s is an integer of 0-28 to 200910007 to 4. Further, Z1 and s in the formula (2) are synonymous with z1 and S in the formula (1). Further, 2! and S in the formula (1) and Z1 and S in the formula (2) may be the same or different from each other. Further, in the formula (1) or the formula (2), when 5 is 2 or more, the plural Z1 may be the same or different, and either of them may be bonded to each other to form a ring. [Chemistry 16]

(2) 上述一般式（1)所表示之香豆素化合物爲吸收感光波長405nm附近之光，激發作爲（b)光聚合起始劑之具肟酯鍵結之化合物。上述一般式（丨）所表示之香豆素化合物以極大吸收波長在3 70nm〜450nm之範圍內的化合物爲佳。又’上述一般式（1)所表示之香豆素化合物中、Z2 以上述一般式（2)所表示之基爲佳。進而，上述一般式 (1)所表示之香豆素化合物以下述式（10)所表示之 7,7’一雙（二乙基胺基）一 3-氧代（keto) -香豆素（（股）綠化學製、商品名：B C )特別佳。藉由使用下述式 (10)所表示之香豆素化合物，可更提升對405nm之光的感度，使經直接描畫曝光法的光阻圖形之形成可以更高解像度進行。 -29- (10) 200910007 [化 17] Ο(2) The coumarin compound represented by the above general formula (1) absorbs light having a wavelength of around 405 nm and excites a compound having an oxime ester bond as (b) a photopolymerization initiator. The coumarin compound represented by the above general formula (丨) is preferably a compound having a maximum absorption wavelength in the range of 3 70 nm to 450 nm. Further, in the coumarin compound represented by the above general formula (1), Z2 is preferably a group represented by the above general formula (2). Further, the coumarin compound represented by the above formula (1) is 7,7'-bis(diethylamino)-methoxy-keto-flavonoid represented by the following formula (10). (share) Green chemical system, trade name: BC) is particularly good. By using the coumarin compound represented by the following formula (10), the sensitivity to light of 405 nm can be further enhanced, and the formation of the photoresist pattern by the direct drawing exposure method can be performed with higher resolution. -29- (10) 200910007 [Chem. 17] Ο

又’ （c)成分的增感劑亦可含上述一般式（i)所表示之香豆素化合物以外之其他增感劑。其他增感劑方面，可舉例如吡唑啉類、二烷氧基蒽等蒽類、香豆素類、咕噸酮類、噻噸酮類、4,4’ 一雙（二烷基胺基）二苯甲酮類、噁唑類、苯並噁唑類、噻唑類、***類、芪類、三嗪類、噻吩類等。此等可1種單獨或2種以上組合使用。感光性樹脂組成物中、（C )成分之含有量以感光性樹脂組成物之固形分全量爲基準，〇.〇1〜5質量％爲佳， 0.1〜2質量％更佳，〇.2〜丨質量％特別佳。藉由此含有量在上述範圍內，可得良好感度。本發明之感光性樹脂組成物由經日安定性良好觀點，以更含（D )具有硫醇基之化合物爲佳。（〇 )具有硫醇基之化合物方面’以可有效作爲氫供給體之化合物爲佳，如此之化合物方面，以下述一般式（丨丨）所表示之化合物爲佳。 -30- 200910007 [化 18]Further, the sensitizer of the component (c) may contain other sensitizers other than the coumarin compound represented by the above general formula (i). Examples of other sensitizers include oximes such as pyrazolines and dialkoxy oximes, coumarins, xanthones, thioxanthones, and 4,4'-di(dialkylamino groups). Dibenzophenones, oxazoles, benzoxazoles, thiazoles, triazoles, anthraquinones, triazines, thiophenes, and the like. These may be used alone or in combination of two or more. The content of the component (C) in the photosensitive resin composition is preferably from 1 to 5 mass%, more preferably from 0.1 to 2 mass%, based on the total solid content of the photosensitive resin composition.丨% by mass is particularly good. By having such a content within the above range, good sensitivity can be obtained. The photosensitive resin composition of the present invention preferably contains (D) a compound having a thiol group from the viewpoint of good day-to-day stability. (〇) The compound having a thiol group is preferably a compound which is effective as a hydrogen donor, and as such a compound, a compound represented by the following general formula (丨丨) is preferred. -30- 200910007 [Chem. 18]

〔式中、Ar表示可有取代基之2價或3價之芳基，X表示氧原子、氮原子或硫原子。〕 (D )具有硫醇基之化合物之具體例方面，可舉例如下述式（12 )所表示之锍基苯並噁唑（MBO )、下述式（ 13 )所表示之锍基苯並噻唑（MBT ) '下述式（14 )所表示之锍基苯並咪唑（MBI )、乙硫醇、苯硫醇、S1E基苯酚、锍基甲苯、2 -锍基乙基胺、锍基乙基醇、锍基二甲苯、硫代苯酚、2 -锍基喹啉、锍基乙酸、α -巯基丙酸、3 -锍基丙酸、锍基琥珀酸、硫代水楊酸、锍基環己烷、α -锍基二苯基甲烷、C-锍基四唑、锍基萘、锍基萘酚、4-巯基聯苯基、锍基次黃嘌呤、巯基吡啶、2 -锍基嘧啶、锍基嘌哈、硫代香豆酮、丁11丨0(：1111101；]1丨32011、丁|完-2,3-二硫醇、硫代三聚氰酸、2,4,6-三锍基-s-三嗪、2-二丁基胺基-4,6-二锍基-s -三嗪、2 -苯胺基-4,6 -二巯基-s -三嗪等。 [化 19][wherein, Ar represents a divalent or trivalent aryl group which may have a substituent, and X represents an oxygen atom, a nitrogen atom or a sulfur atom. Specific examples of the compound having a thiol group include mercaptobenzoxazole (MBO) represented by the following formula (12) and mercaptobenzothiazole represented by the following formula (13). (MBT) 'Mercaptobenzimidazole (MBI) represented by the following formula (14), ethanethiol, phenylthiol, S1E-based phenol, decyltoluene, 2-mercaptoethylamine, decylethyl Alcohol, mercapto xylene, thiophenol, 2-mercaptoquinoline, thioglycolic acid, α-mercaptopropionic acid, 3-mercaptopropionic acid, mercapto succinic acid, thiosalicylic acid, mercaptocyclohexane Alkane, α-mercaptodiphenylmethane, C-mercaptotetrazole, decylnaphthalene, nonylnaphthol, 4-mercaptobiphenyl, fluorenyl hypoxanthine, mercaptopyridine, 2-mercaptopyrimidine, anthracene Base 嘌, thiocoumarin, Ding 11丨0 (:1111101;]1丨32011, Ding|End-2,3-dithiol, thiocyanuric acid, 2,4,6-triazine Base-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, etc. [Chem. 19]

-31 - 200910007 [化 20] 〇c>-sh (13) [化 21]-31 - 200910007 [Chem. 20] 〇c>-sh (13) [Chem. 21]

此等（D )具有硫醇基之化合物可1種單獨或2種以上組合使用。此等中，分子內具疏基之化合物係有效作爲氫供給體，由可使感光性樹脂組成物之感度及經日安定性更提升觀點來看爲佳，具體上，以锍基苯並噁唑（MB Ο ) 、锍基苯並噻唑（Μ B T )及巯基苯並咪唑（Μ B I )爲佳。本發明之感光性樹脂組成物中、（D )成分之含有量以感光性樹脂組成物之固形分全量爲基準，〇. 1〜5質量％爲佳，0 · 3〜3質量％更佳，0 · 5〜1 . 5質量％特別佳。此含有量未達0.1質量％則感光性樹脂組成物之溶液有變易膠體化之傾向，超過5質量％則感度有降低之傾向。本發明之感光性樹脂組成物中，舉例組合上述之（Β )成分、（C )成分及（D )成分，照射紫外線時之推測反應機構、例示化合物，表示於下述反應式（I )〜（V) 。首先，（C)增感劑的上述一般式（1)所表示之香豆素化合物（S e n S )雖吸收4 0 5 n m之光，成爲1重態之激發狀態，此爲迅速進行系間交換，成爲3重態激發狀態（反應 -32- 200910007 式（I ))。亦可想成由此經激發之增感劑能量移動，激發（B)光聚合起始劑的具有肟酯鍵結之上述式（9)所表示之化合物（OXE-01 )(反應式（II))。之後，因成爲 3重態之激發狀態的光聚合起始劑進行分解，產生自由基 (反應式（III ))。接著’生成之自由基與作爲氫供給體之具有（D)硫醇基的上述式（I2)所表示之化合物（ MB〇 )進行反應’連鎖移動，成爲高活性之硫自由基（反應式（IV )及（V ))的機構。此硫自由基推測可成爲促進光聚合反應之有效成分。 [化 22] (Sens ) (I) [化 23]These (D) compounds having a thiol group may be used singly or in combination of two or more kinds. Among these, a compound having a thiol group in the molecule is effective as a hydrogen donor, and it is preferable from the viewpoint of improving the sensitivity and the stability of the photosensitive resin composition, and specifically, the thiol benzoate Oxazole (MB Ο ), mercaptobenzothiazole (Μ BT ) and mercaptobenzimidazole (Μ BI ) are preferred. In the photosensitive resin composition of the present invention, the content of the component (D) is preferably from 1 to 5 mass%, more preferably from 0 to 3 mass%, based on the total solid content of the photosensitive resin composition. 0 · 5 to 1. 5 mass% is particularly good. When the amount is less than 0.1% by mass, the solution of the photosensitive resin composition tends to be colloidal, and when it exceeds 5% by mass, the sensitivity tends to decrease. In the photosensitive resin composition of the present invention, the above-mentioned (Β) component, (C) component, and (D) component are combined, and the estimated reaction mechanism and the exemplified compound when irradiated with ultraviolet rays are shown in the following reaction formula (I)~ (V). First, the coumarin compound (S en S ) represented by the above general formula (1) of the (C) sensitizer absorbs light of 405 nm and becomes a single-state excited state, which is a rapid inter-system exchange. It becomes a 3-fold excited state (Reaction -32- 200910007 Formula (I)). It is also conceivable to activate the (B) photopolymerization initiator having the oxime ester-bonded compound represented by the above formula (9) (OXE-01) by reacting the excited sensitizer energy (reaction formula (II) )). Thereafter, the photopolymerization initiator which is in the excited state of the triplet state is decomposed to generate a radical (reaction formula (III)). Then, the generated radical is reacted with a compound (MB〇) represented by the above formula (I2) having a (D) thiol group as a hydrogen donor, and becomes a highly active sulfur radical (reaction formula ( IV) and (V)) institutions. This sulfur radical is presumed to be an effective component for promoting photopolymerization. [Single 22] (Sens) (I) [Chem. 23]

[化 24][Chem. 24]

[化 25][Chem. 25]

200910007 [化 26] Ο. + 〇Q^sH —^ Ο + C〇^s· (V) 又’本發明之感光性樹脂組成物由可提升耐熱衝撃性及剪斷接著性觀點，以含（E )彈性體爲佳。 (E )彈性體方面，可舉例如苯乙烯系彈性體、烯烴系彈性體、胺基甲酸乙酯系彈性體、聚酯系彈性體、聚醯胺系彈性體、丙烯酸系彈性體及矽酮系彈性體等。此等（ E)彈性體由硬鏈段成分與軟鏈段成分所組成，一般各自係前者賦予耐熱性及強度，後者賦予柔軟性及強靭性。苯乙烯系彈性體方面，可舉例如苯乙烯一丁二烯—苯乙烯嵌段共聚合物、苯乙烯-異戊二烯一苯乙烯嵌段共聚合物、苯乙烯一乙烯- 丁烯-苯乙烯嵌段共聚合物、苯乙烯一乙烯一丙烯一苯乙烯嵌段共聚合物等。構成苯乙烯系彈性體之成分方面，除苯乙烯外，可使用α-甲基苯乙烯、3-甲基苯乙烯、4_丙基苯乙烯、4-環己基苯乙烯等苯乙烯衍生物。具體上，可舉例如Tufprene、 SolpreneT、AsapreneT、Tuftec (以上、旭化成工業（股 )製）、彈性體 AR ( ARONKASEI C0_，LTD 製）、 KratonG、Perre flex (以上、Shell in Japan 製）、JSR-TR ' TSR-SIS、Dynaron (以上、日本合成橡膠（股）製）、 DenkaSTR (電化學工業（股）製）、Quintac (日本 ΖΕΟΝ製）、TPE-SB系列（住友化學工業（股）製）、 -34- 200910007200910007 化. + 〇Q^sH —^ Ο + C〇^s· (V) Further, the photosensitive resin composition of the present invention has a viewpoint of improving heat-resistant squeezing property and shearing adhesion. E) Elastomers are preferred. (E) The elastomer may, for example, be a styrene-based elastomer, an olefin-based elastomer, an urethane-based elastomer, a polyester-based elastomer, a polyamide-based elastomer, an acrylic elastomer, or an anthrone. Elastomers, etc. These (E) elastomers are composed of a hard segment component and a soft segment component, and generally the former imparts heat resistance and strength, and the latter imparts softness and toughness. Examples of the styrene-based elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, and styrene-ethylene-butylene-benzene. Ethylene block copolymer, styrene-ethylene-propylene-styrene block copolymer, and the like. As the component constituting the styrene-based elastomer, a styrene derivative such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene or 4-cyclohexylstyrene can be used in addition to styrene. Specifically, for example, Tufprene, SolpreneT, AsapreneT, Tuftec (above, manufactured by Asahi Kasei Co., Ltd.), elastomer AR (manufactured by ARONKASEI C0_, LTD), KratonG, Perre flex (above, manufactured by Shell in Japan), JSR- TR ' TSR-SIS, Dynaron (above, Japan Synthetic Rubber Co., Ltd.), DenkaSTR (Electrochemical Industry Co., Ltd.), Quintac (manufactured by Nippon Electric Co., Ltd.), TPE-SB series (Sumitomo Chemical Industry Co., Ltd.) , -34- 200910007

Rabalon (三菱化學（股）製）、Septon、Hybrar(以上、 KURARAY CO., LTD.製）、Sumiflex ( SUMITOMO BAKELITE Co. Ltd (股）製）、L E O S T Ο Μ E R、A C T Y Μ E R (以上、理硏乙烯工業製）等。烯烴系彈性體爲乙烯、丙烯、1-丁烯、1-己烯、4-甲基-戊烯等碳數2〜20之α-烯烴之共聚合物，可舉例如 ’乙烯—丙烯共聚合物（EPR )、乙烯一丙烯—二烯共聚合物（EPDM )等。又，烯烴系彈性體方面，可舉例如二環戊二烯、1,4 -己二烯、環辛二烯、甲撐降冰片烯、亞乙基降冰片烯、丁二烯、異戊二烯等碳數2〜20之非共軛二烯與α-烯烴之共聚合物、及 '環氧化聚丁二烯等。又，烯烴系彈性體方面，可舉例如丁二烯一丙烯腈共聚合物與甲基丙烯酸共聚合之羧基改性NBR等。進而，烯烴系彈性體方面，可舉例如乙烯-α -烯烴共聚合物橡膠、乙烯-α -烯烴-非共軛二烯共聚合物橡膠、丙烯-α -烯烴共聚合物橡膠、丁烯-α-烯烴共聚合物橡膠等。烯烴系彈性體方面，具體上，可舉例如Milastomer ( 三井石油化學公司製）、EXACT ( EXXON化學公司製）、ENGAGE ( The Dow Chemical Company 公司製）、氫化苯乙烯一丁二烯橡膠“ DYNABON HSBR”（日本合成橡膠公司製）、丁二烯一丙烯腈共聚合物“ NBR系列”（曰本合成橡膠公司製）、具交聯點之兩末端羧基改性丁二烯一丙烯腈共聚合物之“ XER系列”（日本合成橡膠公司製 )、聚丁二烯部分的環氧化之環氧化聚丁二烯之“BF- -35- 200910007 1 000 (日本曹達公司製）等。胺基甲酸乙脂系彈性體係由低分子（短鏈）二醇及二異氰酸酯所成之硬鏈段與高分子（長鏈）二醇及二異氰酸酯所成之軟鏈段的構造單元所成者。高分子（長鏈）二醇方面，可舉例如聚丙二醇、聚四甲基醚二醇（ Polytetramethylene Oxide)、聚（1,4 -丁燃己二酸）、聚 (乙烯-1,4-丁烯己二酸）、聚己內酯、聚（1,6-伸己基碳酸酯）、聚（1,6-伸己基一新伸戊基己二酸）等。高分子 (長鏈）二醇之數平均分子量以5 00〜1 0000爲佳。低分子（短鏈）二醇方面，可舉例如乙二醇、丙二醇、1,4-丁烷二醇、雙酚A等。短鏈二醇之數平均分子量以48〜500 爲佳。胺基甲酸乙脂系彈性體之具體例方面，可舉例如 P ANDEX T-2185、T-2983N (以上、大日本油墨化學工業公司製）、SilactoneE790 等。聚酯系彈性體方面，可舉例如二羧酸或其衍生物與二醇化合物或其衍生物進行聚縮合所得者。二羧酸之具體例方面，可舉例如對苯二甲酸、異苯二甲酸、萘二羧酸等芳香族二羧酸及此等芳香核之氫原子被甲基、乙基、苯基等取代之芳香族二羧酸、己二酸、癸二酸、十二烷二羧酸等碳數2〜20之脂肪族二羧酸、及環己烷二羧酸等脂環式二羧酸等。此等化合物可1種單獨或2種以上組合使用。二醇化合物之具體例方面，可舉例如乙二醇、1，3·丙烷二醇、1，4-丁烷二醇、1，6-己二醇、1，10-癸烷二醇、1,4-環己二醇等脂肪族二醇及脂環式二醇、或、下述一般式（15) -36- 200910007 所表示之二價苯酚。此等化合物可1種單獨或2種以上組合使用。 [化 27]Rabalon (Mitsubishi Chemical Co., Ltd.), Septon, Hybrar (above, KURARAY CO., LTD.), Sumiflex (made by SUMITOMO BAKELITE Co. Ltd), LEOST Ο ER, ACTY Μ ER (above,硏 ethylene industry system) and so on. The olefin-based elastomer is a copolymer of a carbon number of 2 to 20 α-olefin such as ethylene, propylene, 1-butene, 1-hexene or 4-methyl-pentene, and examples thereof include ethylene-propylene copolymerization. (EPR), ethylene-propylene-diene copolymer (EPDM), and the like. Further, examples of the olefin-based elastomer include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methyl norbornene, ethylidene norbornene, butadiene, and isoprene. a copolymer of a non-conjugated diene having 2 to 20 carbon atoms such as an olefin and an α-olefin, and an epoxidized polybutadiene. Further, examples of the olefin-based elastomer include carboxyl-modified NBR in which a butadiene-acrylonitrile copolymer and methacrylic acid are copolymerized. Further, examples of the olefin-based elastomer include ethylene-α-olefin copolymer rubber, ethylene-α-olefin-non-conjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, and butene- An α-olefin copolymer rubber or the like. Specific examples of the olefin-based elastomer include, for example, Milastomer (manufactured by Mitsui Petrochemical Co., Ltd.), EXACT (manufactured by EXXON Chemical Co., Ltd.), ENGAGE (manufactured by The Dow Chemical Company), and hydrogenated styrene-butadiene rubber "DYNABON HSBR". "Nippon Synthetic Rubber Co., Ltd.", butadiene-acrylonitrile copolymer "NBR series" (manufactured by Sakamoto Synthetic Rubber Co., Ltd.), two-terminal carboxyl-modified butadiene-acrylonitrile copolymer with cross-linking point "XER series" (manufactured by Nippon Synthetic Rubber Co., Ltd.), "BF--35-200910007 1 000 (manufactured by Nippon Soda Co., Ltd.), etc. of epoxidized polybutadiene of polybutadiene portion. The aliphatic elastomer system is composed of a hard segment composed of a low molecular (short chain) diol and a diisocyanate, and a structural unit of a soft segment formed of a polymer (long-chain) diol and a diisocyanate. Examples of the long-chain diol include polypropylene glycol, polytetramethylene diol (polytetramethylene oxylate), poly(1,4-butane adipic acid), and poly(ethylene-1,4-butene hexane). Acid), polycaprolactone, poly (1 , 6-extended hexyl carbonate), poly(1,6-extended hexyl-new pentyl adipic acid), etc. The number average molecular weight of the polymer (long-chain) diol is preferably 50,000 to 10,000. Examples of the molecular (short chain) diol include ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A, etc. The number average molecular weight of the short-chain diol is preferably 48 to 500. Specific examples of the ethyl ester-based elastomer include, for example, P ANDEX T-2185, T-2983N (above, manufactured by Dainippon Ink and Chemicals, Inc.), Silacone E790, etc. Examples of the polyester elastomer include dicarboxylic acid. And a derivative thereof, which is obtained by polycondensation with a diol compound or a derivative thereof, and specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid; An aliphatic dicarboxylic acid having 2 to 20 carbon atoms such as an aromatic dicarboxylic acid, adipic acid, sebacic acid or dodecanedicarboxylic acid in which the hydrogen atom of the aromatic nucleus is substituted with a methyl group, an ethyl group or a phenyl group. An alicyclic dicarboxylic acid such as an acid or a cyclohexanedicarboxylic acid, etc. These compounds may be used alone or in combination of two or more. Specific examples of the compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1, An aliphatic diol such as 4-cyclohexanediol or an alicyclic diol, or a divalent phenol represented by the following general formula (15)-36-200910007. These compounds may be used alone or in combination of two or more. Use. [Chem. 27]

(15) 〔式（15)中，Y11表示單鍵、碳數1〜1〇之伸院基、碳數4〜8之環伸烷基、-〇_、-S_、或、-S02-、R21及R22表示鹵原子或碳數1〜12之烷基，p及q表示0〜4之整數，r爲0或1。〕上述一般式（15)所表示之二價苯酚之具體例方面，可舉例如雙酣A、雙-（4-經基苯基）甲院、雙-（4_經基-3 -甲基苯基）丙烷、間苯二酚等。此等化合物可1種單獨或2種以上組合使用。又，可使用以芳香族聚酯（如，聚對苯二甲酸丁二醇酯）部分爲硬鏈段成分，脂肪族聚酯（如，聚四甲撐乙二醇）部分爲軟鏈段成分之多嵌段共聚合物。依硬鏈段與軟鍵段之種類、比例、分子量之不同，而有各種不问程度者。具體例方面，可舉例如Hytrel ( Du Pont-Toray (股）製 )、Pelprene (東洋紡績（股）製）、ESPEL (日立化成工業（股）製）等。聚醯胺系彈性體大致分爲於硬相使用聚醯胺、於軟相使用聚醚或聚酯之聚醚嵌段醯胺型以及聚醚酯嵌段醯胺型 -37- 200910007 之2種類。聚酸胺方面，可使用如聚醯胺一 6、11、12等 ’聚醚方面’可使用如聚氧化乙烯、聚氧化丙烯、聚四甲撐乙二醇等。聚醯胺系彈性體具體上，如U B E聚醯胺彈性體（宇部興產（股）製）、DIAMIDE ( Daicel-Huels ( 股）製）、PEBAX (東麗（股）製）、GrilonELY ( EMS Japan (股）製）、Nopamid (三菱化學（股）製）、 Gri lax (大日本油墨（股）製）等。丙烯酸系彈性體以丙烯酸酯爲主成分，可使用乙基丙烯酸酯、丁基丙烯酸酯、甲氧基乙基丙烯酸酯、乙氧基乙基丙烯酸酯等。又，交聯點單體方面，可使用縮水甘油甲基丙烯酸酯、烯丙基縮水甘油醚等。進而，亦可使丙烯腈或乙烯共聚合。作爲丙烯酸系彈性體，具體上，如丙烯腈 -丁基丙烯酸酯共聚合物、丙烯腈-丁基丙烯酸酯一乙基丙烯酸酯共聚合物、丙烯腈一丁基丙烯酸酯一縮水甘油甲基丙烯酸酯共聚合物等。矽酮系彈性體方面，以有機聚矽氧烷爲主成分者，可分爲聚二甲基矽氧烷系、聚甲基苯基矽氧烷系、聚二苯基矽氧烷系。亦有一部分爲以乙烯基、烷氧基等改性之者。矽酮系彈性體之具體例方面，可舉例如KE系列（信越化學工業（股）製）、SE系列、CY系列、SH系列（以上 '東麗道康寧矽酮（股）製）等。又，除上述之熱可塑性彈性體以外，可使用橡膠改性之環氧樹脂。橡膠改性之環氧樹脂可藉由使如，上述之雙酚F型環氧樹脂、雙酚A型環氧樹脂、水楊醛型環氧樹脂 -38- 200910007 、苯酣酚醛型環氧樹脂或甲酚酚醛型環氧樹脂之一部全部之環氧基以兩末端羧酸改性型丁二烯一丙烯腈橡末端胺基改性矽酮橡膠等進行改性而得到。此等彈性，剪斷接著性之點，以兩末端羧基改性丁二烯一丙烯聚合物、具有羥基之聚酯系彈性體的ES PEL (曰立化業（股）製、ESPEL1612、 1620)爲佳。本發明之感光性樹脂組成物中、使用（E )彈性，該含有量相對（A)成分100質量份以2〜30質量佳，4〜20質量份更佳。含有量在2〜30質量份範圍則可更降低硬化膜之高溫領域之彈性率。本發明之感光性樹脂組成物以更含（F )稀釋劑。（F )稀釋劑方面，可使用如如有機溶劑及/或光性單體。有機溶劑方面，可舉例如乙基甲基酮、環己酮類、甲苯、二甲苯、四甲基苯等芳香族烴類、甲基劑、丁基溶纖劑、甲基卡必醇、丁基卡必醇、丙二醇基醚、二丙二醇單乙基醚、二丙二醇二乙基醚、三乙單乙基醚等乙二醇醚類、乙酸乙酯、乙酸丁酯、丁基劑乙酸酯、卡必醇乙酸酯等酯類、辛烷、癸烷等脂肪類、石油醚、石腦油、氫化石腦油、溶煤石油精等石溶劑等。又，光聚合性單體方面，可舉例如2-羥基乙基基）丙烯酸酯、2 -羥基丙基（甲基）丙烯酸酯等羥基 (甲基）丙烯酸酯類、乙二醇、甲氧基四乙二醇、聚醇等乙二醇之單或二（甲基）丙烯酸酯類、N，N -二甲份或膠、體中腈共成工體時份爲內，爲佳聚合酮等溶纖單甲二醇溶纖族烴油系 (甲院基乙二基（ -39- 200910007 甲基）丙烯酸醯胺、N -羥甲基（甲基）丙烯酸醯胺等（甲基）丙烯酸醯胺類、N，N-二甲基胺基乙基（甲基）丙烯酸酯等胺基烷基（甲基）丙烯酸酯類、己二醇、三羥甲基丙烷、季戊四醇、雙（三羥甲基）丙烷、二季戊四醇、三一羥基乙基異氰脲酸酯等多價醇或此等環氧乙烷或環氧丙烷加成物之多價（甲基）丙烯酸酯類、苯氧基乙基（甲基）丙烯酸酯、雙酚A之聚乙氧基二（甲基）丙烯酸酯等苯酚類之環氧乙烷或環氧丙烷加成物之（甲基）丙烯酸酯類、甘油二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、三縮水甘油異氰脲酸酯等縮水甘油醚之（甲基）丙嫌酸醋類、及三聚氰胺（甲基）丙烯酸酯等。此等（F )稀釋劑可1種單獨或2種以上組合使用。 (F )稀釋劑之有機溶劑含有量以調整感光性樹脂組成物之黏度爲目的可適宜調整。又，（F )稀釋劑的光聚合性單體含有量以感光性樹脂組成物之固形分全量爲基準，5〜80質量％爲佳，10〜 70質量％更佳，15〜40質量％特別佳。此含有量未達5 質量％，則光感度低’曝光部於顯像中有變易溶出之傾向，超過8 0質量％，則耐熱性有降低之傾向。又，由可更提升耐熱性之觀點，本發明之感光性樹脂組成物可含（G )硬化劑。硬化劑（G )方面’可舉例如以其本身以熱或紫外線等進行硬化之化合物、或感光性樹脂組成物中光硬化性樹脂成分的（A)含乙烯基之酸改性環氧樹酯之羧基或經基 -40 - 200910007 以熱或紫外線等進行反應、硬化之化合物爲佳。使用該（ G )硬化劑，可使最終得到之硬化膜之耐熱性、密著性、耐藥品性等提升。 (G )硬化劑方面，如熱硬化性化合物，可舉例如環氧化合物、三聚氰胺化合物、尿素化合物、噁唑啉化合物、嵌段型異氰酸酯化合物等。環氧化合物方面，可舉例如雙酚A型環氧樹脂、雙酚f型環氧樹脂、氫化雙酚a型環氧樹脂、溴化雙酚A型環氧樹脂、酚醛型環氧樹脂、雙酚S型環氧樹脂、聯苯基型環氧樹脂、或三縮水甘油異氰脲酸酯等雜環式環氧樹脂、雙二甲酚型環氧樹脂等。三聚氰胺化合物方面，可舉例如三胺基三嗪、六甲氧基三聚氰胺、六丁氧基化三聚氰胺等。尿素化合物方面，可舉例如二羥甲基尿素等。此等（G)硬化劑可1種單獨或2種以上組合使用。感光性樹脂組成物中、（G )硬化劑之含有量以感光性樹脂組成物之固形分全量爲基準，2〜50質量％爲佳， 10〜40質量％更佳’ 15〜30質量％特別佳。此含有量未達2質量％ ’則最終硬化塗膜之耐熱性有變低之傾向，超過5 0質量％ ’則顯像性有降低之傾向。本發明之感光性樹脂組成物中，以更提升硬化膜之耐熱性、密著性、耐藥品性等諸特性爲目的，以含環氧樹脂硬化劑爲佳。如此環氧樹脂硬化劑之具體例方面，可舉例如2 _甲基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑' 2-苯 -41 - 200910007 基咪唑、乙醯胍胺撐二胺、胺、尿素 ;此等有 ;乙基二 6-二甲苯胺、Ν,Ν-嗎啉、六酚）、四聚乙烯苯 ;三丁基 η-丁基（鐵等鳞鹽級銨鹽類苯基鏑六等。此等。使用環之固形分量％更佳本發、塗膜硬 i太酸鎖、 2-苯基-4-甲基_5-羥基甲基咪唑等咪、苯並胍胺等胍胺類；二胺基二苯基 m-二甲苯二胺' 二胺基二苯基磺酸、、尿素衍生物 '三聚氰胺、多鹽基酿機酸鹽及/或環氧加成物；三氟化硼胺基-S-三嗪、2,4 -二胺基-s_三嗪、基-S -三曉等三嗪衍生物類；三甲基 —甲基辛基胺、N -苄基二甲基胺、吡 (N -甲基）三聚氰胺、2,4,6_三（二甲基胍、m -胺基苯酚等三級胺類；聚酚溴化物、酚醛樹脂、烷基酚醛樹脂膦、三苯基膦、三·2-氰乙基膦等有| 2，5 -二羥基苯基）漠化銹、十六院基類；苄基三甲基氯化銨、苯基三丁基 :上述之多元酸酐；二苯基碘鑰四氟氟銻酸鹽、2,4,6 -三苯硫基吡啶鑰鹽環氧樹脂硬化劑可1種單獨或2種以氧樹脂硬化劑時，其含有量以感光性全量爲基準，0.01〜20質量％爲佳，〇明之感光性樹脂組成物，進而，以更度等諸特性爲目的，可因應需要，含二氧化矽、滑石、燒成高領土、碳酸唑衍生物：甲院、m-苯二氰基二醯肼等聚胺類之胺錯合物 2,4-二胺基-胺、三乙醇啶、N -甲基甲基胺基苯乙烯苯酚、等聚苯酚類 _膦類；三-三丁基氯化氯化錢等4 硼酸鹽、三六氟磷酸鹽上組合使用樹脂組成物 0· 1〜10質提升密著性有硫酸鋇、鎂、氧化鋁 -42 - 200910007 、氫氧化鋁、雲母等公知之無機塡料。此等可單獨1種或組合2種以上使用。此等中由提升印刷性及硬化膜之硬度觀點以二氧化矽及硫酸鋇爲佳。又，使用無機塡料時，其含有量以感光性樹脂組成物之固形分全量爲基準，2〜80 質量％爲佳，5〜50質量％更佳，10〜40質量％特別佳。本發明之感光性樹脂組成物，可因應需要，可使用鈦菁素·藍、鈦菁素•綠、碘.綠、重氮黃、結晶紫、氧化鈦、碳黑、萘黑等公知著色劑、對苯二酚、甲基對苯二酚、對苯二酚單甲基醚、兒茶酚、焦掊酚等聚合防止劑、澎潤土、蒙脫石等增黏劑、矽酮系、氟系、乙烯樹脂系之消泡劑、矽烷偶合劑等公知慣用的各種添加劑。進而，可使用溴化環氧化合物、酸改性溴化環氧化合物、鍊化合物、及磷系化合物之磷酸鹽化合物、芳香族縮合磷酸酯、含鹵縮合磷酸酯等難燃劑。本發明之感光性樹脂組成物可藉由使上述各搭配成分以輥磨機、珠磨機等進行均一混練、混合而得。本發明之感光性樹脂組成物，在印刷配線板之阻焊劑、高密度多層板之層間絕緣膜、半導體封裝用阻焊劑等電子材料領域中，可用作像形成性、耐熱性、密著性、機械特性、耐藥品性、電特性等優異之永久遮罩光阻。接著，說明關於使用上述本發明之感光性樹脂組成物之感光性元件。圖1爲表示本發明之感光性元件較佳一實施形態的模式剖面圖。圖1所示之感光性元件1係以支持體1 〇、設置於支持體1 0上之感光性樹脂組成物層1 4所 -43- 200910007 構成。感光性樹脂組成物層1 4爲上述本發明之感光性樹脂組成物所成之層。又，本發明之感光性元件1可使與感光性樹脂組成物層1 4上之支持體1 0相反面F 1以保護薄膜被覆。感光性樹脂組成物層1 4以令本發明之感光性樹脂組成物溶於上述溶劑或混合溶劑成爲固形分30〜70質量％左右之溶液後，將該溶液塗佈於支持體1 0上爲佳。感光性樹脂組成物層1 4厚度雖因用途而異，經由加熱及/或吹附熱風除去溶劑之乾燥後厚度以1 0〜1 〇 0 // m 爲佳，20〜60"m更佳。感光性元件1具備之支持體1 〇方面，可舉例如聚對苯二甲酸乙二酯、聚丙烯、聚乙烯、聚酯等具有耐熱性及耐溶劑性之聚合體薄膜等。支持體10之厚度以5〜100//m爲佳，10〜30/zm更佳。上述般支持體1 〇與感光性樹脂組成物層1 4之2層所成之感光性元件1或支持體1 0與感光性樹脂組成物層1 4 與保護薄膜之3層所成之感光性元件可如該狀態保存，或可介著保護薄膜，捲取爲輥筒狀來保管。接著，說明有關本發明之光阻圖形之形成方法。本發明之光阻圖形之形成方法係包含使上述本發明之感光性樹脂組成物所成之感光性樹脂組成物層層合於基板上之層合步驟；於上述感光性樹脂組成物層照射圖像狀活性光線，光硬化曝光部之曝光步驟；使上述感光性樹脂組成物層未 -44- 200910007 曝光部藉由顯像除去之顯像步驟之方法。對基板（貼銅層合板等）上層合感光性樹脂組成物層，如，可使感光性樹脂組成物以網版印刷法、噴霧法、輥塗法、塗佈法、靜電塗佈法等方法以1 0〜2 0 0 # m之膜厚於基板上塗佈’使塗膜在60〜1 10°C進行乾燥而進行。又，亦可使用上述本發明之感光性元件，進行對基板上層合感光性樹脂組成物層。此時層合方法方面，可舉例如在感光性元件具備保護薄膜時，在除去保護薄膜後，使感光性樹脂組成物層邊加熱至70°C〜130°C左右，邊在基板以 O.IMPa〜IMPa 左右（lkgf/cm2 〜l〇kgf/cm2 左右）之壓力進行壓著之方法等。該層合步驟亦可在減壓下進行。層合有感光性樹脂組成物層之基板表面通常爲金屬面，但並無特別限制。如此一來，對於在基板上所層合之感光性樹脂組成物層，通過負或正型遮罩圖型圖像狀照射活性光線，使曝光部光硬化。此時，使用感光性元件層合感光性樹脂組成物層時，雖然成爲感光性樹脂組成物層上存在有支持體，但此支持體對活性光線爲透明時，可透過支持體照射活性光線，支持體對活性光線顯示遮光性時，除去支持體後再於感光性樹脂組成物層照射活性光線。活性光線光源方面，可舉例如以往公知之光源、如，碳弧燈、水銀蒸氣弧燈、高壓水銀燈、氣氣燈等紫外線、有效發射可見光等者。又’本發明之感光性樹脂組成物及感光性元件使用於 -45- 200910007 經雷射直接描畫曝光法形成像之用途。因此、本發明之光阻圖形之形成方法中，上述曝光步驟以藉由雷射直接描畫曝光法進行爲佳。經雷射直接描畫曝光法進行曝光時，上述曝光步驟以經由波長405 nm之雷射光使感光性樹脂組成物層進行直接描畫曝光’使曝光部光硬化之步驟爲佳。又，藉由直接描畫曝光法進行曝光之雷射光方面，亦可使用如波長 355nm之雷射光。又’曝光步驟中、曝光量以1〇〜l〇〇〇mJ/cm2爲佳。曝光部形成後’曝光部以外之感光性樹脂組成物層（未曝光部）藉由顯像除去，以形成光阻圖形。該未曝光部之除去方法方面’可舉例如感光性樹脂組成物層上存在支持體時’以自動曝光機等除去支持體，經由鹼性水溶液、水系顯像液、有機溶劑等顯像液以濕式顯像、或乾式顯像等除去未曝光部而顯像之方法等。濕式顯像所用之鹼性水溶液方面，可舉例如質量％〜5質量％碳酸鈉之稀釋溶液、0.1〜5質量％碳酸鉀之稀釋溶液、〇丨質量％〜5 質量％氫氧化鈉之稀釋溶液等。鹼性水溶液之pH以9〜 1 1之範圍爲佳’其溫度可搭配感光性樹脂組成物層之顯像丨生而調整。又’鹼性水溶液中可混入界面活性劑、消泡 d 有機丨谷劑寺。上述顯像方式方面，可舉例如浸漬方式噴餘方式、刷式、Scrapping等。接者，作爲顯像後處理，經由使曝光部進行後曝光（糸外線曝光）及/或後加熱可充分硬化得到硬化膜。後曝 -46- 200910007 光以1〜5J/cm2之曝光量進行爲佳。後加熱以100〜2 00 °c 進行3 0分〜1 2小時爲佳。本發明之印刷配線板之製造方法中使藉由上述本發明之光阻圖形之形成方法形成有光阻圖形之電路形成用基板進行蝕刻或鍍敷。在此，上述本發明之感光性樹脂組成物所成之光阻圖形可有效作爲像形成性、耐熱性、密著性、機械特性、耐藥品性、電特性等優異之永久遮罩光阻。【實施方式】 [實施例] 以下，基於實施例及比較例更具體說明本發明，但本發明不被以下實施例所限定。 [合成例1] 加入YDF2001 (東都化成（股）製、雙酚F型環氧樹脂、一般式（5)中、γ2 =縮水甘油基、R12 =氫原子之化合物）475質量份、丙烯酸72質量份、對苯二酚〇.5質量份、卡必醇乙酸酯1 2 0質量份’在9 0 °C進行加熱攪拌溶解反應混合物。接著’使所得之溶液冷卻至6 0。^ ’於其加入氯化苄基三甲基銨2質量份’加熱至100°C ’使反應至固形分酸價成爲ImgKOH/g爲止。進而’加入馬來酸酐9 8質量份與卡必醇乙酸酯8 5質量份，加熱至8 0。(3，使反應約6小時。之後’冷卻至室溫’以卡必醇乙酸酯稀釋至固形分濃度成爲60質量％ ’得到作爲（A)成分之 -47 - 200910007 羧酸改性雙酚F型環氧丙烯酸酯（以下、稱「環氧樹脂 A1」）。 [合成例2] 加入YDCN704 (東都化成（股）製、甲酚酚醛型環氧樹脂、一般式（4)中、Y1:縮水甘油基、Rn =甲基之化合物）22 0質量份、丙烯酸72質量份、對苯二酚K0質量份、卡必醇乙酸酯1 8 0質量份，在9 0 °C進行加熱攪拌溶解反應混合物。接著，使所得之溶液冷卻至6〇r ,於其加入氯化节基三甲基鏡1質量份，加熱至1〇〇。(3，使反應至固形分酸價成爲lmgKOH/g爲止。進而’加入四氫苯二甲酸酐1 52質量份與卡必醇乙酸酯1 00質量份，加熱至 8 0 °C，使反應約6小時。之後，冷卻至室溫，以卡必醇乙酸酯稀釋至固形分濃度成爲60質量％，得到作爲（a ) 成分之羧酸改性甲酚酚醛型環氧丙烯酸酯（以下、稱「環氧樹脂A 2」）。 (實施例1〜5及比較例1〜4 ) 遵照下述表1所示之搭配組成（單元：質量份）搭配組成物後，以3支輥磨機進行混練，加入卡必醇乙酸酯至固形分濃度成爲70質量％，得到感光性樹脂組成物。又 ’下述表1中各成分之搭配量表示固形分之搭配量。 -48- 200910007 【i 比較例4 1〇 CVJ Ο ΙΟ (Ν Ο o q 七 1 I 1 1 1 CO o o T— 1 1 I 比較例3 in (N ο ΙΟ CN ο o q 寸 1 1 1 1 CO 〇 1 o t— 1 義 1 比較例2 m CN ο if) CNJ ο o 1 Ο 七 1 1 CO d 1 1 1 1 1 1 匕較例1 LO C\J ο LO CM ο o 1 Ο — CO d 1 1 1 1 1 幽 1 實施例5 m CNJ ο LO CNJ ο o 〇 I CO d 1 1 1 1 1 1 1 ο τ— 實施例4 LO CM ο LO C\J ο o 〇 1 1 CO 〇 1 幽 1 〇 T— 1 1 1 實施例3 LO CM ο LO CNJ ο o q 七 1 CO d 1 1 1 1 1 1 Ο Τ— 1 實施例2 LO C\J ο LO CN ο o o 七 1 CO o ο Τ— 實施例1 l〇 CM ο LO CN ο o o 七 1 CO o 1 1 1 1 o T— I環氧樹脂A1 環氧樹脂Α2 雙酚F型環氧樹脂 I二氧化石夕 i硫酸鋇 DPHA OXE-01 IC907 香豆素(BC) 香豆素 (C-314T) DETX C152 C153 BMO ΜΒΤ ΜΒΙ ΕΑΒ 樹脂充塡劑交聯劑光聚合起始劑增感劑光起始助劑 -49- 200910007 又，表1中各成分之詳細如以下。雙酌F型環氧樹脂（商品名：YSLV-80XY-F、東都化成公司製）、 DPHA (商品名：KAYARADDPHA、曰本化藥公司製、二季戊四醇六丙烯酸醋）、 OXE-01 (商品名、Ciba Specialty Chemicals 公司製、上述式（9)所表示之1,2-辛院二酮-1-〔4-(苯硫基）苯基〕-2-(〇 -苯甲酿基目弓）、 IC907 (商品名：IRGACURE9〇7 、 Ciba sPecialty Chemicals公司製、下述式（16)所表示之化合物）、香豆素（BC )(商品名：BC、（股）綠化學製、上述式（10)所表示之7,7，-雙（二乙基胺基）氧代（ keto)-香豆素、最大吸收波長：449nm)、香豆素（C-314T)(商品名：C-314T、阿克羅司公司製、下述式（17)所表示之化合物、最大吸收波長： 4 3 5 nm )、 DETX (商品名：KayacureDETX-S、日本化藥公司製、二乙基噻噸酮、最大吸收波長：3 8 3 nm )、 C152(商品名·· Coumarin 152、阿克羅司公司製、下述式（18)所表示之化合物、最大吸收波長.394nm)、 C153(商品名：Coumarin 153、阿克羅司公司製、下述式（19)所表示之化合物、最大吸收波長：423nm)、 MB Ο (上述式（1 2 )所表示之疏基苯並嚼哩）、 MBT (上述式（13)所表示之疏基苯並嚷哩）、 -50- 200910007(15) [In the formula (15), Y11 represents a single bond, a carbon number of 1 to 1 Å, a ring of a carbon number of 4 to 8, an alkyl group, -〇_, -S_, or -S02-, R21 and R22 represent a halogen atom or an alkyl group having 1 to 12 carbon atoms, and p and q represent an integer of 0 to 4, and r is 0 or 1. Specific examples of the divalent phenol represented by the above general formula (15) include, for example, biguanide A, bis-(4-pyridylphenyl)methine, and bis-(4-cysyl-3-methyl group). Phenyl)propane, resorcinol, and the like. These compounds may be used alone or in combination of two or more. Further, an aromatic polyester (e.g., polybutylene terephthalate) portion may be used as a hard segment component, and an aliphatic polyester (e.g., polytetramethylene glycol) portion may be a soft segment component. Multi-block copolymer. Depending on the type, ratio, and molecular weight of the hard segment and the soft segment, there are various levels of interest. Specific examples thereof include Hytrel (manufactured by Du Pont-Toray Co., Ltd.), Pelprene (manufactured by Toyobo Co., Ltd.), and ESPEL (manufactured by Hitachi Chemical Co., Ltd.). Polyamine-based elastomers are roughly classified into two types: polyamine using a hard phase, polyether block guanamine type using a polyether or polyester in a soft phase, and polyether ester block guanamine type -37-200910007. . As the polyamine, for example, polyamines 6, 11, 12, etc. can be used. For example, polyethylene oxide, polypropylene oxide, polytetramethylene glycol or the like can be used. Specifically, the polyamine-based elastomer is, for example, UBE polyamide elastomer (manufactured by Ube Industries, Ltd.), DIAMIDE (manufactured by Daicel-Huels), PEBAX (manufactured by Toray Industries, Ltd.), and GrilonELY (EMS). Japan (share) system, Nopamid (Mitsubishi Chemical Co., Ltd.), Gri lax (Daily Ink (share) system), etc. The acrylic elastomer contains acrylate as a main component, and ethyl acrylate, butyl acrylate, methoxyethyl acrylate or ethoxyethyl acrylate can be used. Further, as the crosslinking point monomer, glycidyl methacrylate, allyl glycidyl ether or the like can be used. Further, acrylonitrile or ethylene may be copolymerized. As the acrylic elastomer, specifically, such as acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate monoethyl acrylate copolymer, acrylonitrile monobutyl acrylate monoglycidyl methacrylate Ester copolymers and the like. The fluorenone-based elastomer may be classified into a polydimethyl siloxane, a polymethyl phenyl siloxane or a polydiphenyl siloxane. Some are also modified with vinyl, alkoxy, and the like. Specific examples of the fluorenone-based elastomer include, for example, the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), the SE series, the CY series, and the SH series (above 'Toray Co., Ltd.). Further, in addition to the above thermoplastic elastomer, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin can be obtained by, for example, the above-mentioned bisphenol F-type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin-38-200910007, benzoquinone type epoxy resin Or all of the epoxy groups in one part of the cresol novolac type epoxy resin are obtained by modifying the carboxylic acid-modified butadiene-acrylonitrile rubber-terminated amine-modified anthrone rubber or the like at both ends. These elastic properties, shearing the adhesion point, ES PEL modified by a carboxyl group at both ends and a polyester elastomer having a hydroxyl group (manufactured by Keli Chemical Co., Ltd., ESPEL 1612, 1620) It is better. In the photosensitive resin composition of the present invention, (E) elasticity is used, and the content is preferably 2 to 30 parts by mass, more preferably 4 to 20 parts by mass, per 100 parts by mass of the component (A). When the content is in the range of 2 to 30 parts by mass, the modulus of elasticity in the high temperature region of the cured film can be further lowered. The photosensitive resin composition of the present invention further contains (F) a diluent. As the diluent (F), for example, an organic solvent and/or a photoactive monomer can be used. Examples of the organic solvent include aromatic hydrocarbons such as ethyl methyl ketone, cyclohexanone, toluene, xylene, and tetramethylbenzene, methyl agents, butyl cellosolve, methyl carbitol, and butyl card. Glycol ethers such as diol, propylene glycol ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethyl monoethyl ether, ethyl acetate, butyl acetate, butyl acetate, card An ester such as an alcoholic acetate, a fat such as octane or decane, a petroleum solvent such as petroleum ether, naphtha, hydrogenated naphtha or petroleum-soluble petroleum spirit. Further, examples of the photopolymerizable monomer include hydroxy (meth) acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl (meth) acrylate, ethylene glycol, and methoxy group. Ethylene glycol mono- or di-(meth) acrylate such as tetraethylene glycol or polyalcohol, N, N-dimethyl or gel, or nitrile in the body, which is internal, preferably a polymerized ketone, etc. Solvent-based monomethylol solute-type hydrocarbon oil system (A-based ethylenediyl (-39-200910007 methyl) decylamine, N-hydroxymethyl (meth) decylamine, etc. Amines, aminoalkyl (meth) acrylates such as N,N-dimethylaminoethyl (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol, bis (trishydroxyl) Polyvalent alcohols such as propane, dipentaerythritol, trishydroxyethyl isocyanurate or polyvalent (meth) acrylates, phenoxy ethoxylates of such ethylene oxide or propylene oxide adducts Ethylene oxide or propylene oxide addition of phenols such as poly(ethoxy) di(meth)acrylates of bis(meth)acrylates and bisphenol A (meth)acrylic acid esters such as (meth) acrylates, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc., and melamine (meth) acrylate, etc. These (F) diluents may be used singly or in combination of two or more kinds. (F) The organic solvent content of the diluent may be appropriately adjusted for the purpose of adjusting the viscosity of the photosensitive resin composition. Further, the photopolymerizable monomer content of the (F) diluent is preferably from 5 to 80% by mass, more preferably from 10 to 70% by mass, even more preferably from 15 to 40% by mass based on the total solid content of the photosensitive resin composition. When the content is less than 5% by mass, the light sensitivity is low. The exposed portion tends to be easily eluted during development, and when it exceeds 80% by mass, the heat resistance tends to be lowered. The photosensitive resin composition of the present invention may contain (G) a curing agent. The curing agent (G) may, for example, be a compound which is cured by heat or ultraviolet rays, or a photosensitive resin composition. Photocurable resin component (A) a carboxyl group of a vinyl group-containing acid-modified epoxy resin or a compound which is reacted and hardened by heat or ultraviolet rays, etc., using the (G) hardener, which can be finally obtained. The heat-resistant property, the adhesion, and the chemical resistance of the cured film are improved. (G) The thermosetting compound may, for example, be an epoxy compound, a melamine compound, a urea compound, an oxazoline compound, or a block type. An isocyanate compound, etc. Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol f type epoxy resin, hydrogenated bisphenol a type epoxy resin, brominated bisphenol A type epoxy resin, and phenolic type ring. A heterocyclic epoxy resin such as an oxygen resin, a bisphenol S type epoxy resin, a biphenyl type epoxy resin, or a triglycidyl isocyanurate, or a bisxylenol type epoxy resin. The melamine compound may, for example, be a triamine triazine, a hexamethoxy melamine or a hexabutoxylated melamine. As the urea compound, for example, dimethylol urea or the like can be exemplified. These (G) hardeners may be used singly or in combination of two or more kinds. In the photosensitive resin composition, the content of the (G) curing agent is preferably 2 to 50% by mass, more preferably 10 to 40% by mass, and more preferably 15 to 30% by mass based on the total solid content of the photosensitive resin composition. good. When the content is less than 2% by mass, the heat resistance of the final cured coating film tends to be low, and when it exceeds 50% by mass, the development property tends to be lowered. In the photosensitive resin composition of the present invention, an epoxy resin-containing curing agent is preferably used for the purpose of improving the heat resistance, adhesion, and chemical resistance of the cured film. Specific examples of the epoxy resin hardener include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazolium 2-benzene-41 - 200910007. Imidazole, acetamidinediamine, amine, urea; these are; ethyldi 6-xylyleneamine, hydrazine, hydrazine-morpholine, hexaphenol), tetrapolyvinylbenzene; tributyl η-butyl (Iron scale salt ammonium salt type phenyl hydrazine six, etc.. etc.. Use of the solid component of the ring is better. The hair, the coating film hard i too acid lock, 2-phenyl-4-methyl _5-hydroxyl Methyl imidazole and the like, guanamine such as benzoguanamine; diaminodiphenyl m-xylenediamine 'diaminodiphenyl sulfonic acid, urea derivative 'melamine, multi-salt based brewing acid Salt and/or epoxy adduct; triazine derivatives such as boron trifluoride amine-S-triazine, 2,4-diamino-s-triazine, ke-S-trioxane; a tertiary amine such as benzyl-methyl octylamine, N-benzyldimethylamine, pyridyl (N-methyl) melamine, 2,4,6-tris(dimethylhydrazine, m-aminophenol; Polyphenol bromide, phenolic resin, alkylphenol phenol phosphine, triphenylphosphine, tris-2-cyanoethyl phosphine There are | 2,5-dihydroxyphenyl) desert rust, hexamethylene base; benzyl trimethyl ammonium chloride, phenyl tributyl: the above polybasic acid anhydride; diphenyl iodine PTFE When the acid salt and the 2,4,6-triphenylthiopyridine salt epoxy resin hardener are used alone or in combination with two kinds of oxygen resin hardeners, the content thereof is 0.01 to 20% by mass based on the total amount of photosensitivity. It is preferable that the photosensitive resin composition of Yuming, and furthermore, for the purpose of more characteristics, etc., may contain cerium oxide, talc, high-smelting terephthalic acid, and carbazole derivatives as needed: 甲院, m-benzene Polyamine amine complex such as cyanoquinone 2,4-diamino-amine, triethanol pyridine, N-methylmethylaminostyrene phenol, isopolyphenols-phosphines; Tributyl chlorinated chlorinated acid, etc. 4 borate, trihexafluorophosphate combined resin composition 0·1~10 quality to enhance adhesion, barium sulfate, magnesium, alumina-42 - 200910007, aluminum hydroxide Or known inorganic materials such as mica. These may be used alone or in combination of two or more. In this case, the printability and the hardness of the cured film are improved. The cerium oxide and cerium sulfate are preferred. When the inorganic cerium is used, the content thereof is based on the total solid content of the photosensitive resin composition, preferably 2 to 80% by mass, more preferably 5 to 50% by mass. 10 to 40% by mass is particularly preferable. The photosensitive resin composition of the present invention may be used as needed, such as phthalocyanine blue, phthalocyanine green, iodine, green, diazo yellow, crystal violet, titanium oxide, Commonly known coloring agents such as carbon black and naphthalene black, polymerization inhibitors such as hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol, bentonite, montmorillonite Various known additives such as a tackifier, an anthrone, a fluorine-based, a vinyl-based antifoaming agent, and a decane coupling agent. Further, a brominated epoxy compound, an acid-modified brominated epoxy compound, a chain compound, a phosphorus compound such as a phosphorus compound, an aromatic condensed phosphate, or a halogen-containing condensed phosphate can be used. The photosensitive resin composition of the present invention can be obtained by uniformly kneading and mixing the above-mentioned respective components in a roll mill, a bead mill or the like. The photosensitive resin composition of the present invention can be used as an image forming property, heat resistance, and adhesion in the field of electronic materials such as a solder resist of a printed wiring board, an interlayer insulating film of a high-density multilayer board, and a solder resist for semiconductor packaging. Excellent permanent mask photoresist, mechanical properties, chemical resistance, electrical properties, etc. Next, a photosensitive element using the photosensitive resin composition of the present invention described above will be described. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element of the present invention. The photosensitive element 1 shown in Fig. 1 is composed of a support 1 〇 and a photosensitive resin composition layer 14 provided on a support 10 - 43 - 200910007. The photosensitive resin composition layer 14 is a layer of the photosensitive resin composition of the present invention described above. Further, the photosensitive element 1 of the present invention can be coated with a protective film on the opposite surface F 1 of the support 10 on the photosensitive resin composition layer 14. The photosensitive resin composition layer 14 is prepared by dissolving the photosensitive resin composition of the present invention in a solvent or a mixed solvent to have a solid content of about 30 to 70% by mass, and then applying the solution to the support 10 good. The thickness of the photosensitive resin composition layer 14 varies depending on the application, and the thickness of the solvent after drying by heating and/or blowing hot air is preferably 10 to 1 〇 0 / m, and more preferably 20 to 60 " m. The support member 1 of the photosensitive element 1 may, for example, be a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene or polyester. The thickness of the support 10 is preferably 5 to 100 / / m, more preferably 10 to 30 / zm. Sensitivity of the photosensitive element 1 or the support 10 and the photosensitive resin composition layer 14 and the protective film formed by the two layers of the above-mentioned support 1 〇 and the photosensitive resin composition layer 14 The element can be stored in this state, or can be stored in a roll shape by a protective film. Next, a method of forming the photoresist pattern according to the present invention will be described. The method for forming a photoresist pattern of the present invention comprises a lamination step of laminating a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention on a substrate; and an irradiation pattern of the photosensitive resin composition layer Photoreactive light ray, exposure step of photocuring exposure portion; method of developing the photosensitive resin composition layer by a development step of removing the exposure portion by -44-200910007. The photosensitive resin composition layer is laminated on a substrate (a copper-clad laminate or the like), and the photosensitive resin composition can be subjected to a screen printing method, a spray method, a roll coating method, a coating method, an electrostatic coating method, or the like. The film thickness of 10 0 to 2 0 0 # m is applied to the substrate to dry the coating film at 60 to 10 ° C. Further, the photosensitive resin composition layer of the present invention may be laminated on the substrate by using the photosensitive element of the present invention. In the case of the lamination method, for example, when the photosensitive element is provided with a protective film, after removing the protective film, the photosensitive resin composition layer is heated to about 70 ° C to 130 ° C while the substrate is O. A method in which the pressure of IMPa to IMPa (about lkgf/cm2 to l〇kgf/cm2) is pressed. This lamination step can also be carried out under reduced pressure. The surface of the substrate on which the photosensitive resin composition layer is laminated is usually a metal surface, but is not particularly limited. In this manner, the photosensitive resin composition layer laminated on the substrate is irradiated with active light by a negative or positive mask image, and the exposed portion is photocured. In this case, when the photosensitive resin composition layer is laminated with a photosensitive element, the support is present on the photosensitive resin composition layer. However, when the support is transparent to the active light, the support can be irradiated with the active light. When the support exhibits light-shielding properties to the active light, the support is removed and the active light is applied to the photosensitive resin composition layer. Examples of the active light source include a conventionally known light source such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, an ultraviolet lamp, or the like, and effective emission of visible light. Further, the photosensitive resin composition and the photosensitive element of the present invention are used in the application of the image forming method by the laser direct drawing exposure method from -45 to 200910007. Therefore, in the method of forming a photoresist pattern of the present invention, the exposure step is preferably carried out by a direct direct exposure method by laser. When the exposure is performed by the laser direct drawing exposure method, the exposure step is preferably a step of directly exposing the photosensitive resin composition layer by laser light having a wavelength of 405 nm to light-cure the exposed portion. Further, laser light having a wavelength of 355 nm can also be used in terms of laser light for exposure by direct drawing exposure. Further, in the exposure step, the exposure amount is preferably 1 〇 to l 〇〇〇 mJ/cm 2 . The photosensitive resin composition layer (unexposed portion) other than the exposed portion after the exposure portion is formed is removed by development to form a photoresist pattern. In the method of removing the unexposed portion, for example, when the support is present on the photosensitive resin composition layer, the support is removed by an automatic exposure machine or the like, and the developing solution is passed through an aqueous solution such as an alkaline aqueous solution, a water-based developing solution, or an organic solvent. A method of developing an image by removing an unexposed portion, such as wet development or dry development. The alkaline aqueous solution used for wet development may, for example, be a diluted solution of mass% to 5% by mass of sodium carbonate, a diluted solution of 0.1 to 5% by mass of potassium carbonate, or a dilution of 〇丨% by mass to 5% by mass of sodium hydroxide. Solution, etc. The pH of the alkaline aqueous solution is preferably in the range of 9 to 1 1 and the temperature can be adjusted in accordance with the development of the photosensitive resin composition layer. In addition, a surfactant can be mixed into the alkaline aqueous solution, and the defoaming d organic glutinous rice temple can be mixed. Examples of the above development method include a immersion method, a spray method, a brush type, and a scrapping method. As a post-development treatment, the cured portion can be sufficiently cured by subjecting the exposed portion to post-exposure (external exposure) and/or post-heating to obtain a cured film. After exposure -46- 200910007 light is preferably performed at an exposure of 1 to 5 J/cm 2 . After the heating is carried out at 100 to 2 00 °c for 30 minutes to 1 hour. In the method for producing a printed wiring board of the present invention, the circuit-forming substrate on which the photoresist pattern is formed by the above-described method for forming a photoresist pattern of the present invention is etched or plated. Here, the photoresist pattern formed by the photosensitive resin composition of the present invention can effectively serve as a permanent mask photoresist excellent in image formability, heat resistance, adhesion, mechanical properties, chemical resistance, electrical properties, and the like. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the following examples. [Synthesis Example 1] 475 parts by mass of YDF2001 (manufactured by Tohto Kasei Co., Ltd., bisphenol F type epoxy resin, general formula (5), γ2 = glycidyl group, R12 = hydrogen atom), and acrylic acid 72 mass Parts, hydroquinone oxime. 5 parts by mass, carbitol acetate 120 parts by mass' were heated and stirred at 90 ° C to dissolve the reaction mixture. The resulting solution was then cooled to 60. ^' was added to 2 parts by mass of benzyltrimethylammonium chloride and heated to 100 ° C to bring the reaction to a solid acid value of 1 mgKOH/g. Further, 98 parts by mass of maleic anhydride and 85 parts by mass of carbitol acetate were added and heated to 80. (3, the reaction was allowed to proceed for about 6 hours. After that, 'cooling to room temperature' was diluted with carbitol acetate to a solid content of 60% by mass. ' Obtained as a component (A) -47 - 200910007 Carboxylated bisphenol F-type epoxy acrylate (hereinafter referred to as "epoxy resin A1"). [Synthesis Example 2] YDCN704 (made by Toho Chemical Co., Ltd.), cresol novolac type epoxy resin, general formula (4), Y1: 22 parts by mass of a glycidyl group, a compound of Rn = methyl group, 72 parts by mass of acrylic acid, 60 parts by mass of hydroquinone K, and 80 parts by mass of carbitol acetate, and heated and dissolved at 90 ° C The reaction mixture was then cooled to 6 Torr, and 1 part by mass of a benzyl chloride trimethyl mirror was added thereto, and heated to 1 Torr. (3, the reaction was carried out until the solid value of the acid was 1 mgKOH/g. Further, '52 parts by mass of tetrahydrophthalic anhydride and 100 parts by weight of carbitol acetate were added, and the mixture was heated to 80 ° C to carry out a reaction for about 6 hours. Thereafter, it was cooled to room temperature to form a card. The alcohol acetate was diluted to a solid content concentration of 60% by mass to obtain a carboxylic acid-modified cresol novolac type as the component (a). Epoxy acrylate (hereinafter referred to as "epoxy resin A 2"). (Examples 1 to 5 and Comparative Examples 1 to 4) According to the composition (unit: parts by mass) shown in Table 1 below, the composition was mixed. The mixture was kneaded by three roll mills, and carbitol acetate was added until the solid content concentration became 70% by mass to obtain a photosensitive resin composition. Further, the combination of the components in the following Table 1 indicates the combination of the solid components. -48- 200910007 [i Comparative Example 4 1〇CVJ Ο ΙΟ (Ν Ο oq 七 1 I 1 1 1 CO oo T-1 1 I Comparative Example 3 in (N ο ΙΟ CN ο oq 寸 1 1 1 1 CO 〇1 ot-1 义1 Comparative Example 2 m CN ο if) CNJ ο o 1 Ο 七 1 1 CO d 1 1 1 1 1 1 匕Comparative example 1 LO C\J ο LO CM ο o 1 Ο — CO d 1 1 1 1 1 幽1 Example 5 m CNJ ο LO CNJ ο o 〇I CO d 1 1 1 1 1 1 1 ο τ - Example 4 LO CM ο LO C\J ο o 〇1 1 CO 〇1 幽1 〇T—1 1 1 Example 3 LO CM ο LO CNJ ο oq VII 1 CO d 1 1 1 1 1 1 Ο Τ — 1 Example 2 LO C\J ο LO CN ο oo 七 1 CO o ο Τ — Implementation Example 1 l〇CM ο LO CN ο oo 7 1 CO o 1 1 1 1 o T—I Epoxy Resin A1 Epoxy Resin Α2 Bisphenol F-type Epoxy Resin I Disulfide 夕i Sulfate DPHA OXE-01 IC907 Coumarin (BC) Coumarin (C-314T) DETX C152 C153 BMO ΜΒΤ ΜΒΙ 树脂 Resin-filling agent crosslinking agent Photopolymerization initiator sensitizer Photoinitiator-49- 200910007 Further, the details of each component in Table 1 are as follows. Double-type F-type epoxy resin (trade name: YSLV-80XY-F, manufactured by Tohto Kasei Co., Ltd.), DPHA (trade name: KAYARADDPHA, manufactured by Sakamoto Chemical Co., Ltd., dipentaerythritol hexaacrylate), OXE-01 (trade name) 1,2-Xinyuan Dione-1-[4-(phenylthio)phenyl]-2-(anthracene-benzoyl) ketone, which is represented by the above formula (9), manufactured by Ciba Specialty Chemicals Co., Ltd. , IC907 (trade name: IRGACURE 9〇7, a compound of the following formula (16), manufactured by Ciba sPecialty Chemicals Co., Ltd.), coumarin (BC) (trade name: BC, (share) green chemical system, the above formula ( 10) 7,7,-bis(diethylamino)oxo (keto)-coumarin, maximum absorption wavelength: 449 nm), coumarin (C-314T) (trade name: C-314T) , a compound represented by the following formula (17), maximum absorption wavelength: 4 3 5 nm ), DETX (trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd., diethyl thioxanthone) , Maximum absorption wavelength: 3 8 3 nm ), C152 (trade name · Coumarin 152, Acroix company, compound represented by the following formula (18), maximum absorption 394 nm), C153 (trade name: Coumarin 153, compound of Acroix, compound represented by the following formula (19), maximum absorption wavelength: 423 nm), MB Ο (expressed by the above formula (1 2 )疏基苯制哩), MBT (the base benzopyrene represented by the above formula (13)), -50- 200910007

[化 30][化30]

(H3C)2N(H3C) 2N

[化 31][化31]

(18)(18)

<評估基板之製作〉 -51 - (19) 200910007 使實施例1〜5及比較例1〜4之感光性樹脂組成物以網版印刷法，使用12 0網目之帝特龍網，以乾燥後厚度成爲約20#m之方式，於貼銅層合板進行塗佈，藉由熱風循環式乾燥機，在80 °C進行30分鐘乾燥。藉此，於貼銅層合板上層合有感光性樹脂組成物所成之感光性樹脂組成物層的評估基板。使用所得到之基板，以下所示之方法進行各特性之評估。其結果一倂表示於表2。 (光感度）於評估基板之感光性樹脂組成物層上搭載負像掩模（ StauffeMl段階梯板），再於其上搭載使波長4〇5±30nm 之光進行分光之帶通濾波器的朝日分光股份公司製分光濾光片（商品名：H G 0 4 0 5 )，在此狀態，使用5 k W短弧燈爲光源之平行光曝光機（商品名：EXM-1201、ORC MANUFACTURING CO., LTD.製），照射曝光量 lOOmJ/cm2之紫外線。又，使透過帶通濾波器之光的照度以紫外線累積光量計（商品名：UIT -1 5 0 - A、U s h i ο I n c .製、亦可使用作爲照度計）及受光器之「UVD-S405」（商品名、感度波長域：320nm〜470nm、絕對校正波長： 40 5 nm )進行測定，定照度X曝光時間爲曝光量。之後，以1質量％之碳酸鈉水溶液（30。(：）、60秒、1 .8kgf/cm2 之壓力進行噴霧顯像，溶解除去未曝光部。除去未曝光部後’錯由測定於貼銅層合板上所形成之光硬化膜之階梯板的段數’評估感光性樹脂組成物之光感度。光感度以階梯 -52- 200910007 板段數表示，此階梯板段數愈高，光感度愈高。 (顯像性）於評估基板之感光性樹脂組成物層上，放置via mask 開口尺寸爲100/ζιη之遮罩，再於其上，搭載令波長4〇5土 3 Onm之光進行分光之帶通濾波器的朝日分光股份公司製分光濾光片（商品名：HG0405 )，在此狀態，使用5kW 短弧燈爲光源之平行光曝光機（商品名：EXM-1201、 ORC MANUFACTURING CO., LTD.製），照射曝光量 1 00m J/cm2之紫外線。又，使透過帶通濾波器之光的照度以紫外線累積光量計（商品名：UIT-150-A、Ushio Inc_製、亦可使用作爲照度計）及受光器之「UVD-S405」（商品名、感度波長域：3 2 0 n m〜4 7 0 n m、絕對校正波長： 405 nm )進行測定，定照度x曝光時間爲曝光量。之後，以1 %之碳酸鈉水溶液（3 0 °C ) 、6 0秒、〇 · 1 8 Μ P a之壓力進行噴霧顯像。之後，目視觀察所形成之via開口部，用以下標準進行顯像性評估。 A :可得開口尺寸爲8 0 # m以上之v i a開口部的情況 B:可得開口尺寸爲60#111以上未達80/zm之via開口部的情況， C: via開口部之開口尺寸爲未達60/zm的情況。 <試驗板之製作> -53- 200910007 於評估基板之感光性樹脂組成物層上搭載使波長405 ±3 Onm之光進行分光之帶通濾波器的朝日分光股份公司製分光濾光片（商品名：HG0405 )，在此狀態，使用5kW 短弧燈爲光源之平行光曝光機（商品名：EXM-1201、 ORC MANUFACTURING CO., LTD.製），照射曝光量 1 0 0mJ/Cm2之紫外線。又，使透過帶通濾波器之光的照度以紫外線累積光量計（商品名：UIT-150-A、Ushio Inc.製、亦可使用作爲照度計）及受光器之「UVD-S405」（商品名、感度波長域：3 20nm〜470nm、絕對校正波長： 405 nm )進行測定，定照度X曝光時間爲曝光量。之後，以1質量％之碳酸鈉水溶液（3 0 °C ) 、6 0秒、1 · 8 k g f / c m2 之壓力進行噴霧顯像，溶解除去未曝光部。接著，以1 5 0 °C進行1小時加熱，製作具有感光性樹脂組成物層之硬化膜之試驗板。使用所得之試驗板，以下所示之方法進行各特性之評估。其結果一倂表示於表2。 (密著性）對試驗板，藉由以JIS K5400爲基準之方法，進行剝離試驗。即，於試驗板之硬化膜上製作1 mm之棋盤格 1 00個，在棋盤格貼附玻璃紙膠帶後剝離。觀察剝離後的棋盤格之剝離狀態，用以下基準進行密著性評估。 A :棋盤格之90/ 1 00以上無剝離， B:棋盤格之50/100以上未達90/100爲無剝離， C :棋盤格之未達5 0/ 1 00爲無剝離。 -54- 200910007 (耐溶劑性）使試驗板在異丙基醇中’在室溫進行3 0分鐘浸漬後 ’目視觀察硬化膜之外觀有無異常。之後，使玻璃紙膠帶貼附於硬化膜’再撕起進行剝離試驗，確認硬化膜是否由貼銅層合板剝離。由該等結果，用以下基準進行耐溶劑性評估。 A :硬化膜之外觀無異常，且剝離試驗中無剝離者， B :硬化膜之外觀有異常’或、剝離試驗中有剝離者 (焊接耐熱性）於試驗板之硬化膜表面塗佈松香系助熔劑後，'浸漬於 26 0°C焊接槽1 〇秒。以此作爲1循環，重複6循環後，目視觀察硬化膜之外觀，用以下基準進行焊接耐熱性之評估〇 A:硬化膜之外觀無異常（剝離、膨脹），無焊接之沈浸(solder submersion )者、 B :硬化膜之外觀有異常（剝離、膨賬）、或、有焊接之沈浸者。 <經日安定性評估用溶液之調製及經日安定性之評估> 表1所示之組成中，除去硬化劑之雙酌F型環氧樹脂、及光聚合性化合物之環氧樹脂A 1及A 2 ’加入卡必醇乙 -55- 200910007 酸酯調整黏度至50Pa«s，得到經所得溶液放置於室溫（25 t )，膠體化爲止之時間。其結果如表曰安定性評估用溶液。將測定溶液變不流動或產生 2所示。 -56- 200910007 【cnim 比較例4 CM < Ο ο ο >3個月比較例3 CO < Ο ο ο >3個月比較例2 無法形成像 >3個月 I 比較例1 無法形成像 >3個月 I 實施例5 00 0Q < < < 1曰 (膠體）實施例4 σ> < < < < >3個月實施例3 CD < < < < >3個月實施例2 σ> < < < < ί >3個月實施例1 ο Τ— < < < < >3個月光感度 (405nm) 顯像性耐溶劑性焊接耐熱性密著性經曰安定性 -57- 200910007 由表2所示之結果可知’實施例1〜5之感光性樹脂組成物，與比較例1〜4之感光性樹脂組成物比較’確認其光感度優。又’比較例1及2之感光性樹脂組成物對 405nm之波長的光感度不足，故經曝光不會光硬化’無法形成像。 [產業上之利用可能性] 如以上說明，根據本發明，可提供使用波長3 7〇nm〜 4 5 0 n m之範圍內之曝光光的光阻圖形形成時、尤其係’使用波長40 5nm之雷射光的直接描畫曝光法之光阻圖形形成時之感度優異的感光性樹脂組成物、使用其之感光性元件、光阻圖形之形成方法及印刷配線板之製造方法。又，根據本發明之感光性樹脂組成物及感光性元件，以波長 405 nm之藍色雷射光作爲光源之直接描畫曝光法中、可形成以往製造困難之高密度光阻圖形，且可得耐熱性、耐濕熱性（剪斷接著性）、密著性、機械特性、電特性優異之高性能硬化膜。因此、本發明之感光性樹脂組成物及感光性元件適用於印刷配線板、高密度多層板及半導體封裝等之製造。【圖式簡單說明】 [圖1 ]表示本發明之感光性元件較佳之一實施形態的模式剖面圖。 -58- 200910007 【主要元件符號說明】 1 :感光性元件 1 〇 :支持體 1 4 :感光性樹脂組成物層 -59-<Production of Evaluation Substrate> -51 - (19) 200910007 The photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were dried by a screen printing method using a 120 mesh mesh After the thickness was about 20 #m, it was applied to a copper-clad laminate, and dried at 80 ° C for 30 minutes by a hot air circulation dryer. Thereby, an evaluation substrate of the photosensitive resin composition layer formed of the photosensitive resin composition was laminated on the copper-clad laminate. Using the obtained substrate, the evaluation of each characteristic was carried out by the method shown below. The results are shown in Table 2. (Light sensitivity) A negative image mask (a Stauffe M1 step plate) is mounted on the photosensitive resin composition layer of the evaluation substrate, and a solar-passive filter for band-passing the light having a wavelength of 4 〇 5 ± 30 nm is mounted thereon. A spectroscopic filter made by Seiko Co., Ltd. (trade name: HG 0 4 0 5 ). In this state, a parallel light exposure machine using a 5 k W short arc lamp as a light source (trade name: EXM-1201, ORC MANUFACTURING CO., LTD.), irradiated with an exposure amount of 100 mJ/cm2 of ultraviolet light. Further, the illuminance of the light transmitted through the band pass filter is measured by an ultraviolet light accumulation amount (trade name: UIT -1 150-A, U shi I I nc. can also be used as an illuminometer) and "UVD of the light receiver". -S405" (trade name, sensitivity wavelength range: 320 nm to 470 nm, absolute correction wavelength: 40 5 nm) was measured, and the illuminance X exposure time was the exposure amount. Thereafter, spray development was carried out with a 1% by mass aqueous sodium carbonate solution (30% (:), 60 seconds, and 1.8 kgf/cm2 to dissolve and remove the unexposed portion. After the unexposed portion was removed, the error was measured by copper plating. The number of segments of the stepped plate of the photohardenable film formed on the laminate plate is evaluated as the light sensitivity of the photosensitive resin composition. The light sensitivity is expressed by the number of steps -52 - 200910007, and the higher the number of the step plates, the higher the light sensitivity (Development) On the photosensitive resin composition layer of the evaluation substrate, a mask having a via mask opening size of 100/ζι is placed, and then a light having a wavelength of 4 〇 5 Å 3 Onm is mounted thereon. A spectroscopic filter (product name: HG0405) manufactured by Asahi Seiki Co., Ltd., a parallel light exposure machine using a 5 kW short arc lamp as a light source (trade name: EXM-1201, ORC MANUFACTURING CO. , manufactured by LTD., irradiated with an ultraviolet ray of 1 00 m J/cm 2 , and the illuminance of the light transmitted through the band pass filter is measured by an ultraviolet ray (trade name: UIT-150-A, Ushio Inc., also "UVD-S405 can be used as an illuminometer" and a light receiver (Product name, sensitivity wavelength range: 3 2 0 nm to 4 70 nm, absolute correction wavelength: 405 nm), the illuminance x exposure time is the exposure amount. After that, 1% sodium carbonate aqueous solution (3 0) Spray development was carried out at a pressure of 60 ° C, 〇·1 8 Μ P a. Thereafter, the via opening formed was visually observed, and the development evaluation was performed by the following criteria: A : Available opening size was 8 In the case of the opening portion of the 0 # m or more, the case where the opening size is 60#111 or more and the via opening portion of 80/zm is not available, and the opening size of the C: via opening portion is less than 60/zm. <Production of Test Plate> -53-200910007 A spectroscopic filter made by Asahi Seisaku Co., Ltd. is mounted on a photosensitive resin composition layer of the evaluation substrate, and a band pass filter that splits light having a wavelength of 405 ± 3 Onm is mounted ( Product name: HG0405) In this state, a parallel light exposure machine (trade name: EXM-1201, ORC MANUFACTURING CO., LTD.) using a 5 kW short arc lamp as a light source, and an ultraviolet light having an exposure amount of 100 mJ/cm 2 In addition, the illuminance of the light transmitted through the band pass filter is accumulated by ultraviolet light. "Product name: UIT-150-A, Ushio Inc., can also be used as an illuminometer" and "UVD-S405" (light name: sensitivity wavelength range: 3 20 nm to 470 nm, absolute correction wavelength: 405) The measurement is performed in nm, and the exposure time X exposure time is the exposure amount. Thereafter, spray development was carried out at a pressure of 1% by mass of sodium carbonate aqueous solution (30 ° C), 60 seconds, and 1·8 k g f / c m 2 to dissolve and remove the unexposed portion. Subsequently, the film was heated at 150 ° C for 1 hour to prepare a test plate having a cured film of a photosensitive resin composition layer. Using the obtained test panels, the evaluation of each characteristic was carried out by the method shown below. The results are shown in Table 2. (Adhesion) The test piece was subjected to a peeling test by a method based on JIS K5400. That is, 100 pieces of 1 mm checkerboard was made on the cured film of the test plate, and peeled off after attaching the cellophane tape to the checkerboard. The peeling state of the checkerboard after peeling was observed, and the adhesion evaluation was performed using the following criteria. A: There is no peeling of 90/100 00 or more in the checkerboard, B: 50/100 or more of the checkerboard is less than 90/100, and there is no peeling. C: The checkerboard is less than 5 0/100. -54-200910007 (Solvent resistance) After the test plate was immersed in isopropyl alcohol at room temperature for 30 minutes, the appearance of the cured film was visually observed for abnormality. Thereafter, the cellophane tape was attached to the cured film and peeled off again to carry out a peeling test, and it was confirmed whether or not the cured film was peeled off from the copper-clad laminate. From these results, the solvent resistance evaluation was performed using the following criteria. A: The appearance of the cured film is not abnormal, and there is no peeling in the peeling test. B: The appearance of the cured film is abnormal. ' Or the peeling test has peeled off (welding heat resistance). The rosin is coated on the surface of the cured film of the test plate. After the flux, 'immersed in a solder bath at 260 ° C for 1 sec. Using this as one cycle, after repeating 6 cycles, the appearance of the cured film was visually observed, and the solder heat resistance was evaluated by the following criteria: A: The appearance of the cured film was free from abnormalities (peeling, swelling), and solder submersion. , B: The appearance of the cured film is abnormal (peeling, bulging), or there is a weld immersion. <Preparation of the solution for the evaluation of the stability of the sun and the evaluation of the stability of the day-by-day stability> In the composition shown in Table 1, the double-type F-type epoxy resin from which the hardener is removed, and the epoxy resin A of the photopolymerizable compound 1 and A 2 'Add carbitol B-55-200910007 The acid ester was adjusted to a viscosity of 50 Pa «s, and the resulting solution was allowed to stand at room temperature (25 t ) for gelatinization. The results are shown in the table for stability evaluation. The measurement solution is not flowed or produced as shown in 2. -56- 200910007 [cnim Comparative Example 4 CM < Ο ο ο > 3 months Comparative Example 3 CO < Ο ο ο > 3 months Comparative Example 2 Unable to form like > 3 months I Comparative Example 1 Formation image > 3 months I Example 5 00 0Q <<< 1 曰 (colloid) Example 4 σ ><<<>> 3 months Example 3 CD <<<<> 3 months Example 2 σ ><<< ί > 3 months Example 1 ο Τ - <<<<> 3 months light sensitivity (405 nm Developmental solvent-resistant soldering heat-resistant adhesiveness stability -57-200910007 From the results shown in Table 2, the photosensitive resin compositions of Examples 1 to 5 and the photosensitive sheets of Comparative Examples 1 to 4 were known. The comparison of the composition of the resin was confirmed to be excellent in light sensitivity. Further, in the photosensitive resin compositions of Comparative Examples 1 and 2, the light sensitivity at a wavelength of 405 nm was insufficient, so that the image could not be formed by exposure without photo-curing. [Industrial Applicability] As described above, according to the present invention, it is possible to provide a resist pattern using exposure light in a wavelength range of 3 7 〇 nm to 450 nm, in particular, a wavelength of 40 5 nm is used. A photosensitive resin composition excellent in sensitivity when forming a resist pattern of a direct light exposure method of a laser light, a photosensitive element using the same, a method of forming a photoresist pattern, and a method of manufacturing a printed wiring board. Further, according to the photosensitive resin composition and the photosensitive element of the present invention, in the direct drawing exposure method using blue laser light having a wavelength of 405 nm as a light source, a high-density photoresist pattern which is difficult to manufacture in the past can be formed, and heat resistance can be obtained. A high-performance cured film excellent in properties, heat and humidity resistance (shear adhesion), adhesion, mechanical properties, and electrical properties. Therefore, the photosensitive resin composition and the photosensitive element of the present invention are suitable for use in the production of printed wiring boards, high-density multilayer boards, and semiconductor packages. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element of the present invention. -58- 200910007 [Explanation of main component symbols] 1 : Photosensitive element 1 〇 : Support 1 4 : Photosensitive resin composition layer -59-

Claims

200910007 十、申請專利範圍 1 · 一種感光性樹脂組成物，其特徵係含有： (A) 含乙烯基之酸改性環氧樹酯、 (B) 含具有肟酯鍵結之化合物的光聚合起始劑、 (C) 含下述一般式（1)所表示之香豆素化合物之增感劑， [化1] 〇200910007 X. Patent Application No. 1 · A photosensitive resin composition characterized by: (A) a vinyl-containing acid-modified epoxy resin, (B) a photopolymerization containing a compound having a oxime ester bond Starting agent, (C) a sensitizing agent containing a coumarin compound represented by the following general formula (1), [Chemical Formula 1] 〇

Z2 (1) 〔式（1)中，Z1表示鹵原子、碳數1〜20之烷基、碳數 3〜10之環烷基、碳數6〜14之芳基、胺基、碳數1〜1〇之烷基胺基、碳數1〜20之二烷基胺基、锍基、碳數1〜 1 〇之烷基锍基、烯丙基、碳數1〜20之羥基烷基、羧基、烷基之碳數係1〜10之羧基烷基、烷基之碳數係1〜10之醯基、碳數1〜20之烷氧基、碳數1〜20之烷氧基羰基、或、含雜環之基，Z2表示鹵原子、碳數1〜20之烷基、碳數3〜10之環烷基 '碳數6〜14之芳基、胺基、碳數1〜 10之烷基胺基、碳數1〜20之二烷基胺基、锍基 '碳數1 〜10之烷基锍基、烯丙基、碳數1〜20之羥基烷基、烷基之碳數係1〜10之醯基、碳數1〜20之烷氧基、含雜環之基、或、下述一般式（2)所表示之基，s表示〇〜4之整數，又，式（2)中之Z1及s與式（1)中之Ζι及s同義 -60- 200910007 。又，式（1)中之Z1及s與式（2)中之z1及s可各自相同或相異，進而，式（1)或式（2)中，S爲2以上時 ’複數存在之Z 1可各自相同或相異，任二者可互相鍵結形成環〕 miZ2 (1) [In the formula (1), Z1 represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amine group, and a carbon number of 1 a monoalkylamino group having 1 to 20 Å, a dialkylamino group having 1 to 20 carbon atoms, a fluorenyl group, an alkyl fluorenyl group having 1 to 1 carbon atom, an allyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, The carboxyl group and the alkyl group have a carboxyalkyl group of 1 to 10, a carbon number of the alkyl group of 1 to 10, an alkoxy group having 1 to 20 carbon atoms, and an alkoxycarbonyl group having 1 to 20 carbon atoms. Or a heterocyclic group-containing group, Z2 represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amine group, and a carbon number of 1 to 10 Alkylamino group, dialkylamino group having 1 to 20 carbon atoms, alkyl fluorenyl group having 1 to 10 carbon atoms of fluorenyl group, allyl group, hydroxyalkyl group having 1 to 20 carbon atoms, and carbon number of alkyl group a fluorenyl group of 1 to 10, an alkoxy group having 1 to 20 carbon atoms, a heterocyclic group-containing group, or a group represented by the following general formula (2), and s represents an integer of 〇~4, and 2) Z1 and s are synonymous with Ζι and s in formula (1) -60- 200910007. Further, Z1 and s in the formula (1) and z1 and s in the formula (2) may be the same or different, and in the formula (1) or (2), when S is 2 or more, the plural is present. Z 1 may be the same or different, and any two may be bonded to each other to form a ring] mi

2 .如申請專利範圍第1項之感光性樹脂組成物，其中更含有（D)具硫醇基之化合物。 3.如申請專利範圍第1或2項之感光性樹脂組成物，其中該具肟酯鍵結之化合物係含下述一般式（3 )或（4 )所表示之化合物之至少一種者， [化3]2. The photosensitive resin composition of claim 1, wherein (D) a compound having a thiol group is further contained. 3. The photosensitive resin composition according to claim 1 or 2, wherein the oxime ester-bonded compound contains at least one of the compounds represented by the following general formula (3) or (4), [ 3]

鏈院酿基（alkanoyl)、雙鍵係不與羯基共軛之碳數4〜6 $ 取代或未取代之鏈烯醯基（alkenoyl)、取代或未取代，％、<本甲醒基、碳數2〜6之取代或未取代之烷氧基羰基、或取代或未取代之苯氧基羰基，R2、r3及R4各自獨立，表 -61 - 200910007 示鹵原子、碳數1〜12之取代或未取代之烷基、取代或未取代之環戊基、取代或未取代之環己基、取代或未取代之本基、取代或未取代之苄基、取代或未取代之苯甲酿基' 碳數2〜12之取代或未取代之鏈烷醯基、碳數2〜12之取代或未取代之烷氧基羰基、或、取代或未取代之苯氧基羰基，ml表示〇〜4之整數，m2及m3各自獨立，表示〇〜 5之整數，又，ml爲2以上時，複數存在之艮2可各自相同或相異，m2爲2以上時，複數存在之R3可各自相同或相異，m3爲2以上時，複數存在之R4可各自相同或相異Alkanoyl, double bond, carbon number conjugated to sulfhydryl groups 4~6 $ substituted or unsubstituted alkenoyl, substituted or unsubstituted, %, < a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted phenoxycarbonyl group, and R2, r3 and R4 are each independently, and the halogen atom and the carbon number are 1 to 12 in Table-61 - 200910007. Substituted or unsubstituted alkyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted base, substituted or unsubstituted benzyl, substituted or unsubstituted benzoate a substituted or unsubstituted alkane fluorenyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, or a substituted or unsubstituted phenoxycarbonyl group, and ml represents 〇~ An integer of 4, m2 and m3 are each independent, and represent an integer of 〇~5. When ml is 2 or more, 艮2 of the plural may be the same or different, and when m2 is 2 or more, R3 of the plural may be the same Or different, when m3 is 2 or more, the plural R4 may be the same or different

〔式（4)中，R5表示取代或未取代之苯基、碳數] 6之取代或未取代之烷基、取代或未取代之苯基、碳數 —20之取代或未取代之烷基、碳數5〜8之取代或未取代之環烷基、碳數2〜20之取代或未取代之鏈烷醯基、或、取代或未取代之苯甲酿基，R6表示碳數2〜12之取代或未取代之鏈院醯基、雙鍵係不與羯基共軛之碳數4〜6之取代或未取代之㈣縣、取代或未取代之苯甲醯基、碳數 2 6之取代或未取代之院氧基_基、⑤、取代或未取代之苯氧鞋基，r7表示氫原子、_原子、碳數卜Μ之取代 -62 - 200910007 或未取代之烷基、取代或未取代之環戊基、取代或未取代之環己基、取代或未取代之苯基、取代或未取代之苄基、取代或未取代之苯甲醯基、碳數2〜12之取代或未取代之鏈烷醯基、碳數2〜12之取代或未取代之烷氧基羰基、或、取代或未取代之苯氧基鑛基’ R8、R9及R1Q各自獨立，表示鹵原子、碳數1〜12之取代或未取代之烷基、取代或未取代之環戊基、取代或未取代之環己基、取代或未取代之苯基、取代或未取代之苄基、取代或未取代之苯甲醯基、碳數2〜12之取代或未取代之鏈烷醯基、碳數2〜12之取代或未取代之烷氧基羰基、或、取代或未取代之苯氧基鑛基，m4及m5各自獨立，表不〇〜3之整數，m6表示〇〜5之整數，又，m4爲2以上時’複數存在之R8可各自相同或相異，m5爲2以上時’複數存在之R9可各自相同或相異，m6爲2以上時，複數存在之R1G可各自相同或相異〕。 4.如申請專利範圍第1〜3項中任一項之感光性樹脂組成物，其中該（A )含乙烯基之酸改性環氧樹酯係選自下述一般式（5)所表示之酚醛型環氧樹脂、下述一般式 (6)所表示之雙酚型環氧樹脂、及、下述一般式（7)所表示之水楊醛型環氧樹脂所成群之至少1種環氧樹脂（a )與含乙烯基單羧酸（b)進行反應所得之樹脂， -63- 200910007 [化5][In the formula (4), R5 represents a substituted or unsubstituted phenyl group, a carbon number] 6 substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a carbon number of 20 substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group having 5 to 8 carbon atoms, a substituted or unsubstituted alkane group having 2 to 20 carbon atoms, or a substituted or unsubstituted benzoyl group, and R6 represents a carbon number of 2~ a substituted or unsubstituted chain fluorenyl group, a double bond, a carbon number of 4 to 6 which is not conjugated to a fluorenyl group, or a substituted or unsubstituted (IV) county, substituted or unsubstituted benzamidine group, carbon number of 2 6 Substituted or unsubstituted oxyl group, 5, substituted or unsubstituted phenoxy shoe base, r7 represents a hydrogen atom, a _ atom, a carbon number dip substitution -62 - 200910007 or an unsubstituted alkyl group, a substitution Or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted benzinyl, substituted with carbon number 2~12 or Unsubstituted alkane fluorenyl group, substituted or unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, or substituted or unsubstituted phenoxy mineral group 'R8, R9 and R1Q are each independently and represent a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, and a substitution. Or an unsubstituted benzyl group, a substituted or unsubstituted benzinyl group, a substituted or unsubstituted alkaneyl group having 2 to 12 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, or a substituted or unsubstituted phenoxy mineral group, m4 and m5 are each independently, and represent an integer of ～3, m6 represents an integer of 〇~5, and when m4 is 2 or more, the plural R8 may be the same or Differently, when m5 is 2 or more, the plural R9 may be the same or different, and when m6 is 2 or more, the plural R1G may be the same or different. 4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (A) vinyl group-containing acid-modified epoxy resin is selected from the group consisting of the following general formula (5) At least one of the phenolic epoxy resin, the bisphenol epoxy resin represented by the following general formula (6), and the salicylaldehyde epoxy resin represented by the following general formula (7) A resin obtained by reacting an epoxy resin (a) with a vinyl-containing monocarboxylic acid (b), -63- 200910007 [Chemical 5]

〔式（5)中’ R11表示氫原子或甲基，γΐ表示氫原子或縮水甘油基（但’氫原子/縮水甘油基（莫耳比）爲0 / 100〜30/70) ，nl表示1以上之整數，又，複數存在之 R11及Y1可各自相同或相異〕 [化6][In the formula (5), 'R11 represents a hydrogen atom or a methyl group, and γΐ represents a hydrogen atom or a glycidyl group (but 'hydrogen atom/glycidyl group (mole ratio) is 0 / 100 to 30/70), and nl represents 1 The above integers, in addition, the plural R11 and Y1 may be the same or different] [Chem. 6]

〔式（6)中’ R12表示氫原子或甲基’ γ2表示氳原子或縮水甘油基（但，氫原子/縮水甘油基（莫耳比）爲〇/ 100〜3 0/ 7〇 )’ n2表示1以上之整數，又，複數存在之 R1 2及Y2可各自相同或相異〕 -64- 200910007 [化7][In the formula (6), 'R12 represents a hydrogen atom or a methyl group' γ2 represents a halogen atom or a glycidyl group (however, the hydrogen atom/glycidyl group (mole ratio) is 〇/100~3 0/7〇)' n2 An integer representing 1 or more, and R1 2 and Y2 in the plural may be the same or different. -64- 200910007 [Chem. 7]

，氫原子 n3表示1 相同或相與於該支一項之感含：使由組成物所驟；於該令曝光部未曝光部成方法，直接描繪光硬化之對藉由申〔式（7 )中，Y3表示氫原子或縮水甘油基（但 /縮水甘油基（莫耳比）爲0/ 100〜3 0/ 70 )，以上之整數，又，複數存在之R11及Υ3可各自異〕。 5. 一種感光性元件，其特徵係具備支持體持體上所形成之由申請專利範圍第1〜4項中任光性樹脂組成物所成之感光性樹脂組成物層。 6. 一種光阻圖形之形成方法，其特徵係包申請專利範圍第1〜4項中任一項之感光性樹脂成之感光性樹脂組成物層層合於基板上之層合步感光性樹脂組成物層，圖像狀照射活性光線後，光硬化之曝光步驟；使該感光性樹脂組成物層之經由顯像除去之顯像步驟。 7. 如申請專利範圍第6項之光阻圖形之形其中該曝光步驟爲經由波長405nm之雷射光，以之方式曝光該感光性樹脂組成物層後，使曝光部步驟。 8. 一種印刷配線板之製造方法，其特徵係請專利範圍第6或7項之光阻圖形之形成方法形成有光阻 -65 - 200910007 圖形之電路形成用基板進行蝕刻或鍍敷。 -66-, the hydrogen atom n3 represents the same or the same as the sense of the branch: the composition is caused by the step; in the exposure portion of the exposed portion of the method, directly depicting the photohardening pair by the formula (7 In the formula, Y3 represents a hydrogen atom or a glycidyl group (but / glycidyl group (mole ratio) is 0/100 to 3 0/70), the above integer, and, in the plural, R11 and Υ3 may be different. A photosensitive element comprising a photosensitive resin composition layer formed of a photosensitive resin composition of the first to fourth aspects of the invention, which is formed on a support body. A method for forming a photoresist pattern, characterized in that the photosensitive resin composition layer of the photosensitive resin according to any one of claims 1 to 4 is laminated on the substrate, and the laminating step photosensitive resin is laminated on the substrate. The composition layer is an exposure step of photocuring after irradiating the active light with an image, and a developing step of removing the photosensitive resin composition layer by development. 7. The shape of the photoresist pattern according to claim 6 wherein the exposure step is to expose the photosensitive resin composition layer by laser light having a wavelength of 405 nm, and then expose the portion. A method of manufacturing a printed wiring board, characterized in that the method for forming a photoresist pattern according to the sixth or seventh aspect of the invention is formed by etching or plating a substrate for forming a circuit of a photoresist - 65 - 200910007. -66-