11216twf.doc/006 玖、發明說明： 發明所屬之枝術領域 本發明是有關於一種聚脲酯(polyurethane，簡稱爲pu 或polyurethane-urea，簡稱爲PUR)硏磨墊的製造方法，且 特別是有關於一種應用於晶圓及光學鏡頭硏磨之具多功能 與微孔洞的PU/PUR硏磨墊的製造方法。 先前技術 在記憶體晶圓（memory wafer)或邏輯晶圓（logic wafer) 等半導體元件的製作中，爲了提高電子元件的積集度以及 降低生產成本，所以近來在製程上有逐漸提高深寬比 (aspect ratio)且增加導線層(conductive circuit layer)之堆疊 層數的趨勢。不過，在製作此多層導線層結構時，隨著堆 疊層數的增加，於晶片表面所產生之凹凸或扭曲等不平坦 的現象會日益顯著，因此能在製程中消除晶圓表面之不平 坦並達到所謂之完全平坦化（global planarity)的技術係成爲 眾所矚目的焦點。使用此完全平坦化技術不但可以在元件 上使用多層之導線結構，而且還能確保所製得之元件的良 率。最早提出完全平坦化的技術是美國IBM公司，其利 用完全平坦化技術之一的化學機械硏磨法（chemical mechanical polishing，CMP)來進行埋入式導線之間金屬鑲 嵌(damascene)製程。在化學機械硏磨的過程中，其係藉由 具有懸浮硏磨粒子（abrasive particle)的硏磨液（slurry)以及 具有適當的彈性（elasticity)與硬度（hardness)的之硏磨墊， 在晶圓表面彼此進行相對運動以達成平坦化的目的。換言 之，當硏磨墊以按壓的方式於晶圓上移動時，晶圓表面與 11216twf.doc/006 硏磨液中的硏磨粒子會彼此接觸產生摩擦使得晶圓表面產 生耗損，以使其表面逐漸平坦。因此’硏磨墊之硬度與其 表面的粗糙度等等的物理性質都是影響硏磨的重要因素， 這些因素會使得硏磨粒子之間在水平方向以及垂直方向產 生不規則之作用關係。此外，在特定的壓力下，硏磨墊之 水平方向的施力是決定平坦化好壞的關鍵，以化學機械硏 磨的製程來說，硏磨墊需承受來自硏磨頭的壓力並將其傳 送至晶圓表面以維持硏磨之平坦度。另外，硏磨液中的硏 磨粒子其分佈均勻與否亦會影響硏磨後之表面均勻性。因 此，硏磨墊必須具有足夠的硬度以提供硏磨之用，除此之 外，其還必須具有孔洞以容納硏磨液中的硏磨粒子。一般 來說，越大的孔洞可以使硏磨粒子更均勻分佈，而且還可 容納硏磨所移除之殘渣與失效之硏磨液，但是，過大的孔 洞往往會使得硏磨時無法維持一定的壓力，進而使得硏磨 表面的平坦度下降。 當硏磨墊使用一段時間之後，由於硏磨殘渣以及硏磨 粒子累積於硏磨墊的孔洞中，因此需藉由刮去與刷淨等調 整（conditioning)步驟以淸除這些孔洞中的沈積物。然而， 當硏磨墊產生玻璃化（glazing)時，其係表示此時無法藉由 調整步驟使硏磨墊恢復硏磨功效，意即此硏磨墊已耗損至 無法使用。因此，基於降低成本並提高產率之考量，延長 硏磨墊的使用壽命已成爲業界積極硏究之課題。 過去曾使用如美國專利第3,284,274號所記載之多孔 性材料作爲硏磨材料。此外，在1989年由Rodel公司所 提之美國專利第4,841，680號揭示具有上下倒置孔洞的濕 11216twf.doc/006 式PU硏磨墊，這個PU硏磨墊係以習知之溶劑/無溶劑聚 合物凝結技術(polymer coagulation technology)製作而成， 此製程係先以聚醇類（polyol)與異氰酸酯（isocyanate)在攝 氏80度下進行反應，然後將其溶於二甲基甲醯胺(N，N，_ dimethylformamide，縮寫爲DMF)而形成聚合物溶液。之後 在基材上塗覆此聚合物溶液，再將其浸入水浴中使聚合物 完全凝結。然後再以另一溶劑（例如是水)將原來的溶劑（例 如是DMF)置換出來，之後藉由高溫、乾燥等步驟使聚合 物中的溶劑揮發，形成具有不規則形狀之孔洞的硏磨墊。 另外，在2000年Rodel公司承襲上述製程又所提出 美國專利第6,094,902號案，此案係使用聚醚多元醇 (polyether polyol)與聚酯多元醇(polyester polyol)之共聚合 反應，當然，亦可使用含三種形式以上之多元醇，以製造 出具有多孔與彈性之濕式PU硏磨墊。上述兩件專利案均 利用另一溶劑置換或利用高溫使殘餘溶劑揮發的方式以形 成內部具有不規則大小之孔洞的聚合物，然後，再將此聚 合物以刀片或旋轉硏磨機(rotating mill)去除表層以使其下 方之孔洞外露’之後將此聚合物與基材貼合而完成硏磨墊 製程。除此之外，亦可於模具中使聚合物發泡形成圓柱狀 (cake)，之後經裁切單片，再黏貼至基材上而完成硏磨墊 製程。由於上述之硏磨墊的方法必須藉由形成PU發泡聚 合物、去除表層/切成單片及貼合等步驟才能完成，因此 十分耗時費工。此外，去除表層/切成單片的過程並不易 控制，因此會導致這些孔洞無法具有較佳的一致性、孔洞 之表面開口（surface opening)小（例如表片開口直徑小於底 11216twf.doc/006 部直徑）以及工作表面(working surface)中的孔壁比例增加 等問題。上述這些問題會影響硏磨墊的穩定性而造成硏磨 墊的使用壽命難以評估，甚至產生硏磨粒子與被硏磨表面 彼此接觸不均等問題。 此外，在1996年Rodel公司所獲准之美國專利第 5,578,362號案，其中揭示一種包括以數個具有中空、可 撓性（flexible)之有機聚合微單元（polymeric microelement) 所浸漬之聚合基質(polymeric matrix)的硏磨墊，此硏磨墊 具有工作表面以及接近工作表面之次表面（subsurface)，在 工作表面之聚合微單元其暴露於工作環境中，且可容納硏 磨液，而埋在次表面之聚合微單元並未暴露於工作環境 中。由於工作表面之聚合微單元其暴露於工作環境中，因 此工作表面比次表面柔軟，此外，在進行硏磨時，硏磨墊 之工作表面會產生耗損，而使埋在次表面之的聚合微單元 暴露於工作環境中，進而產生另一個具有硏磨特性之新的 工作表面。不過，由於上述之方法需經由混合聚合基底、 摻合中空彈性聚合微球(microsphere)、將混合物灌入模具、 在高溫下硬化（curing)此混合物、冷卻此混合物以及進行 表面處理等步驟以完成硏磨墊的製作，因此，此製程不僅 費時而且不易維持穩定的操作條件，故大幅降低此方法於 產業界之可利用性。 另外，在2000年Rodel公司所獲准之美國專利第 6,022,268號案揭示一種具有親水性硏磨層之硏磨墊，此 硏磨墊本身不具有吸收或輸送硏磨粒子的功能，且其係藉 由固化(solidifying)可流動物質使得每一硏磨層表面具有不 11216twf.doc/006 規則之表面形狀以及大型紋路，此製程由於以固化的方式 製作硏磨墊而不由較大的材料來裁切硏磨墊，而且於硏磨 表面上使用至少一部份的大型紋路，故不需要裁切或切削 硏磨表面。此外，由上述專利第6,022,268號的實施例可 知，除了藉由具有所要求硏磨墊之最終尺寸及溝槽設計的 模具以射出成型(injection molding)完成製程外，其餘所用 之組成成分及成型條件均與美國專利第5,578,362號案相 同。然而，雖然此專利可有效改善硏磨效能以及因裁切硏 磨表面所造成的大型缺陷（macro-defects)，但是仍存在著 製作費時等缺點。 另外，在2001年Fuji Spinning公司所獲准之美國專 利第6,239，188號案揭示一種具有更佳硏磨平坦度與更佳 硏磨速率之硏磨墊的脲酯(urthane)模製產物，其係先於末 端爲異氰酸酯之脲酯預聚物以及包含活性氫之化合物中加 入特定比例之兩種大小之膨脹的微球物（nncfoballon)，其 大小係爲1〇至50微米與80至100微米，之後再熟化此 化合物。雖然此專利改善了習知使用一種微球狀物而無法 使得硏磨物具有極佳的平坦度的缺點，但是其仍需要使用 較高之製程溫度，此外其硬化時間過長，故不利於產業的 應用。因此，由上述數個習知專利發明可知，業界對於可 快速量產並提供穩定且具有優異硏磨特性的硏磨墊有其迫 切的需求性。 豐明內容 有鑑於此，本發明的目的是提供一種添加輔助氣體之 PU硏磨墊的製造方法，此方法係在高壓下，以反應射出、 593453 11216twf.doc/006 壓模成型的方式獲得具有高度平坦度、孔洞大小均句之pu 硏磨墊。 本發明的另一目的是提供一種可用於硏磨半導體晶 圓、冶金樣品、記憶碟片表面、光學元件、玻璃、鏡片或 晶圓光罩等高精密產品之PU硏磨墊。 本發明提出一種添加輔助氣體之聚脲酯（pU/pUR)硏磨 墊的製造方法，此方法係首先於包含活性氫官能基之樹脂 中加入特定量的輔助氣體，之後將無機（或有機）之化學（或 物理）發泡劑與包含異氰酸官能基（_NC0)之樹脂以特定比 例混合形成一混合物，然後，將此混合物以反應射出、壓 模成型方式製作出具有高平坦性且孔洞大小均勻之添加輔 助氣體之PU硏磨墊。 爲讓本發明之上述和其他目的、特徵、和優點能更明 顯易懂，下文特舉一較佳實施例，並配合所附圖式，作詳 細說明如下： 實施方式 添加輔助氣體之PU硏磨墊的製造方法係首先以包含 異氰酸官能基之脂肪族（aliphatic)異氰酸酯樹酯或芳香族 (aromatic)異氰酸酯樹脂作爲原料，之後在高壓下將此原 料、包含活性氫官能基之另一樹脂以及一些添加劑均勻混 合。其中包含活性氫官能基的樹脂例如是包含羥基官能基 (-0H)之聚醇類樹脂、包含胺官能基（-NH)之聚胺樹脂、或 包含氫硫官能基（-SH)之聚硫醇樹脂等。除此之外，上述 的添加劑例如是鏈延長劑(chain extender)、發泡劑（foaming agent)、整泡劑（foam stabilizer)、催化劑或輔助氣體等， 9 11216twf.doc/006 其中輔助氣體例如是空氣、氮氣或惰性氣體等。然後，將 上述均勻混合後的溶液注入模具中以射出成型的方式完成 具有微孔（microcellular)之PU硏磨墊的製作。 由上可知，利用本發明所製作出來的PU硏磨墊，其 具有良好的強度（strength)以及可撓性。此外，在發泡之後， 此位於PU硏磨墊上之有效的硏磨部分的孔洞，其孔洞大 小一致且分佈均勻，而且大部分的孔洞經過表面處理後可 成爲開放式孔洞（open cell)。 添加輔助氣體之PU硏磨墊的製造方法屬於批次製 造，而此方法係首先將包含羥基官能基（-0H)之樹脂加入 添加劑中並充分混合，其中此添加劑例如是鏈延長劑、發 泡劑、整泡劑、催化劑與輔助氣體，而此鏈延長劑之重量 百分濃度例如是介於5%至30%之間，發泡劑之重量百分 濃度例如是介於0.1%至1〇%之間，整泡劑之重量百分濃 度例如是介於0.1%至1.0%之間’催化劑之重量百分濃度 例如是介於0.1%至1.0%之間’輔助氣體之體積百分比例 如是介於5%至30%之間’此輔助氣體例如是空氣、氮氣 或惰性氣體，且其加入的量又以體積百分比10%至15%之 間的效果爲最佳。然後，加入包含異氰酸官能基（-NCO)之 樹脂與上述之包含羥基官能基之樹脂和添加劑充分混合形 成一混合液，此包含異氰酸官能基之樹脂例如是預聚合型 之異氰酸酯樹脂，且此包含異氰酸官能基之樹脂與包含羥 基官能基之樹脂其中之異氰酸官能基與羥基官能基的混合 比例係介於0.6至1.5之間’其中此混合比例又以〇·95至 1.1之間的效果爲佳。然後在特定的溫度及壓力下，將上 593453 11216twf.doc/006 述之混合液以射出反應注入模具中，並且快速發泡以形成 一具有聚脲酯結構的PU硏磨墊。其中此射出成型的溫度 例如是介於攝氏20至100度，其又以攝氏20至60度效 果爲佳，而此射出成型的壓力例如是介於2至20MPa，其 又以5至20MPa效果爲佳。更値得一提的是，上述之射 出成型的過程只需花費3至5分鐘即可完成。 因此，利用本發明的製程技術，可視產品的需要調整 聚醇樹脂的成分以獲得不同硬度、密度、伸長率（elongation) 以及強度之具有均勻且連續之開放孔洞的可撓性PU硏磨 墊。除此之外，亦可藉由模具的設計以及包含活性氫的樹 脂之添加量（或組成）的改變，製作出單片對稱式PU微孔 發泡產品，此對稱式PU微孔發泡產品係在接近模具的表 面不發泡，而在逐漸遠離表面處進行發泡以形成連續對稱 式之孔洞。另外，此對稱式PU微孔發泡產品可於中間處 對稱切割而形成二片具有雙層結構的產品，其雙層結構包 括相對較硬之表面層，以及位於表面層下方且相對較軟之 緩衝層，此表面層可以在硏磨時具提供被硏磨物一較佳的 平坦度，而此緩衝層係可藉由發泡劑與輔助氣體的作用在 硏磨時提供較佳的均勻度。 此外，藉由高壓反應射出成型所製作出來的添加輔助 氣體之單片PU硏磨墊，當給予適當的表面處理時，可以 形成一單層的複合結構，此複合結構包括發泡PU產品以 及感壓膠帶（pressure-sensitive type)。由於本發明之PU硏 磨墊具有適當的硬度，因此可以確保其平坦化效果且其品 質也較佳，此外，硏磨墊的表面隨著硏磨晶片之表面而起 11 593453 11216twf.doc/006 伏，因此其硏磨均勻度也較佳。 在本發明中之聚異氰酸酯寡聚合物包括有脂肪族與芳 香族之異氰酸酯樹脂單體，以及混合不同比例之4,4’聚氰 酸酯樹脂和2’，4聚氰酸酯樹脂，其中此4,4’聚氰酸酯樹脂 和2’，4聚氰酸酯樹脂具有不同的官能基。此外，這些異氰 酸酯樹脂單體例如是甲苯二異氰酸酯（toluene diisocyanate)、三苯基甲院-4,4’，4’’-三異氰酸酯 (triphenylmethane-4,4’，4’ ’-triisocyanate)、苯-1，3,5-三異氰 酸酯（benzene-1，3,5-triisocyanate)、六甲撐二異氰酸酯 (hexamethylene-diisocyanate)、苯撐甲基二異氰酸酯 (xylene-diisocyanate)、氯苯撐二異氰酸酯 (chlorophenylene-diisocyanate)、二環己基甲院 4,4’二異氰 酸酯（dicyclohexylmethane-4,4’-diisocyanate)或甲撐雙二苯 基二異氰酸酯（methylenebisdiphenyl-diisocyanate)。 另外，在本發明中之包含活性氫之樹脂包括聚醚多元 醇類、聚酯多元醇類、聚己內酯類、聚胺樹脂、聚硫醇樹 脂或其混合物等，而上述之多元醇樹脂例如是聚氧化丙烯 醚多元醇（polypropylene oxide ether polyol，PPG)、聚合物 多元醇(polymer polyol)(聚苯乙嫌與丙儲之共聚物）、聚稀 羥多元醇(polyolefin polyols)(由聚丁二稀腈合成）、共聚醚 多元醇（copolymerized ether polyol)、聚醚多元胺（polyether polyamine)或聚四氫咲喃多元醇（polytetramethylene oxide polyols，PTMEG)。 此外，本發明所使用之鏈延長劑例如是1，4-丁二醇、 乙二醇、丙二醇、甘油、4,4’-亞甲基雙（3-氯-2,6-乙苯基 12 593453 11216twf.doc/006 月女）(4,4’-methylene-bis-(3_chloro-2,6_ethylaniline))、三乙 胺醇、三異丙醇胺、芳香族多元胺或脂肪族多元胺。而且 上述之鏈延長劑的添加量係介於重量百分比5%至30%之 -間，其中又以間添加重量百分比10%至20%之間效果較佳。 另外，本發明所使用之發泡劑包括無機發泡劑以及有 機發泡劑。其中無機發泡劑例如是水或二氧化碳，而有機 發泡劑例如是丙烷、丁烷、戊烷、丙酮、二氯甲烷、氫化 氟氯碳化物（例如HCFC-22、HCFC-141b等）或氫化氟碳化 物（例如 HFC-134a、HFC-365mfc、HFC-227ea、HFC-245fa) ❿ 等。 此外，本發明所使用之整泡劑包括矽氧烷化合物、環 氧乙烷化之聚醇類或其混合物，另外，這些整泡劑更例如 是Ϊ哀氧乙院化聚多兀醇（ethylene oxidized polymeric polyols)、砂氧院化之環氧乙院（siloxanized ethylene oxide) 或丙院之共接枝化合物（propane-cografted compound)。 以下特舉出數個實施例加以說明，當然本發明並非只 限於以下之實施方式。 實施例1 : · 組成成分 重量百分比 聚合物多元醇（分子量= 6000) 79 1，4-丁二醇 21 有機胺觸媒 0.46 水 0.2 矽氧烷整泡劑 1.0 MDI異氰酸系預聚合物（NCO = 23%) 50 13 11216twf.doc/006 在上述之實施例l中，其混合溫度爲攝氏32度，所 添加之空氣量係爲8。/。之體積百分比’丨旲具之溫度爲攝氏5〇 度，反應射出成形之機台所使用的壓力爲15MPa，利用上 述製程條件所製得之硏磨墊， 其所測得之物性如下： 抗張強度（MPa) 15 伸長率（％) 120 硬度（shore-D) 55 密度（g/cm3) 0.78 壓縮率（％) 1.02 實施例2 : 組成成分 重量百分比 聚酉旨多元醇（分子量= 1000) 84 乙二醇 16 有機胺觸媒 1.0 水 0.2 矽氧烷整泡劑 1.0 MDI異氰酸系預聚合物（NCO = 29.5%) 100 在上述之實施例2中，其混合溫度爲攝氏55度，所 添加之空氣量係爲12%之體積百分比，模具之溫度爲攝氏 60度，反應射出成形之機台所使用的壓力爲15Mpa。此外 利用掃描式電子顯微鏡（Scanning Electronic Microscope， SEM)之觀察，可看出其氣泡之連續性及均勻性良好（如第 1圖所示）。另外，利用上述製程條件所製得之硏磨墊，其 所測得之物性如下： 593453 11216twf.doc/006 抗張強度（MPa) 19 伸長率（％) 180 硬度（shore-D) 60 密度（g/cm3) 0.7 壓縮率（％) 0.98 實施例3 : 組成成分 重量百分比 聚己内多元醇（分子量= 1000) 84 乙二醇 16 有機胺觸媒 0.45 戊烧 6 矽氧烷整泡劑 1.0 MDI異氰酸系預聚合物（NCO = 28%) 10011216twf.doc / 006 发明, Description of the invention: The field of branching technology of the invention The present invention relates to a method for manufacturing a polyurethane pad (polyurethane (abbreviated as pu or polyurethane-urea, abbreviated as PUR)), and in particular The invention relates to a method for manufacturing a PU / PUR honing pad with multi-function and micro-holes, which is applied to wafer and optical lens honing. In the production of semiconductor components such as memory wafers and logic wafers, in the prior art, in order to improve the integration of electronic components and reduce production costs, recently, the aspect ratio has been gradually increased in the manufacturing process. (aspect ratio) and a tendency to increase the number of stacked layers of conductive circuit layers. However, when manufacturing this multilayer wiring layer structure, as the number of stacked layers increases, unevenness such as unevenness or distortion on the surface of the wafer will become increasingly prominent, so the unevenness on the surface of the wafer can be eliminated during the manufacturing process. The technology that achieves so-called global planarity has become the focus of much attention. Using this complete planarization technique not only allows the use of multiple layers of wire structures on the component, but also ensures the yield of the resulting component. The earliest proposed full flattening technology was IBM Corporation of the United States, which uses chemical mechanical polishing (CMP), one of the full flattening technologies, to perform damascene process between buried wires. In the process of chemical mechanical honing, it uses a honing slurry with suspended honing particles and a honing pad with appropriate elasticity and hardness. The circular surfaces move relative to each other to achieve the purpose of flattening. In other words, when the honing pad is moved on the wafer in a pressing manner, the wafer surface and the honing particles in the honing fluid of 11216twf.doc / 006 will come into contact with each other to cause friction, which will cause wear on the wafer surface to make its surface Gradually flat. Therefore, the hardness of the honing pad and its physical properties such as surface roughness are important factors that affect honing. These factors will cause irregular interactions between the honing particles in the horizontal direction and the vertical direction. In addition, under a certain pressure, the horizontal force of the honing pad is the key to determining the quality of the flattening. For the chemical mechanical honing process, the honing pad must withstand the pressure from the honing head and Transfer to wafer surface to maintain flatness of honing. In addition, whether the distribution of the honing particles in the honing liquid is uniform will also affect the surface uniformity after honing. Therefore, the honing pad must have sufficient hardness to provide honing, and in addition, it must have holes to hold the honing particles in the honing fluid. Generally speaking, larger holes can make the honing particles more uniformly distributed, and can also contain the residue and the honing fluid removed by honing. However, too large holes often make it impossible to maintain a certain amount of honing during honing. Pressure in turn reduces the flatness of the honing surface. After the honing pad is used for a period of time, since honing residues and honing particles accumulate in the holes of the honing pad, it is necessary to remove the deposits in these holes by shaving and cleaning. . However, when the honing pad is glazing, it means that the honing pad cannot be restored to its honing effect through the adjustment step at this time, which means that the honing pad has been worn out and cannot be used. Therefore, based on the consideration of reducing costs and increasing productivity, prolonging the service life of honing pads has become an active research subject in the industry. Porous materials such as those described in U.S. Patent No. 3,284,274 have been used as honing materials in the past. In addition, U.S. Patent No. 4,841,680, filed by Rodel in 1989, discloses a wet 11216twf.doc / 006 type PU honing pad with upside down holes. This PU honing pad is polymerized with a conventional solvent / solvent-free solution. Polymer coagulation technology (polymer coagulation technology), this process is based on polyols and isocyanates at 80 degrees Celsius, and then dissolved in dimethylformamide (N, N, dimethylformamide (abbreviated as DMF) to form a polymer solution. The polymer solution is then applied to the substrate and immersed in a water bath to allow the polymer to fully coagulate. Then replace the original solvent (such as DMF) with another solvent (such as water), and then volatilize the solvent in the polymer through steps such as high temperature and drying to form a honing pad with irregularly shaped holes. . In addition, in 2000, Rodel Corporation inherited the above process and filed US Patent No. 6,094,902. This case uses a copolymerization reaction of polyether polyol and polyester polyol. Of course, it can also be used. Polyols containing more than three forms are used to produce wet PU honing pads with porosity and elasticity. Both of the above patents use another solvent to replace or use high temperature to volatilize the residual solvent to form a polymer with irregularly-sized holes in the interior. Then, the polymer is razor or rotary mill. ) Remove the surface layer to expose the holes below it, and then attach the polymer to the substrate to complete the honing pad process. In addition, the polymer can also be foamed into a cake in a mold, and then a single piece is cut and then adhered to the substrate to complete the honing pad process. The method of honing pads described above must be completed through the steps of forming a PU foamed polymer, removing the surface layer / cutting into a single sheet, and laminating, which is very time-consuming and labor-intensive. In addition, the process of removing the surface layer / cutting into a single piece is not easy to control, so these holes cannot have better consistency, and the surface openings of the holes are small (for example, the diameter of the surface opening is smaller than the bottom 11216twf.doc / 006 Part diameter) and the increase in the ratio of the hole wall in the working surface. These problems will affect the stability of the honing pad, making it difficult to evaluate the service life of the honing pad, and even causing uneven contact between the honing particles and the surface being honed. In addition, U.S. Patent No. 5,578,362, which was granted by Rodel in 1996, discloses a polymeric matrix impregnated with a number of hollow, flexible organic polymer microelements. The honing pad has a working surface and a subsurface close to the working surface. The polymerized micro-units on the working surface are exposed to the working environment, and can contain honing fluid and be buried on the subsurface. The polymerized microcells are not exposed to the working environment. Because the polymerized micro-units on the working surface are exposed to the working environment, the working surface is softer than the secondary surface. In addition, when honing, the working surface of the honing pad will be depleted, and the polymerized micro-buried on the secondary surface will The unit is exposed to the working environment, which creates another new working surface with honing characteristics. However, the above method is completed by the steps of mixing and polymerizing the substrate, blending hollow elastic polymer microspheres, filling the mixture into a mold, curing the mixture at high temperature, cooling the mixture, and performing surface treatment. The manufacture of honing pads, therefore, this process is not only time consuming but also difficult to maintain stable operating conditions, so the usability of this method in the industry is greatly reduced. In addition, U.S. Patent No. 6,022,268, granted by Rodel in 2000, discloses a honing pad with a hydrophilic honing layer. The honing pad itself does not have the function of absorbing or transporting honing particles. The solidifying flowable material makes the surface of each honing layer have a surface shape and large grains that do not have the rule of 11216twf.doc / 006. This process is not used to cut the larger material because the honing pad is made by curing. Grinding pads, and at least a part of the large grains are used on the honing surface, so there is no need to cut or cut the honing surface. In addition, according to the example of the above-mentioned patent No. 6,022,268, it is known that in addition to completing the manufacturing process by injection molding with a mold having the required final size and groove design of the honing pad, the remaining components and molding conditions are used. Both are the same as U.S. Patent No. 5,578,362. However, although this patent can effectively improve the honing efficiency and macro-defects caused by cutting the honing surface, there are still disadvantages such as time-consuming fabrication. In addition, U.S. Patent No. 6,239,188 granted to Fuji Spinning in 2001 disclosed a urthane molded product of a honing pad having better honing flatness and a better honing rate. Two types of swollen microspheres (nncfoballon) with specific proportions are added to the urea ester prepolymer with isocyanate ends and the compound containing active hydrogen, and their sizes are 10 to 50 microns and 80 to 100 microns. This compound is then matured. Although this patent improves the shortcoming of using a microsphere to make the honing object with excellent flatness, it still needs to use a higher process temperature, and its hardening time is too long, which is not good for the industry. Applications. Therefore, from the above several conventional patented inventions, it is known that the industry has an urgent demand for a honing pad which can be mass-produced quickly and provides stable and excellent honing characteristics. In view of this, the purpose of the present invention is to provide a method for manufacturing a PU honing pad with an auxiliary gas, which method is obtained by reaction injection under high pressure, 593453 11216twf.doc / 006, and has a molding method. The pu honing pad with high flatness and hole size. Another object of the present invention is to provide a PU honing pad which can be used for honing high precision products such as semiconductor wafers, metallurgical samples, the surface of memory discs, optical elements, glass, lenses or wafer masks. The invention proposes a method for manufacturing a polyurea ester (pU / pUR) honing pad with an auxiliary gas. This method firstly adds a specific amount of auxiliary gas to a resin containing an active hydrogen functional group, and then inorganic (or organic) The chemical (or physical) foaming agent is mixed with a resin containing an isocyanate functional group (_NC0) in a specific ratio to form a mixture. Then, the mixture is reacted by injection and compression molding to produce a high flatness and voids. PU honing pad with uniform size and auxiliary gas. In order to make the above and other objects, features, and advantages of the present invention more comprehensible, a preferred embodiment is given below in conjunction with the accompanying drawings to describe in detail as follows: Implementation PU honing with auxiliary gas The manufacturing method of the mat is firstly using an aliphatic isocyanate resin or an aromatic isocyanate resin containing an isocyanate functional group as a raw material, and then, under a high pressure, this raw material and another resin containing an active hydrogen functional group are used as a raw material. And some additives are evenly mixed. The resin containing an active hydrogen functional group therein is, for example, a polyol resin containing a hydroxyl functional group (-0H), a polyamine resin containing an amine functional group (-NH), or a polysulfide containing a hydrogen sulfur functional group (-SH). Alcohol resin, etc. In addition, the aforementioned additives are, for example, a chain extender, a foaming agent, a foam stabilizer, a catalyst, or an auxiliary gas, etc. 9 11216twf.doc / 006 where the auxiliary gas is, for example, It is air, nitrogen or inert gas. Then, the uniformly mixed solution is injected into a mold to complete the production of a PU honing pad with microcellular by injection molding. From the above, it can be seen that the PU honing pad produced by the present invention has good strength and flexibility. In addition, after foaming, the holes of the effective honing portion on the PU honing pad have uniform and uniform holes, and most of the holes can be open cells after surface treatment. The manufacturing method of the PU honing pad with auxiliary gas is batch manufacturing, and this method is to first add a resin containing a hydroxyl functional group (-0H) to an additive and mix it thoroughly, such as a chain extender, foam Agent, foam stabilizer, catalyst and auxiliary gas, and the weight percentage concentration of the chain extender is, for example, between 5% and 30%, and the weight percentage concentration of the foaming agent is, for example, between 0.1% and 1%. %, The weight percentage concentration of the foam stabilizer is, for example, between 0.1% and 1.0%, and the weight percentage concentration of the catalyst is, for example, between 0.1% and 1.0%. Between 5% and 30% 'This auxiliary gas is, for example, air, nitrogen or an inert gas, and the added amount thereof is most preferably between 10% and 15% by volume. Then, add a resin containing an isocyanate functional group (-NCO) and the above-mentioned resin containing a hydroxyl functional group and an additive to sufficiently mix to form a mixed solution. The resin containing an isocyanate functional group is, for example, a prepolymerized isocyanate resin. And the mixing ratio of the isocyanate functional group and the hydroxyl functional group in the resin containing an isocyanate functional group and the resin containing a hydroxyl functional group is between 0.6 and 1.5 ', where the mixing ratio is again 0.95 The effect between 1.1 and 1.1 is better. Then at a specific temperature and pressure, the mixed solution described in 593453 11216twf.doc / 006 is injected into the mold by injection reaction, and is rapidly foamed to form a PU honing pad having a polyurea structure. The injection molding temperature is, for example, between 20 and 100 degrees Celsius, and the effect of 20 to 60 degrees Celsius is better, and the injection molding pressure is, for example, between 2 and 20 MPa, and the effect is 5 to 20 MPa. good. What's more, the injection molding process mentioned above takes only 3 to 5 minutes to complete. Therefore, using the process technology of the present invention, the composition of the polyol resin can be adjusted according to the needs of the product to obtain a flexible PU honing pad with uniform and continuous open holes with different hardness, density, elongation, and strength. In addition, the single-piece symmetrical PU microcellular foamed product can also be manufactured by changing the design of the mold and the addition amount (or composition) of the resin containing active hydrogen. This symmetrical PU microcellular foamed product It is not foamed on the surface close to the mold, but foamed gradually away from the surface to form continuous symmetrical holes. In addition, this symmetrical PU microcellular foamed product can be cut symmetrically in the middle to form two sheets of products with a double-layer structure. The double-layer structure includes a relatively hard surface layer and a relatively soft layer below the surface layer. Buffer layer, this surface layer can provide a better flatness of the object to be honed during honing, and this buffer layer can provide better uniformity during honing by the action of foaming agent and auxiliary gas . In addition, the auxiliary gas-added single-piece PU honing pad produced by high-pressure reaction injection molding can form a single-layer composite structure when the surface is treated appropriately. The composite structure includes foamed PU products and a sense of Pressure-sensitive tape. Because the PU honing pad of the present invention has a proper hardness, it can ensure its flattening effect and its quality is better. In addition, the surface of the honing pad follows the surface of the honing wafer 11 593453 11216twf.doc / 006 Therefore, its honing uniformity is also better. The polyisocyanate oligomer in the present invention includes aliphatic and aromatic isocyanate resin monomers, and 4,4 'polycyanate resin and 2', 4 polycyanate resin are mixed in different proportions. 4,4 'polycyanate resin and 2', 4 polycyanate resin have different functional groups. In addition, these isocyanate resin monomers are, for example, toluene diisocyanate, triphenylmethane-4,4 ', 4' '-triisomethane-4,4', 4'-triisocyanate, benzene -1,3,5-triisocyanate (benzene-1,3,5-triisocyanate), hexamethylene-diisocyanate, phenylene diisocyanate (xylene-diisocyanate), chlorophenylene diisocyanate (chlorophenylene -diisocyanate), dicyclohexylmethane-4,4'-diisocyanate or methylenebisdiphenyl-diisocyanate. In addition, the active hydrogen-containing resin in the present invention includes polyether polyols, polyester polyols, polycaprolactones, polyamine resins, polythiol resins, or mixtures thereof, and the above-mentioned polyol resins For example, it is a polypropylene oxide ether polyol (PPG), a polymer polyol (a copolymer of polystyrene and propylene storage), a polyol (polyols) Synthesis of succinic nitrile), copolymerized ether polyol, polyether polyamine or polytetramethylene oxide polyols (PTMEG). In addition, the chain extender used in the present invention is, for example, 1,4-butanediol, ethylene glycol, propylene glycol, glycerol, 4,4'-methylenebis (3-chloro-2,6-ethylphenyl 12 593453 11216twf.doc / 006 month female) (4,4'-methylene-bis- (3_chloro-2,6_ethylaniline)), triethylamine alcohol, triisopropanolamine, aromatic polyamine or aliphatic polyamine. In addition, the amount of the chain extender mentioned above is between 5% and 30% by weight, and it is better to add between 10% and 20% by weight. In addition, the foaming agent used in the present invention includes an inorganic foaming agent and an organic foaming agent. Wherein the inorganic foaming agent is, for example, water or carbon dioxide, and the organic foaming agent is, for example, propane, butane, pentane, acetone, methylene chloride, hydrochlorofluorocarbon (for example, HCFC-22, HCFC-141b, etc.) or hydrogenation. Fluorocarbons (such as HFC-134a, HFC-365mfc, HFC-227ea, HFC-245fa), etc. In addition, the foam stabilizer used in the present invention includes a siloxane compound, an oxiraneated polyalcohol, or a mixture thereof. In addition, these foam stabilizers are, for example, ethylene oxide poly (ethylene glycol). oxidized polymeric polyols), siloxanized ethylene oxide or propane-cografted compound. Several examples are given below for explanation, but the present invention is not limited to the following embodiments. Example 1: Weight percent polymer polyol (molecular weight = 6000) 79 1,4-butanediol 21 Organic amine catalyst 0.46 Water 0.2 Silane foam stabilizer 1.0 MDI isocyanate prepolymer ( (NCO = 23%) 50 13 11216twf.doc / 006 In the above Example 1, the mixing temperature was 32 degrees Celsius, and the amount of air added was 8. /. Volume percentage '丨 The temperature of the tool is 50 ° C, the pressure used in the reaction injection molding machine is 15MPa, and the honing pad prepared by using the above process conditions, the measured physical properties are as follows: tensile strength (MPa) 15 Elongation (%) 120 Hardness (shore-D) 55 Density (g / cm3) 0.78 Compression ratio (%) 1.02 Example 2: Weight percentage of the composition Polypolyol (molecular weight = 1000) 84 B Diol 16 Organic amine catalyst 1.0 Water 0.2 Silane foam stabilizer 1.0 MDI Isocyanate prepolymer (NCO = 29.5%) 100 In the above Example 2, the mixing temperature was 55 ° C. The air volume is 12% by volume, the temperature of the mold is 60 degrees Celsius, and the pressure used by the injection molding machine is 15Mpa. In addition, using scanning electron microscope (SEM) observation, it can be seen that the continuity and uniformity of the bubbles are good (as shown in Figure 1). In addition, the measured physical properties of the honing pads made using the above process conditions are as follows: 593453 11216twf.doc / 006 Tensile strength (MPa) 19 Elongation (%) 180 Hardness (shore-D) 60 Density ( g / cm3) 0.7 Compression ratio (%) 0.98 Example 3: Composition weight percentage polycaprolactone (molecular weight = 1000) 84 Glycol 16 Organic amine catalyst 0.45 Pentamyl 6 Silane foam stabilizer 1.0 MDI Isocyanate prepolymer (NCO = 28%) 100
抗張強度（MPa) 17.8 伸長率（％) 156 硬度（shore-D) 58 密度（g/cm3) 0.7 壓縮率（％) 1.01 由上述數個實施例可知，所製作出來之硏磨墊其密度 在上述之實施例3中，其混合溫度爲攝氏50度，所 添加之空氣量係爲15%之體積百分比，模具之溫度爲攝氏 60度，反應射出成形之機台所使用的壓力爲15Mpa。此外 利用掃描式電子顯微鏡之觀察，可看出其氣泡之連續性及 均勻性良好(如第2圖所示）。另外，利用上述製程條件所 製得之硏磨墊，其所測得之物性如下： _ 15 11216twf.doc/006 的差異主要受添加不同量之鏈延長劑或發泡劑，或注入金 屬模具之量的影響，因此，使用者可依照本身之需求自行 調整上述之組成成分以及混合比例，以得到不同物性或不 同物理參數之PU硏磨墊。 雖然本發明已以一較佳實施例揭露如上，然其並非用 以限定本發明，任何熟習此技藝者，在不脫離本發明之精 神和範圍內，當可作些許之更動與潤飾，因此本發明之保 護範圍當視後附之申請專利範圍所界定者爲準。 圖式簡單胃分明 第1圖是利用掃描式電子顯微鏡放大100倍時，觀察 第2實施例之氣泡連續性與均勻性的結果圖；以及 第2圖是利用掃描式電子顯微鏡放大100倍時，觀察 第3實施例之氣泡連續性與均勻性的結果圖。Tensile strength (MPa) 17.8 Elongation (%) 156 Hardness (shore-D) 58 Density (g / cm3) 0.7 Compression (%) 1.01 As can be seen from the above examples, the density of the honing pads produced In the above Example 3, the mixing temperature is 50 degrees Celsius, the amount of air added is 15% by volume, the temperature of the mold is 60 degrees Celsius, and the pressure used by the reaction injection molding machine is 15Mpa. In addition, observation with a scanning electron microscope revealed that the continuity and uniformity of the bubbles were good (as shown in Figure 2). In addition, the measured physical properties of the honing pads made using the above process conditions are as follows: _ 15 11216twf.doc / 006 The difference is mainly due to the addition of different amounts of chain extender or foaming agent, or the injection of metal molds. Therefore, users can adjust the above composition and mixing ratio according to their own needs to obtain PU honing pads with different physical properties or different physical parameters. Although the present invention has been disclosed as above with a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can make some changes and retouch without departing from the spirit and scope of the present invention. The scope of protection of the invention shall be determined by the scope of the attached patent application. The figure is simple and clear. The first figure is a result of observing the continuity and uniformity of bubbles in the second embodiment when the scanning electron microscope is magnified 100 times. The second figure is when the magnification is 100 times using a scanning electron microscope. Observe the results of the bubble continuity and uniformity in the third example.