200922396 六、發明說明： 【發明所屬之技術領域] 本發明係關於多層印刷佈線板用絕緣樹脂組成物、 '材之絕緣樹脂片、多層印刷佈線板及半導體裝置。土 . 【先前技術】 一近年來，隨著電子機器之高機能化等之要求，電子零件之 两密度集錢、甚至高密度絲化等正進㈣，使用於此等 C)之高密度安裝對應的印刷佈線板等，係較習知更進一步 展著小型化及高密度化。對於此印刷佈線板等之高密度化的 對應，大多採用增層方式之多層印刷佈線板。 增層方式之乡層印_線板，料係將由樹驗成物所構 成之厚度町的絕緣層解體f路層進行積層成形 而製造。又’作為導體電路層間之連接方法，係取代習知之 鑽孔加卫’可舉例如雷射法、光照法等之針孔形成。此等方 〇法係藉由自由地配置小孔徑之針孔以達成高密度化，並提案 對應於各方法之各種增層用層間絕緣材料。 :、、;而’以雷射照射進行開孔後，於以開孔部之樹脂殘逢去 除步驟中有去鑽渣（desmear)性降低的問題。 此問題在要求伴隨近年來之高密度減化之細微佈線加 、隋况或為了抑制多層印刷佈線板之翘曲而使樹脂組成 物之線熱膨脹係數降低的情況，將顯著地發生。 (專利文獻1)日本專利特開平〇7_1〇6767號公報 97132656 200922396 (專利文獻2)日本專利特開2002-305374號公報 (專利文獻3)日本專利特開2003-73543號公報 【發明内容】 . (發明所欲解決之問題） 本發明係提供一種於多層印刷佈線板製作步驟中之雷射 照射後的樹脂殘渣去除步驟中，去鑽渣性優越的多層印刷佈 線板用絕緣樹脂組成物，以及附有基材之絕緣樹脂片，並提 〇 供使用本案發明之多層印刷佈線板用絕緣樹脂組成物的熱 衝擊性或吸濕焊料耐熱性等之可靠性優越的多層印刷佈線 板以及半導體裝置。 (解決問題之手段） 此種目的可藉由下述（1M10)記載之本發明而達成。 (1)一種絕緣樹脂組成物，係多層印刷佈線板用絕緣樹脂組 成物，其特徵為，以 ❼ （A)胺基矽烷偶合劑 (B) 平均粒控2. 0 // m以下之二氧化石夕 (C) 環氧樹脂 • (D)苯氧基樹脂 '=為必要成分’並含有樹脂組成物之14重·X上且79重 量％以下的上述（C)環氧樹脂，樹脂組成物之硬化物的線熱膨 脹係數在25ΐ至15代之範圍内為35卿以下，且玻璃轉移 溫度（¾)為靴以下，樹脂組成物之最低動態黏度為 97132656 200922396 2000Pa · s 以下。 (2)如（1)之樹脂組成物，其中，上述（a)胺基矽烷偶合劑為 N-苯基-3-胺基丙基三曱氧基矽烷。 - (3)如（1)之樹脂組成物，其中，上述（B)二氧化矽之比表面 - 積為1. 〇m2/g以上且200m2/g以下。 (4) 如（1)之樹脂組成物，其中，上述（B)二氧化矽之含量為 樹脂組成物之20重量％以上且85重量％以下。 (5) 如（1)之樹脂組成物，其中，上述（C)環氧樹脂係選自雙 酚A型環氧樹脂、聯苯基芳烷基型環氧樹脂、四甲基聯苯基 型環氧樹脂所組成群的至少1種。 (6) 如（1)之樹脂組成物，其中，上述樹脂組成物係進一步含 有含氮原子之硬化促進劑。 (7) 如（1)之樹脂組成物，其中，上述苯氧基樹脂係具有選自 雙紛A骨架、雙紛F骨架及雙紛s骨架所組成群之至少i 〇 種骨架的苯氧基樹脂。 -種附有基材之絕緣樹脂片，係於基材上形成由⑴之樹 脂組成物所形成之絕緣層而成。 •⑼一種多層印刷佈線板，係將⑻之附有基材之絕緣樹脂片 -重疊於内層電路板之單面或雙面上，並予以加熱加壓成型而 成0 係於(9)之多層印刷佈線板上搭載半 (10)—種半導體裝置， 導體元件而成。 97132656 200922396 (發明效果） 本發明中於基板上形成由多層印刷饰線板用絕緣樹^且 成物所構成之絕緣層而成的附有基材 _層印刷佈線板製作步驟中之雷射照射後的樹脂殘渔去除: .驟巾’去鑽錄優越，且使贱多層印刷佈線㈣絕緣· 組成物❹層印刷佈線板、半導體裝置係熱衝擊性或吸濕^ 料耐熱性等之可靠性優越。 、 〇 【實施方式】 以下針對本發明之多層印刷佈線板用絕緣樹脂组成物 行詳細說明。 本發明之多層印刷佈線板用絕緣樹脂組成物，係以 (A) 胺基矽烷偶合劑 (B) 平均粒徑2.0# m以下之二氧化石夕 (C) 環氧樹脂 (D) 笨氧基樹脂 作為必要成分，並含有樹脂組成物之14重量％以上且Μ重 «以下的上述⑹環氧樹脂，樹月旨組成物之硬化物的線熱臉 .脹係數在25t至15(rc之範圍内為35酬以下，且玻璃轉移 -溫度（Tg)為1’以下，樹月旨組成物之最低動態黏度為 2000Pa · s 以下。 樹脂組成物之硬化物的線熱膨脹係數，係於25它至15〇 C之fe圍内為35ppm以下，藉此，可抑制在製造多層印刷佈 97132656 200922396 線板時將由該樹脂組成物所構成之絕緣層形成於基材上而 成的附有基材之絕緣樹脂片進行壓製成形時的輕曲，並可抑 制多層印刷佈線板之翹曲。又，使用該樹脂組成物之多層印 - 刷佈線板’係可抑制回焊時之基板翹•曲。再者，使用該樹脂 . 組成物之半導體裝置，係於熱衝擊試驗中可抑制習知半導體 裝置中常出現的導體電路層之剝離或裂痕的發生。 樹脂組成物之硬化物的線熱膨脹係數較佳為3〇ppm以 C^ 下。更佳為20ppm以下。藉此，可使其他特性之均衡優越。 於此’所謂「樹脂組成物之硬化物的線熱膨脹係數」，係 指於使s亥樹脂組成物硬化而製作多層印刷佈線板時之條件 下，使该樹脂組成物硬化而得之硬化物的線熱膨脹係數。亦 即’於與使用樹脂組成物製作附有基材之絕緣樹脂片，至使 用δ亥附有基材之絕緣樹脂片製作多層印刷佈線板的步驟為 相同的條件下，使該樹脂組成物硬化而得之硬化物的線熱膨 〇 脹係數。 另外，該線熱膨脹係數「在25°c至150°c之範圍内為35ppm 以下」，係指將該樹脂組成物於與多層印刷佈線板之製作條 . 件相同之條件下進行硬化而得到硬化物，將該硬化物以既定 - 升溫速度自25°C升溫至150Ϊ為止時的線熱膨脹量，使用熱 機械分析裝置（TMA)，測定硬化物於25°C下之長度T1與150 C下之長度T2，藉此予以算出。作為具體之測定條件，較 佳係依5C/分鐘之固定速度將測試片自25°C升溫至150 97132656 200922396 乞。又’作為線熱膨脹係數之測定的測域片，可使用與實際 之多層印刷佈線板中之絕緣層為相同膜厚者，或者亦 較實際之多層印刷佈線板中之絕緣層更厚之膜厚者。例如， .可使用使實際之多層印刷佈線板所使用之附有基材之絕緣 .樹脂片2片重疊並予以硬化者，作為測試片。如此，藉由使 用較實際絕緣層更厚之測試片，可提高線熱膨服係數:測定 再現性^ 〇 該樹脂組成物之最低動態黏度為2000Pa· s以下。藉此， 提升多層印刷佈線板製造時之成形性，且藉由與含有⑷胺 基石夕烧偶合劑的相乘效果’而使多層印刷佈線板製造步驟中 之雷射照射後之樹脂殘渣去除步驟中的去鑽渣性優越。 樹脂組成物之最低動態黏度，可針對自將樹脂組成物塗佈 於基材上並予以乾燥所得的絕緣層樹脂片剝離基材的片 材，藉由使用黏彈性測定裝置而進行測定。又，該片材並非 Ci使樹脂組成物硬化的硬化物，而是在將樹脂組成物塗佈於基 材上日守，以去除為了對該樹脂組成物賦予塗佈性而與該樹脂 組成物混合的溶劑為目的，使基材上之該樹脂組成物乾燥的 - 狀態。 • 具體而言，係對上述片材，使用黏彈性測定裝置，於既定 之頻率條件下，進行以既定升溫速度升溫至既定溫度時的平 面摩擦測定’將所得之複數黏度（complex viscosity)之極 少值作為樹脂組成物之最低動態黏度。更具體而言，上述黏 97132656 9 200922396 彈性測定裝置之平面摩擦測定，較佳係依頻率1〇Hz、升溫 速度3°C/分鐘自50°C升溫至22CTC而實施。又，升溫速度 並不限定於3 °C /分鐘。 -另外，除了上述線熱膨脹係數為35ppm以下以及上述最低 .動態黏度為2, OOOPa· s以下，藉由使樹脂組成物之硬化物 的玻璃轉移溫度為190°C以下，可使多層印刷佈線板製造步 驟中之雷射照射後之樹脂殘渣去除步驟的去鑽潰性更加提 〇 升。又，可得到多層印刷佈線板之與鄰接層之密接性優越的 絕緣層。 於此’「樹脂組成物之硬化物的玻璃轉移溫度」，係指於使 該樹脂組成物硬化而製作多層印刷佈線板時之相同條件 下，使§亥樹脂組成物硬化而得之硬化物的玻璃轉移溫度。亦 即，於與使用樹脂組成物製作附有基材之絕緣樹脂片、至使 用該附有基材之絕緣樹脂片製作多層印刷佈線板為止的步 ϋ 驟為相同的條件下’使該樹脂組成物硬化而得之硬化物的玻 璃轉移溫度。 該硬化物之玻璃轉移溫度，可使用一般手法進行測定，例 . 如使用動態黏彈性測定裝置。具體而言，較佳係將以3Χ：/ . 分鐘之升溫速度將測試片進行升溫時之tand之峰值位置 作為樹脂組成物之硬化物的玻璃轉移溫度。 本發明之樹脂組成物中所使用之（A)胺基矽烷偶合劑，並 無特別限定，可舉例如：N-丁基胺基丙基三曱氧基矽烷、N_ 97132656 10 200922396 乙基胺基異丁基三甲氧基矽烷、N-曱基胺基丙基三曱氧基矽 烷、N-苯基-3-胺基丙基三曱氧基矽烷、3_(N_烯丙基胺基） 丙基三曱氧基矽烷、（環己基胺基曱基）三乙氧基矽烷、N_ - 環己基胺基丙基三甲氧基石夕院、N-乙基胺基異丁基甲氧基二 • 乙氧基矽烷、（苯基胺基甲基）甲基二甲氧基矽烧、N-苯基胺 基曱基三乙氧基矽烷、N-甲基胺基丙基曱基二甲氧基矽烷 等。此等之中，較佳為N-苯基_3一胺基丙基三甲氧基矽烷。 0 藉此，於多層印刷佈線板製造步驟中之雷射照射後之樹脂殘 清去除步射’可㈣去鑽紐優綱乡層印刷佈線板用絕 緣樹脂組成物。 (A)胺基矽烷偶合劑之含量係相對於（幻二氧化矽重 量份，較佳為〇.〇1重量％以上且5重量％以下。更佳為 重里％以上且3重置％以下。若偶合劑之含量超過上述上限 值，則於製造多層印刷佈線時，有由本發明之樹脂組成物所 U形成之絕緣層出關痕的情形，若未滿上述下限值，則有電 路與由本發明之樹脂組成物所形成之絕緣層間的密接力降 低的情形。 本發明之樹脂組成物所使用之上述⑻二氧切，較佳為 氧切1佳為球狀熔融二氧化[⑻二氧化石夕相 Π他f機填充材，由低熱膨脹性優越的方面而言為較 使二大有破碎狀、球狀等，較佳為球狀。若為球狀 即使夕層印刷佈線板用絕緣樹脂組成財之⑻二氧化石夕含 97132656 11 200922396 量多’流動性仍優越。又，上述球狀二氧切之製造方法並 無特別限定，可藉公知方法而獲得嗜為±述球狀二氧化石夕 之製造方法’可舉例如乾式二氧切法、赋二氧化石夕法、 • 由溶膠-凝膠法進行之二氧化矽製造方法等。 • 上述⑻二氧化石夕之含量並無特別限定，較佳為樹脂組成 物之20重量％以上且85重量％以下。更佳為25重量％以上且 75重量％以下。若⑻二氧化石夕之含量未滿上述下限值，則 〇有線熱膨脹係數變高或吸水率變高的情況。另外，若超過上 述上限值，則由於樹脂組成物之流動性降低，故有絕緣層之 成形性降低的情形。藉由使二氧化石夕之含量成為上述範圍 内，可使樹脂組成物之線熱膨脹係數成為35卯m以下。 尚且，本發明中，含有成分相對於樹脂組成物之含量，係 指將以含有成分之溶解及/或分散為目的而含有之溶劑予以 去除之成分的合計量設為100重量％者。 〇 上述⑻二氧化碎之平均粒徑為2/^以下。藉由使用平均 粒徑為以下之二氧化石夕，可防止樹脂清漆中之⑻二氧 化石夕沉殿等之現象。另—方面，⑻二氧化歡平均粒徑較 -佳為〇. 〇5"m以上。若⑻二氧化石夕之平均粒徑未滿〇· 〇5 則於使用本㈣〇層印刷佈線板賴緣樹脂組成物 調製樹脂清漆時，由於樹脂清漆之黏度變高，故有對製作附 有基材之絕緣樹脂片時之作業性造成影響的情形。藉由將⑻ 二氧化石夕之平均粒徑設為上述範圍内，可使此等特性之均衡 97132656 12 200922396 優越。⑻一氣化矽之平均粒徑之更 以下。 υ.ίβιη以上且ίο -㈣财㈣島津製作所孤ΙΜ_等 夕之粗粒:割程度並無特別限定，較 此，可去除5_上Τ即不含粒徑5㈣以上之粗粒。藉 Ο[Technical Field] The present invention relates to an insulating resin composition for a multilayer printed wiring board, an insulating resin sheet of a material, a multilayer printed wiring board, and a semiconductor device. [Prior Art] In recent years, with the high functionalization of electronic equipment, etc., the two-density collection of electronic parts, even high-density silking, etc. (4), use this high-density installation of C) Corresponding printed wiring boards and the like are further miniaturized and increased in density. In order to increase the density of the printed wiring board or the like, a multilayer printed wiring board of a build-up type is often used. In the layering method of the layering method, the material is produced by laminating the insulating layer disintegration layer of the thickness of the thickness of the tree. Further, as a method of connecting the conductor circuit layers, a pinhole formation such as a laser method or a light illumination method can be used instead of the conventional hole drilling. These methods are to achieve high density by freely arranging pinholes of small apertures, and various interlayer insulating materials for layering corresponding to the respective methods are proposed. After the opening is performed by laser irradiation, there is a problem that the desmear property is lowered in the resin residue removal step in the opening portion. This problem occurs remarkably in the case where it is required to reduce the linear thermal expansion coefficient of the resin composition with the fine wiring addition, the entanglement, or the warpage of the multilayer printed wiring board. (Patent Document 1) Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. 2003-30543 (Patent Document 3). (Problem to be Solved by the Invention) The present invention provides an insulating resin composition for a multilayer printed wiring board excellent in slag-removing property in a resin residue removing step after laser irradiation in a multilayer printed wiring board manufacturing step, and A multilayer printed wiring board and a semiconductor device having excellent reliability such as thermal shock resistance or heat-absorbing solder heat resistance of the insulating resin composition for a multilayer printed wiring board of the present invention are used. (Means for Solving the Problem) Such an object can be achieved by the present invention described in the following (1M10). (1) An insulating resin composition, which is an insulating resin composition for a multilayer printed wiring board, characterized in that the bismuth (A) amino decane coupling agent (B) has an average particle size of 2. 0 // m or less. Shi Xi (C) Epoxy Resin • (D) phenoxy resin '= is an essential component' and contains the above-mentioned (C) epoxy resin, resin composition of 14 parts by weight of the resin composition and 79% by weight or less. The linear thermal expansion coefficient of the cured product is 35 sec or less in the range of 25 ΐ to 15 generations, and the glass transition temperature (3⁄4) is below the boot, and the lowest dynamic viscosity of the resin composition is 97,132,656, 2009, 22, 396, 2000 Pa·s or less. (2) A resin composition according to (1), wherein the (a) amino decane coupling agent is N-phenyl-3-aminopropyltrimethoxy decane. (3) The resin composition according to (1), wherein the surface area-product of the (B) cerium oxide is 1. 〇m2/g or more and 200 m2/g or less. (4) The resin composition of (1), wherein the content of the (B) cerium oxide is 20% by weight or more and 85% by weight or less based on the resin composition. (5) The resin composition according to (1), wherein the (C) epoxy resin is selected from the group consisting of bisphenol A type epoxy resins, biphenyl aralkyl type epoxy resins, and tetramethylbiphenyl type At least one of the groups consisting of epoxy resins. (6) The resin composition according to (1), wherein the resin composition further contains a hardening accelerator containing a nitrogen atom. (7) The resin composition according to (1), wherein the phenoxy resin has a phenoxy group selected from the group consisting of a double A skeleton, a double F skeleton, and a double s skeleton. Resin. An insulating resin sheet having a substrate attached thereto is formed by forming an insulating layer formed of the resin composition of (1) on a substrate. (9) A multilayer printed wiring board in which the insulating resin sheet with the substrate attached to (8) is superposed on one or both sides of the inner layer circuit board, and is heated and pressed to form a multilayer of (9) A half (10) semiconductor device and a conductor element are mounted on the printed wiring board. 97132656 200922396 (Effect of the Invention) In the present invention, laser light is formed in a step of fabricating a substrate-layer printed wiring board in which an insulating layer composed of an insulating tree for a multilayer printed wiring board is formed on a substrate. Residual resin fishing after removal: .Surveying of the 'sliding towel' is excellent, and the reliability of the multilayer printed wiring (4), the composition of the printed circuit board, the thermal shock of the semiconductor device, or the heat resistance of the moisture absorption device superior. [Embodiment] The following is a detailed description of the insulating resin composition for a multilayer printed wiring board of the present invention. The insulating resin composition for a multilayer printed wiring board of the present invention is an (A) amino decane coupling agent (B) having an average particle diameter of 2.0 # m or less of cerium oxide (C) epoxy resin (D) The resin is an essential component, and contains the above-mentioned (6) epoxy resin having a weight of 14% by weight or more of the resin composition, and the linear thermal expansion coefficient of the cured product of the composition of the tree is 25t to 15 (the range of rc) The inside is 35 or less, and the glass transition-temperature (Tg) is 1' or less, and the lowest dynamic viscosity of the composition of the tree is 2000 Pa·s or less. The linear thermal expansion coefficient of the cured product of the resin composition is 25 The inside of the 15 〇C is 35 ppm or less, thereby suppressing the insulation of the substrate which is formed by forming an insulating layer composed of the resin composition on the substrate when manufacturing the multilayer printed fabric 97132656 200922396. The resin sheet is lightly bent during press forming, and warpage of the multilayer printed wiring board can be suppressed. Further, the multilayer printed wiring board using the resin composition can suppress the warpage of the substrate during reflow. Using the resin. The semiconductor package of the composition It is possible to suppress the occurrence of peeling or cracking of the conductor circuit layer which is often found in conventional semiconductor devices in the thermal shock test. The linear thermal expansion coefficient of the cured product of the resin composition is preferably 3 〇ppm to C^. More preferably In addition, the balance of the other characteristics is excellent. The term "linear thermal expansion coefficient of the cured product of the resin composition" means the condition for producing a multilayer printed wiring board by curing the resin composition. The linear thermal expansion coefficient of the cured product obtained by curing the resin composition, that is, the insulating resin sheet with the substrate formed by using the resin composition, and the insulating resin sheet with the substrate attached thereto The step of multilayer printed wiring board is a linear thermal expansion coefficient of the cured product obtained by hardening the resin composition under the same conditions. Further, the linear thermal expansion coefficient is "in the range of 25 ° C to 150 ° C. 35 ppm or less means that the resin composition is cured under the same conditions as those of the multilayer printed wiring board, and the cured product is obtained at a predetermined temperature increase rate from 2 The amount of linear thermal expansion when the temperature was raised to 150 Torr at 5 ° C was measured by measuring the length T1 of the cured product at 25 ° C and the length T2 at 150 C using a thermomechanical analyzer (TMA). The condition is preferably that the test piece is heated from 25 ° C to 150 97132656 200922396 固定 at a fixed speed of 5 C / min. Further, as a measuring piece for measuring the thermal expansion coefficient of the wire, it can be used in the actual multilayer printed wiring board. The insulating layer is the same film thickness, or is thicker than the insulating layer in the actual multilayer printed wiring board. For example, the substrate may be used for insulating the actual multilayer printed wiring board. Two sheets of the resin sheet were overlapped and hardened as a test piece. Thus, by using a test piece thicker than the actual insulating layer, the coefficient of linear thermal expansion can be improved: measurement reproducibility 〇 The minimum dynamic viscosity of the resin composition is 2,000 Pa·s or less. Thereby, the moldability at the time of manufacture of the multilayer printed wiring board is improved, and the resin residue removal step after the laser irradiation in the multilayer printed wiring board manufacturing step is performed by the multiplication effect with the (4) amine-based smouldering agent. The slag-removing property in the middle is superior. The lowest dynamic viscosity of the resin composition can be measured by peeling the substrate from the insulating resin sheet obtained by applying the resin composition onto the substrate and drying it, using a viscoelasticity measuring device. Moreover, this sheet is not a cured product in which the resin composition is cured by Ci, but the resin composition is applied to the substrate, and the resin composition is removed to impart coating properties to the resin composition. The solvent is mixed for the purpose of drying the resin composition on the substrate. • Specifically, the above-mentioned sheet is subjected to a flat friction measurement when the temperature is raised to a predetermined temperature at a predetermined temperature increase rate using a viscoelasticity measuring device, and the complex viscosity obtained is extremely small. The value is the lowest dynamic viscosity of the resin composition. More specifically, the above-mentioned adhesion 97132656 9 200922396 The flat friction measurement of the elastic measuring device is preferably carried out by raising the temperature from 50 ° C to 22 CTC at a frequency of 1 〇 Hz and a temperature increase rate of 3 ° C / min. Further, the temperature increase rate is not limited to 3 ° C / min. Further, in addition to the above-mentioned linear thermal expansion coefficient of 35 ppm or less and the above minimum dynamic viscosity of 2, OOO Pa·s or less, the multilayer printed wiring board can be obtained by setting the glass transition temperature of the cured product of the resin composition to 190 ° C or lower. The de-drilling property of the resin residue removal step after laser irradiation in the manufacturing step is further increased. Further, an insulating layer excellent in adhesion to the adjacent layer of the multilayer printed wiring board can be obtained. The term "glass transition temperature of the cured product of the resin composition" refers to a cured product obtained by curing the resin composition under the same conditions when the resin composition is cured to produce a multilayer printed wiring board. Glass transfer temperature. That is, the resin composition is made under the same conditions as those in the case where the resin composition with the resin composition is used to form the insulating resin sheet with the substrate, and the insulating resin sheet with the substrate is used to produce the multilayer printed wiring board. The glass transition temperature of the hardened material obtained by hardening the object. The glass transition temperature of the cured product can be measured by a general method, for example, using a dynamic viscoelasticity measuring device. Specifically, it is preferable to use the peak position of the tand when the test piece is heated at a temperature increase rate of 3 Χ: / . minute as the glass transition temperature of the cured product of the resin composition. The (A) amino decane coupling agent used in the resin composition of the present invention is not particularly limited, and examples thereof include N-butylaminopropyltrimethoxy decane, and N_97132656 10 200922396 ethylamino group. Isobutyltrimethoxydecane, N-decylaminopropyltrimethoxy decane, N-phenyl-3-aminopropyltrimethoxy decane, 3-(N-allylamino)propyl Tris-methoxy decane, (cyclohexylamino fluorenyl) triethoxy decane, N-cyclohexylaminopropyl trimethoxy sylvestre, N-ethylaminoisobutyl methoxy bis ethoxylate Decane, (phenylaminomethyl)methyldimethoxysulfonium, N-phenylaminomercaptotriethoxydecane, N-methylaminopropylmercaptodimethoxydecane, and the like. Among these, N-phenyl-3-monopropyltrimethoxydecane is preferred. In this way, the resin residue after the laser irradiation in the manufacturing process of the multilayer printed wiring board is removed, and the insulating resin composition for the printed wiring board of the New Zealand line can be drilled. The content of the (A) amino decane coupling agent is preferably 〇 〇 1% by weight or more and 5% by weight or less, more preferably 5% by weight or more and 3 % by weight or less, based on the weight fraction of the imaginary cerium oxide. When the content of the coupling agent exceeds the above upper limit, when the multilayer printed wiring is produced, there is a case where the insulating layer formed of the resin composition U of the present invention has a mark, and if the lower limit is not satisfied, the circuit and the circuit are The case where the adhesion between the insulating layers formed by the resin composition of the present invention is lowered. The above (8) dioxo used in the resin composition of the present invention, preferably oxygen cut 1 is preferably spherical molten dioxide [(8) dioxide. Shi Xixiang Π f f f f f , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Resin composition (8) sulphur dioxide eve 97232656 11 200922396 The amount of liquidity is still superior. Further, the method for producing the spheroidal dioxo prior is not particularly limited, and a known method can be used to obtain a spheroidal shape. Oxidized stone eve method of manufacture For example, a dry dioxane method, a cerium dioxide method, a cerium oxide production method by a sol-gel method, etc. • The content of the above (8) sulphur dioxide is not particularly limited, and is preferably a resin composition. 20% by weight or more and 85% by weight or less, more preferably 25% by weight or more and 75% by weight or less. If the content of the (8) silica dioxide is less than the above lower limit value, the linear thermal expansion coefficient of the crucible becomes high or the water absorption rate becomes In addition, when the above-mentioned upper limit is exceeded, the fluidity of the resin composition is lowered, so that the moldability of the insulating layer is lowered. By setting the content of the silica dioxide to the above range, The linear thermal expansion coefficient of the resin composition is 35 卯m or less. In the present invention, the content of the component to the resin composition is determined by removing the solvent contained for the purpose of dissolving and/or dispersing the component. The total amount of the components is 100% by weight. The average particle diameter of the above (8) oxidized granules is 2/cm or less. By using a silica dioxide having an average particle diameter of the following, it is possible to prevent the resin varnish from being used. (8) the phenomenon of the sulphur dioxide sulphate temple, etc. On the other hand, (8) the average particle size of bismuth oxide is better than 佳. 〇5"m or more. If (8) the average particle size of the dioxide is not full 〇· 〇 (5) When the resin varnish is prepared by using the resin composition of the (4) layer printed wiring board, the resin varnish has a high viscosity, which may affect the workability in producing the insulating resin sheet with the substrate. By setting the average particle size of (8) sulphur dioxide to the above range, the balance of these characteristics is superior to 97132656 12 200922396. (8) The average particle size of a gasified ruthenium is more than 。. ίβιη以上 and ίο - (4) Wealth (4) Shimadzu Manufacturing Co., Ltd. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Borrow
G 之粗粒’亦可去除異物。 以上且2〇〇^切之比表面積並無_限定，較佳為· 二氧―若比表面積超過上述上難，則⑻ 的情形。又，樹脂組成物之構造變得不穩定 填充至L 限值’則有難以將⑻二氧切 L穑二線板用絕緣樹脂組成物中的情況。又，比 表面積可猎BET法而求取。 比 二⑻二氧化㈣可事先以含官能基之術貞及/或烧 ::二V:;s:ane)_行响^ “表面處理’可抑制二氧切之凝集，並可使二氧 好t分散於本發明之樹脂組成物中。X，由於提升⑹縣 樹脂與（B)二氧化矽表面之密 之絕緣層。 ，文可得到機械強度優越 作為上述含有Μ基之魏駭/錢基魏類的含官能 基之魏類，可使用公知者。可舉例如：環氧基傾、笨乙 稀基魏、甲基丙烯氧基錢、_氧基雜、魅 97132656 13 200922396 N-丁基胺基丙基三甲氧基矽烷、.乙基胺基異丁基三曱氧基 矽烷、N-甲基胺基丙基三甲氧基矽烷、N一苯基_3_胺基丙基 一甲氧基矽烷、3-(N-烯丙基胺基）丙基三曱氧基矽烷、（環 '己基胺基甲基）三乙氧基石风、N_環己基胺基丙基三甲氧基 •石浅、基胺基異丁基甲氧基二乙氧基石浅、（苯基胺基 甲基）曱基二甲氧基石夕烧、N_苯基胺基曱基三乙氧基石夕院、 N-曱基胺基丙基甲基二甲氧基矽烷、乙烯基矽烷、異氰酸酯 石夕:^硫化石夕燒、氯丙基石夕烧、服石夕院化合物等。 作為上述烷基矽氮類，可舉例如六曱基二矽氮（HMDS)、 1，3-二乙烯基_113,3一四曱基二矽氮八甲基三矽氮六 曱基％ — ；^氮等。此等之中，作魏基⑦氮類，較佳為六甲 基二矽氮（HMDS)。 對上述（B)二氧化石夕預先進行表面處理之含官能基之石夕烧 類及/或貌基石夕氮類的量，並無特別限定，較佳係相對於上 述⑻二氧化石夕100重量份為〇.〇1重量％以上且5重量％以 下。更佳為0· 1重量％以上且3重量％以下。若偶合劑之含量 超過上述上限值，則有於製造多層印刷佈線板時在絕緣層發 • 线痕的情形，若未滿上述下限值，則有樹脂成分與⑻二 氧化矽之結合力降低的情形。 尚且’作為（B)二氧化石夕之表面處理所使用之上述含官能 基之魏類，在於絲魏偶合财制域分的情況，該 表面處理用胺基石夕烧偶合劑係定為屬於本案樹脂組成物之 97132656 ,, 200922396 必要成分的（A)胺基矽烷偶合劑。亦即，表面處理用胺基石夕 烷偶合劑之使用量係以（A)胺基矽烷偶合劑之使用量而進行 計算。 •將上述（B)二氧化矽預先以含官能基之矽烷類及/或烷基 • 矽氮類進行表面處理的方法，並無特別限定，較佳為濕式方 式或乾式方式。特佳為濕式方法。濕式方式的情況係相較於 乾式方式，可對（B)二氧化石夕表面進行均勻處理。 ° 本發明之樹脂組成物中所使用的（C)環氧樹脂，並無特別 限定，較佳係實質上不含i原子。於此，所謂「實質上不含 ㈣子」’係指容許來自環氧樹脂之合成過程中所使用之齒 素系成分的i素，即使經由鹵素去除步驟仍殘存於環氧樹脂 中的通常，較佳係於環氧樹脂中不含超過別卿之齒 υ 作為不含i原子之環氧樹腊，可舉例如雙盼α型環氧樹 脂、魏F型環氧樹脂、雙盼Ε型環氧樹脂、伽s型環氧 ^型,環氧樹脂（4,4, —（1暑伸苯基二異亞丙基） 二異亞丙：):！_型環氧樹脂(4,4, -(1，3,苯基 搭、、主、、夫型“又齡型核乳樹赌)等之雙酚型環氧樹脂；紛-盼 漆型環…心！環氧樹脂等之祕清 基型環：::苯氧樹脂，環氧樹脂、峨 P本基方燒基型環氧樹月旨、聯苯基二亞甲基 97132656 15 200922396 型環氧樹脂、四f基聯苯基型環氧樹脂等之芳基伸絲型環 氧樹脂；萘型環氧樹脂、蒽型環氧樹月旨、笨氧基型環氧樹脂、 二環戊二稀型環氧樹脂、降福稀型環氧樹脂、金剛烧型環氧 樹脂、㈣環氧樹料。可單獨使用此等之中的丨種，亦可 •併用具有不同重量平均分子量之2種以上，亦可併们種或 2種以上與其等之預聚物。 此等核氧樹脂之中，特佳為雙紛A型環氧樹脂、聯苯基芳 ° 型環氧樹脂、㈣基聯苯基型環氧樹脂。藉此，可提升 吸濕焊料耐熱性及難燃性。 曰。上述（〇環氧樹脂之含量係設為上述樹脂組成物之14重 量、上且79重1%以下。若含量未滿上述下限值，則有樹 知’’成物之硬化性降低或所得之製品的耐濕性降低的情 *超過上述上限值，則有低熱膨脹性、耐熱性降低的情 形（C)環氧树脂之含量較佳為樹脂組成物之25重量％以上 (J 且75重量％以下。 、，上述（C)%氧樹脂之重量平均分子量並無特別限定，重量 、’二刀子里較佳為1. 〇xl 02以上且2. ΟχΙ 〇4以下。若重量平 均刀子罝未滿上述下限值，則有於絕緣層表面發生黏性的情 形右超過上述上限值，則有焊料耐熱性降低的情形。藉由 ；里平均分子量設為上述範圍内，可使此等特性之均衡優 越。 上述％氧樹脂之重量平均分子量例如可以Gpc進行測定。 97132656 16 200922396 本發明之樹脂組成物可進一步使用酚系硬化劑。作為酚系 劑可早獨使用或組合使用2種以上之盼-酴經·清漆樹 月曰、烧基吩·'酚醛清漆樹脂、雙酚A酚醛清漆樹脂、二環戊 一烯型酚樹脂、XYL0K型酚樹脂、萜改質酚樹脂、聚乙烯基 ， 酚類等公知慣用者。 本發明之樹脂組成物較佳係進一步含有含氮原子之硬化 促進劑。作為含氮原子之硬化促進劑，可使用公知化合物。 較佳為例如咪唑化合物。藉此，可提升吸濕焊料耐熱性。上 述味嗅化合物並無特別限定，可舉例如1-节基-2-甲基咪 唾、1-苄基-2-苯基咪唑、2-苯基-4-曱基咪唑、2-乙基-4-曱基咪唑、2,4-二胺基-6-[2，-曱基咪唑基-(1’）]-乙基 3-二讲、2,4-二胺基-6-(2’_十一烧基味唾基）_乙基-5_ 二0井、2,4-二胺基-6-[2’ -乙基-4-曱基〇求η坐基_(ι’ ）]-乙 基一s_二0井、2-苯基-4, 5-二經基甲基11米唾、2_苯基-4-曱基 G -5-經基曱基咪峻等。 此等之中’較佳為1-苯基-2-甲基味唾、节基_2-苯基 咪唑及2-乙基-4-曱基咪唑。此等咪唑化合物由於尤其在本 發明之樹脂組成物中具有優越之相溶性，故可得到均勻性高 之硬化物，且可於絕緣層表面形成細微且均句之粗化面，故 可容易地形成細微之導體電路’並可使多層印刷佈線板表現 高耐熱性。 並無特別限定， 作為上述含氮原子之硬化促進劑的含量， 97132656 17 200922396 較佳為樹脂組成物之〇· 〇1重量％以上且5重量％以下，特佳 為0.05重罝％以上且3重量％以下。藉此’尤其可提升耐熱 性。 作為本發明之樹脂組成物所使用之上述（D)苯氧基樹脂， . 並無特別限定，可舉例如具有雙酚A骨架之笨氧基樹脂、具 有雙盼F骨架之苯氧基樹脂、具有雙齡s骨架之苯氧基樹 脂、具有雙酚Μ骨架（4, 4，-(1，3-伸苯基二異亞丙基）雙酚 骨架）之苯氧基樹脂、具有雙紛Ρ(4, 4’ -(1, 4)-伸苯基二異 亞丙基）雙酚骨架）骨架之苯氧基樹脂、具有雙酚ζ(4,4, _ 環己二烯雙酚骨架）骨架之苯氧基樹脂等具有雙酚骨架的苯 氧基樹脂；具有酚醛清漆骨架之苯氧基樹脂；具有蒽骨架之 苯氧基樹脂；具# i骨架之苯氧基樹脂；具有二環戊二稀骨 架之苯氧基樹脂；具有降稻烯骨架之苯氧基樹脂；具有萘骨 架之苯氧基樹脂；具有聯笨基t架之笨氧基樹脂；具有金剛 ί) 烷骨架之苯氧基樹脂等。 另外’作為（D)苯氧基樹月旨，可使用具有複數種此等骨架 的構造’亦可使用各自骨架之比率不同的苯氧基樹脂。再 "者，亦可使用複數種之不同骨架之苯氧基樹脂，或使用複數 •種之具有㈣重f平均分子量的苯氧基樹脂，或併用此等之 預聚物。 此等之中’較佳係具有雙紛A骨架、雙紛F骨架及雙盼s 月架的苯氧基樹脂。更佳為具有雙盼A骨架與雙紛F骨架之 97132656 18 200922396 造多層印刷佈線板時提 兩骨架的苯氧基樹脂。藉此，可於製 升對内層電路基板之密接性。 作為上述苯減_之分子量並無㈣限&重量平均分 子量較佳為5.0xl〇3以上且l.〇xl〇5 *刀 r更佳為1. OxlO4 以上且7. 0x1 〇4以下。 若苯氧基樹脂之重量平均分子量未滿上述下限值，則有提 升密接性之效料足的情形。另―方面，若超過上述上限 Ο 值，則有苯氧細脂之溶解性降彳叫_。藉由將苯氧基樹 脂之重量平均分子量設為上述_内，可使此等特性之均衡 優越。 ⑼苯氧基樹脂之含量仙對於樹脂組成物，較佳為〇1 重量％以上且2G重量％以下。更佳為1{)重量％以上且1〇 〇 重Ι/d以下。若（D)苯氧基樹脂之含量超過上述上限值，則有 所得之絕緣層之耐熱性降低、熱衝擊性降低、黏度上升之 虞，若未滿上述下限值，則有所得之絕緣層之密接性降低之 虞。 本發明之樹脂組成物亦可進一步併用聚醯亞胺樹脂、聚醯 胺醯亞胺樹脂、聚苯醚樹脂、聚醚砜樹脂、聚酯樹脂、聚乙 烯樹脂、聚苯乙烯樹脂等之熱可塑性樹脂；苯乙烯-丁二烯 共聚物、苯乙烯-異戊二烯共聚物等之聚苯乙烯系熱可塑性 彈性體及聚烯烴系熱可塑性彈性體、聚醯胺系彈性體、聚酯 系彈性體等之熱可塑性彈性體；聚丁二烯、環氧基改質聚丁 97132656 19 200922396 二稀、丙烯酸改質聚丁二烯、曱基丙烯酸改質聚丁二烯等之 二烯系彈性體。 另外’上述多層印刷佈線板用絕緣樹脂組成物中，視需要 —亦可添加顏料、染料、消泡劑、均平劑、紫外線吸收劑、發 泡劑、抗氧化劑、難燃劑、離子捕捉劑等之上述成分以外的 添加物。 其次，說明本發明之附有基材之絕緣樹脂片。 f丨 本發明之附有基材之絕緣樹脂片係將由上述本發明之樹 月曰、、且成物所構成之絕緣層積層於基材上而成的附有基材之 絕緣糾曰片，製作附有基材之絕緣樹脂片的方法並無特別限 疋，可舉例如：將樹脂組成物溶解•分散於溶劑等中而調製 树月曰^漆，使用各種塗佈裝置，將樹脂清漆塗佈至基材上 後’使其乾燥的方法；藉喷霧裝置將樹脂清漆噴霧塗佈至基 材上後，將其乾燥之方法等。 此等之令’較佳係使用刮刀式塗佈機（c〇mma c〇afer)、剛 权塗佈機（(1^(：0&1:叶）等各種塗佈裝置，將樹脂清漆塗佈至 基材上後’使其乾燥的方法。藉此，可效率佳地製造無孔隙、 " 具有均勻絕、緣樹脂片々之厚度的附有基材之絕緣樹脂片。 . 將本發明之樹脂組成物溶解•分散於溶劑等中而調製清漆 時所使用的溶媒’最好對於樹脂組成物中之樹脂成分顯示良 好的溶解性，但在不造成不良影響的範圍内亦可使用貧溶媒 (poor solvent)。作為顯示良好溶解性之溶媒，可舉例如丙 97132656 20 200922396 酮、甲基乙基i同、甲其里 土"、j基鲷、環己酮、四氫呋喃等之酮 類；酷酸乙酿、醋酸丁酷、 乙酸酯、卡必醇乙酸酯等 4 赛路蘇乙酸酯、丙二醇單甲基醚 之醋酸酯類；賽路蘇、丁基赛路蘇 等之賽路蘇類；卡必醇、 J暴卡必醇等之卡必醇類；甲芏 二f苯等之芳香族庐；二田甘 ^ 7本 ’基¥酿胺、二f基乙醢胺、二尹 基亞„此等可單獨或組合二種以上使用。一 本發明之附有基材之絕緣樹月旨片中，作為絕緣層之厚度並 無特別限定，較佳為5〜1〇〇 " _ L, ^ ^ # m。藉此，使用此附有基材之 絕緣樹脂U製造多層印_線㈣，可填充㈣電路之凹 凸而成形’並可確保較佳之絕緣層厚度。 本發明之附有基材之絕緣樹脂片所使狀基材並無特別 限定，可使用例如聚對苯二甲酸乙二§旨、聚對苯二甲酸丁二 醋等之聚S旨樹脂’氟系樹脂，聚醯亞胺樹脂等之具有耐熱性 的熱可塑性樹脂薄膜;或銅及/或銅系合金、鋁及/或鉬系、人 金、鐵及/或_合金、銀及/或銀系合金、金及金系合金°、 鋅及鋅系合金、鎳及鎳系合金、錫及錫系合金等之金屬箱等。 作為上述基材之厚度並無特別限定，若使用 者’則製造财基材之崎樹脂㈣之操作性良好，而較β m 尚且’於製造本發明之附有基材之絕緣樹脂片時，較^圭 使與絕緣層相接之基材面的凹凸極力地減小。藉此，可彳糸 緣層與電路之密接性良好，並使細微佈線加工容易。使絕 本發明之附有基材之絕緣樹脂片之絕緣層，在製造多層Η 97132656 21 200922396 刷佈線板的㈣中若使關如過㈣鹽 劑進行絕緣層表面之粗化處理’則可於粗化處理;:::: 表面多數地形成高均勻性的微小凹凸形狀。 糾此種粗化處理後之絕緣層表面進行金屬_處理，則 •由於粗化處理面之平滑性高，故可精度佳地形成細微之導體 電路。又’藉由微小凹凸形狀而提高錨固(a·)效 於絕緣層與鍍敷金屬之間賦予高密接性。 其次，針對使用本發明之附有基材之絕緣樹脂片的 刷佈線板進行說明。 多層印刷佈線㈣將上軸有基材之絕緣樹㈣重最於 内層電路板之單面或雙面上並進行加熱加麗成形而成者。 具體而言’可將上述本發明之附有基材之絕緣樹月旨片之絕 緣層側與内層電路板對齊，使用真空加屋式層合機襄置等進 Ο 行真空加熱加壓成形，其後，以熱風乾燥h等將絕緣層進 行加熱硬化而獲得。 於此，作為加熱加屢成形之條件並無特別限定，若列舉其 一例’可依溫度60〜16代、勤Μ、·贿實施。又、 加熱硬化之條件並無特別限定，若列兴 ,η,ΛΟ 牛再一例，可依溫度 140〜240C、時間30〜120分鐘進行實施。 或者，可藉由將上述本發明之附有其 ..« .. ^ ^ 土材之絕緣樹脂片之絕 緣層側與内層電路板重疊，將其使用 熱加壓成形而獲得。於此，作為加熱加壓 —一…板壓製裝置等進行加 成形之條件並無特 97132656 22 200922396 另J限定右列舉其-例，可依溫度i4〇〜24〇e>c、壓力卜·a 進行實知。以此種平板壓製裝置等進行之加熱加壓成形中， 係”加熱加壓成形同時進行絕緣層之加熱硬化。 — 絕緣層之硬化係為了使其次之雷射照射及樹脂殘渣的去 除gn而提升麵紐，亦有先作成半硬化狀態的情 形。又’亦可藉由將第_層絕緣層以較—般加熱溫度更低之 /皿度進行加熱*使其—部分硬化（半硬化），於絕緣層上再形 (、成-層或複數層之絕緣層，並再度對半硬化之絕緣層加熱硬 化至實用上無関的程度’藉此提升絕緣層間及絕緣層與電 路間的密接力。此時之半硬化的溫度較佳為8(rc~2〇(rc、 更佳為lG(T〇18G°C。又’於其次步驟中係照射雷射而於絕 緣層形成開口部，但在此之前必需將基材剝離。基材之剝離 可於形成絕緣層後、加熱硬化前、或加熱硬化後進行，均無 特別問題。 〇 尚且，於得到上述多層印刷佈線板時所使用之内層電路 板’可適合使用例如於覆銅積層板之兩面上，藉餘刻等形成 既定之導體電路，將導體電路部分進行黑化處理者。 •其次’對絕緣層照射雷射，形成開孔部。上述雷射可使用 • 準分子雷射、UV雷射及二氧化碳氣體雷射等。 雷射照射後之樹脂殘渣等較佳係藉由過錳酸鹽、重絡酸鹽 等之氧化劑等去除。又’可將平滑之絕緣層表面同時進行粗 化，並可提升其次藉金屬鍍敷所形成之導電佈線電路的密接 97132656 23 200922396 性。 其次’形成外層電路。外層電路之形成方法係藉由金屬梦 敷達到絕緣層間之連接，藉蝕刻進行外層電路圖案形成； 使用附有基材之絕緣樹脂片時同樣地可得到多層印刷佈 . 板。 ' 尚且，於基材中使用金屬镇時，亦可不剝離基材，為了將 其使用作為導體電路而藉餘刻進行電路形成。此時，若使用 f、有厚_之附有基材之絕緣龍#，則於錢之電路圖案形 成時，難以進行細間距（fine pitch)化，故亦有使用 _之極薄銅fi，或進行將12m之_藉綱減薄至 1〜5#m的半蚀刻的情形。 再者，亦可將附有基材之絕緣層予以積層，進行上述同樣 之電路形成’條多層印刷佈線板之設計上，於最外層係在 電轉成後形姐焊層。卩辑層之㈣方法並無特別限定， /例如可藉ώ下述料形成：將乾賴形紅崎層進行積層 (層合），精曝光及顯影予以形成的方法；或將印刷有液狀阻 劑者藉曝光及顯料以形成的方法。又，在將所得之多層印 •刷佈線板使驗半導體裝置時，係為了安裝半導體元件而設 、妾用電極連接用電極部可以鍵金、鏡鎳及錢焊料等 之金屬皮膜予以適當被覆。藉此種方法，可製造多層印刷佈 線板。 其-人’針對本發明之半導體裝置進行說明。 97132656 24 200922396 ;述所知之多層印刷佈線板且 體元件，經由焊料凸塊❹p料凸塊之半導 接。而且，於多層印刷備多層印刷佈線板之連 封樹脂，形成半導體::板與半導體元件之間填充液狀密 心成體裝置。㈣凸 銀、銅，形成之合成所構成。係由办錯、 半導體元件與多層印刷佈線板之 片接合器等進行美柘去’係使用倒裝晶 、料凸塊的定m ::接㈣極部財導以件之焊 /、後，使用IR迴焊裝置、埶 裝置將焊料凸塊加熱至炼點以上，將“、、、他加熱 凸塊進躲融接合，藉此予以連接。又;=佈線极與焊料 良好，亦可預先於多層印刷佈線板上之連接二=可靠性 焊錫t等炫點較低之金屬的層。於此接合步驟之前1 = 由於焊料凸塊及或多層印刷佈線板上之連…曰 層上塗佈焊劑⑴ux)而提升連接可靠性。 極狀表 (實施例） 二下’藉實施例及比較例說明本發明之樹脂組成物、附有 基材之絕緣樹脂片、多層印刷佈線板及半導體裝置之一例， 但本發明並不限定於此。 實施例及比較例所使用之原料係如以下。 ⑴⑴胺基石夕烧偶合劑|笨基_3—胺基丙基三甲氧基石夕 烷：東麗•道康寧聚矽氧股份有限公司製，「兑6〇83」土 ⑵環氡基魏偶合劑：GE東芝料氧股份有限公司製， 97132656 25 200922396 「A-187」 (3) (B)二氧化矽/球狀熔融二氧化矽：Admatechs公司製， 25R」’平均粒徑約〇. 5//m ,比表面積約6. 25m2/g ⑷（C)%氧樹脂（C1)/雙酚A型環氧樹脂：japan Epoxy ReSln(股）公司製’「EPIKOTE 828」，環氧當量185 (5) (C)環氧樹脂（(：2)/聯苯基芳烷基型環氧樹脂：日本化藥 公司製’「NC3000」，環氧當量275 。⑹⑹核氧樹脂（C3)/四曱基聯苯基型環氧樹脂：Japan Epoxy Resin(股）公司製’「γχ_4〇〇〇」，環氧當量18〇 (7) 硬化劑/酚—酚醛清漆樹脂：大日本油墨化學工業（股） 公司製’「Phenol ite」，經基當量1〇5 (8) 苯氧基樹脂/聯苯基型環氧樹脂與雙酚s型環氧樹脂之 共聚物’於末端部具有環氧基。]apan EpQxy Resin(股） 公司製，「YX-8100H30」，重量平均分子量3〇〇〇〇 〇 (9)含氮原子之硬化促進劑/咪唑化合物：四國化成工業公 司製，「CUREZOL 1B2PZC1-苄基-2-苯基咪唑）」 (1)樹脂清漆之調製 〈實施例1> 將作為（A)胺基矽烷偶合劑之N—苯基胺基丙基三曱氧 基矽烷0.4重量份、作為（B)二氧化矽之s〇_25R 6〇 4重量 份、作為（c)環氧樹脂之雙酚A型環氧樹脂（C1)22.2重量 份、作為硬化劑之Phen〇l ite 12. 9重量份、苯氧基樹脂3. 9 97132656 26 200922396 重量份、作為含氮原子之硬化促進劑的1B2PZ 〇· 2重量份， 溶解•混合至曱基異丁基酮中。其次，使用高速攪拌裝置進 行攪拌而調製成樹脂清漆。 (2) 附有基材之絕緣樹脂片之製造 - 將上述所得之樹脂清漆使用刮刀式塗佈機裝置，於厚度 38//m之PET(聚對苯二曱酸乙二酯：三菱聚酯公司製， 「SFB-38」）薄膜之單面上塗佈成乾燥後之絕緣層厚度為 〇 ，將其以110〜150X：之乾燥裝置進行乾燥，製造附有基 材之絕緣樹脂片。 (3) 多層印刷佈線板之製造 使用厚度0. 3mm且銅箔厚度為18/zm之雙面覆銅積層板 (住友Bakelite(股）製ELC-4765GS)，以鑽孔機進行開孔 後，以無電解鍍敷達到上下銅箔間之導通，將上述雙面銅箔 藉蝕刻而於雙面上形成内層電路。（L/s=12〇/l8〇 ， U 孔1咖必、3mm0，狹縫2mm)。 其次’對内層電路噴霧吹附以過氧化氫水與硫酸為主成分 之藥液（尤私化工業（股）製TECH S0-G)，藉此進行粗化處理 - 之凹凸形成。 ，、人將上述所得之附有基材之絕緣樹脂片使用真空積層 裝置積層於内層電路上。其次_基材，以溫度17代、時 間60分鐘進行加熱，使絕緣層半硬化。又，將附有基材之 絕緣樹脂片進行積層之條件設為溫度1〇〇七、麼力隐、3〇 97132656 27 200922396 秒。 接著，於上述所得之多層印刷佈線板1之絕緣層上，使用 二氧化碳氣體雷射裝置形成06〇//m之開孔部（未穿針孔， blind pinhole) ’ 浸潰於 70°C 之膨潤液（Atotech Japan 公 • 司製，Swelling Dip Securigant P)10 分鐘，再浸潰於 80 °C之過錳酸鉀水溶液（Atotech Japan公司製，Concentrate Compact CP)20分鐘後’予以中和而進行粗化處理。其次， 〇 經過脫脂、觸媒賦予、活性化之步驟後，將無電解銅鍍皮膜 形成為約0.5ym之給電層。其次，於此給電層表面上藉熱 親層合機貼合厚度2 5 /z m之紫外線感光性乾薄膜（旭化成公 司製AQ-2558) ’使用描繪了最小線寬/線間為20/20 ΑΠ!之 圖案的鉻蒸鍍遮罩（TOUWA PROCESS公司製），進行定位，以 曝光裝置（USI0電機公司製UX-1100 SM-AJN01)進行曝光， 並以碳酸鈉水溶液進行顯影，形成阻鍍層。 〇 其次，以給電層作為電極，進行電解銅鑛（奥野製藥公司 製81-HL) 3A/dm2、30分鐘，形成厚度約25//m之銅佈線。 於此’使用2階段剝離機，剝離上述阻鑛層。各藥液係分別 於第1階段之鹼水溶液層使用單乙醇胺溶液（三菱氣體化學 公司製R-100)，於第2階段之氧化性樹脂蝕刻劑使用以過 猛酸卸與鼠氧化納為主成分之水溶液（日本MacDermid公司 製MACUDIZER9275、9276)，於中和使用酸性胺水溶液（日本 MacDermid 公司製 MACUDIZER9279)。 97132656 28 200922396 其次，將給電層於過硫酸銨水溶液（Meltex(股）製AD-485) 進行浸潰處理，而去除#刻劑，確保佈線間之絕緣。接著將 絕緣層以溫度20(TC、時間60分鐘進行最終硬化，最後於 電路表面形成阻焊層（太陽油墨公司製psR4〇〇〇/AUS3〇8)而 - 得到多層印刷佈線板。 (5)半導體裝置之製造 上述多層印刷佈線板係使用：將配置有經實施了與半導體 兀件之焊料凸塊相當之鎳金鍍敷處理的連接用電極部者，切 斷為50mmx50mm之尺寸者。半導體元件（TEG晶片，尺寸15咖 xl5mm’厚度〇.8mm)係使用由Sn/Pb組成之共晶所形成的焊 料凸塊’半導體元件之電路賴_制由正題光性樹脂 (住友Bakelite公司製CRC-8300)所形成者。半導體裝置之 、、且裝係首先於;料凸塊上藉轉印法均勾地塗佈焊劑材，其次 使用倒裝晶片接合器裝置，於多層印刷佈線板上進行加熱壓 5黏^予以搭載。接著’以IR迴焊爐將焊料凸塊熔融接合後， 填充液狀密封樹脂（住友Bakelite公司製，cRp_4i5⑻，使 液狀密封樹脂硬化，藉此得到半導體裂置。又，液狀密封樹 • 脂之硬化條件為溫度15(TC、120分鐘之條件。 〈實施例2> 將作為（A)胺基石夕烧偶合劑之卜笨基j胺基丙基三甲氧 夕，元0. 3重量伤、作為（β)二氧化矽之如訊65. 2重量 份'作為（c)環氧樹脂之養Α型環氧樹脂（⑴19 6重量 97132656 29 200922396 份、作為硬化劑之Phenolite 11.3重量份、笨氧基樹脂3 4 重量份 '作為含氮原子之硬化促進劑的1β2ρζ 〇. 2重量份， 溶解•混合至曱基異丁基酮中。其次，使用高速攪拌裝置進 -行攪拌而調製成樹脂清漆，與實施例1同樣地進行得到附有 - 基材之絕緣樹脂片、多層印刷佈線板、半導體裝置。 〈實施例3> 將作為（A)胺基矽烷偶合劑之N-苯基-3-胺基丙基三甲氧 基矽烷2. 2重量份、作為（B)二氧化矽之s〇_25R 6〇. 6重量 份、作為（C)環氧樹脂之雙酚A型環氧樹脂（C1)2M重量 份、作為硬化劑之Phenolite 12· 2重量份、苯氧基樹脂3. 7 重1份、作為含氮原子之硬化促進劑的1B2PZ 0. 2重量份， 溶解•混合至曱基異丁基酮中。其次，使用高速攪拌裝置進 行攪拌而調製成樹脂清漆，與實施例1同樣地進行得到附有 基材之絕緣樹脂片、多層印刷佈線板、半導體裝置。 〇 〈實施例4> 將作為（A)胺基矽烷偶合劑之N-苯基_3_胺基丙基三曱氧 基矽烷0.4重量份、作為（B)二氧化矽之s〇_25R 6〇·6重量 . 份、作為（c)環氧樹脂之聯苯基芳烷基型環氧樹脂（(：2)25 2 •重讀、作為硬化劑之PhenQlite9· 7 4量份、苯氧基樹脂 .重里伤、作為含氣原子之硬化促進劑的ΐβ2ρζ 〇 2重量 伤命解•混合至曱基異丁基酮中。其次，使用高速授摔裝 置進行搜拌而調製成樹脂清漆，與實施例1同樣地進行得到 97132656 30 200922396 附有基材之絕緣樹脂片、多層印刷佈線板、半導體裝置。 〈實施例5> 將作為（Α)胺基矽烷偶合劑之苯基-3-胺基丙基三曱氧 基矽烷0.4重量份、作為（Β)二氧化矽之s〇_25R 6〇 4重量 份、作為（C)環氧樹脂之四曱基聯苯基型環氧樹脂（C3)22. 2 重量份、作為硬化劑之Phenolite 12. 9重量份、苯氧基樹 Γ Ο 脂3.9重量份、作為含氮原子之硬化促進劑的1B2pz 〇 2 重量份，溶解•混合至曱基異丁基财。其次，使用高速搜 拌裝置進行而調製成賴清漆，與實_ 1同樣地進行 得到附有基材之絕緣樹脂片、多層印刷佈線板、半導 〈比較例1> 將作為偶合劑之環氧基矽烷偶合劑（A-187)〇 7重旦严 =氧切之so__.2重量份'作為(心:脂 之又盼A型環氧樹脂(⑴22.〇重量份、作為The coarse particles of G can also remove foreign matter. The above specific surface area is not limited to ≤, and it is preferable that the dioxo-specific surface area exceeds the above-mentioned difficulty, and (8). Further, the structure of the resin composition becomes unstable. When it is filled in the L limit value, it is difficult to use the (8) oxydisulfide L 穑 second-line insulating resin composition. Further, the specific surface area can be obtained by hunting the BET method. Compared with the two (8) dioxide (4), it can be pre-treated with a functional group and/or burned:: two V:; s: ane) _ row ^ "surface treatment" can inhibit the aerobic agglutination, and can make dioxane Preferably, it is dispersed in the resin composition of the present invention. X, due to the adhesion of the (6) county resin to the (B) cerium oxide surface, the mechanical strength is superior as the above-mentioned Μ-based Wei Wei / Qian The Wei group containing a functional group may be a known one, and may be, for example, an epoxy group, a stupid ethylene group, a methacryloxy group, an oxy group, a charm 97132656 13 200922396 N-butyl. Aminopropyltrimethoxydecane, ethylaminoisobutyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenyl-3-aminopropyl-A Oxydecane, 3-(N-allylamino)propyltrimethoxy decane, (cyclo-hexylaminomethyl) triethoxy stone, N-cyclohexylaminopropyltrimethoxy Stone-light, amide-based isobutyl methoxydiethoxylate, (phenylaminomethyl) decyl dimethoxy zephyr, N-phenylamino fluorenyl triethoxy sylvestre, N- Mercaptoamine Propylmethyldimethoxydecane, vinyl decane, isocyanate, sulphate, sulphide sulphate, chloropropyl sulphate, shoji compound, etc. As the alkyl hydrazine nitrogen, for example, six oxime Dimethyl hydrazine (HMDS), 1,3-divinyl _113, 3 1,4-decyl quinone octadecyl octamethyl sulphide hexamethyl fluorenyl 5%, etc. 7 nitrogen, preferably hexamethyldiazepine nitrogen (HMDS). The amount of the functional group-containing zeafoam and/or the phenotype of the genus Nitrogen, which is previously subjected to the surface treatment of the above (B) sulphur dioxide, It is not particularly limited, and is preferably 重量.〇1% by weight and 5% by weight or less, more preferably 0.1% by weight or more and 3% by weight or less, based on 100 parts by weight of the above (8) silica dioxide. When the content of the mixture exceeds the above-mentioned upper limit, there is a case where a line mark is formed in the insulating layer when the multilayer printed wiring board is manufactured, and if the lower limit is not satisfied, the bonding strength between the resin component and (8) cerium oxide is lowered. In the case of the above-mentioned functional group-containing Wei class used as the surface treatment of (B) dioxide, it is In the case of the financial system, the surface treatment amine germination coupling agent is defined as the (A) amino decane coupling agent which is an essential component of the resin composition of the present invention, 97132656, 200922396. The amount of the base cyclane coupling agent used is calculated based on the amount of the (A) amino decane coupling agent used. • The above (B) cerium oxide is previously prepared as a functional group-containing decane and/or an alkyl group. The method of surface treatment is not particularly limited, and is preferably a wet method or a dry method. Particularly preferred is a wet method. In the case of a wet method, (B) a dioxide dioxide can be used as compared with a dry method. The surface is subjected to uniform treatment. The (C) epoxy resin used in the resin composition of the present invention is not particularly limited, and is preferably substantially free of i atoms. Here, the term "substantially does not contain (four)" means that the elemental substance which is allowed to be used in the synthesis process of the epoxy resin remains in the epoxy resin even after the halogen removal step. It is preferable that the epoxy resin does not contain more than the enamel of the enamel. As the epoxy wax which does not contain the i atom, for example, a double-prepared α-type epoxy resin, a Wei F-type epoxy resin, and a double-presence type ring Oxygen resin, gamma-type epoxy type, epoxy resin (4,4,-(1), diphenylidene): _ type epoxy resin (4,4, -(1,3, phenyl, 、, main, 夫 type "old age nucleus gambling" bisphenol type epoxy resin; ...heart! Epoxy resin and other secret base ring::: phenoxy resin, epoxy resin, 峨P carbene-based epoxy resin, biphenyl dimethylene 97132656 15 200922396 ring An aryl-based epoxy resin such as an oxy-resin or a tetra-f-based biphenyl-based epoxy resin; a naphthalene-based epoxy resin, a fluorene-type epoxy resin, a styrene-based epoxy resin, and a dicyclopentadiene Epoxy resin, epoxy resin, diamond-fired epoxy resin, (4) epoxy tree material. The above-mentioned species can be used alone or in combination with two or more different weight average molecular weights. It is also possible to plant or more than two kinds of prepolymers of the same type. Among these nucleating oxygen resins, special ones are A-type epoxy resin, biphenyl aryl type epoxy resin, and (iv) phenylene. The base type epoxy resin can improve the heat resistance and flame retardancy of the moisture absorbing solder. The above (the content of the epoxy resin is set to 14 parts by weight of the above resin composition, and 79% by weight When the content is less than the above lower limit, it is known that the hardening property of the product is lowered or the moisture resistance of the obtained product is lowered. If the content exceeds the above upper limit, the thermal expansion property and the heat resistance are lowered. (C) The content of the epoxy resin is preferably 25% by weight or more (J and 75% by weight or less) of the resin composition. The weight average molecular weight of the (C)% oxygen resin is not particularly limited, and the weight is ' In the second knives, it is preferably 1. 〇xl 02 or more and 2. ΟχΙ 〇 4 or less. If the weight average knives 罝 are not above the lower limit value, the case where the surface of the insulating layer is viscous is more than the above upper limit value. In the case where the solder heat resistance is lowered, the average molecular weight in the range is within the above range, and the balance of these characteristics can be excellent. The weight average molecular weight of the above-mentioned % oxygen resin can be measured, for example, by Gpc. 97132656 16 200922396 Further, a phenol-based curing agent can be used as the resin composition. As the phenol-based agent, two or more kinds of the desired ones can be used alone or in combination, and the phthalocyanine varnish, the phenolic varnish resin, the bisphenol A phenol varnish A resin, a cyclopentene phenol resin, an XYL0K phenol resin, a phenolic phenol resin, a polyvinyl group, or a phenol is known. The resin composition of the present invention preferably further contains a hardening promoter containing a nitrogen atom. A known compound can be used as the hardening accelerator containing a nitrogen atom. Preferably, for example, an imidazole compound is used, whereby the heat resistance of the moisture-absorbing solder can be improved. The above-described odorant compound is not particularly limited, and examples thereof include a 1-block base. -2-methylmeridene, 1-benzyl-2-phenylimidazole, 2-phenyl-4-mercaptoimidazole, 2-ethyl-4-mercaptoimidazole, 2,4-diamino-6 -[2,-mercaptoimidazolyl-(1')]-ethyl-3-dis, 2,4-diamino-6-(2'-edecyl sulphate)-ethyl-5_ 20,000 well, 2,4-diamino-6-[2'-ethyl-4-indenyl η η 坐基_(ι' )]-ethyl-s_二0 well, 2-phenyl -4, 5-dipyridylmethyl 11 m saliva, 2-phenyl-4-indenyl G-5-pyridyl thiophene et al. Among these, 'preferably 1-phenyl-2-methyl sulphate, benzyl-2-phenylimidazole and 2-ethyl-4-mercaptoimidazole. Since these imidazole compounds have excellent compatibility especially in the resin composition of the present invention, a cured product having high uniformity can be obtained, and a fine and uniform roughened surface can be formed on the surface of the insulating layer, so that it can be easily A fine conductor circuit is formed and the multilayer printed wiring board can exhibit high heat resistance. It is not particularly limited, and the content of the hardening accelerator containing a nitrogen atom is preferably 97, 162, 656, and 1, 2009, 396, and is preferably 5% by weight or more and 5% by weight or less, more preferably 0.05% by weight or more, and 3 parts by weight of the resin composition. Below weight%. In this way, heat resistance can be particularly improved. The (D) phenoxy resin to be used in the resin composition of the present invention is not particularly limited, and examples thereof include a phenoxy resin having a bisphenol A skeleton and a phenoxy resin having a double-hop F skeleton. a phenoxy resin having a double age s skeleton, a phenoxy resin having a bisphenol fluorene skeleton (4, 4,-(1,3-phenylenediisopropyl) bisphenol skeleton), having a double enthalpy (4, 4'-(1, 4)-phenylene diisopropylidene) bisphenol skeleton) phenoxy resin having bisphenol hydrazine (4,4, _cyclohexadiene bisphenol skeleton) a phenoxy resin having a bisphenol skeleton such as a phenoxy resin of a skeleton; a phenoxy resin having a novolac skeleton; a phenoxy resin having an anthracene skeleton; a phenoxy resin having a # i skeleton; having a dicyclopentane a phenoxy resin having a dilute skeleton; a phenoxy resin having a reduced olefinic skeleton; a phenoxy resin having a naphthalene skeleton; a stupid oxy resin having a stupid base; a phenoxy having a ruthenium skeleton Base resin, etc. Further, as the (D) phenoxy tree, a structure having a plurality of such skeletons may be used. A phenoxy resin having a different ratio of the respective skeletons may be used. Further, a plurality of different kinds of skeleton phenoxy resins may be used, or a plurality of phenoxy resins having a (four) weight average molecular weight may be used, or a prepolymer of these may be used in combination. Among these, it is preferred to have a phenoxy resin having a double A skeleton, a double F skeleton, and a double s month frame. More preferably, it has a double-awaiting A skeleton and a double-fragmented F skeleton. 97132656 18 200922396 Two-frame phenoxy resin is provided when a multilayer printed wiring board is produced. Thereby, the adhesion to the inner layer circuit substrate can be improved. The amount of the above-mentioned benzene minus _ is not (4) and the weight average molecular weight is preferably 5.0xl 〇 3 or more and l. 〇 xl 〇 5 * knife r is preferably 1. OxlO4 or more and 7. 0x1 〇 4 or less. If the weight average molecular weight of the phenoxy resin is less than the above lower limit, there is a case where the effect of improving the adhesion is sufficient. On the other hand, if the above upper limit Ο is exceeded, the solubility of phenoxylate is lowered. By setting the weight average molecular weight of the phenoxy resin to the above-mentioned _, the balance of these characteristics can be excellent. (9) The content of the phenoxy resin is preferably 〇1% by weight or more and 2% by weight or less based on the resin composition. More preferably, it is 1 {)% by weight or more and 1 〇 〇 is Ι/d or less. When the content of the (D) phenoxy resin exceeds the above upper limit, the heat resistance of the obtained insulating layer is lowered, the thermal shock resistance is lowered, and the viscosity is increased. If the lower limit is not satisfied, the resulting insulation is obtained. The adhesion of the layers is reduced. The resin composition of the present invention may further be used in combination with thermoplasticity of polyimine resin, polyamidoximine resin, polyphenylene ether resin, polyether sulfone resin, polyester resin, polyethylene resin, polystyrene resin, and the like. Resin; polystyrene-based thermoplastic elastomer such as styrene-butadiene copolymer or styrene-isoprene copolymer, polyolefin-based thermoplastic elastomer, polyamine-based elastomer, and polyester-based elastomer Thermoplastic elastomer of bulk; polybutadiene, epoxy modified polybutan 97132656 19 200922396 diene elastomer of dilute, acrylic modified polybutadiene, decyl acrylate modified polybutadiene . Further, in the above-mentioned insulating resin composition for a multilayer printed wiring board, if necessary, a pigment, a dye, an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, and an ion trapping agent may be added. Additives other than the above components. Next, an insulating resin sheet with a substrate attached to the present invention will be described. The substrate-attached insulating resin sheet according to the present invention is an insulating entangled sheet with a substrate which is formed by laminating an insulating layer composed of the above-described tree of the present invention and a substrate. The method of producing the insulating resin sheet with the base material is not particularly limited, and for example, a resin composition is prepared by dissolving and dispersing the resin composition in a solvent or the like, and varnishing the resin varnish using various coating devices. A method of drying the cloth after it is applied to the substrate; a method of drying the resin varnish onto the substrate by a spray device, drying it, and the like. It is preferable to apply a resin varnish by using various coating devices such as a knife coater (c〇mma c〇afer) and a rigid coater ((1^(:0&1: leaf)). A method of drying the cloth after it is applied to the substrate. Thereby, the substrate-free insulating resin sheet having no thickness and having a uniform thickness of the edge of the resin sheet can be efficiently produced. The solvent composition used for dissolving and dispersing the resin composition in a solvent or the like to prepare a varnish preferably exhibits good solubility in the resin component in the resin composition, but may also use a poor solvent in a range that does not cause adverse effects. (poor solvent). Examples of the solvent which exhibits good solubility include ketones such as C 97132656 20 200922396 ketone, methyl ethyl i ketone, keto mulberry ", j hydrazine, cyclohexanone, tetrahydrofuran; 4 acid, such as sulphuric acid, butyl acetate, acetate, carbitol acetate, acetate, propylene glycol monomethyl ether, etc.; 赛赛苏, butyl 赛路苏, etc. Lu Su category; carbitol, J carbamide, etc. Aromatic scorpion; Ertiangan ^ 7 ' 酿 酿 酿 酿 二 二 二 酿 酿 酿 酿 酿 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此In the moon sheet, the thickness of the insulating layer is not particularly limited, and is preferably 5 to 1 〇〇 " _ L, ^ ^ # m. Thereby, the multilayer resin is produced using the insulating resin U with the substrate _ The wire (4) can be filled with (4) the unevenness of the circuit to be formed, and the thickness of the insulating layer can be ensured. The base material of the substrate-attached insulating resin sheet of the present invention is not particularly limited, and for example, polyterephthalic acid can be used. A heat-resistant thermoplastic resin film such as a resin such as a fluorine-based resin or a polyimide resin; or a copper and/or copper-based alloy or aluminum, which is a polyethylene resin such as polybutylene terephthalate or the like. And/or molybdenum, human gold, iron and/or alloy, silver and/or silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys, etc. The thickness of the above-mentioned base material is not particularly limited, and the operability of the resin (4) of the base material is manufactured by the user. It is good, and the β-m is still used to manufacture the insulating resin sheet with the substrate of the present invention, and the unevenness of the surface of the substrate which is in contact with the insulating layer is reduced as much as possible. The adhesion between the layer and the circuit is good, and the fine wiring is easy to process. The insulating layer of the insulating resin sheet with the substrate of the present invention is made in the fourth layer of the manufacturing of the multilayer wiring board (123). (4) The salting agent performs the roughening treatment on the surface of the insulating layer', which can be roughened; ::::: The surface is formed with a large uniformity of fine unevenness. The surface of the insulating layer after the roughening treatment is subjected to metal treatment. Then, since the smoothness of the roughened surface is high, a fine conductor circuit can be formed with high precision. Further, the anchoring (a·) is improved by the fine uneven shape to provide high adhesion between the insulating layer and the plated metal. Next, a description will be given of a brush wiring board using the insulating resin sheet with a substrate of the present invention. Multilayer printed wiring (4) The insulating tree (4) with the substrate on the upper shaft is placed on one side or both sides of the inner circuit board and heated and formed. Specifically, the insulating layer side of the substrate-attached insulating tree of the present invention can be aligned with the inner layer circuit board, and the vacuum heating and pressure forming can be performed by using a vacuum chamber laminating machine or the like. Thereafter, the insulating layer is heat-cured by hot air drying or the like. Here, the conditions for the heating and the additional molding are not particularly limited, and an example thereof can be carried out according to the temperature of 60 to 16 generations, diligence, and bribery. Further, the conditions for the heat curing are not particularly limited. For example, Levi, η, and yak may be carried out at a temperature of 140 to 240 C for 30 to 120 minutes. Alternatively, it may be obtained by superposing the insulating layer side of the above-mentioned insulating material sheet of the present invention with the inner layer circuit board and the inner layer circuit board. Here, the conditions for addition and forming as a heating and pressurizing-plate pressing device are not particularly limited to 97132656 22 200922396. The other is exemplified by the right example, and can be based on the temperature i4〇~24〇e>c, pressure bu·a Carry out the actual knowledge. In the heat and pressure molding by the flat pressing device or the like, the heating and hardening of the insulating layer is performed simultaneously with the heating and press forming. - The hardening of the insulating layer is performed in order to enhance the subsequent laser irradiation and the removal of the resin residue gn. Face-to-face, also in the case of a semi-hardened state. It can also be partially hardened (semi-hardened) by heating the _ layer of insulating layer at a lower heating temperature/dish degree. The insulating layer is reshaped (the layer of the layer or the plurality of layers, and the semi-hardened insulating layer is heated and hardened to a practically unrelated degree) to thereby improve the adhesion between the insulating layers and the insulating layer and the circuit. The semi-hardening temperature at this time is preferably 8 (rc~2 〇 (rc, more preferably lG (T 〇 18 G ° C. In addition, in the second step, the laser is irradiated to form an opening in the insulating layer, but in Before this, it is necessary to peel off the substrate. The peeling of the substrate can be carried out after the formation of the insulating layer, before the heat curing, or after the heat curing, and there is no particular problem. Further, the inner layer circuit used in the above multilayer printed wiring board is obtained. Board 'is suitable for use For example, on both sides of the copper clad laminate, a predetermined conductor circuit is formed by a residual engraving, and the conductor circuit portion is blackened. • Secondly, the insulating layer is irradiated with a laser to form an opening portion. The above laser can be used. • Excimer laser, UV laser, and carbon dioxide gas laser, etc. The resin residue after laser irradiation is preferably removed by an oxidizing agent such as permanganate or a heavy complex. The surface of the insulating layer is simultaneously roughened, and the adhesion of the conductive wiring circuit formed by the metal plating is improved. Next, the outer layer circuit is formed. The outer layer circuit is formed by the metal dream coating to achieve the interlayer between the insulating layers. Connecting, forming an outer layer circuit pattern by etching; when using an insulating resin sheet with a base material, a multilayer printed cloth can be obtained in the same manner. 'When the metal is used in the substrate, the substrate may not be peeled off, in order to It is used as a conductor circuit to form a circuit by means of a residual. In this case, if f is used, and there is a thick _ with an insulating dragon # with a substrate, then when the circuit pattern of Qian is formed It is difficult to perform fine pitching, so there is also a case where a very thin copper fi is used, or a half etching of a 12 m thinning to 1 to 5 #m is performed. The insulating layer with the substrate is laminated, and the same circuit is used to form the 'multilayer printed wiring board. The outermost layer is electrically converted into a post-shaped solder layer. The method of the fourth layer is not particularly limited. / / For example, it can be formed by laminating (laminating) a layer of dried lyophilized erythris, by precise exposure and development, or by exposing and exposing a liquid resist. In addition, when the semiconductor device is mounted on the multilayer printed circuit board, the electrode portion for electrode connection is provided for the mounting of the semiconductor element, and the metal film such as the key gold, the mirror nickel, and the solder can be appropriately used. Covered. In this way, a multilayer printed wiring board can be manufactured. The human device will be described with respect to the semiconductor device of the present invention. 97132656 24 200922396; The multilayer printed wiring board and the body element are known to be semi-conductive via bumps of solder bumps. Further, the sealing resin of the multilayer printed wiring board is printed on the multilayer to form a liquid-filled compact device between the semiconductor::-board and the semiconductor element. (4) The combination of convex silver and copper. It is made by the wrong component, the semiconductor component and the chip bonder of the multilayer printed wiring board, etc., using the flip-chip, the bump of the material, and the soldering of the material. Use the IR reflow device and the crucible device to heat the solder bumps above the refining point, and then heat the bumps into the fused joints to connect them. Also; = the wiring poles and the solder are good, and may be pre-existing Connection on the multilayer printed wiring board = reliability metal solder layer t and other layers with lower redness. Before this bonding step 1 = soldering on the solder bump and or on the multilayer printed wiring board (1) ux) to improve the connection reliability. The polar table (Example) The following is a description of the resin composition of the present invention, the insulating resin sheet with a substrate, the multilayer printed wiring board, and the semiconductor device. However, the present invention is not limited thereto. The raw materials used in the examples and comparative examples are as follows. (1) (1) Amine stone sinter coupling agent | Stupyl _3 - aminopropyltrimethoxy oxalate: Toray Dow Corning Polyoxane Co., Ltd., "6 against 83" Earth (2) Cyclodecyl Wei Coupling Agent: GE Toshiba Oxygen Co., Ltd., 97132656 25 200922396 "A-187" (3) (B) cerium oxide / spherical molten cerium oxide: manufactured by Admatechs, 25R "The average particle size is about 5. 5 / / m, the specific surface area is about 6. 25m2 / g (4) (C)% oxygen resin (C1) / bisphenol A type epoxy resin: japan Epoxy ReSln (share) company's "" EPIKOTE 828", epoxy equivalent 185 (5) (C) Epoxy resin ((:2) / biphenyl aralkyl type epoxy resin: "NC3000" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 275. (6) (6) Nuclear Oxygen Resin (C3)/Tetrakisyl Biphenyl Epoxy Resin: 'γγχ4〇〇〇, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 18〇(7) Hardener/phenol-novolac resin : Dainippon Ink Chemical Industry Co., Ltd. 'Phenol ite', a base equivalent of 1〇5 (8) phenoxy resin / copolymer of biphenyl type epoxy resin and bisphenol s type epoxy resin' It has an epoxy group at the end.] apan EpQxy Resin Co., Ltd., "YX-8100H30", weight average molecular weight 3〇〇〇〇〇(9) Hardening accelerator containing nitrogen atom/imidazole Compound: "CUREZOL 1B2PZC1-benzyl-2-phenylimidazole" (1) Preparation of resin varnish <Example 1> N-phenyl group as (A) amino decane coupling agent 0.4 parts by weight of aminopropyltrimethoxy decane, 4 parts by weight of s〇_25R 6 作为 as (B) cerium oxide, and bisphenol A type epoxy resin (C1) 22.2 as (c) epoxy resin Parts by weight, as a hardening agent, Phen〇l ite 12. 9 parts by weight, phenoxy resin 3. 9 97132656 26 200922396 parts by weight, as a hardening accelerator containing a nitrogen atom, 1B2PZ 〇 · 2 parts by weight, dissolved and mixed to In decyl isobutyl ketone. Next, stirring was carried out using a high-speed stirring device to prepare a resin varnish. (2) Manufacture of insulating resin sheet with substrate - The resin varnish obtained above was used in a doctor blade apparatus at a thickness of 38/m PET (polyethylene terephthalate: Mitsubishi polyester) The thickness of the insulating layer after drying on the single side of the "SFB-38" film was 〇, and it was dried by a drying apparatus of 110 to 150X: to produce an insulating resin sheet with a substrate. (3) The multilayer printed wiring board is manufactured by using a double-sided copper-clad laminate (ELC-4765GS manufactured by Sumitomo Bakelite) having a thickness of 0.3 mm and a copper foil thickness of 18/zm. The electroless plating is used to achieve conduction between the upper and lower copper foils, and the double-sided copper foil is etched to form an inner layer circuit on both sides. (L/s=12〇/l8〇, U hole 1 coffee, 3mm0, slit 2mm). Next, a chemical liquid containing hydrogen peroxide water and sulfuric acid as a main component (TECH S0-G manufactured by Seiko Co., Ltd.) was spray-sprayed to the inner layer circuit to perform roughening treatment. Then, the insulating resin sheet with the substrate obtained as described above was laminated on the inner layer circuit using a vacuum laminating apparatus. Next, the substrate was heated at a temperature of 17 generations and a time of 60 minutes to semi-harden the insulating layer. Further, the conditions for laminating the insulating resin sheet with the substrate were set to a temperature of 1 〇〇, 力力隐, 3〇 97132656 27 200922396 seconds. Next, on the insulating layer of the multilayer printed wiring board 1 obtained above, a carbon dioxide gas laser device was used to form an opening portion (blind pinhole) of 06 〇//m, which was immersed at 70 ° C. The solution (Stowing Dip Securigant P, manufactured by Atotech Japan Co., Ltd.) was immersed in a potassium permanganate solution (Concentrate Compact CP, manufactured by Atotech Japan Co., Ltd.) at 80 °C for 20 minutes, and then neutralized and coarsened. Processing. Next, after the steps of degreasing, catalyst application, and activation, the electroless copper plating film was formed into a power supply layer of about 0.5 μm. Next, on the surface of the electric layer, a UV-sensitive dry film (AQ-2558 manufactured by Asahi Kasei Co., Ltd.) having a thickness of 2 5 /zm was attached to the surface of the electric layer. The minimum line width/line is 20/20 使用. The chromium vapor deposition mask (manufactured by TOUWA PROCESS Co., Ltd.) of the pattern was subjected to positioning, exposed to an exposure apparatus (UX-1100 SM-AJN01 manufactured by USI0 Motor Co., Ltd.), and developed with an aqueous solution of sodium carbonate to form a plating resist. Next, an electrolytic copper ore (81-HL manufactured by Okuno Chemical Co., Ltd.) 3A/dm2, 30 minutes was used as an electrode to form a copper wiring having a thickness of about 25/m. Here, the above-mentioned barrier layer was peeled off using a two-stage peeling machine. In each of the chemical liquid layers, a monoethanolamine solution (R-100, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used in the first aqueous alkali solution layer, and the second-stage oxidizing resin etchant was used in the second-stage oxidizing resin etchant. An aqueous solution of the components (MACUDIZER9275, 9276, manufactured by MacDermid Co., Ltd., Japan) was used for neutralization using an aqueous solution of an acidic amine (MACUDIZER 9279, manufactured by MacDermid, Japan). 97132656 28 200922396 Next, the electric layer was subjected to an impregnation treatment with an aqueous ammonium persulfate solution (AD-485 manufactured by Meltex) to remove the engraving agent to ensure insulation between wirings. Then, the insulating layer was finally hardened at a temperature of 20 (TC, time 60 minutes, and finally a solder resist layer (psR4〇〇〇/AUS3〇8 manufactured by Sun Ink Co., Ltd.) was formed on the surface of the circuit to obtain a multilayer printed wiring board. (5) In the above-described multilayer printed wiring board, the connection electrode portion to which the nickel gold plating treatment corresponding to the solder bump of the semiconductor element is placed is cut to a size of 50 mm x 50 mm. (TEG wafer, size 15 coffee x 15mm 'thickness 〇. 8mm) is a solder bump formed by using a eutectic composed of Sn/Pb. The circuit of the semiconductor element is made of the title photo-resin (CRC-made by Sumitomo Bakelite) 8300) formed by the semiconductor device, and installed first on the material bump by the transfer method to apply the flux material, and then using the flip chip bonder device, heating on the multilayer printed wiring board After the solder bumps were melt-bonded in an IR reflow oven, liquid sealing resin (cRp_4i5(8), manufactured by Sumitomo Bakelite Co., Ltd., was used to harden the liquid sealing resin, thereby obtaining a half. The conductor is cleaved. Further, the liquid sealing tree • The hardening condition of the fat is the condition of temperature 15 (TC, 120 minutes. <Example 2> will be used as the (A) amine-based sulphur coupling agent. 3重量重量, as a (β) cerium oxide as a message 65. 2 parts by weight as a (c) epoxy resin-type epoxy resin ((1) 19 6 weight 97132656 29 200922396 parts 2 parts by weight of Phenolite as a hardener, and 34 parts by weight of a stupid oxy-resin as a hardening accelerator of a nitrogen atom, 2β2ρζ 〇. 2 parts by weight, dissolved and mixed into decyl isobutyl ketone. Secondly, used The high-speed stirring apparatus was stirred to prepare a resin varnish, and an insulating resin sheet, a multilayer printed wiring board, and a semiconductor device with a base material were obtained in the same manner as in Example 1. <Example 3> As an amine (A) 2 parts by weight of N-phenyl-3-aminopropyltrimethoxydecane of the decane coupling agent, as (B) cerium oxide s 〇 2525 〇 6 parts by weight, as (C) ring Oxygen resin bisphenol A type epoxy resin (C1) 2M parts by weight, as a hardener Phenolite 12· 2 weight 1 parts by weight of phenoxy resin 3.7 parts by weight of 1B2PZ as a hardening accelerator containing a nitrogen atom, dissolved and mixed into decyl isobutyl ketone. Secondly, stirring is carried out using a high-speed stirring device. In the same manner as in Example 1, an insulating resin sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were prepared in the same manner as in Example 1. 实施 <Example 4> N-Benzene as (A) amino decane coupling agent 0.4 parts by weight of the base_3_aminopropyltrimethoxy decane, as the (B) cerium oxide s 〇 _25R 6 〇 · 6 parts by weight, as (c) epoxy resin biphenyl aralkyl Base type epoxy resin ((:2)25 2 • Rereading, PhenQlite9·7 4 parts as hardener, phenoxy resin. Heavy injury, ΐβ2ρζ 〇2 weight loss solution as a hardening accelerator containing gas atoms • Mix into decyl isobutyl ketone. Then, a resin varnish was prepared by mixing with a high-speed throwing device, and an insulating resin sheet, a multilayer printed wiring board, and a semiconductor device with a substrate of 97132656 30 200922396 were obtained in the same manner as in the first embodiment. <Example 5> 0.4 part by weight of phenyl-3-aminopropyltrimethoxy decane as a (hydrazine) amino decane coupling agent, and s〇_25R 6〇4 weight of (Β) cerium oxide And 2 parts by weight of the tetrakisylbiphenyl type epoxy resin (C3) as the (C) epoxy resin, 12.9 parts by weight of Phenolite as a curing agent, and 3.9 parts by weight of phenoxy sulfonate. 1 part by weight of 1B2pz 〇2 as a hardening accelerator containing a nitrogen atom, dissolved and mixed to a thiol isobutyl group. Then, an insulating resin sheet with a substrate, a multilayer printed wiring board, and a semiconducting film were obtained in the same manner as in the real one using a high-speed pick-up device. <Comparative Example 1> Epoxy as a coupling agent Base argon coupling agent (A-187) 〇 7 heavy denier = oxygen cut so__. 2 parts by weight 'as (heart: fat is expected to type A epoxy resin ((1) 22. 〇 by weight, as
Phendite 12·4重量份、苯氧基樹脂34 4 卜 玉里切 '作為含 氮原子之硬化促進劑的1B2pz〇.3重量 /合鮮•現人至曱 基^:基酮中。其次，使用高速嶋置進行搜掉而： 樹月曰清漆’與實施例丨同樣地進行得到 Η、容爲化口，丄 材之絕緣樹脂 片夕層印刷佈線板、半導體裝置。 〈比較例2> 將作為偶合劑之環氧基矽烷偶合劑（Α-187)〇 7 θ 作為⑻二氧化石夕之S0-25R 30. 2重量份、作為重置伤 環氧樹脂 97132656 31 200922396 之雙酚A型環氧樹脂（Cl)39.2重量份、作為硬化劑之 Phenolite 22. 7重量份、苯氧基樹脂6. 9重量份、作為含 氮原子之硬化促進劑的1B2PZ 0. 3重量份，溶解•混合至甲 - 基異丁基酮中。其次，使用高速攪拌裝置進行攪拌而調製成 . 樹脂清漆，與實施例1同樣地進行得到附有基材之絕緣樹脂 片、多層印刷佈線板、半導體裝置。 針對上述所得之附有基材之絕緣樹脂片、多層印刷佈線板 D 及半導體裝置，進行以下評價項目之評價。又，將實施例及 比較例之樹脂組成物之調配組成、各物性值、評價結果示於 表1。又，表中各調配量係表示「重量份」。 97132656 32 200922396 /‘ 比較例2 卜 〇 οα CD CO οα ctJ CO 卜 c>i oa CJi cd CO CD 100. 0 X 〇 ◎ X X X 比較例1 卜 c=> οα d CO o οά (M 呀 CNJ 寸 CO CO d CD CD CD t—< X 〇 X X X X 實施例5 寸 C? <〇 CO CNI CNl 03 oi CD CO 03 d> 〇> ◦ 0 1 1 〇 〇 ◎ 〇 〇 〇 實施例4 CD <=> CD C<1 l〇 卜 05 05 CO oa o <〇 <zi o r—H 〇 〇 〇 〇 〇 〇 實施例3 CvJ c<! CO o CO i—H 1—H <N1 (N1 (>a T—H 卜 CO C<1 cz> o o ζΣ> 〇 〇 〇 〇 〇 〇 實施例2 CO <〇 CN1 L〇 CD 19. 6 CO 呀 CO CNI 〇> CD 〇 CD r—i 〇 〇 ◎ 〇 〇 〇 實施例1 1 〇 CO CsJ CV3 12. 9 ① CO oa d CD <〇 CD i—H 〇 〇 ◎ 〇 〇 〇 SZ6083 A-187 S0-25R EPIK0TE828 NC3000 YX-4000 Phenolite YX8100H30 1B2PZ 合計 硬化物之線熱膨脹係數 硬化物之玻璃轉移溫度 最低動態黏度 去鑽渣性評價 吸濕焊料耐熱性評價 熱衝擊試驗 胺基矽烷偶合劑 環氧基矽烷偶合劑 二氧化矽 CO 硬化劑 苯氧基樹脂 含氮原子之硬化促進劑 環氧樹脂 g 荽 ^ 9S3€U6 200922396 物性值之評價方法係如下述。 (1) 硬化物之線熱膨脹係數 準備2片上述所得之附有基材之絕緣樹脂片，將附有基材 之絕緣樹脂片之絕緣層面作為内侧而予以貼合，使用真空加 . 壓式層合機裝置，依溫度100°C、壓力IMPa進行真空加熱 加壓成形，其後，以熱風乾燥裝置依170°C進行加熱硬化60 分鐘，去除薄膜而得到厚度80# m之絕緣層。自所得之絕緣 (') 層切出4mmx40mm之測試片，使用TMA依5°C/分鐘之拉伸條 件測定自25°C至150°C之範圍内的線熱膨脹係數。 各符號係如以下所述。 〇：線熱膨脹係數為35ppm以下 X :線熱膨脹係數大於35ppm (2) 硬化物之玻璃轉移溫度 自於線熱膨脹係數之測定所製作之厚度80/zm的絕緣層 切出10匪X 60mm之測試片，以動態黏彈性測定裝置 (DMA983，TA Instruments公司製）依3°C/分鐘進行升溫， 將tan 5之峰值位置作為玻璃轉移溫度。 ^ 各符號係如以下所述。Phendite 12·4 parts by weight, phenoxy resin 34 4 卜 玉切 '1B2pz 〇.3 weight / freshening as a hardening accelerator containing nitrogen atoms · now human to 曱 base ^: ketone. Then, it was searched for using a high-speed device, and the sapphire varnish was obtained in the same manner as in the example 绝缘, and the insulating resin was printed on the wiring board and the semiconductor device. <Comparative Example 2> An epoxy decane coupling agent (Α-187) 〇7 θ as a coupling agent was used as (8) S0-25R 30. 2 parts by weight of a sulfur dioxide, as a reset-resistance epoxy resin 97132656 31 200922396 3重量重量的为1B2PZ 0. 3重量。 The bisphenol A type epoxy resin (Cl) 39.2 parts by weight, as a hardener Phenolite 22. 7 parts by weight, phenoxy resin 6.9 parts by weight, as a nitrogen atom-containing hardening accelerator 1B2PZ 0. 3 weight Dissolve and mix into methyl-isobutyl ketone. Then, a resin varnish was prepared by stirring with a high-speed stirring device, and an insulating resin sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1. The following evaluation items were evaluated for the insulating resin sheet, the multilayer printed wiring board D, and the semiconductor device with the substrate obtained as described above. Further, the blending compositions, physical property values, and evaluation results of the resin compositions of the examples and the comparative examples are shown in Table 1. In addition, each quantity in a table shows "weight part." 97132656 32 200922396 /' Comparative Example 2 〇 〇α CD CO οα ctJ CO 卜 c&i; i oa CJi cd CO CD 100. 0 X 〇 ◎ XXX Comparative Example 1 卜c=> οα d CO o οά (M 呀 CNJ inch CO CO d CD CD CD t-<X 〇XXXX Example 5 inch C? <〇CO CNI CNl 03 oi CD CO 03 d>〇> ◦ 0 1 1 〇〇 ◎ 〇〇〇 Example 4 CD < ;=> CD C<1 l〇布05 05 CO oa o <〇<zi or—H 〇〇〇〇〇〇Example 3 CvJ c<! CO o CO i-H 1—H <N1 (N1 (>a T-H Bu CO C<1 cz> oo ζΣ> 〇〇〇〇〇〇Example 2 CO <〇CN1 L〇CD 19. 6 CO 呀CO CNI 〇> CD 〇CD r —i 〇〇◎ 〇〇〇Example 1 1 〇CO CsJ CV3 12. 9 1 CO oa d CD <〇CD i—H 〇〇◎ 〇〇〇SZ6083 A-187 S0-25R EPIK0TE828 NC3000 YX-4000 Phenolite YX8100H30 1B2PZ Total Hardening Property Linear Thermal Expansion Coefficient Hardening Glass Transition Temperature Minimum Dynamic Viscosity Drilling Slag Evaluation Evaluation of Moisture Resistant Solder Heat Resistance Thermal Shock Test Aminodecane Mixture Epoxy decane coupling agent Ceria CO Hardener phenoxy resin Hardening accelerator containing nitrogen atom epoxy resin g 荽^ 9S3€U6 200922396 The evaluation method of physical property value is as follows: (1) Line of hardened material Thermal expansion coefficient Two sheets of the insulating resin sheet with a base material obtained as described above were prepared, and the insulating layer of the insulating resin sheet with the base material was attached as an inner side, and a vacuum laminating apparatus was used, and the temperature was 100. Vacuum heating and press forming at ° C and pressure IMPa, followed by heat curing at 170 ° C for 60 minutes in a hot air drying apparatus, and removing the film to obtain an insulating layer having a thickness of 80 # m. The resulting insulating (') layer was cut. A test piece of 4 mm x 40 mm was taken, and the coefficient of linear thermal expansion in the range from 25 ° C to 150 ° C was measured using TMA under tensile conditions of 5 ° C / min. Each symbol is as follows. 〇: The coefficient of thermal expansion of the line is 35 ppm or less. X: The coefficient of thermal expansion of the line is greater than 35 ppm. (2) The glass transition temperature of the cured product. The test piece of the thickness of 80/zm produced by the measurement of the coefficient of thermal expansion of the line is cut out by 10 匪 X 60 mm. The temperature was raised at 3 ° C /min using a dynamic viscoelasticity measuring apparatus (DMA983, manufactured by TA Instruments), and the peak position of tan 5 was taken as the glass transition temperature. ^ Each symbol is as follows.
- 〇：玻璃轉移溫度為190°C以下 X :玻璃轉移溫度高於190°C (3) 最低動態黏度 自上述所得之附有基材之絕緣樹脂片去除基材，作為樣 97132656 34 200922396 本。以黏彈性測定裝置（Anton Par公司製），測定頻率1 OHz、 升溫速度5°C/min、溫度50〜220°C之平面摩擦測定。最低動 態黏度係作為複數黏度（77 * )之極小值。 各符號係如以下所述。 . ◎:未滿 lOOOPa · s 〇：lOOOPa · s 以上、2000Pa · s 以下 X :高於 2000Pa · s 〇 其次，使用多層印刷佈線板及半導體裝置所進行之評價方 法係如下述。 (1)去鑽渣性評價 製作多層印刷佈線板後，觀察剖面，並觀察雷射之開孔 部，確定是否有破裂或樹脂殘渣之殘留。 〇：良好之開孔狀態 X:有破裂或樹脂殘渣之狀態 I) (2)吸濕焊料耐熱性評價 使用上述所得之多層印刷佈線板，以121°C之壓力鍋進行 處理2小時後，將多層印刷佈線板投入至最高溫度為260 • °C、於200°C以上曝露5分鐘之條件的IR迴焊爐中，調查 ^ 有無多層印刷佈線板之外觀異常。 〇：無異常 X:發生膨脹或裂痕 (3)熱衝擊試驗 97132656 35 200922396 將上述所得之半導體裝置於Fluorinert中以ς(:。 τ 从、55。(：1〇 分 鐘、125°Cl〇分鐘、_55°C10分鐘作為丨周期 ，進行 1〇〇〇 周期處理，確認於半導體裝置有無發生裂痕。 〇：無異常 X:發生裂痕 由表1可明白，實施例1〜5係去鑽渣性、吸濕烊料耐熱（ 熱衝擊試驗優越。相對於此，比較例1〜2係去 〇 '續凌性、吸湛 焊料耐熱性、熱衝擊試驗差劣。若使用本發明之±匕…、 物，由於提升去鑽渣性，故推判亦提升多芦£ 祕知組成 θ |刷佈線扳與半 導體裝置之可罪性。 (產業上之可利用性） 本發明之樹脂組成物係低線膨脹，去鑽湩性亦優越，故可 細微佈線加工之薄型多層印刷佈線板中，以及使 Q 夕曰印刷佈線板之半導體裝置中。 97132656 36- 〇: glass transition temperature is 190 ° C or less X : glass transition temperature is higher than 190 ° C (3) Minimum dynamic viscosity The substrate is removed from the substrate-attached insulating resin sheet obtained as described above, as a sample 97132656 34 200922396. A plane friction measurement of a frequency of 10 Hz, a temperature increase rate of 5 ° C/min, and a temperature of 50 to 220 ° C was measured using a viscoelasticity measuring apparatus (manufactured by Anton Par). The lowest dynamic viscosity is the minimum value of the complex viscosity (77 * ). Each symbol is as follows. ◎: Not full lOOOPa · s 〇: lOOOPa · s or more, 2000Pa · s or less X : more than 2000Pa · s 〇 Next, the evaluation method using a multilayer printed wiring board and a semiconductor device is as follows. (1) Drilling slag evaluation After the multilayer printed wiring board was produced, the cross section was observed, and the opening of the laser was observed to determine whether or not there was cracking or residue of the resin residue. 〇: good opening state X: state of cracking or resin residue I) (2) evaluation of heat resistance of moisture absorbing solder Using the multilayer printed wiring board obtained above, it was treated in a pressure cooker at 121 ° C for 2 hours, and then multilayered. The printed wiring board was placed in an IR reflow furnace with a maximum temperature of 260 ° C and exposed at 200 ° C for 5 minutes, and the presence or absence of the multilayer printed wiring board was abnormal. 〇: no abnormality X: expansion or cracking occurred (3) thermal shock test 97132656 35 200922396 The semiconductor device obtained above was used in Fluorinert as ς (: τ 、, 55. (: 1 〇 minute, 125 ° Cl 〇 minutes, _55 ° C for 10 minutes as a helium cycle, and a cycle of 1 cycle was performed to confirm the presence or absence of cracks in the semiconductor device. 〇: no abnormality X: cracking occurred. It can be understood from Table 1 that Examples 1 to 5 are slag-drilling and sucking. The wet mash is heat-resistant (the thermal shock test is superior. In contrast, the comparative examples 1 and 2 are sturdy, the solder heat resistance, and the thermal shock test are inferior. If the 匕..., the object of the present invention is used, Since the slag-reducing property is improved, the smear of the θ | brush wiring board and the semiconductor device is also improved. (Industrial Applicability) The resin composition of the present invention is low-line expansion, It is also superior in drillability, so it can be used for fine wiring of thin multilayer printed wiring boards, and for semiconductor devices of Q-ray printed wiring boards. 97132656 36