200806785 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種模具清潔組成物，其為—種用於模具 清潔、更新及其類似工作的模具清潔材料，該等模具諸2 用於熱塑性樹脂組成物成形材料，已被重複模製工^污2 之模具，特定言之’該模具清潔材料係用於供轉注成= 模具的模具清潔、更新及其類似工作，該等模具係用‘藉 由使用環氧樹脂成形材料進行轉注成形來模製半導體元 的模製工作。 _ 【先前技術】 對於習知的模具清潔方法，已知藉由將模具自模製裝置 拆卸下來進行模具清潔工作的方法，諸如喷砂法、噴乾冰 法、噴水法及強鹼清潔法。然而，在藉由將模具自模製裝 置拆卸下來進行模具清潔工作的情況下，該工作需要長工 作時間且需要大量勞動。因此，愈來愈多地使用在模具安 裝於模製裝置上的情況下進行清潔工作的方法，且使用三 聚氰胺樹脂的清潔方法、使用紫外線照射的清潔方法、使 用片狀清潔組成物的清潔方法及類似方法已作為該清潔方 法進仃。其中，已進行藉由使置放於模具中之片狀清潔組 成物熱固化及移除固化之片狀清潔組成物以將污染物轉移 至該固化之片狀清潔組成物上來自模具中移除污染物的模 具清潔方法，由於該方法具有優良的工作效率。 對於該片狀清潔組成物，可提及例如使用未硫化橡膠之 杈具清潔組成物（參見專利文獻丨）。又，可提及片狀基本材 121307.doc 200806785 料經可經成形用於清潔的化合物塗覆之模具清潔材料（參 見專利文獻2)。 專利文獻 1 : JP-A-9-262843 專利文獻 2 : JP-T-63-502497 【發明内容】 ^而，使用片狀清潔組成物且將污染物轉移至該片狀清 潔組成物上以移除污染物的模具清潔方法存在一個問題： 視模具之腔的形狀及尺寸而定，在模製過程中空氣包含在 腔中，且空氣在腔的角落處積累導致片狀清潔組成物無法 填充在角落中的狀況，從而導致不能充分移除污染物。'舉 二而言’㈣·Α·9_262843中所揭示之模具清潔組成物而 言’必需在夹緊過程中藉纟略微打開上下模具以留出約工 麵至1.5 mm的間隙’以防止橡膠片在模具中熱硫化之後 在移除橡膠片的過程中將橡膠片切斷，且防止橡膠片殘留 在槟具中 '然％，在具有小尺寸及大深度之模具腔的腔 中’空氣陷於腔角落’導致形成未填充部分。因此，產生 未填充部分處之污染物未充分移除的問題。同樣，就jp-T_ 63_502497中所揭示之模具清潔材料而言，由於腔的整個 表面均被覆蓋，陷入空氣無法自腔中溢出從而形成未填充 部分’導致未填充部分處之污染物未充分移除的問題。、 因此，由於不適合在面臨上述問題的模具中使 方Γ於該等模具採用不同於使用片狀清潔^ ”月泳方法ϋ，如上所述，其他清潔方法需要較長 時間，且大量勞動實際上難以負擔。 乂 121307.doc 200806785 鐾於上述情況而實現本發明，且本發明之目的在於提供 一種具有優良模具填充性能且在模具中實現優良污染物清 潔效果的模具清潔組成物。 【實施方式】 為實現上述目的，本發明之模具清潔組成物為一種用於 供反覆熱成形用以模製成形材料之模具的清潔組成物，其 含有作為基本成份之未硫化橡膠、清潔劑及硫化劑，根據 藉由凝膠滲透層析法（GPC)的量測，該清潔組成物整體具 有設在200,000至460,000之範圍内的重量平均分子量 (Mw) 〇 本發明之發明者已進行了深入研究以獲得一種在使用模 具清潔組成物進行模具清潔工作過程中能夠藉由防止形成 另外由產生空氣陷入所致的未填充部分而令人滿意地填充 於模具腔之每一部分中，以及能夠有效移除模具腔中之污 染物的清潔組成物。發明者注重對模具腔的填充性能且主 要對在將清潔組成物填充於模具腔中的過程中能夠將空氣 fe入降至最低之清潔組成物的流動性進行了 一系列研究。 更具體言之，為增強對模具腔的填充性能，必需獲得在填 充清潔組成物的過程中能夠將空氣陷入降至最低的流動狀 態，以及必需減小模製過程中的模具間隙以提高模具腔的 内壓。詳言之，就對模具腔之配合性能的角度而言，清潔 組成物可較佳具有低黏度，但黏度過低時，模製過程中模 具腔之内壓降低而無法擠出陷入空氣，從而導致形成未填 充邛刀另方面，當清潔組成物黏度過高時，對模具腔 121307.doc 200806785 的配口性旎變差，從而導致容易形成未填充部分。基於上 述發現，#明者進行了進一步研究以獲得具有適當黏度之 /月β、、且成物，且發現根據藉由凝膠滲透層析法的量 測，重量平均分子量（Mw)在上述指定範圍内的清潔組成物 能夠具有適當黏度及良好的填充性能，藉此實現本發明。 亦即’本發明係關於以下各項。 (1) 一種模具清潔組成物，其包含未硫化橡膠、清潔劑 及硫化劑，其中根據藉由凝膠滲透層析法（Gpc)的量測， 該清潔組成物整體具有在200,000至46〇,〇〇〇之範圍内的重 量平均分子量（Mw)。 (2) 如（1)之模具清潔組成物，其中根據藉由凝膠滲透層 析法（GPC)的量測，清潔組成物整體具有在22〇,〇〇〇至 43 0,000之範圍内的重量平均分子量（]^^¥)。 (3) 如（1)或（2)之模具清潔組成物，其形狀為片狀或帶 狀。 (4) 如（1)至（3)中任一項之模具清潔組成物，其中該清潔 劑為選自由下列各物組成之群之至少一員：二醇醚、味 唑、咪唑啉及胺基醇。 (5) 如（1)至（4)中任一項之模具清潔組成物，其中該清潔 劑之含量相對於100重量份的未硫化橡膠為1〇至6〇重量 份。 (6) 如（1)至（5)中任一項之模具清潔組成物，其進一步包 含1重量％至20重量％量之水。 (7) 如（1)至（6)中任一項之模具清潔組成物，其進一步包 121307.doc 200806785 含脫模劑。 (8) 如（1)至（7)中任一項之模具清潔組成物，其中該模具 清潔組成物之形狀為片狀，其中複數個線性縫隙在一個方 向上以預定間距且彼此平行設置於其片表面上。 (9) 如（8)之模具清潔組成物，其中該等縫隙經設置以使 得該片狀模具清潔組成物能夠折疊。 (10) 如（8)之模具清潔組成物，其中該等縫隙經設置以使 得該片狀模具清潔組成物能夠沿該等縫隙切割。 (Π)如（1)至（10)中任一項之模具清潔組成物，其為用於 供反覆熱成形用以模製成形材料之模具的清潔組成物。 如上所述，本發明之模具清潔組成物含有未硫化橡膠、 /月潔劑及硫化劑作為基本成份，且根據藉由凝膠滲透層析 法(GPC)的量測，作為一整體，其重量平均分子量㈣係 在扣定範圍内。因此，該清潔組成物具有適當黏度且實現 優良的填充於模具中之性能。因&，當藉由使用本發明之 模具清潔組成物來清潔模具表面時，模具腔經模具清潔組 成物均勻填充以使得模具表面上之污染物黏附於該模具清 潔組成物上，藉此有效地將污染物與模具清潔組成物自模 具整體式移除。舉例而言，將用於模製半導體元件之轉注 成形之模具（其已反覆用於使用環氧樹脂組成物進行的模 製中）表面上的污染物組合於待自該才莫具有&移除之由該 ^具清潔組成物製得的模製物品中，#此可有效進行模具 清潔。ϋ此，藉由使用經本發明之模具清潔组成物清潔的 模具形成的半導體器件具有優良外觀。 121307.doc 200806785 在模具清潔組成物呈片狀或帶狀的情況下，可能容易地 定位該模具清潔組成物以清潔模具腔。 此外’藉&使H咪4 ϋ琳或胺基醇作為清 各劑可能獲得優良的模具清潔效果。 *模具清潔組成物含有1重量％至2〇重量％量之水時，可 能獲得更優良的清潔性能。 當模具清潔組成物經模製以呈片狀且於其片表面上具有 複數個設置於-個方向上的線性縫隙時，藉由沿該等縫隙 折疊該片可能容易地將其堆疊。在此情況下，由於由平行 縫隙分割開的各別塊狀片段在該等縫隙以下的部分處彼此 連接，因此可將該片整齊地堆疊而在折疊過程中無需移 置，且各別塊狀片段在堆疊時不相交或出現類似現象。因 此，所得堆疊形狀規則。藉由使用整齊堆疊之片狀清潔組 成物來清潔模具，可能消除另外由（例如）未硫化橡膠與模 具表面之間壓力接觸不足所引起的清潔缺陷。此外，由於 不必量測該片之尺寸以將該片切割成相同尺寸的片段，且 不必進行將所切片段對齊的複雜工作用於堆疊，因此可能 簡化清潔工作。 此外，當模具清潔組成物呈片狀，且尤其在其片表面上 具有複數個設置於一個方向上的線性縫隙以便沿該等縫隙 切割片狀模具清潔組成物時，可能容易地切割該片以配合 規則的較小模具尺寸。 以下將描述本發明之實施例。 本發明之模具清潔組成物整體具有特定重量平均分子量 121307.doc •10- 200806785 清潔劑及硫化劑 且可藉由使用I硫化橡膠用4乍基本材料 作為主要成份獲得。 用作未硫化橡膠之橡膠材料的實例包括，但不特別地限 於’習知橡膠’諸如丁二烯橡膠⑽）、乙稀.丙稀_二稀橡 膠卿M)、乙稀_丙稀橡膠(EpM)及苯乙烯-丁二稀橡膠 (SBR)。該等橡膠可單獨使用或其中之二或多者组人使 用。使該等未硫化橡膠之每一者於模具中硫化成硫：橡 膠。 其中’ EPM、EPDM、BR或其混合物可較佳用作未硫化 橡膠’因為當使用模具使該等橡膠在模具中硫化時，其污 染較少且在硫化過程中臭味較小。 更具體言之，EPDM為含有乙烯、心烯烴（尤其為丙烯） 及以下所列之多烯單體的三元聚合物，且多烯單體之實例 包括二環戊二烯、丨，5•環辛二烯、環辛二烯、1，6_環十 二-二烯、1，7_環十二_二烯、環十二·三烯、i，4-環庚 二烯、1，4-環己二烯，降廿宿二烯、亞甲基降冰片烯、孓 甲基戊二烯-1，4，1，5-己二烯、；ι，6_庚二烯、甲基·四氫茚及 1，4_己二稀。 EPDM中每一單體的聚合比例可為，三元聚合物中乙烯 為 30 mol% 至 80 mol%，多烯單體為oj mol% 至 2〇 m〇1%， 且其餘為a-細經。更佳地’乙稀為30 mol%至60 mol%。較 佳使用重量平均分子量（Mw)為100,000至300,000，更佳為 150,000至 250,000 的 EPDM 〇 對於丁二烯橡膠（BR)，可使用l，2-聚丁二烯、ι，4-聚丁 121307.doc -11 - 200806785 二烯或其混合物。丁二烯橡膠之摩尼黏度（M〇〇ney ViSC〇Sity)MLl+4(100°C)可為 20至80，更佳為 35至60。較佳 使用重®平均分子量（Mw)為200,000至6〇〇,〇〇〇，更佳為 400,000 至 6〇〇,00〇 的 丁二烯橡膠。 /月/名诏的實例包括二醇醚、咪唑、咪唑啉及胺基醇。該 等清潔劑可單獨使用或其中之二或多者組合使用。 上述二醇醚為下式（1)所示之化合物： R】〇 —CH2 —Rt …（1) (在式（1)中，η為正整數，且心與尺2各自為氫或烷基。當& 與r2中之-者為氫時’另—者為院基。與R2均為烧基 時’ Ri與R2可相同或不同。） 式（1)所示之二醇醚之實例包括乙二醇二甲醚、二乙二 醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、聚乙二醇 二甲醚、〔乙二醇單丙醚、二乙二醇單丁⑽、二乙二醇二 ***二乙二醇單甲㈣、乙二醇單乙縫、乙二醇單丙鍵及乙 二酵单丁喊°該等二_可單獨使用或其中之二或多者組 合使用。 在式⑴所不之上述二醇峻中，較佳使用重複數福u 2 //、 2中之者為具有1至4個碳原子的烷基同時另一者 為氫的，或重複數η為且當及1與&2均為烧基 時，其為具有1至4個碳原子的院基。本文中，在重複數η 為3或更广的情況下，與橡膠的相容性變差。此外，在烷 基中的奴原子數目為5或更大的情況下，對氧化降解脫模 121307.doc -12- 200806785 劑層或其類似層的滲透性變差。二醇醚之沸點可較佳為約 130°C至250°C。更具體言之，因為模具模製通常係在 150 C至185 C下進行，因此當二醇醚之沸點低於13〇。〇 時’清潔過程中的蒸發非常快而使清潔工作環境在某些情 況下劣化。當沸點超過25(rc時，蒸發變得困難而使二醇 _殘遠在石鼠化橡膠中，從而使得清潔後的硫化橡膠強度降 低且在自模具取出清潔組成物後硫化橡膠可出現斷裂或類 似現象。因此’難以令人滿意地將氧化降解脫模劑層或其 類似層自模具表面剝離，從而導致清潔工作效率降低的傾 向。 在使用中’每一種二醇醚可按原狀使用或與水，諸如甲 醇、乙醇及正丙醇之醇或諸如曱苯及二曱苯之有機溶劑混 合使用。在將二醇醚與有機溶劑混合的情況下，相對於 1 〇〇重畺份的二醇醚，有機溶劑的量較佳設為5〇重量份或 更少，更佳為20重量份或更少。 藉由使用下式（2)所示之咪唑作為上述咪唑可獲得良好 效果：200806785 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a mold cleaning composition, which is a mold cleaning material for mold cleaning, renewal, and the like, which are used for thermoplastics. The resin composition forming material has been repeatedly molded into the mold of the mold 2, specifically, the mold cleaning material is used for the transfer of the mold = mold cleaning, updating and the like, and the molds are used. The molding work of the semiconductor element is molded by transfer molding using an epoxy resin molding material. [Prior Art] For the conventional mold cleaning method, a method of cleaning the mold by removing the mold from the molding apparatus, such as a sand blasting method, a spray drying method, a water spray method, and a strong alkali cleaning method, is known. However, in the case where the mold is cleaned by detaching the mold from the molding apparatus, the work requires a long working time and requires a lot of labor. Therefore, more and more methods for performing cleaning work in the case where the mold is mounted on the molding apparatus, a cleaning method using melamine resin, a cleaning method using ultraviolet irradiation, a cleaning method using a sheet-like cleaning composition, and the like are increasingly used. A similar method has been adopted as the cleaning method. Wherein, it has been carried out by thermally curing the sheet-like cleaning composition placed in the mold and removing the cured sheet-like cleaning composition to transfer contaminants to the cured sheet-like cleaning composition from the mold. The mold cleaning method for contaminants has excellent working efficiency due to the method. For the sheet-like cleaning composition, for example, a cookware cleaning composition using an unvulcanized rubber can be mentioned (see Patent Document 丨). Further, a sheet-like base material 121307.doc 200806785 may be mentioned as a compound-coated mold cleaning material which can be shaped for cleaning (see Patent Document 2). Patent Document 1: JP-A-9-262843 Patent Document 2: JP-T-63-502497 [Summary of the Invention] ^, a sheet-like cleaning composition is used and contaminants are transferred to the sheet-like cleaning composition to be moved There is a problem with the mold cleaning method except for contaminants: Depending on the shape and size of the cavity of the mold, air is contained in the cavity during the molding process, and air accumulates at the corners of the cavity, so that the sheet-like cleaning composition cannot be filled. The condition in the corner, resulting in insufficient removal of contaminants. In the case of the mold cleaning composition disclosed in the '2' (4) Α 9_262843, it is necessary to slightly open the upper and lower molds during the clamping process to leave a gap of about 1.5 mm to prevent the rubber sheet. After the hot vulcanization in the mold, the rubber sheet is cut during the process of removing the rubber sheet, and the rubber sheet is prevented from remaining in the betel nut. In the cavity of the mold cavity having a small size and a large depth, the air is trapped in the cavity. The corner 'leads to form an unfilled portion. Therefore, there is a problem that the contaminants at the unfilled portion are not sufficiently removed. Similarly, in the case of the mold cleaning material disclosed in jp-T_63_502497, since the entire surface of the cavity is covered, the trapped air cannot overflow from the cavity to form an unfilled portion, resulting in insufficient contamination of the unfilled portion. Except for the problem. Therefore, since it is not suitable for the molds facing the above problems to be used in the molds differently than the use of the sheet cleaning method, as described above, other cleaning methods take a long time, and a large amount of labor actually It is difficult to afford. 乂121307.doc 200806785 The present invention has been achieved in view of the above circumstances, and an object of the present invention is to provide a mold cleaning composition which has excellent mold filling performance and achieves excellent contaminant cleaning effect in a mold. In order to achieve the above object, the mold cleaning composition of the present invention is a cleaning composition for a mold for reversing thermoforming for molding a material, which contains an unvulcanized rubber as a basic component, a detergent, and a vulcanizing agent. The cleaning composition as a whole has a weight average molecular weight (Mw) set in the range of 200,000 to 460,000 as measured by gel permeation chromatography (GPC). The inventors of the present invention have conducted intensive studies to obtain a Using mold cleaning components to perform mold cleaning work can be prevented by forming additional The unfilled portion of the air is trapped and satisfactorily filled in each portion of the mold cavity, and a cleaning composition capable of effectively removing contaminants in the mold cavity. The inventors focused on the filling performance of the mold cavity and mainly A series of studies have been conducted on the fluidity of the cleaning composition capable of minimizing air entrapment during filling of the cleaning composition into the mold cavity. More specifically, in order to enhance the filling performance of the mold cavity, it is necessary to obtain In the process of filling the cleaning composition, the air can be plunged into a minimum flow state, and the mold gap in the molding process must be reduced to increase the internal pressure of the mold cavity. In detail, the fit of the mold cavity In terms of angle, the cleaning composition may preferably have a low viscosity, but when the viscosity is too low, the internal pressure of the mold cavity is lowered during the molding process and cannot be squeezed into the air, thereby causing the formation of an unfilled trowel, when cleaning the composition When the viscosity of the object is too high, the miscibility of the mold cavity 121307.doc 200806785 is poor, resulting in easy formation of an unfilled portion. Based on the above findings, #明者 carried out further research to obtain the appropriate viscosity / month β, and the composition, and found that according to the measurement by gel permeation chromatography, the weight average molecular weight (Mw) within the above specified range of cleaning The composition can have an appropriate viscosity and good filling properties, thereby realizing the present invention. That is, the present invention relates to the following. (1) A mold cleaning composition comprising an unvulcanized rubber, a detergent, and a vulcanizing agent, wherein According to the measurement by gel permeation chromatography (Gpc), the cleaning composition as a whole has a weight average molecular weight (Mw) in the range of 200,000 to 46 Torr, (2) as in (1) A mold cleaning composition in which the cleaning composition as a whole has a weight average molecular weight (in the range of 22 〇, 〇〇〇 to 43 0,000) according to the measurement by gel permeation chromatography (GPC). . (3) The mold cleaning composition according to (1) or (2), which is in the form of a sheet or a belt. (4) The mold cleaning composition according to any one of (1) to (3), wherein the cleaning agent is at least one member selected from the group consisting of glycol ethers, oxazoles, imidazolines, and amine groups. alcohol. (5) The mold cleaning composition according to any one of (1) to (4), wherein the detergent is contained in an amount of from 1 to 6 parts by weight based on 100 parts by weight of the unvulcanized rubber. (6) The mold cleaning composition according to any one of (1) to (5), which further comprises water in an amount of from 1% by weight to 20% by weight. (7) The mold cleaning composition according to any one of (1) to (6), further comprising a mold release agent, 121307.doc 200806785. (8) The mold cleaning composition according to any one of (1) to (7) wherein the mold cleaning composition has a shape of a sheet, wherein the plurality of linear slits are disposed at a predetermined pitch in one direction and in parallel with each other On the surface of the piece. (9) The mold cleaning composition of (8), wherein the slits are disposed such that the sheet mold cleaning composition can be folded. (10) The mold cleaning composition of (8), wherein the slits are disposed such that the sheet mold cleaning composition can be cut along the slits. The mold cleaning composition according to any one of (1) to (10) which is a cleaning composition for a mold for reversing thermoforming to mold a material. As described above, the mold cleaning composition of the present invention contains an unvulcanized rubber, a detergent, and a vulcanizing agent as essential components, and the weight average is measured as a whole by gel permeation chromatography (GPC). The molecular weight (4) is within the bound range. Therefore, the cleaning composition has an appropriate viscosity and achieves excellent properties of being filled in a mold. When the mold surface is cleaned by using the mold cleaning composition of the present invention, the mold cavity is uniformly filled by the mold cleaning composition to adhere the contaminant on the mold surface to the mold cleaning composition, thereby effectively The contaminant and mold cleaning composition are removed from the mold in one piece. For example, a contaminant on a surface of a mold for molding a molded semiconductor element that has been repeatedly used for molding using an epoxy resin composition is combined with a target to be removed from In addition to the molded article obtained from the cleaning composition, this can effectively perform mold cleaning. Thus, the semiconductor device formed by using the mold cleaned by the mold cleaning composition of the present invention has an excellent appearance. 121307.doc 200806785 In the case where the mold cleaning composition is in the form of a sheet or a belt, the mold cleaning composition may be easily positioned to clean the mold cavity. In addition, it is possible to obtain excellent mold cleaning results by using "H&M; * When the mold cleaning composition contains water in an amount of from 1% by weight to 2% by weight, more excellent cleaning performance may be obtained. When the mold cleaning composition is molded to have a sheet shape and has a plurality of linear slits disposed on the surface of the sheet in one direction, it may be easily stacked by folding the sheets along the slits. In this case, since the individual block segments separated by the parallel slits are connected to each other at portions below the slits, the sheets can be neatly stacked without dislocation during the folding process, and each block Fragments do not intersect or appear similar when stacked. Therefore, the resulting stack shape is regular. By using a neatly stacked sheet-like cleaning composition to clean the mold, it is possible to eliminate cleaning defects caused by, for example, insufficient pressure contact between the unvulcanized rubber and the surface of the mold. Further, since it is not necessary to measure the size of the sheet to cut the sheet into pieces of the same size, and it is not necessary to perform complicated work of aligning the cut pieces for stacking, it is possible to simplify the cleaning work. Further, when the mold cleaning composition is in the form of a sheet, and particularly has a plurality of linear slits disposed in one direction on the surface of the sheet to cut the sheet mold cleaning composition along the slits, the sheet may be easily cut to Match the smaller mold size of the rule. Embodiments of the invention will be described below. The mold cleaning composition of the present invention has a specific weight average molecular weight as a whole. 121307.doc •10- 200806785 A detergent and a vulcanizing agent can be obtained by using a vulcanized rubber as a main component using a 4 Å base material. Examples of the rubber material used as the unvulcanized rubber include, but are not particularly limited to, 'conventional rubbers' such as butadiene rubber (10), ethylene, propylene, propylene, rubber, and EpM. And styrene-butadiene rubber (SBR). These rubbers may be used singly or in combination of two or more of them. Each of the unvulcanized rubbers is vulcanized into a sulphur: rubber in a mold. Among them, 'EPM, EPDM, BR or a mixture thereof can be preferably used as the unvulcanized rubber' because when the rubber is vulcanized in a mold using a mold, it is less contaminated and has less odor during vulcanization. More specifically, EPDM is a terpolymer containing ethylene, a heart olefin (especially propylene) and a polyene monomer listed below, and examples of the polyene monomer include dicyclopentadiene, hydrazine, 5• Cyclooctadiene, cyclooctadiene, 1,6-cyclododeca-diene, 1,7-cyclododecaene, cyclododecatriene, i,4-cycloheptadiene, 1, 4-cyclohexadiene, halocene, methylene norbornene, indole methylpentadiene-1,4,1,5-hexadiene; i,6-heptadiene, methyl · Tetrahydroanthracene and 1,4_hexane dilute. The polymerization ratio of each monomer in the EPDM may be 30 mol% to 80 mol% of ethylene in the terpolymer, oj mol% to 2〇m〇1% of the polyene monomer, and the rest is a-fine . More preferably, the amount of ethylene is from 30 mol% to 60 mol%. It is preferred to use EPDM having a weight average molecular weight (Mw) of from 100,000 to 300,000, more preferably from 150,000 to 250,000. For butadiene rubber (BR), l,2-polybutadiene, iota, 4-polybutyl 121307 can be used. .doc -11 - 200806785 Diene or a mixture thereof. The butadiene rubber has a Mooney viscosity (M〇〇ney ViSC〇Sity) MLl+4 (100 ° C) of 20 to 80, more preferably 35 to 60. It is preferred to use a butadiene rubber having a weight average molecular weight (Mw) of 200,000 to 6 Å, 〇〇〇, more preferably 400,000 to 6 Å, 00 Å. Examples of /month/name include glycol ethers, imidazoles, imidazolines, and amino alcohols. These detergents may be used singly or in combination of two or more of them. The above glycol ether is a compound represented by the following formula (1): R] 〇-CH2 - Rt (1) (In the formula (1), η is a positive integer, and each of the core and the scale 2 is hydrogen or an alkyl group. When & and r2 are hydrogen, the other is the base. When R2 is a base, 'R and R2 may be the same or different.) Example of the glycol ether represented by formula (1) Including ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, [ethylene glycol monopropyl ether, two ethyl Glycol monobutyl (10), diethylene glycol diethyl ether diethylene glycol monomethyl (tetra), ethylene glycol monoethyl sulphate, ethylene glycol monopropyl bond, and ethylene glycol singly singularly Two or more are used in combination. In the above-mentioned diols which are not in the formula (1), it is preferred to use a repeating number of Fu 2 / 2, 2 as an alkyl group having 1 to 4 carbon atoms while the other is hydrogen, or a repeating number η And when both 1 and & 2 are a burn group, it is a hospital base having 1 to 4 carbon atoms. Herein, in the case where the repetition number η is 3 or more, the compatibility with the rubber is deteriorated. Further, in the case where the number of slave atoms in the alkyl group is 5 or more, the permeability to the oxidative degradation demolding 121307.doc -12-200806785 agent layer or the like is deteriorated. The boiling point of the glycol ether may preferably be from about 130 ° C to 250 ° C. More specifically, since the mold is usually molded at 150 C to 185 C, the boiling point of the glycol ether is less than 13 Torr. 〇 When the cleaning process is very fast, the cleaning work environment deteriorates under certain conditions. When the boiling point exceeds 25 (rc, evaporation becomes difficult and the diol is left in the stone rubber, so that the strength of the vulcanized rubber after cleaning is lowered and the vulcanized rubber may be broken or the like after the cleaning composition is taken out from the mold. Therefore, it is difficult to satisfactorily peel off the oxidative degradation release agent layer or the like from the mold surface, resulting in a tendency to reduce the cleaning work efficiency. In use, 'each glycol ether can be used as it is or with water, An alcohol such as methanol, ethanol and n-propanol or an organic solvent such as toluene and diphenylbenzene is used in combination with a glycol ether and an organic solvent, relative to 1 gram of the glycol ether, The amount of the organic solvent is preferably set to 5 parts by weight or less, more preferably 20 parts by weight or less. A good effect can be obtained by using the imidazole represented by the following formula (2) as the above imidazole:
…（2) (在式（2)中，每一 R，為η、具有取代基且具有1〇個或1〇個以 下石反原子之直鏈烴基、不具有取代基且具有1〇個或1〇個以 下碳原子之直鏈烴基，或芳基，且R，可相同或不同。） 121307.doc -13- 200806785 ―該咪唑之實例包括2-曱基咪唑、2-乙基·4_曱基咪唑、2_ 苯土 Ή 1 ¥基-2-甲基咪吐及2,4_二胺基_6[2’_甲基味〇坐 土（）]乙基-s-二η井。肖等咪唑可單獨使用或其中之二或 多者組合使用。 藉由使用下式（3)所示之味唾琳作為上述味Q圭琳可獲得 良好效果：(2) (In the formula (2), each R is a linear hydrocarbon group having η, a substituent and having 1 or less than one stone anti-atom, having no substituent and having 1 or a linear hydrocarbon group of 1 or less carbon atoms, or an aryl group, and R, which may be the same or different.) 121307.doc -13- 200806785 - Examples of the imidazole include 2-mercaptoimidazole, 2-ethyl·4_ Mercaptoimidazole, 2_ benzophenone 1 ¥-2-methylmoxi and 2,4-diamino _6 [2'-methyl miso sputum ()] ethyl-s-two η well. The imidazole such as shawyl may be used singly or in combination of two or more thereof. By using the taste saliva shown in the following formula (3) as the above-mentioned flavor Q Guilin, good results can be obtained:
(在式（3)中，每一 R’為H、具有取代基且具有10個或10個以 下碳原子之直鏈烴基、不具有取代基且具有1〇個或ι〇個以 下碳原子之直鏈烴基，或芳基，且R，可相同或不同。） 米唑啉之實例包括2_甲基咪唑啉、2-甲基·4_乙基咪唑 琳2-苯基味嗤琳、in】·曱基咪唾啉、苯基_心甲基_ 5’基曱基咪㈣、2,4_二胺基_6[2’·甲基咪嗤琳基_⑴，]乙 基s_一呼、2,4_一胺基_6[2，_甲基·4，·哺唑啉基-⑴t]乙基_s· 三喷、1-氰基乙基-2-甲基咪唑啉及丨_氰基乙基^甲基_4_乙 基咪唑啉。該等咪唑啉可單獨使用或其中之二或多者組合 使用。 與二醇醚之情況相同，在使用中，咪唑及咪唑啉之每一 者可接原狀使用或與諸如甲醇、乙醇及正丙醇之醇或諸如 甲苯及二甲苯之有機溶劑混合使用。纟將^坐與醇或有機 溶劑混合的情況下，相對於1〇〇重量份的咪唑及咪唑啉中 121307.doc -14- 200806785 之至少一者，醇或有機溶劑的量較佳設為5〇重量份或更 少，更佳為20重量份或更少。 對於上述胺基醇，可使用下列胺基醇來獲得良好效果。 胺基醇之代表性實例包括單乙胺醇、二乙胺醇、三乙胺 醇、N-甲基乙胺醇，N，N_:甲基乙胺醇、N，N-二丁基乙胺 醇、N，N-二乙基乙胺醇、n_甲基-N，N_二乙胺醇、2-胺基_ 2-甲基丙醇、3-胺基丙醇及2-胺基丙醇。該等胺基醇可單 獨使用或其中之二或多者組合使用。 與上述其他清潔劑之情況相同，在使用中，胺基醇可按 原狀使用或與諸如甲醇、乙醇及正丙醇之醇或諸如甲苯及 一甲苯之有機溶劑混合使用。在將醇胺與醇及或有機溶劑 混合的情況下，相對於100重量份的胺基醇，醇或有機溶 劑的量可較佳設為50重量份或更少，更佳為2〇重量份或更 少〇 相對於1 00重里份的未硫化橡膠，清潔劑（二醇鱗、口东 唑、咪唑啉或胺基醇）的含量可較佳地設在1 〇重量份至6〇 重Ϊ份、更佳15重量份至25重量份之範圍内。當清潔劑的 含量小於10重量份時，難以展示出對模具之令人滿意的清 潔效果。當在藉由使用由此獲得的模具清潔組成物來清潔 模具的情況下清潔劑之含量超過60重量份時，組成物黏著 於模具上，從而使自模具剝離組成物的工作效率降低。 每硫化劑無特別限制，且可使用習知的硫化劑。硫化劑之 貝例包括硫及有機過氧化物，諸如正丁基-4,4-雙（第三丁 基過乳基）戊駿S旨及二（第三丁基過氧基）_3,3,5·三甲基 121307.doc -15- 200806785 環己燒。該等硫化劑可單獨使用或其中之二或多者組合使 用。相對於100重量份的未硫化橡膠，硫化劑的含量可較 佳没在1重量份至3重量份之範圍内。 此外’本發明之模具清潔組成物除含有未硫化橡膠、清 潔劑及硫化劑外，可視情況含有脫模劑、增強劑及其類似 物。 脫模劑無特別限制，且可使用習知的脫模劑。脫模劑之 實例包括：長鏈脂肪酸，諸如硬脂酸及二十二碳烷酸；長 鍵脂肪酸的金屬鹽，以硬脂酸鋅及硬脂酸鈣為代表；酯基 壤’以巴西棕櫚蠟（carnauba wax)、褐煤蠟及褐煤酸的部 分息化自旨為代表；長鏈脂族醯胺，以硬脂醯基乙二胺為代 表；及石蠟，以聚乙烯蠟為代表。 相對於模具清潔組成物的總重量，脫模劑的含量可較佳 没在1重量％至1〇重量％之範圍内。當脫模劑的含量小於1 重量％時，難以展示出足夠的脫模效果。當其含量超過10 重ϊ %時，清潔能力可能降低且藉由使用重複利用之後的 模具製造的模製物品之外觀受到影響。 增強劑之實例包括無機增強劑（填充劑），諸如二氧化 矽、氧化鋁、碳黑、碳酸鈣、矽酸鈣、氫氧化鋁、二氧化 鈦及氧化鈦。相對於100重量份的未硫化橡膠，增強劑的 含塁可較佳設在1〇重量份至5〇重量份之範圍内。 此外，當清潔組成物含有未硫化橡膠膏團作為基本材料 時’可向未硫化橡膠中添加水。相對於模具清潔組成物的 總重夏’水的含量可較佳設在1重量。/◦至20重量％之範圍 121307.doc -16- 200806785 内。 本發明之模具清潔組成物可（例如）如下所述製造。將用 作基本材料的未硫化橡膠、清潔劑、硫化劑及其他添加劑 此5，且將混合物經分批型捏合機捏合，且接著使用擠壓 機或親使其形成片狀或帶狀，藉此獲得模具清潔組成物。 在模具清潔組成物以片形式使用的情況下，片的厚度通常 設為3 mm至1 〇 mm。 必需將由此獲得之模具清潔組成物整體的重量平均分子 l(Mw)調整為200，_至46〇,〇〇〇，其係藉由凝膠渗透層析 法（GPC)里測。其重量平均分子量（Mw)尤其較佳為 至430，_。當Mw小於_，_時，模具清潔組成物之黏度 降低，且在模製過程中，壓力自模具間隙溢出，使得模具 清潔組成物無法散布於模具的各個部分，因為模具腔内部 壓力降低，從而導致形成未填充部分。當其Mw超過 460’〇〇〇時，模具清潔組成物之黏度增大，降低模具清潔 組成物與模具腔的配合性，從而導致形成未填充部分。 (例如）如下所述進行Gpc量測。將所得模具清潔組成物 α泡於氣仿中且靜置3天。接著，將氯仿可溶部分於熱板 上加熱以使其乾燥及凝固。藉由使用0.1重量％四氫呋喃 (THF)溶液調整所得經乾燥及凝固的物質以使其靜置1天。 接著，藉由使用〇·45 μιη膜過濾器將溶液過濾，且藉由使 用預疋为析儀在預定條件下對濾出液進行GPC量測。在 置測中，所用溶劑不限於丁hf溶液且可根據量測對象 清潔組成物之組成適當地選擇。 121307.doc -17- 200806785 模具清潔組成物可較佳具有淺色，諸如白色及接近白色 =色。#由調整顏色，在模具清潔後’可能容易地用肉 眼確定污染物自模具移除且黏附於模具清潔組成物上，藉 此實現可能容易地確定模具清潔狀態的效果。 曰 *在使用本發明之模具清潔組成物的情況了，較佳使用經 模製成片料模具清潔組成物。在使用片_具清潔组= 物時，就藉由使用片狀模具清潔組成物來進行模具清淨工 作的容易性及其類似性能的角度而言’適合使用中 所示片表面具有複數個以預定間距且彼此平行設置的線性 縫隙11以使得片10可折疊的片1〇。更佳地，片10具有—帶 有條紋圖案的片表面。藉由使用該等縫隙u折疊片1〇,= 能將片10整齊堆疊。(In the formula (3), each R' is H, a linear hydrocarbon group having a substituent and having 10 or less carbon atoms, having no substituent and having 1 or less than 1 carbon atom a linear hydrocarbon group, or an aryl group, and R, which may be the same or different.) Examples of the oxazoline include 2-methylimidazoline, 2-methyl-4-isoimidazoline 2-phenyl misoline, in 】·曱基imilin, phenyl_heart methyl _ 5′ 曱 曱 咪 (4), 2,4_diamino _6[2'·methyl imiline _ (1),] ethyl s_ One call, 2,4_monoamine _6[2,_methyl·4,·oxazoline-(1)t]ethyl_s·three-spray, 1-cyanoethyl-2-methylimidazoline And 丨 cyanoethyl ^ methyl _ 4 - ethyl imidazoline. These imidazolines may be used singly or in combination of two or more of them. As in the case of the glycol ether, in use, each of the imidazole and the imidazoline may be used as it is or in combination with an alcohol such as methanol, ethanol and n-propanol or an organic solvent such as toluene and xylene. When the hydrazine is mixed with an alcohol or an organic solvent, the amount of the alcohol or the organic solvent is preferably set to 5 with respect to at least one of 121 307. doc - 14 to 200806785 in 1 part by weight of imidazole and imidazoline. The 〇 part by weight or less is more preferably 20 parts by weight or less. For the above amino alcohol, the following amino alcohol can be used to obtain a good effect. Representative examples of amino alcohols include monoethylamine, diethylamine, triethylamine, N-methylethylamine, N,N-: methylethylamine, N,N-dibutylethylamine Alcohol, N,N-diethylethylamine, n-methyl-N,N-diethylaminol, 2-amino-2-methylpropanol, 3-aminopropanol and 2-amino Propanol. These amino alcohols may be used singly or in combination of two or more of them. As in the case of the above other cleaning agents, in use, the amino alcohol may be used as it is or in combination with an alcohol such as methanol, ethanol and n-propanol or an organic solvent such as toluene and mono-toluene. In the case where the alcohol amine is mixed with an alcohol and or an organic solvent, the amount of the alcohol or the organic solvent may preferably be 50 parts by weight or less, more preferably 2 parts by weight, based on 100 parts by weight of the amino alcohol. Or less 〇 with respect to 100 parts by weight of unvulcanized rubber, the content of detergent (diol scale, crotonazole, imidazoline or amino alcohol) may preferably be set at 1 part by weight to 6 parts by weight More preferably, it is in the range of 15 parts by weight to 25 parts by weight. When the content of the detergent is less than 10 parts by weight, it is difficult to exhibit a satisfactory cleaning effect on the mold. When the content of the detergent exceeds 60 parts by weight in the case where the mold is cleaned by using the thus obtained mold cleaning composition, the composition adheres to the mold, thereby lowering the work efficiency of peeling the composition from the mold. Each vulcanizing agent is not particularly limited, and a conventional vulcanizing agent can be used. Examples of vulcanizing agents include sulfur and organic peroxides such as n-butyl-4,4-bis(t-butylperlacyl) sulfonate and di(t-butylperoxy)_3,3 ,5·Trimethyl 121307.doc -15- 200806785 Cyclohexene. These vulcanizing agents may be used singly or in combination of two or more of them. The content of the vulcanizing agent may preferably be in the range of from 1 part by weight to 3 parts by weight based on 100 parts by weight of the unvulcanized rubber. Further, the mold cleaning composition of the present invention may contain, in addition to the unvulcanized rubber, the cleaning agent and the vulcanizing agent, a release agent, a reinforcing agent and the like. The release agent is not particularly limited, and a conventional release agent can be used. Examples of the release agent include: long-chain fatty acids such as stearic acid and behenic acid; metal salts of long-chain fatty acids, represented by zinc stearate and calcium stearate; ester-based soils with Brazilian palm The partial enzymatic content of wax (carnauba wax), montan wax and montanic acid is represented by the purpose; long-chain aliphatic decylamine, represented by stearyl ethylenediamine; and paraffin wax, represented by polyethylene wax. The content of the releasing agent may preferably not be in the range of 1% by weight to 1% by weight based on the total weight of the mold cleaning composition. When the content of the release agent is less than 1% by weight, it is difficult to exhibit a sufficient release effect. When the content exceeds 10% by weight, the cleaning ability may be lowered and the appearance of the molded article manufactured by using the mold after repeated use is affected. Examples of the reinforcing agent include inorganic reinforcing agents (fillers) such as cerium oxide, aluminum oxide, carbon black, calcium carbonate, calcium silicate, aluminum hydroxide, titanium oxide, and titanium oxide. The cerium of the reinforcing agent may preferably be in the range of from 1 part by weight to 5 parts by weight relative to 100 parts by weight of the unvulcanized rubber. Further, when the cleaning composition contains an unvulcanized rubber paste as a base material, water can be added to the unvulcanized rubber. The content of water in the total weight of the cleaning composition relative to the mold may be preferably set to 1 weight. /◦ to the range of 20% by weight 121307.doc -16- 200806785. The mold cleaning composition of the present invention can be produced, for example, as described below. An unvulcanized rubber, a cleaning agent, a vulcanizing agent, and other additives to be used as a base material, and the mixture is kneaded by a batch type kneader, and then formed into a sheet shape or a belt shape by using an extruder or a member. A mold cleaning composition is obtained. In the case where the mold cleaning composition is used in the form of a sheet, the thickness of the sheet is usually set to 3 mm to 1 〇 mm. It is necessary to adjust the weight average molecular weight (Mw) of the entire mold cleaning composition thus obtained to 200, _ to 46 Torr, which is measured by gel permeation chromatography (GPC). The weight average molecular weight (Mw) thereof is particularly preferably from 430 to _. When Mw is less than _, _, the viscosity of the mold cleaning composition is lowered, and during the molding process, the pressure overflows from the mold gap, so that the mold cleaning composition cannot be dispersed in various parts of the mold because the internal pressure of the mold cavity is lowered, thereby Causes an unfilled portion to form. When the Mw exceeds 460' Torr, the viscosity of the mold cleaning composition is increased to lower the fit of the mold cleaning composition to the mold cavity, resulting in the formation of an unfilled portion. (For example) Gpc measurement is performed as described below. The resulting mold cleaning composition α was bubbled in the air and allowed to stand for 3 days. Next, the chloroform-soluble portion was heated on a hot plate to dry and solidify. The resulting dried and solidified material was adjusted to stand for 1 day by using a 0.1% by weight tetrahydrofuran (THF) solution. Next, the solution was filtered by using a 〇·45 μm membrane filter, and the filtrate was subjected to GPC measurement under predetermined conditions by using a pre-former. In the case of the measurement, the solvent to be used is not limited to the butyl hf solution and can be appropriately selected depending on the composition of the measurement object cleaning composition. 121307.doc -17- 200806785 The mold cleaning composition may preferably have a light color such as white and near white = color. # By adjusting the color, after the mold is cleaned, it may be easily determined by the naked eye that the contaminant is removed from the mold and adhered to the mold cleaning composition, thereby realizing the effect that the mold cleaning state can be easily determined.曰 * In the case of cleaning the composition using the mold of the present invention, it is preferred to use a mold to form a sheet mold cleaning composition. In the case of using the sheet cleaning group, the sheet surface has a plurality of sheets for the purpose of ease of mold cleaning work and the like by using a sheet mold cleaning composition. The linear slits 11 which are spaced apart and arranged in parallel with each other are such that the sheet 10 is foldable. More preferably, the sheet 10 has a sheet surface with a striped pattern. By folding the sheets 1 using the slits u, the sheets 10 can be stacked neatly.
具有縫隙11的片10可如下所述製造。將如上所述得到的 軋製片切割成預定形狀及尺寸得到片10，且於每一片10之 上表面上形成縫隙n。縫隙丨丨的形成係（例如）如圖2中所 示，藉由使用盤紙分切機（ribbon slitter)進行，其中圓开）切 割刀片13連接於旋轉軸12上，且移動切割刀片13，切割刀 片13自片1〇之上表面且在片1〇之橫向方向上***片1〇中預 定深度以形成彼此平行的縫隙U。藉由重複上述操作，於 片10之整個上表面上形成以恆定間距且彼此平行設置的縫 隙11。片1 〇經縫隙11分割成相同尺寸的塊狀片段1 〇 a。由 於縫隙11係以恆定間距形成，所以當折疊片時，縫隙丨工具 有標尺功能，因此可能根據待清潔之模具或腔的尺寸切割 或折疊片10。 121307.doc -18 - 200806785 f外：如圖3中所示，每-縫隙11之末端與朝向縫隙u 之该末端之片表面之間的距離D可較佳設為約〇」酿至〇·8 麵’更佳為約G·2職至mm。當距離小於(M mm時， 塊狀片段10a趨向於容易地分離，且當距離超過❹.8酿 時’折疊較不順暢。 “精由使用本發明之形成為片狀之模具清潔組成物來清潔 模具的方法係對欲用於模製半導體器件之模具進行。舉例 而言，將處於未硫化狀態的片置放於模具中，且接著使1 熱硫化以使污染物整體式黏附於片上。接著藉由自模具移 除經硫化之片來進行模具清潔。 以下將根據事件順序來詳細描述使用片狀模具清潔組成 物的模具清潔方法。 以製備本發明之片狀模具清潔組成物開始。接著，如圖 4中所示，將片狀模具清潔組成物1 〇置放於形成有凹陷3a 的上模具1與形成有凹陷3b的下模具2之間，且如圖5中所 不，將上模具1與下模具2夾緊以將片狀模具清潔組成物⑺ 夾於其中進行壓力模製。使片10填充於由形成於上模具1 中的凹陷3a與形成於下模具2中的凹陷补形成的腔3中，且 用於模製之壓力使其與模具表面壓力接觸。在此狀態下， 用於模製之熱將未硫化橡膠熱硫化成硫化橡膠，由此使腔 3中形成之氧化降解脫模劑層及其類似層與硫化橡膠結 合。在某些情況下，腔3周圍的毛邊亦與硫化橡膠結合。 接著，如圖6中所示，經預定時間週期後，打開上模具工與 下模具2以自上模具1與下模具2剝離已成為硫化橡膠的片 121307.doc -19- 200806785 狀模具清潔組成物10,藉此自上模具i與下模具2的表面剝 離與片ίο結合的氧化降解層及其類似層。由此進行模具清 潔。 對於片狀挺具清潔組成物，可能使用如圖1中所示，具 有複數個以預定間距且彼此平行形成於片表面上的線性縫 隙11以使得片10可折疊的片狀模具清潔組成物。 在使用該片狀清潔組成物的情況下，如圖7所示，沿縫 隙11自片切割所要數目之塊狀片段1 Ga。可藉由用手指挑 起片10且沿縫隙u重複折疊或藉由使用小刀或其類似物來 進行該切割。接著，如圖8中所示，沿縫隙11折疊片10， 八中片10之上表面（形成有縫隙丨J之表面）朝外（此處，在圖 8中切割下4個塊狀片段i〇a)，且將片1〇連續折疊，直至其 下表面彼此接觸以將塊狀片段10a堆疊，如圖8所示。在折 疊過程中，10a並未彼此分離，因為塊狀片段1〇a在縫隙u 之底部1 la彼此連接。因此，僅藉由簡單的折疊操作，便 可能將塊狀片段10a整齊堆疊，其中塊狀片段1〇a沿縱向方 向及橫向方向對齊且塊狀片段1 〇a之間並不彼此交又。因 此’可能省去量測片10尺寸以將片1〇切割成具有相同尺寸 之片段或使分離塊狀片段10a對齊的勞動。 雖然圖8中展示藉由將4個自片切割的塊狀片段i〇a在該 等阻塊10a之中心處折疊來將2個塊狀片段1〇3堆疊於另2個 塊狀片段10a上的狀態，但本發明並不限於此，且可能根 據待清潔之模具及腔的尺寸，切割並折疊適當數目之塊狀 片段10 a以將該等塊狀片段1 〇 a堆疊成適當尺寸（舉例而 121307.doc -20- 200806785 吕，將3個塊狀片段10a堆疊於另3個塊狀片段i〇a上以使用 6個塊狀片段l〇a)。 欲使用本發明之模具清潔組成物的模具之一實例為（例 如）用於模製半導體器件的模具，藉由使用熱固性樹脂組 成物以該模具進行重複模製。 在用於模製半導體器件的模具（其為使用本發明之模具 清潔組成物之模具的實例)中，欲用作成形樹脂材料的熱 固性樹脂組成物的實例包括含有作為主要成份之環氧樹脂 的氧樹脂組成物。 在熱固性樹脂組成物中，固化劑通常與用作±要成份之 氧樹脂一起使用。 由於用本發明之模具清潔組成物清潔的模衫含污染物 且恢復至初始狀態的模具表面，因此通常在使用用作模且 材料的熱固性樹脂組成物來模製半導體包裝之前於模且表 面上塗覆脫模劑。舉例而言，在模製含有作為脫模劑i褐 煤酸电的核具材料時，較佳塗覆褐煤酸蟻。對於在模且表 面上塗覆褐煤酸蠛的方法，較佳使用含有褐煤酸犧且形成 為片狀的未硫化橡軸成物，諸如可藉由將前述未硫化橡 膠與脫模劑混合獲得之片。以盥 ^ ^ ^ ，、便用片狀模具清潔組成物 耒^1法中所用方式相同的方式，冑由含有褐煤酸蟻的 未硫化橡膠組成物形成之片置放於模具中且加熱，由此^ 其中所含有的褐煤酸蟻塗覆於模具表面上。認為未硫化橡 膠組成物中之褐煤酸蟻藉由熱硫化而熔融幻 面上，從而在該表面上形成均勾的脫模劑膜。i表 121307.doc -21- 200806785 未硫化橡膠組成物中，相對於100重量份的橡膠材料， 褐煤酸織的含量可較佳設為15重量份至35重量份、更佳⑼ 重量份至30重量份之比率。當褐煤酸蠟之含量小於ΐ5重量 份時，未展示出足夠的脫模效果。當其含量超過35重量= 時，過量褐煤酸蠟塗覆於模具表面上從而影響藉由使用= 潔及重複利用之後的模具獲得的模製物品外觀。 β 以下描述實例及比較實例。 實例1至6及比較實例丨至5 將表1至2中所示的組份按比例混合，且藉由使用捏合機 捏合各混合物且使用壓力輥進行輥軋以得到厚度為5瓜瓜的 片’藉此獲得所要片狀模具清潔組成物。 如下所述量測每一片狀模具清潔組成物的重量平均分子 畺（Mw)。將片狀模具清潔組成物浸泡於氣仿中以靜置3 天。接著，將氣仿可溶部分於熱板上於5(rc下加熱以使其 乾燥及凝固，且藉由使用〇」重量％四氫呋喃（THF)溶液調 整所得經乾燥及凝固的物質以使其靜置丨天。接著，藉由 使用0·45 μιη膜過濾器將溶液過濾，且藉由使用Gpc分析儀 (HLC-8120GPC ’ 由 Tosoh Corporation 製造）在以下量測條 件下量測濾出液的重量平均分子量（Mw)。 量測條件： 管柱·· GMHXL+GMHXL+G3000HXL，由 Tosoh Corporation 製造 管柱尺寸··各自具有7 8 mmx30 cm之直徑，總尺寸：90 cm 121307.doc 22- 200806785 管柱溫度：40°C 溶離溶液：THF 流動速率：〇.8ml/min 入口壓力·· 2.3 MPa 注入量·· 100 μΐ 偵測器··示差折射器（RI) 標準樣本：聚苯乙烯（PS) 數據處理裝置· GPC-8020’由Tosoh Corporation製造The sheet 10 having the slits 11 can be manufactured as follows. The rolled sheet obtained as described above is cut into a predetermined shape and size to obtain a sheet 10, and a slit n is formed on the upper surface of each sheet 10. The formation of the slit ridge is performed, for example, as shown in FIG. 2, by using a ribbon slitter in which the cutting blade 13 is attached to the rotary shaft 12, and the cutting blade 13 is moved, The cutting blade 13 is inserted into the upper surface of the sheet 1 from the upper surface of the sheet 1 in the lateral direction of the sheet 1〇 to form a slit U parallel to each other. By repeating the above operation, the slits 11 which are disposed at a constant pitch and which are disposed in parallel with each other are formed on the entire upper surface of the sheet 10. The slice 1 is divided into the block segments 1 〇 a of the same size via the slit 11. Since the slits 11 are formed at a constant pitch, the slit 丨 tool has a scale function when the sheet is folded, so that the sheet 10 may be cut or folded depending on the size of the mold or cavity to be cleaned. 121307.doc -18 - 200806785 f outside: as shown in Fig. 3, the distance D between the end of each slit 11 and the surface of the sheet facing the end of the slit u can preferably be set to about 〇 8 face 'better is about G·2 job to mm. When the distance is less than (M mm, the block segments 10a tend to be easily separated, and when the distance exceeds ❹8, the folding is less smooth. "The fines are formed by using the mold cleaning composition of the present invention which is formed into a sheet shape. The method of cleaning the mold is performed on a mold to be used for molding a semiconductor device. For example, a sheet in an unvulcanized state is placed in a mold, and then 1 is thermally vulcanized to integrally adhere the contaminants to the sheet. The mold cleaning is then carried out by removing the vulcanized sheet from the mold. The mold cleaning method using the sheet mold cleaning composition will be described in detail below according to the sequence of events. The preparation of the sheet mold cleaning composition of the present invention is started. As shown in FIG. 4, the sheet-shaped mold cleaning composition 1 is placed between the upper mold 1 in which the recess 3a is formed and the lower mold 2 in which the recess 3b is formed, and as shown in FIG. The mold 1 is clamped with the lower mold 2 to sandwich the sheet-shaped mold cleaning composition (7) for pressure molding. The sheet 10 is filled in a recess 3a formed in the upper mold 1 and a recess formed in the lower mold 2 Forming In 3, and the pressure for molding is brought into pressure contact with the surface of the mold. In this state, the heat for molding heat-vulcanizes the unvulcanized rubber into a vulcanized rubber, thereby causing an oxidative degradation release agent formed in the cavity 3. The layer and the like are combined with the vulcanized rubber. In some cases, the burrs around the cavity 3 are also combined with the vulcanized rubber. Next, as shown in Fig. 6, after a predetermined period of time, the upper mold and the lower mold 2 are opened. The upper mold 1 and the lower mold 2 peel off the sheet 121307.doc -19-200806785-shaped mold cleaning composition 10 which has become a vulcanized rubber, whereby the oxidative degradation layer bonded to the surface of the lower mold 2 and the lower mold 2 is peeled off from the upper mold i and the lower mold 2 A similar layer is thereby performed for mold cleaning. For the sheet-like cleaning composition, it is possible to use a plurality of linear slits 11 formed at a predetermined pitch and parallel to each other on the surface of the sheet as shown in FIG. 1 so that the sheet 10 can be The folded sheet mold cleaning composition. In the case of using the sheet-like cleaning composition, as shown in Fig. 7, the desired number of block segments 1 Ga are cut from the sheet along the slit 11. The sheet can be picked up by fingers 10 and repeating the folding along the slit u or by using a knife or the like to perform the cutting. Next, as shown in Fig. 8, the sheet 10 is folded along the slit 11, and the upper surface of the eighth sheet 10 is formed with a slit 丨J The surface) faces outward (here, four block segments i〇a are cut in Fig. 8), and the sheets 1〇 are continuously folded until their lower surfaces are in contact with each other to stack the block segments 10a, as shown in Fig. 8. As shown in the figure, 10a is not separated from each other because the block segments 1〇a are connected to each other at the bottom 1 la of the slit u. Therefore, it is possible to stack the block segments 10a neatly by simple folding operation. , wherein the block segments 1〇a are aligned in the longitudinal direction and the lateral direction and the block segments 1 〇a do not intersect each other. Therefore, it is possible to omit the size of the measurement sheet 10 to cut the sheet 1〇 into the same size. A fragment or a labor that aligns the separated block segments 10a. Although FIG. 8 shows that two block segments 1〇3 are stacked on the other two block segments 10a by folding four block segments i〇a cut from the chip at the center of the blocks 10a. State, but the present invention is not limited thereto, and it is possible to cut and fold an appropriate number of block segments 10 a according to the size of the mold and cavity to be cleaned to stack the block segments 1 〇 a into appropriate sizes (for example And 121307.doc -20-200806785 L, stacking 3 block segments 10a on the other 3 block segments i〇a to use 6 block segments l〇a). An example of a mold for cleaning a composition using the mold of the present invention is, for example, a mold for molding a semiconductor device, which is repeatedly molded by using a mold using a thermosetting resin composition. In the mold for molding a semiconductor device which is an example of a mold for cleaning a composition using the mold of the present invention, examples of the thermosetting resin composition to be used as a molding resin material include an epoxy resin containing a main component. Oxygen resin composition. In the thermosetting resin composition, a curing agent is usually used together with an oxygen resin used as a component. Since the mold cleaned with the mold of the present invention contains the contaminants and returns to the original mold surface, it is usually applied to the mold and the surface before molding the semiconductor package using the thermosetting resin composition used as the mold and the material. Release the release agent. For example, when molding a core material containing lignite as a release agent, it is preferred to coat a lignite ant. For the method of coating montanic acid on the surface of the mold, it is preferred to use an unvulcanized rubber-containing product containing montanic acid and formed into a sheet form, such as a sheet obtainable by mixing the aforementioned unvulcanized rubber with a releasing agent. A sheet formed of an unvulcanized rubber composition containing montanic acid ants is placed in a mold and heated by the same method as that used in the method of cleaning the composition of the sheet mold by 盥^^^. ^ The montanic acid ants contained therein are applied to the surface of the mold. It is considered that the montanic acid ant in the unvulcanized rubber composition is melted on the phantom by thermal vulcanization to form a uniform release film on the surface. i. 121307.doc -21- 200806785 In the unvulcanized rubber composition, the content of the montanic acid woven may be preferably from 15 parts by weight to 35 parts by weight, more preferably from (9) parts by weight to 30% by weight based on 100 parts by weight of the rubber material. The ratio of shares. When the content of the montanic acid wax is less than 5% by weight, a sufficient release effect is not exhibited. When the content exceeds 35 wt = , excess montanic acid wax is applied to the surface of the mold to affect the appearance of the molded article obtained by using the mold after cleaning and recycling. β The following describes examples and comparative examples. Examples 1 to 6 and Comparative Examples 丨 to 5 The components shown in Tables 1 to 2 were mixed in proportion, and each mixture was kneaded by using a kneader and rolled using a pressure roll to obtain a sheet having a thickness of 5 melons. 'Thereby obtaining the desired sheet mold cleaning composition. The weight average molecular weight (Mw) of each of the sheet mold cleaning compositions was measured as described below. The sheet mold cleaning composition was immersed in the air sample to stand for 3 days. Next, the gas-soluble portion is heated on a hot plate at 5 (rc to dry and solidify, and the dried and solidified material is adjusted by using a hydrazine wt% tetrahydrofuran (THF) solution to make it stand still. The solution was filtered, and the solution was filtered by using a 0·45 μm membrane filter, and the weight of the filtrate was measured by the following measurement conditions by using a Gpc analyzer (HLC-8120GPC ' manufactured by Tosoh Corporation). Average molecular weight (Mw) Measurement conditions: Columns · · GMHXL + GMHXL + G3000HXL, manufactured by Tosoh Corporation Column size · Each with a diameter of 7 8 mm x 30 cm, total size: 90 cm 121307.doc 22- 200806785 Column temperature: 40 ° C Dissolved solution: THF Flow rate: 〇.8 ml/min Inlet pressure · 2.3 MPa Injection volume · · 100 μΐ Detector··Differential refractor (RI) Standard sample: Polystyrene (PS) Data Processing Unit · GPC-8020' manufactured by Tosoh Corporation
如下所述評價實例、比較實例及習知實例之每一由此獲 得之片狀模具清潔組成物的填充性能。藉由使用用於填充 性能評價的模具[模具尺寸·· 24 mmx91 mm :模具腔尺 寸：4 mmx5 mmx2.0 mm(上腔與下腔的總深度乃，評價16 個腔中填充性能最差的腔的填充率。結果展示於表丨與表2 中〇 填充率係藉由計算模具腔之底表面積及所得模製物品之 腔部分之底表面積，且接著計算該等底表面積之比率來摘 測。如圖4中所示，在上模具i與下模具2形成的模具中，8 個腔3成彼此平行的兩列對齊。如上所述彼此平行設置的 腔3之間的間距為1() mm，且每—列中8個對齊的腔3係以】 画之間隔設置。用作樣本之片狀模具清潔組成物_尺 寸設為1〇麵寬度，91随長度，及5醜厚度，且將樣本 设置於权具中腔3之列之間以進行評價，接著關閉模且用 於熱成形。對於成形條件，成形係在175。(：下進彳_5八 且夾緊的模具之間的間隙為〇 5 mm。 丁刀、里， 121307.doc -23- 200806785 表1 (份數） 實例 1 2 3 4 5 6 EPDM*1 100 30 50 30 30 30 BR*2 - 70 50 70 70 70 白碳 40 40 40 40 40 40 褐煤酸蠟 12 12 12 12 12 12 咪唑*3 10 10 5 - 讎 咪唑琳*4 - - 5 - - 二醇醚*5 - - - - 10 - 胺基醇*6 - - - - - 5 有機過氧化物*7 2 2 2 2 2 2 水 5 5 5 5 5 5 模具清潔組成物 之重量平均分子 量(Mw) 220,000 430,000 370,000 430,000 430,000 430,000 腔填充率(％) 100% 100% 100% 100% 100% 100% *1 :乙烯（a)、丙烯（b)及亞乙基降冰片烯（c)之共聚莫耳 比為67/31/2 ;重量平均分子量（Mw)為220,000。 *2 : 1，4-聚丁 二烯；摩尼黏度ML1+4(100°C )為 45 Μ ;重 量平均分子量（Mw)為490,000。 *3 : 2,4-二胺基·6[2’_甲基咪唑啉基-(1)’]乙基-s-三畊。 *4 : 2-甲基-4-乙基咪唑啉。 *5 :乙二醇單甲醚。 *6 : 2-胺基-2-曱基丙醇。 *7:正丁基-4,4-雙（第三丁基過氧基）戊酸酯。 121307.doc 24- 200806785 表2 (份數） 比較實例 1 2 3 4 5 EPDM*1 100 - 100 100 100 BR*2 - 100 - - - 白碳 40 40 40 40 40 褐煤酸蠟 12 12 12 12 12 咪唑*3 10 10 - - - 口米。圭琳*4 - 5 - - 二醇醚*5 _ - - 10 讎 胺基醇*6 - - - - 5 有機過氧化物*7 2 2 2 2 2 水 5 5 5 5 5 模具清潔組成物 之重量平均分子 量(Mw) 180,000 柳，000 180,000 180,000 180,000 腔填充率(％) 80% 90% 75% 70% 75% *1 :乙烯（a)、丙烯（b)及亞乙基降冰片烯（c)的共聚莫耳 比為64/34/2 ;重量平均分子量（Mw)為180,000。 *2 : 1，4-聚丁 二烯；摩尼黏度 ML1+4(100°C )為 45 Μ ;重 量平均分子量（Mw)為490,000。 *3 ·· 2,4-二胺基-6[2匕甲基咪唑啉基-(1)]乙基-s-三畊。 *4 : 2-甲基-4_乙基咪唑啉。 * 5 :乙二醇單甲醚。 *6 : 2-胺基-2-甲基丙醇。 *7 :正丁基-4,4-雙（第三丁基過氧基）戊酸酯。 自上述結果，各自重量平均分子量（Mw)在特定範圍内 的片狀清潔組成物實例樣本展示出100%之填充率，此為 非常優良的填充性能。相反地，各自重量平均分子量（Mw) 不在特定範圍内的片狀清潔組成物比較實例樣本之填充率 121307.doc -25- 200806785 低於實例樣本之填充率， 、兄半且因填充性能差，比較實例難以 實際使用。 以下將描述使用具有缝隙之片狀模具清潔組成物 例。 實例7The filling properties of each of the thus obtained sheet-like mold cleaning compositions were evaluated as described below, in the comparative examples and the conventional examples. By using a mold for filling performance evaluation [mold size · · 24 mm x 91 mm : mold cavity size: 4 mm x 5 mm x 2.0 mm (total depth of upper and lower chambers, evaluation of the worst filling performance in 16 chambers) The filling rate of the cavity. The results are shown in Table 丨 and Table 2. The filling rate is calculated by calculating the bottom surface area of the mold cavity and the bottom surface area of the cavity portion of the obtained molded article, and then calculating the ratio of the bottom surface areas. As shown in Fig. 4, in the mold formed by the upper mold i and the lower mold 2, the eight chambers 3 are aligned in two columns parallel to each other. The spacing between the cavities 3 disposed parallel to each other as described above is 1 (). Mm, and 8 aligned cavities 3 in each column are arranged at intervals of the drawing. The sheet-like mold cleaning composition used as a sample _ size is set to 1 宽度 width, 91 with length, and 5 ugly thickness, and The sample was placed between the columns of the holders in the holder 3 for evaluation, then the mold was closed and used for thermoforming. For the forming conditions, the forming system was at 175. (: 下5_8 and clamped between the molds The clearance is 〇5 mm. Dingdao, Li, 121307.doc -23- 200806785 Table 1 (number of copies) Example 1 2 3 4 5 6 EPDM*1 100 30 50 30 30 30 BR*2 - 70 50 70 70 70 White carbon 40 40 40 40 40 40 Brown coal wax 12 12 12 12 12 12 Imidazole *3 10 10 5 - 雠Imidazoline*4 - - 5 - - glycol ether *5 - - - - 10 - amino alcohol *6 - - - - - 5 organic peroxide *7 2 2 2 2 2 2 water 5 5 5 5 5 5 Weight average molecular weight (Mw) of mold cleaning composition 220,000 430,000 370,000 430,000 430,000 430,000 Cavity filling ratio (%) 100% 100% 100% 100% 100% 100% *1 : Ethylene (a), propylene (b) and The norbornene (c) has a copolymerization molar ratio of 67/3 1/2; a weight average molecular weight (Mw) of 220,000. *2 : 1,4-polybutadiene; Mani viscosity ML1+4 (100 ° C ) is 45 Μ; weight average molecular weight (Mw) is 490,000. *3 : 2,4-diamino group 6 [2'-methylimidazolinyl-(1)'] ethyl-s-three tillage. 4: 2-methyl-4-ethylimidazoline. *5: ethylene glycol monomethyl ether. *6: 2-amino-2-mercaptopropanol. *7: n-butyl-4,4- Bis(t-butylperoxy)valerate 121307.doc 24-200806785 Table 2 (parts) Comparative Example 1 2 3 4 5 EPDM*1 100 - 100 100 100 BR*2 - 100 - - - Carbon 4040404040 montanic acid wax 1212121212 imidazol * 3 10 10 - - - m port.圭琳*4 - 5 - - glycol ether *5 _ - - 10 雠-amino alcohol *6 - - - - 5 organic peroxide *7 2 2 2 2 2 water 5 5 5 5 5 mold cleaning composition Weight average molecular weight (Mw) 180,000 Willow, 000 180,000 180,000 180,000 Cavity filling rate (%) 80% 90% 75% 70% 75% *1: Ethylene (a), propylene (b) and ethylidene norbornene (c The copolymerized molar ratio was 64/34/2; the weight average molecular weight (Mw) was 180,000. *2 : 1,4-polybutadiene; Mooney viscosity ML1+4 (100 ° C) is 45 Μ; weight average molecular weight (Mw) is 490,000. *3 ·· 2,4-Diamino-6[2匕methylimidazolinyl-(1)]ethyl-s-three tillage. *4 : 2-methyl-4_ethylimidazoline. * 5 : Ethylene glycol monomethyl ether. *6 : 2-Amino-2-methylpropanol. *7: n-Butyl-4,4-bis(t-butylperoxy)valerate. From the above results, the sample of the sheet-like cleaning composition having a weight average molecular weight (Mw) within a specific range exhibited a filling ratio of 100%, which is a very excellent filling property. Conversely, the filling ratio of the sample of the sheet-like cleaning composition in which the weight average molecular weight (Mw) is not within the specific range is 121307.doc -25-200806785, which is lower than the filling rate of the example sample, and the half-length and poor filling performance. Comparative examples are difficult to use in practice. An example of cleaning a composition using a sheet mold having a slit will be described below. Example 7
如圖1中所示，將上述實例1至6中所獲得的每一片狀模 具清潔組成物（厚度（圖丨中為τ)為5叫切割成各自寬度（圖 1中為A)為230随、長度（圖1中為B)為300 _的片10。在 片10的整個上表面上在片1〇的寬度方向上以15 _之間隔 (圖1中為C)形成各自深度為4 5酿的彼此平行的縫隙11。 亦即每一縫隙11之末端與朝向該末端之片10的片表面之 間的距離（圖3中為D)為0.5 mme在該片1〇中，形成2〇個塊 :大片奴10a。根據模具尺寸不同的若干種類型之轉注成形 裝置切割每一具有縫隙11的片狀模具清潔組成物1〇且在縫 隙11之部分處將其折疊以呈堆疊之方式置放於模具中。之 後i關閉模具進行熱成形以量測填充率。結果，<貞測到如 同則述片狀模具清潔組成物’填充率較高且填充性能非常 優良。 本發明之模具清潔組成物適用於清潔及重複利用諸如用 於熱固性樹脂成形材料之模具’例如用於清潔及重複利用 用於轉注成形之模具，料模具制於藉由使料氧樹脂 成形材料進行轉注成形來模製半導體元件。 羽雖然本發明已詳細且根據其特定實施例加以描述，但熟 白此項技術者應想到在不择離本發明之精神及範圍下可對. 121307.doc -26- 200806785 其作各種改變及修改。 本申請案係基於2006年5月25曰申請之曰本專利申請案 第2006-145 544號，該申請案之全部内容以引用之方式併 入本文中。 【圖式簡單說明】 圖1為展示根據本發明之一實施例的片狀模具清潔組成 物的透視圖。 圖2為在片狀模具清潔組成物上形成縫隙之狀態的說 明。 圖3為展示該等缝隙之一部分的放大側視圖。 圖4為展示使用该片狀模具清潔組成物之狀態的透視 之狀態的透視 圖5為展示使用該片狀模具清潔組成物 組成物之狀態的透視 圖6為展示使用該片狀模具清潔 果的說明。 圖7為該片狀模具清潔組成物 用於模製半導體器件之效 果的說明。 圖8為該片狀模具清潔組成物 用於模製半導體器件之效 【主要元件符號說明】 上模具 下模具 腔 121307.doc •27· 200806785As shown in Fig. 1, each of the sheet-like mold cleaning compositions obtained in the above Examples 1 to 6 (thickness (τ in the figure) was cut into respective widths (A in Fig. 1) of 230). The length 10 (B in Fig. 1) is 300 _. The film 10 is formed on the entire upper surface of the sheet 10 at intervals of 15 _ in the width direction of the sheet 1 (C in Fig. 1). 5 stuffed slits 11 which are parallel to each other. That is, the distance between the end of each slit 11 and the sheet surface of the sheet 10 facing the end (D in Fig. 3) is 0.5 mme in the sheet 1 , forming 2 One block: a large piece of slave 10a. Each of the types of transfer forming devices different in the size of the die cuts each of the sheet-like mold cleaning compositions 1 having the slits 11 and folds them at the portions of the slits 11 in a stacked manner. After placing in the mold, i closes the mold for thermoforming to measure the filling rate. As a result, <measures that the sheet-like mold cleaning composition has a higher filling rate and excellent filling performance. The cleaning composition is suitable for cleaning and recycling molds such as those used for thermosetting resin molding materials. 'For example, for cleaning and reusing a mold for transfer forming, the mold is made by molding a semiconductor element by transferring an oxygen-forming resin forming material. Feather, although the invention has been described in detail and in accordance with a specific embodiment thereof However, those skilled in the art should be able to make various changes and modifications without departing from the spirit and scope of the present invention. This application is based on May 25, 2006. The present application is hereby incorporated by reference in its entirety in its entirety herein in its entirety in the the the the the the the the the the Fig. 2 is an explanatory view showing a state in which a slit is formed in the sheet-like mold cleaning composition. Fig. 3 is an enlarged side view showing a part of the slits. Fig. 4 is a view showing the cleaning of the composition using the sheet mold. A perspective view 5 of a state of perspective of the state is a perspective view showing a state in which the composition of the composition is cleaned using the sheet-shaped mold. FIG. 6 is an illustration showing the cleaning of the fruit using the sheet-shaped mold. 7 is an illustration of the effect of the sheet mold cleaning composition for molding a semiconductor device. Fig. 8 is a view showing the effect of the sheet mold cleaning composition for molding a semiconductor device. [Main component symbol description] Upper mold lower mold cavity 121307 .doc •27· 200806785
3a 3b 10 10a 11 12 13 A B C D T 凹陷 凹陷 片 塊狀片段 缝隙 旋轉軸 切割刀片 寬度 長度 間距 距離 厚度 121307.doc -283a 3b 10 10a 11 12 13 A B C D T Sag Depression Piece Block Fragment Rotary Axis Cutting Blade Width Length Spacing Distance Thickness 121307.doc -28