201200964 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用 合物以及藉其在PCB切=成通孔之感先性環氧樹脂组 發明係關於-種包之方法。更具體而言，本 ^ 用於形成通孔之環氧樹脂與光酸產生 感光性環氧樹脂組合物以及—種其以在PCB上形 成通孔的方法。 【先前技術】 當要在多層印刷線路板的層間介電層上形成通孔時， 傳統技術是藉由形成—硬化薄膜而進行，其係硬化一環氧 樹月曰組合物而作為多層印刷線路板之層間介電層，並藉由 雷射鑽孔或鑽孔尖端程序來形成通孔；然而，由於近^在 PCB上每一平板係具有數以萬計、甚至數十萬個通孔，故 其在δ又備與製造時間上會有其缺點。 光微影也已用於形成通孔。光微影技術係改質環氧樹 脂’並透過曝光程序利用光起始劑形成精細圖樣。然而。 即使利用此種曝光裎序來形成精細圖樣，在曝光程序中仍 會喪失環氧樹脂的特性，因此’藉由使用這種曝光及顯影 程序可一次形成所有的孔洞，但會降低P C Β的物理性質（例 如抗熱性、黏著性與熱膨脹係數等），且此技術無法用於需 高度可靠性之PKG產品。 【發明内容】 201200964 在此技術環境下，本發明之發明人㈣發出一種在 PCB上形成通孔的方法，其_用包括光酸產生劑與用於 形成通孔之環氧樹脂的感光性環氧樹月旨組合物，可在低製 造成本中仍保持層間介電特性。 因此本發明的態樣之-在於提供一種感光性環氧樹脂 組合物與-種在PCB上形成通孔的方法。該感光性環氧樹 脂組合物包括-光酸產生劑與-環氣樹脂以形成通孔；該 : 方法包括在一 PCB上積層一環氧樹脂組合物，並進行曝光 : 與顯影，以解決與傳統通孔形成方法相關的上述問題。 根據本發明之一態樣，所提供者係—種感光性環氧樹 脂組合物，其包括一光酸產生劑與一環氧樹脂以形成通孔。 根據本發明之一具體實施例’用於形成通孔之該感光 性環氧樹脂組合物更包括一光增強劑、—硬化劑與一無機 填充劑。 根據本發明之一具體實施例’該光酸產生劑係鑌鹽。 根據本發明之一具體實施例’該鏽鹽係三芳基錄鹽 (triarylsulfonium salt)或二芳基錤鹽（diaryliodonium salt)。 J 根據本發明之一具體實施例，該光酸產生劑的含量為 : 該環氧樹脂的0.1至10wt%。 根據本發明之一具體實施例，該環氧樹脂係選自由雙 酚A型、雙酚F型、苯酚酚醛、曱酚酚醛以及經橡膠改質 之環氧樹脂所組成之群組中之至少一者。 根據本發明之一具體實施例’該光增強劑係η塞吨酉同 (thioxanthone)化合物0 201200964 根據本發明之一具體實施例，該噻吨酮化合物係選自 於由異丙基嗟吨嗣、2-氯嗟吨酮以及二乙基噻吨酮所組成 之群組中之至少一者。 根據本發明之一具體實施例，該光增強劑的含量係該 光酸產生劑的2〇〇wt%或以下。 根據本發明之一具體實施例，該硬化劑係選自於由酸 酐與一潛在硬化劑所組成之群組中之至少—者。 根據本發明之一具體實施例，該潛在硬化劑係選自於 由吼嗪鑌（pyrazinium)鹽化合物、吡咬陽離子（pyridinium) 鹽化合物以及哌啶鏽(piperidinium)鹽化合物所組成之群組 中之至少一者。 根據本發明之一具體實施例’ δ亥無機填充劑係選自於 由滑石、矽石、硫酸鋇以及氧化鈦所組成之群組中之至少 —種0 根據本發明之一具體實施例，該無機填充物之直徑係 ΙΟμιη或以下。 根據本發明之另一具體實施例，所提供者係一種用於 在一;PCB上形成通孔之方法，其包括製備一種用於形成通 孔之感光性環氧樹脂組合物；在一 PCB上積層該環氧樹脂 組合物；在該板體上放置具有圖樣之一玻璃遮罩或一^ 膜，並暴露於UV;顯影經暴露之板體；以及乾燥經顯影之 板體，並藉由加熱進行後硬化。 根據本發明之一具體實施例，所述在一 PCB上積芦該 %氧樹脂組合物之步驟係藉由直接對_ pCB塗佈該環氧樹 201200964 脂組合物而進行。 根據本發明之一具體實施例，所述在一 PCB上積層該 環氧樹脂組合物之步驟係藉由將該環氧樹脂組合物塗佈於 一薄膜上並將其乾燥以製備一乾燥薄膜，且將該乾燥薄膜 轉移至一板體而進行。 根據本發明之一具體實施例，在所述暴露於UV之步 驟中，UV的波長係介於350至450nm的範圍内。 根據本發明之一具體實施例，所述顯影經暴露之板體 之步驟係藉由選自於由下列方法所組成之群組中的其中一 者而進行：對該板體喷塗一顯影溶液；將該板體浸沒於一 顯影溶液中然後使其搖晃；以及將該板體浸沒於—顯影溶 液中然後進行超音波處理。 根據本發明之-具體實施例，所述藉由加熱之後硬化 之步驟係於120至200〇C下進行1〇至9〇分於 根據本發明，通孔係藉由使用包括光^生劑之感光 性核氧樹驗合物透祕光錢影㈣成。细本發明中 用於形成通孔之感光性環氧樹脂組合物^ 傳統方法更簡單，且可降低製造成本。 ^ 、 孔形成方法可保持層間介電層的物 ’本發明之^ 技術中在環氧樹脂改質程序期間對環’其解決了傳, 問題。除此之外，本發明提供了 1 =特性有害的相關 性環氧樹脂組合物，其可用於必須維成通孔的感先 如抗熱性、黏著性、抗化學性、物 r樹脂之特性（例 況。 X/、電絕緣性等）的情 201200964 【實施方式】 本發明係參照特定的具體實施例加以說明，然應知該 領域技術人士可對其進行各種變化與修飾，其皆不背離如 附申請專利範圍及其均等物中所定義之本發明精神與範 疇。在本發明之說明中，在描述與發明點無關之某一技術 時，將省略其詳細說明。 根據本發明之一態樣，所提供者係一種感光性環氧樹 脂組合物，其包括一光酸產生劑與一環氧樹脂以形成通孔。 光酸產生劑並不特別受限，且可藉由光而產生酸的任 何化合物皆可作為光酸產生劑。光酸產生劑的例子包括鑌 鹽、可能的磺酸、齒金屬-S_三畊、金屬芳香類(metall〇cene)、 氯化乙醯苯以及苯甲醯基苯基醚等。根據本發明之一具體 實施例，特別是使用鑌鹽作為光酸產生劑。鑌鹽的例子包 括了方基重氮鐵鹽（aryl diazonium)、二芳基錐鹽、三芳基 鏑鹽、二芳基石西鏽鹽(triaryl selenonium)、二院基苯甲醯曱 基銃鹽（dialkyl phenacyl sulfonium)、三芳基亞砜鏽鹽(triaryl solfoxonium)、芳氧基二芳基亞礙鏽鹽（aryl〇xydiaryl solfoxonium)以及二烷基苯甲醯甲基亞砜鏽鹽（dialkyl phenacyl solfoxonium salt)等’但並不限於此。較佳為使用 三芳基疏鹽或二芳基錤鹽作為鏽鹽。 錄鹽的含里為壤氧樹脂的01至10wt%。當低於環氧 樹脂的o.lwt%時，便需要過多量之曝光，且其即因塗佈薄 膜在顯影期間溶解而難以形成精細圖樣。另一方面，當其 咼於10wt°/〇時，組合物的單價就會增加，且難以控制所需 201200964 精細圖樣的形成。 根據本發明之一具體實施例，環氧樹脂係選自雙酚A 型、雙酚F型、苯酚酚醛、甲酚酚醛以及經橡膠改質環氣 樹脂中的至少一種’但其並不限於此。 例如雙酚A型環氧樹脂、雙酚F型環氧樹脂等環氧樹 脂係可選自曱基乙基酮（MEK，methylethylketone)、二甲義 曱醯胺（DMF, dimethyl formamide)、乙二醇甲鱗（Mcs methyl cellosolve)、卡必醇醋酸酯（cabitol acetate)、卡必醇 (cabitol)、PGMEA、PGME、曱苯、二甲苯、NMP、2-甲氧 基乙醇等之至少一者。由於可獲得具高抗熱性之硬化材料 以及具較佳熱穩定性之板體，顯然酚醛型環氧樹脂可為笨 酚酚醛或曱酚酚醛環氧樹脂。 經橡膠改質之環氧樹脂可以DGEBA (雙酚A之二縮 水甘油醚（diglycidyl ether of bisphenol A))與 CTBN (以叛 基為末端之丁一稀-丙烯腈共聚物（carb〇Xy terminated butadiene acrylonitrile cop〇lymer))之混合物之形式使用。 壞氧樹脂可用選自曱基乙基嗣（MEK)、二曱基曱酿胺 (DMF)、乙二醇曱謎（MCS)、卡必醇醋酸酯、卡必醇、 PGMEA、PGME、曱苯、二曱笨、NMP、2·曱氧基乙醇等 中之至少兩種物質之混合物來溶解而使用。 根據本發明之一具體實施例，用於形成通孔之感光性 環氧樹脂組合物進一步包括光増強劑、硬化劑與無機填充 劑。 添加光增強劑係可增加對包括光酸產生劑之環氧樹脂 201200964 組合物的曝光波長的敏感性。根據本發明之一具體實施 例光增強劑係嗔吨自同(thioxanthone)化合物，其例子選自 異丙基嗟吨酮、2-氯噻吨酮與二乙基噻吨酮中之至少一 種° °塞吨酮化合物讓光酸產生劑可輕易達到激發態而產生 酸。根據本發明之一具體實施例’光增強劑的含量係為光 酸產生劑的200wt%或以下，當其高於20〇wt%時，即幾無 降低曝光量之效果。 添加硬化劑係可增進絕緣材料的熱穩定性，且硬化劑 可選自酸酐與潛在硬化劑中之至少一種。 酸軒的例子包括甲基四氫鄰苯二曱酸酐（methyl tetrahydrophthalic anhydride)、曱基六氫鄰苯二曱酸肝、甲 基降冰片烯二酸酐(methyl himic anhydride)、四氫鄰苯二曱 酸酐、三烧基四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、曱 基環己烷二羧酸酐、鄰苯二甲酸酐、苯偏三酸酐(trimellitic anhydride)、焦蜜石酸酐(pyromellitic anhydride)、二苯基酮 四緩酸酐（benzophenone tetracarboxylic anhydride)以及伸乙 甘醇雙苯偏三酸酐（ethylene glycol bistrimellitic anhydride) 等。 根據本發明之一具體實施例，潛在硬化劑係選自吼嗪 鐳(pyrazinium)鹽化合物、°比咬陽離子(pyridinium)鹽化合物 以及哌啶鏽(piperidinium)鹽化合物中之至少一種。 硬化劑的添加量係介於一般用於環氧樹脂硬化劑相對 於總環氧樹脂當量之當量比的範圍内。 此外，添加無機填充劑係為增進環氧樹脂組合物的物 201200964 理性質，如抗熱性與強度；所使 型無機填充劑。根據本發 的例子係選自滑石、矽$ . ‘、，、機填充劑 -種，苴不… 硫夂鋇、以及氧化鈦中之至少 禋仁八不限於此。根據本發明之一且 填充劑的直徑為10；^+ 八 列，無機 無法適當形成通孔。心^下；若直徑大於1G微米，則 脂 人:外可於本發明之用於形成通孔之感光性環氧樹 組合物的應用中添加顏料或染料。 衣氧树 ，據本發明之另1樣，所提供係—種料在— 、板上形成通孔之方法，其包括製備一種用於 之感光性環氧樹脂級人物. 、形成通孔 合物;在該板體上=广板艘上積層該環氧樹脂組 並暴露於uv;顯if::圖Γ: 一玻璃遮罩或-薄膜， 體，並藉由加熱進行’以及乾_顯影之板 ㈣上形成通孔的=硬化。第2圖說明了本發明用以在 根，本㈣之—具體實闕，所述在-PCB上積層該 環氧樹脂組合物之步驟後 、曰μ 脂組合物而進行；· ^由直接對—⑽塗佈該環氧樹 膜上並將其乾燥以製；：=樹脂組合物塗佈於-薄 至-PCB而進行 乾㈣膜，且將該乾燥薄膜轉移 根據本發明之一具體實施例，在所述暴露於UV之步 驟中’ UV的波長係介於35G至45Gnm的範圍内。 所述顯影經暴露之板體之步驟係藉由選自於由下列方 法所組成之群組令的其中之一而進行··對該板體喷塗一顯 201200964 影溶液；將該板體浸沒於一顯影溶液中然後使其搖晃；以 及將該板體浸沒於一顯影溶液中然後進行超音波處理。 本發明餘在PCB上形成通狀方法純括乾燥經顯 影之板體並以熱處理進行後硬化(p〇st_curing)，其係為藉由 乾燥而移除經顯影之板體上所殘留的任何溶劑，並藉由在 兩溫下進行後硬化而增加環氧樹脂的硬化密度。 根據本發明之一具體實施例，所述藉由加熱之後硬化 之步驟係於120至200°C下進行1〇至90分鐘。若後硬化 之加熱溫度低於120°C，則會導致硬化速度慢；另一方面， 若高於200°C，便會增加製造成本。 以下將提出實施例說明本發明之更多細節，然應理解 該等實施例僅為說明之用，而非用於限制本發明。 用於形成通孔之感光性環氧樹脂組合物的製備 根據實例1至4以及比較例1與2,感光性環氧樹脂組 合物係以表1所示之組成加以製備。 12 201200964 表1 實例1 實例2 實例3 實例4 比較例1 比較例2 YD-128 30 30 30 30 30 - YDCN-500-80P 50 50 50 50 50 30 環氧丙烯酸酯樹脂 - - - • 垂 70 乙二醇曱醚 20 20 20 20 20 • DAI-01 2 2 - 一 TAS-01 - 2 2 - MS-7 - - - _ 3 滑石 20 20 20 20 20 20 MeTHPA 40 - 40 . 60 鱗 SP-600 - 2 - 2 編 2MZ - - - - 2 • (單位：克） YD-128、YDCN-500-80P :環氧樹脂（Kukdo Chemical 製造） 環氧丙烯酸酯樹脂：（SMC製造） 乙二醇曱醚：（Tedia製造） DAI-01、TAS-01 :光酸產生劑(SMC製造） MS-7 :光起始劑（Miwon Commercial Co” Ltd.製造) 滑石：（Jin Chemical 製造）201200964 VI. OBJECTS OF THE INVENTION: 1. Field of the Invention The present invention relates to a composition and a method for forming a prior art epoxy resin by cutting into a through-hole on a PCB. More specifically, the epoxy resin and photoacid used to form the via holes produce a photosensitive epoxy resin composition and a method of forming a via hole on the PCB. [Prior Art] When a through hole is to be formed in an interlayer dielectric layer of a multilayer printed wiring board, the conventional technique is carried out by forming a hardened film which is used as a multilayer printed wiring by hardening an epoxy resin composition a dielectric layer between the layers of the board, and a via hole is formed by a laser drilling or drilling tip program; however, since each panel has tens of thousands or even hundreds of thousands of through holes on the PCB, Therefore, it has its shortcomings in terms of δ preparation and manufacturing time. Photolithography has also been used to form vias. The photolithography technique is to modify the epoxy resin and form a fine pattern using a photoinitiator through an exposure procedure. however. Even if such an exposure sequence is used to form a fine pattern, the characteristics of the epoxy resin are lost in the exposure process, so that all holes can be formed at one time by using this exposure and development process, but the physical properties of the PC are reduced. Properties (such as heat resistance, adhesion and thermal expansion coefficient, etc.), and this technology cannot be used for PKG products requiring high reliability. SUMMARY OF THE INVENTION 201200964 In this technical environment, the inventors of the present invention (4) issued a method of forming a via hole on a PCB, which comprises a photosensitive ring comprising a photoacid generator and an epoxy resin for forming a via hole. The oxygen tree composition can maintain interlayer dielectric properties at low manufacturing costs. It is therefore an aspect of the present invention to provide a photosensitive epoxy resin composition and a method of forming a via hole in a PCB. The photosensitive epoxy resin composition comprises a photoacid generator and a ring gas resin to form a through hole; the method comprises laminating an epoxy resin composition on a PCB, and performing exposure: and developing to solve The above problems related to the conventional through hole forming method. According to one aspect of the present invention, there is provided a photosensitive epoxy resin composition comprising a photoacid generator and an epoxy resin to form via holes. The photosensitive epoxy resin composition for forming a through hole according to an embodiment of the present invention further comprises a light enhancer, a hardener and an inorganic filler. According to an embodiment of the present invention, the photoacid generator is a phosphonium salt. According to an embodiment of the present invention, the rust salt is a triarylsulfonium salt or a diaryliodonium salt. J According to a specific embodiment of the invention, the photoacid generator is present in an amount of from 0.1 to 10% by weight of the epoxy resin. According to a specific embodiment of the present invention, the epoxy resin is selected from at least one selected from the group consisting of bisphenol A type, bisphenol F type, phenol novolac, nonylphenol phenolic, and rubber modified epoxy resin. By. According to an embodiment of the present invention, the photointensifier is a thioxanthone compound 0 201200964. According to an embodiment of the present invention, the thioxanthone compound is selected from the group consisting of isopropyl xanthene. At least one of the group consisting of 2-chloroxanthone and diethylthioxanthone. According to a specific embodiment of the present invention, the photointensifier is contained in an amount of 2% by weight or less based on the photoacid generator. According to a particular embodiment of the invention, the hardener is selected from at least one of the group consisting of an acid anhydride and a latent hardener. According to a specific embodiment of the present invention, the latent hardener is selected from the group consisting of a pyrazinium salt compound, a pyridinium salt compound, and a piperidinium salt compound. At least one of them. According to an embodiment of the present invention, the δH inorganic filler is selected from at least one of the group consisting of talc, vermiculite, barium sulfate, and titanium oxide. According to an embodiment of the present invention, The diameter of the inorganic filler is ΙΟμηη or below. According to another embodiment of the present invention, there is provided a method for forming a via hole in a PCB, comprising preparing a photosensitive epoxy resin composition for forming a via hole; Laminating the epoxy resin composition; placing a glass mask or a film on the plate body and exposing it to UV; developing the exposed plate body; and drying the developed plate body, and heating by heating After hardening. According to an embodiment of the present invention, the step of accumulating the % oxygen resin composition on a PCB is carried out by directly coating the epoxy tree 201200964 fat composition on _pCB. According to an embodiment of the present invention, the step of laminating the epoxy resin composition on a PCB is performed by coating the epoxy resin composition on a film and drying it to prepare a dry film. And transferring the dried film to a plate body. According to an embodiment of the invention, in the step of exposing to UV, the wavelength of UV is in the range of 350 to 450 nm. According to a specific embodiment of the present invention, the step of developing the exposed plate body is performed by one selected from the group consisting of: spraying a developing solution on the plate body The plate is immersed in a developing solution and then shaken; and the plate is immersed in a developing solution and then subjected to ultrasonic treatment. According to a specific embodiment of the present invention, the step of hardening by heating is carried out at 120 to 200 ° C for 1 to 9 Torr. According to the present invention, the through hole is used by using a photocatalyst. The photosensitive nuclear oxygen tree test compound penetrates the secret light shadow (four) into. The photosensitive epoxy resin composition for forming a through hole in the present invention is simpler and can reduce the manufacturing cost. ^, the hole formation method can maintain the interlayer dielectric layer. The technique of the present invention solves the problem of the ring during the epoxy resin modification procedure. In addition, the present invention provides a 1 = characteristically harmful correlation epoxy resin composition which can be used for the properties of the through-holes such as heat resistance, adhesion, chemical resistance, and properties of the resin. Example: X/, Electrical Insulation, etc., 201200964 [Embodiment] The present invention has been described with reference to specific embodiments, and it should be understood that various changes and modifications may be made by those skilled in the art without departing from the invention. The spirit and scope of the invention as defined in the appended claims and their equivalents. In the description of the present invention, a detailed description of a technique that is not related to the point of the invention will be omitted. According to one aspect of the present invention, there is provided a photosensitive epoxy resin composition comprising a photoacid generator and an epoxy resin to form via holes. The photoacid generator is not particularly limited, and any compound which can generate an acid by light can be used as a photoacid generator. Examples of the photoacid generator include sulfonium salts, possible sulfonic acids, tooth metal-S_three tillages, metal aryl groups, chlorinated benzene benzene, and benzhydryl phenyl ether. According to a particular embodiment of the invention, in particular a cerium salt is used as the photoacid generator. Examples of the onium salt include an aryl diazonium, a diaryl taper salt, a triarylsulfonium salt, a triaryl selenonium salt, and a difenyl benzamidine salt. Dialkyl phenacyl sulfonium), triaryl solfoxonium, aryl xydiaryl solfoxonium, and dialkyl phenacyl solfoxonium salt ) etc. 'but not limited to this. It is preferred to use a triarylsulfonium salt or a diarylsulfonium salt as the rust salt. The content of the recorded salt is from 01 to 10% by weight of the lime resin. When it is less than 0.1% by weight of the epoxy resin, an excessive amount of exposure is required, and it is difficult to form a fine pattern because the coating film dissolves during development. On the other hand, when it is at 10 wt/min, the unit price of the composition increases, and it is difficult to control the formation of the required fine pattern of 201200964. According to a specific embodiment of the present invention, the epoxy resin is selected from at least one of bisphenol A type, bisphenol F type, phenol novolac, cresol novolac, and rubber modified ring gas resin', but it is not limited thereto. . For example, an epoxy resin such as a bisphenol A epoxy resin or a bisphenol F epoxy resin may be selected from the group consisting of methyl ethylketone (MEK), dimethyl formamide (DMF), and ethylene. At least one of Mcs methyl cellosolve, cabitol acetate, cabitol, PGMEA, PGME, toluene, xylene, NMP, 2-methoxyethanol, and the like. Since a hardened material having high heat resistance and a plate having better heat stability can be obtained, it is apparent that the novolac type epoxy resin may be a phenol novolac or a nonylphenol novolac epoxy resin. The rubber-modified epoxy resin can be DGEBA (diglycidyl ether of bisphenol A) and CTBN (dead-based butyl-acrylonitrile copolymer (carb〇Xy terminated butadiene) Use in the form of a mixture of acrylonitrile cop〇lymer)). The bad oxygen resin may be selected from the group consisting of mercaptoethyl hydrazine (MEK), dimercapto phthalic acid (DMF), ethylene glycol ruthenium (MCS), carbitol acetate, carbitol, PGMEA, PGME, toluene, A mixture of at least two of dioxane, NMP, 2, nonyloxyethanol, and the like is dissolved and used. According to a specific embodiment of the present invention, the photosensitive epoxy resin composition for forming a through hole further includes a photo-reinforcing agent, a hardener, and an inorganic filler. The addition of a light enhancer can increase the sensitivity to the exposure wavelength of the epoxy resin 201200964 composition including the photoacid generator. According to a specific embodiment of the present invention, the photointensifier is a thioxanthone compound, and examples thereof are at least one selected from the group consisting of isopropyl xanthone, 2-chlorothioxanthone and diethyl thioxanthone. The tonoxone compound allows the photoacid generator to easily reach an excited state to generate an acid. According to a specific embodiment of the present invention, the content of the photointensifier is 200% by weight or less of the photoacid generator, and when it is higher than 20% by weight, there is little effect of lowering the exposure amount. The addition of a hardener enhances the thermal stability of the insulating material, and the hardener may be selected from at least one of an acid anhydride and a latent hardener. Examples of the acid sulphate include methyl tetrahydrophthalic anhydride, decyl hexahydrophthalic acid liver, methyl himic anhydride, tetrahydrophthalic anhydride Anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, nonylcyclohexanedicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyrogallic anhydride ( Pyromellitic anhydride), benzophenone tetracarboxylic anhydride, and ethylene glycol bistrimellitic anhydride. According to a specific embodiment of the present invention, the latent hardener is at least one selected from the group consisting of a pyrazine salt compound, a pyridinium salt compound, and a piperidinium salt compound. The amount of the hardener added is in a range generally equivalent to the equivalent ratio of the epoxy resin hardener to the total epoxy equivalent. Further, the inorganic filler is added to promote the properties of the epoxy resin composition, such as heat resistance and strength; and the type of inorganic filler. The examples according to the present invention are selected from the group consisting of talc, 矽$. ‘,, machine filler-type, 苴... 夂钡 夂钡, and at least at least one of the titanium oxides is not limited thereto. According to one of the present invention, and the filler has a diameter of 10; ^ + eight columns, the inorganic holes cannot be appropriately formed. If the diameter is larger than 1 Gm, the fat can be added to the application of the photosensitive epoxy resin composition for forming a through hole of the present invention. Oxygen tree, according to another aspect of the present invention, there is provided a method for forming a through hole in a plate, comprising preparing a photosensitive epoxy resin grade member, forming a through hole. The epoxy resin group is laminated on the plate body = wide plate and exposed to uv; display:: a glass mask or - film, body, and by heating 'and dry_developing Forming the through hole on the plate (4) = hardening. Figure 2 illustrates the invention for use in the root, the present invention, after the step of laminating the epoxy resin composition on the -PCB, the 曰μ grease composition is carried out; - (10) coating the epoxy resin film and drying it to make;: = resin composition is applied to - thin to -PCB to dry (four) film, and transferring the dried film according to a specific embodiment of the present invention In the step of exposing to UV, the wavelength of UV is in the range of 35G to 45Gnm. The step of developing the exposed plate body is performed by one selected from the group consisting of the following methods: spraying the plate with a 201200964 shadow solution; immersing the plate body And then shaking it in a developing solution; and immersing the plate in a developing solution and then performing ultrasonic treatment. The invention forms a pass-through method on the PCB, which comprises drying the developed plate body and performing post-hardening (p〇st_curing) by heat treatment, which removes any solvent remaining on the developed plate body by drying. And increase the hardening density of the epoxy resin by post-hardening at two temperatures. According to an embodiment of the present invention, the step of hardening by heating is carried out at 120 to 200 ° C for 1 to 90 minutes. If the heating temperature of the post-hardening is lower than 120 ° C, the curing speed is slow; on the other hand, if it is higher than 200 ° C, the manufacturing cost is increased. The invention is described in detail below with reference to the accompanying drawings. Preparation of Photosensitive Epoxy Resin Composition for Forming Through Holes According to Examples 1 to 4 and Comparative Examples 1 and 2, a photosensitive epoxy resin composition was prepared in the composition shown in Table 1. 12 201200964 Table 1 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 YD-128 30 30 30 30 30 - YDCN-500-80P 50 50 50 50 50 30 Epoxy acrylate resin - - - • 垂 70 B Glycol oxime ether 20 20 20 20 20 • DAI-01 2 2 - One TAS-01 - 2 2 - MS-7 - - - _ 3 Talc 20 20 20 20 20 20 MeTHPA 40 - 40 . 60 Scale SP-600 - 2 - 2 2MZ - - - - 2 • (Unit: gram) YD-128, YDCN-500-80P: Epoxy resin (manufactured by Kukdo Chemical) Epoxy acrylate resin: (manufactured by SMC) Ethylene glycol oxime ether: (manufactured by Tedia) DAI-01, TAS-01: Photoacid generator (manufactured by SMC) MS-7: Photoinitiator (manufactured by Miwon Commercial Co. Ltd.) Talc: (manufactured by Jin Chemical)
MeTHPA :酸酐(Lonza 製造） SP-600 :潛在硬化劑（SMC製造） 2MZ :硬化加速劑（sigma Aldrich製造） 實例1 13 201200964 將環氧樹脂、3〇克YD-128與％克YDCN_5〇〇_8〇p加 入15克乙二醇曱醚，並將混合溶液於80°C下加熱並攪拌 3/、日^將2〇克滑石加人混合溶液，並以三滾輪研磨器研 磨一-人以使滑石完全分散。將作為光酸產生劑並溶於5克 乙二醇甲鲢的2克DAI_〇1溶液加入混合溶液中。將牝 Me™PA力〜所產生之溶液中，並在室溫下攪拌i小時。 實例2 將溶於5克乙二醇甲趟且作為光酸產生 DAI-01與作為潛在硬化劑之2克sp_6〇〇之溶液加入 例1所製備之混合溶液中，並在室溫下擾掉！小時。 實例3 來製備感光性環氧 來製備感光性環氧 以TAS_01取代實例1中的DAI-01 樹脂組合物。 實例4 以TAS-01取代實例2中的dai_〇1 樹脂組合物。 比較例1 乙二醇甲醚中之60克 實例丨，備之混合溶 將作為硬化加速劑並溶於5克 MeTHPA與2克2MZ的溶液加入如 液中，並在室溫下攪拌1小時。 201200964 比較例2 將30克YDCN-500-80P加入70克環氧丙烯酸醋樹脂 中，並將混合溶液於40°C下加熱並授拌4小時。將3克光 起始劑MS-7加入混合溶液中，並使其在室溫下反應3小時 以得到一澄清錯合樹脂。將20克滑石加入錯合樹脂中，並 以三滚輪研磨器研磨三次以使滑石完全分散。 試驗例.實例1至4中所製備之組合物與比較例〖和2 所製備者在硬化後的物理性質比較 根據實例1至4與比較例1和2所製備之每一纟且合物 係直接塗佈於一印刷電路板上’並藉由乾燥移除溶劑:具 有塗饰薄膜之板體係藉由曝光機進行曝光，並於含乙一醇 曱醚之顯影溶液中顯影與乾燥。經乾燥之板體係二 下進行後硬化40分鐘。 利用TA公司之TMA Q_熱重儀來確定各個經硬化 之組合物的Tg (玻璃轉換溫度）冑CTE (熱膨張係數），MeTHPA: anhydride (manufactured by Lonza) SP-600: latent hardener (manufactured by SMC) 2MZ: hardening accelerator (manufactured by sigma Aldrich) Example 1 13 201200964 Epoxy resin, 3 gram YD-128 and % gram YDCN_5 〇〇 8 〇p was added 15 g of ethylene glycol oxime ether, and the mixed solution was heated at 80 ° C and stirred for 3 /, day 2 2 gram of talc was added to the mixed solution, and ground with a three-roller grinder The talc is completely dispersed. A solution of 2 g of DAI_〇1 as a photoacid generator dissolved in 5 g of ethylene glycol formamidine was added to the mixed solution. Place 牝MeTMPA in the resulting solution and stir for 1 hour at room temperature. Example 2 A solution prepared by dissolving 5 g of ethylene glycol onyrene as a photoacid to produce DAI-01 and 2 g of sp_6 oxime as a latent hardener was added to the mixed solution prepared in Example 1 and disturbed at room temperature. ! hour. Example 3 Preparation of Photosensitive Epoxy to Prepare Photosensitive Epoxy The DAI-01 resin composition of Example 1 was replaced with TAS_01. Example 4 The dai_〇1 resin composition of Example 2 was replaced with TAS-01. Comparative Example 1 60 g of ethylene glycol methyl ether Example 丨, mixed solution was added as a hardening accelerator and dissolved in 5 g of MeTHPA and 2 g of 2 MZ into a liquid, and stirred at room temperature for 1 hour. 201200964 Comparative Example 2 30 g of YDCN-500-80P was placed in 70 g of epoxy acrylate resin, and the mixed solution was heated at 40 ° C and mixed for 4 hours. 3 g of the photoinitiator MS-7 was added to the mixed solution, and allowed to react at room temperature for 3 hours to obtain a clear-knit resin. 20 g of talc was added to the miscible resin and ground three times with a three-roll mill to completely disperse the talc. Test Example. Physical properties of the compositions prepared in Examples 1 to 4 and those prepared in Comparative Examples 〖 and 2 after hardening according to Examples 1 to 4 and Comparative Examples 1 and 2 Directly coated on a printed circuit board 'and solvent removed by drying: the plate system with the coated film is exposed by an exposure machine and developed and dried in a developing solution containing oxime ether. The dried plate system was post-hardened for 40 minutes. The Tg (glass transition temperature) 胄CTE (thermal expansion coefficient) of each hardened composition was determined using TA's TMA Q_thermometer.
Tg係以25至250〇C間、升溫率為1〇。〇咖下進行第二士 掃猫所得數值而決定。 利用十字切割U〇x1〇)膠帶測試來評估硬化薄膜的黏The Tg is between 25 and 250 ° C and the heating rate is 1 Torr. It is decided by the value of the second person sweeping the cat under the coffee. Use the cross-cut U〇x1〇) tape test to evaluate the adhesion of the hardened film
著性。在硬化薄膜上進行_次切割，並在其上黏貼3M 膠帶，然後將其撕離。接著計算剩下未被撕離的十字 部分的數量’其結果係表示為m/100,其中m是剩餘切割 數_ 在曝光與顯影步驟之後，利賴微鏡觀察通孔以評估 201200964 開孔狀況；結果係總結於表2中。 表2 實例 實例2 實例3 實例4 比較例1 比較例2 Tg (°C) 172 168 170 165 170 105 CTE (α,) 40 38 39 41 43 55 黏著數 100/10 0 100/10 0 loo/io 0 100/10 0 100/100 100/100 開孔（100/60)μιη 〇 〇 0 〇 X 〇 如表2所示’可注思右比較根據比較例1和2所製備 之組合物以及根據實例1至4所製備之組合物的Tg與CTE 值時，比較例1和2之組合物無法作為板體材料，但實例丄 至4的組合物則具有高Tg值與低CTE值。實例1至4的 物理性質係優於比較例1和2。 此外，開孔數係如第1圖中所示，其為透過顯微鏡所 觀察之相片，其說明利用實施例1所製備之感光性環^棺 脂組合物在PCB上形成之通孔。 t 本發明係參照特定的具體實施例加以說明，然鹿失 領域技術人士可對其進行各種變化與修飾，其皆 ^ /、 穿離如 附申請專利範圍及其均等物中所定義之本發明具體實 之精神與範疇。 例 【圖式簡單說明】 第ί圖為透過顯微鏡所觀察之相片，其說明利用 例1所製備之感光性環氧樹脂組合物在PCB上形成之砭 16 201200964 孔。 第2圖說明本發明中在PCB上形成通孔之方法。 【主要元件符號說明】 無。 17Sexuality. The cut was made on the hardened film, and the 3M tape was adhered thereto and then peeled off. Next, calculate the number of cross portions that are not torn off. The result is expressed as m/100, where m is the number of remaining cuts. After the exposure and development steps, the Rayleigh microscope observes the through holes to evaluate the 201200964 opening condition. The results are summarized in Table 2. Table 2 Example Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Tg (°C) 172 168 170 165 170 105 CTE (α,) 40 38 39 41 43 55 Adhesive number 100/10 0 100/10 0 loo/io 0 100/10 0 100/100 100/100 opening (100/60) μιη 〇〇0 〇X 〇 As shown in Table 2, the compositions prepared according to Comparative Examples 1 and 2 can be compared and according to the examples. When the Tg and CTE values of the compositions prepared from 1 to 4 were used, the compositions of Comparative Examples 1 and 2 could not be used as the plate material, but the compositions of Examples 丄 to 4 had high Tg values and low CTE values. The physical properties of Examples 1 to 4 were superior to Comparative Examples 1 and 2. Further, the number of openings is as shown in Fig. 1, which is a photograph observed through a microscope, and illustrates a through hole formed in the PCB by the photosensitive ring-fat composition prepared in Example 1. The present invention has been described with reference to the specific embodiments thereof, and various modifications and changes can be made thereto by those skilled in the art, and the present invention is defined by the scope of the appended claims and their equivalents. The concrete spirit and scope. EXAMPLES BRIEF DESCRIPTION OF THE DRAWINGS Fig. ui is a photograph observed through a microscope, which illustrates a 2012 16 201200964 hole formed on a PCB by the photosensitive epoxy resin composition prepared in Example 1. Fig. 2 illustrates a method of forming a via hole in a PCB in the present invention. [Main component symbol description] None. 17