201107462 六、發明說明： 【發明所屬之技術領域】 本發明係關於欲用於模具之清潔、整新及諸如此類的模 具清潔組合物及模具清潔材料，該等模具已因諸如注射模 製或轉移模製等重複性模製作業受到污染，例如，用於執 , 目性樹脂組合物之模製作業的半導體器件模製闕具及諸 如此類，且係關於使用其之模具清潔方法。 【先前技術】 一般而言，當重複諸如注射模製或轉移模製等模製作業 時’模具因在加熱模製材料時生成的揮發性組份之沈積、 至模製物件表面上之滲出物質、欲在模製時使用的脫模劑 及諸如此類、及另外該等沈積物因氧化降解而受到污染。 當模具因此受到污染時，會對模製物件之最終尺寸、外 觀、脫模性質及諸如此類產生有害影響且因此不期望受到 污染。 、因此’為了防止此-污染模具引發的有害影響，對欲在 ’射模製或轉移模製中使用的模具實施週期性清潔作業且 應自模具表面去除上述污染物。作為模具之習用清潔方 J如已知種使用強驗溶液或溶劑以使模具與模製 裝置分離之清潔方法。 」而’使用強鹼溶液或溶劑自模製裝置分離模具之清潔 套而要冷部/升溫、分離及模具清潔之步驟且具有需要 時門’月冰之問題亦及需要大量勞力及另外對人類及環境 構成巨大負擔之問題，例如藉由使用強驗溶液及溶劑及清 149716.doc 201107462 潔後的廢液處理而對工作人員造成有害影響。 出於該等原因，人們已提出且部分地實踐藉由以下方式 來清潔模具表面之方法：使用熱固性三聚氰胺樹脂模製材 料、未硫化橡膠化合物或諸如此類，藉由在使用其之模具 中杈製物件來使模具表面上形成的污染物與模製物件結 5及自模具移除模製物件（例如，參見專利文件1)。 專利文件 1 : JP-A-10-226799 【發明内容】 舉例而言，在熱固性樹脂組合物之模製作業中使用的半 導體器件模製用模具可藉由上述方法來清潔，但上述熱固 性樹脂組合物端視所需特性而具有不同的組份組成且形式 多樣。此外，藉由重複性模製作業及污染物組份本身所生 成的模具污染狀態亦各式各樣。其中，當使用不含以錯及 南素為代表的環境負擔才勿質的無鹵素環境友好型樹脂模事 ㈣重複模製時，在模具上形成的污染物尤其嚴重地烤乾 於杈具表面上且因此藉由習用清潔方法使用上述熱固性樹 脂組合物或未硫化橡膠化合物不可能完全去除該等污染 物。因此，人們需要能夠清潔此等污染物之清潔材料。 本發明係基於對此等情形之考慮而設計，且其一目的係 提供對重複性模製作業所污染之模具展示優良清潔效果之 模具清潔組合物及模具清潔材料亦及使用其之模具清潔方 法。 為了達成上述目#，本發明之第一態樣在於用於熱模製 之模具清潔組合物’其中使用模製材料重複地實施模製， 1497l6.doc 201107462 ， Λ、’且°物包括：用作基材之合成橡膠及合成樹脂中之至少 者’驗金屬鹽及驗金屬氫氧化物中之至少—者；及水及 有機溶劑中之至少一者。 、此外’本發明之第二態樣在於使用模具清潔組合物形成 為片樣形狀之模具清潔材料。 此外’本發明之第三態樣在於模具清潔方法，該方法包 括將包括模具清潔組合物之模具清潔材料置於敞開的模 具之模具平面上之步驟；藉由夾緊模具以將模具清潔材料 夾於中間並隨後加熱及加壓來使模具表面上形成的污染物 〃模〃 π /糸材料結合之步驟；及藉由自模具剝離與污染物 結合的模具清潔材料來清潔模具表面之步驟。 亦即，本發明者已對如何獲得能夠有效清潔及甚至去除 在使用上述無_素環境友好型樹脂模製材料重複模製時在 模具上形成的污染物之清潔組合物進行了深入研究。因 此’本發明者已發;見，當含有用作基材之合成橡膠及合成 樹脂中之至少一者、鹼金屬鹽及鹼金屬氫氧化物中之至少 一者及水及有機溶劑中之至少一者時，水或有機溶劑之作 用可引發污染物之溶解及分解作用並且鹼金屬鹽及鹼金屬 氫氧化物中之至少一者之同時存在亦可起到促進污染物之 溶解及分解作用之作用，從而使得相對於習用方法藉助該 等物質之協同作用可展示更優良的清潔效果。因此，其已 達成本發明。 如上文所述，本發明模具清潔組合物含有用作基材之合 成橡膠及合成樹脂中之至少一者、鹼金屬鹽及鹼金屬氫氧201107462 VI. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to mold cleaning compositions and mold cleaning materials to be used for cleaning, refreshing, and the like of molds, such as injection molding or transfer molds. Repetitive molding operations such as making are contaminated, for example, semiconductor device molding cookers for molding operations of the resin composition, and the like, and are related to a mold cleaning method using the same. [Prior Art] In general, when a molding operation such as injection molding or transfer molding is repeated, 'the mold is deposited due to the volatile component generated when the molding material is heated, and the exudate on the surface of the molded article. The release agent to be used in molding, and the like, and the other deposits are contaminated by oxidative degradation. When the mold is thus contaminated, it can have a detrimental effect on the final size, appearance, release properties and the like of the molded article and is therefore not expected to be contaminated. Therefore, in order to prevent the harmful effects caused by this-contaminated mold, a periodic cleaning operation is performed on the mold to be used in the injection molding or transfer molding, and the above contaminants should be removed from the mold surface. As a conventional cleaning method for a mold, a cleaning method using a strong solution or solvent to separate a mold from a molding device is known. And 'using a strong alkali solution or solvent to separate the cleaning sleeve of the mold from the molding device, and the steps of cold/warming, separation and mold cleaning have the problem of requiring the door's ice and the need for a lot of labor and other humans. And the environment poses a huge burden, for example, by using a strong solution and solvent and the waste treatment after cleaning. For such reasons, methods have been proposed and partially practiced to clean the surface of the mold by using a thermosetting melamine resin molding material, an unvulcanized rubber compound or the like by tanning the object in a mold using the same. The contaminants formed on the surface of the mold are attached to the molded article knot 5 and the molded article is removed from the mold (for example, see Patent Document 1). Patent Document 1: JP-A-10-226799 SUMMARY OF THE INVENTION For example, a mold for molding a semiconductor device used in a molding operation of a thermosetting resin composition can be cleaned by the above method, but the above thermosetting resin combination The object has different component compositions and various forms depending on the desired characteristics. In addition, mold contamination conditions resulting from repetitive molding operations and the contaminant component itself are varied. Among them, when using a halogen-free environment-friendly resin mold which does not contain the environmental burden represented by the fault and the south, (4) repeated molding, the contaminants formed on the mold are particularly heavily baked on the surface of the cookware. It is therefore impossible to completely remove such contaminants by using the above-described thermosetting resin composition or unvulcanized rubber compound by a conventional cleaning method. Therefore, there is a need for cleaning materials that are capable of cleaning such contaminants. The present invention is designed based on considerations of such circumstances, and an object thereof is to provide a mold cleaning composition and a mold cleaning material which exhibit excellent cleaning effects on a mold contaminated by a repetitive molding operation, and a mold cleaning method using the same. . In order to achieve the above-mentioned object #, the first aspect of the present invention resides in a mold cleaning composition for hot molding, in which molding is repeatedly performed using a molding material, 1497l6.doc 201107462, Λ, '°° includes: At least one of a synthetic rubber and a synthetic resin as at least one of a metal salt and a metal hydroxide; and at least one of water and an organic solvent. Further, the second aspect of the present invention resides in a mold cleaning material formed into a sheet shape using a mold cleaning composition. Further, the third aspect of the present invention resides in a mold cleaning method comprising the steps of placing a mold cleaning material including a mold cleaning composition on a mold plane of an open mold; clamping the mold cleaning material by clamping the mold a step of bonding the contaminant 〃π /糸 material formed on the surface of the mold in the middle and then heating and pressurizing; and cleaning the surface of the mold by peeling off the mold cleaning material combined with the contaminant from the mold. That is, the inventors have conducted intensive studies on how to obtain a cleaning composition capable of effectively cleaning and even removing contaminants formed on a mold during repeated molding using the above-described non-form environmentally-friendly resin molding material. Therefore, the present inventors have issued; see, at least one of the synthetic rubber and the synthetic resin used as the substrate, at least one of the alkali metal salt and the alkali metal hydroxide, and at least one of water and an organic solvent. In one case, the action of water or an organic solvent may cause dissolution and decomposition of the contaminant and the simultaneous presence of at least one of the alkali metal salt and the alkali metal hydroxide may also promote the dissolution and decomposition of the contaminant. The effect is such that a superior cleaning effect can be exhibited by the synergistic action of the substances with respect to the conventional method. Therefore, it has been achieved by the present invention. As described above, the mold cleaning composition of the present invention contains at least one of a synthetic rubber and a synthetic resin used as a substrate, an alkali metal salt and an alkali metal hydroxide.
S 149716.doc ^ 201107462 ， 化物中之至少一者及水及有機溶劑中之至少一者作為基本 組份。因此，甚至針對重複性模製作業所形成之污染物、 尤其在重複模製作業時在模具表面上形成的利用任一習用 清潔組合物皆難以充分清潔的污染物（該模製作業使用在 熱固性樹脂組合物中不含以錯、鹵素及錄為代表的環境負 擔物質的無齒素環境友好型樹脂模製材料），水或有機溶 劑之作用可引發污染物之溶解及分解作用並且藉由鹼金屬 鹽及鹼金屬氫氧化物中之至少一者之同時存在，藉助促進 π染物之溶解及分解作用之效果之協同作用亦可展示優良 的清潔/去除效果。因此，使模具表面上形成的污染物黏 附至模具清潔組合物並與其結合且因此可藉由使用本發明 模具清潔組合物來清潔模具表面而自模具有效去除污染 物。舉例而言，使半導體元件囊封用模具（其中已使用環 氧樹脂組合物實施重複性模製）表面上之污染物與包括模 具清潔組合物之模製物件結合並自模具有效去除該等污染 物，藉此對模具實施有效清潔。因此，獲得使用利用本發 明杈具清潔組合物清潔的模具所形成的半導體器件，其為 在外觀上亦無任何問題之優良產品。此外，在將包括本發 明模具清潔組合物之模具清潔材料置於敞開的模具之模具 平面上之後’藉由夾緊模具以將模具清潔材料夾於中間並 加熱及加壓來使模具表面上形成的污染物與模具清潔材料 結合且隨後藉由自模具剝離與污染物結合的模具清潔材 料’藉此可清潔模具表面。 具體而言’當合成橡膠係乙烯-丙烯橡膠及丁二烯橡膠 I49716.doc 201107462 中之至少一者時，模具清潔處理將變得很容易並因此改良 清潔作業能力。 此外，當相對於100份數用作基材之合成橡膠及合成樹 脂中之至少一者，將鹼金屬鹽及鹼金屬氫氧化物中之至少 一者之含量設定為特定比率時，可獲得更優良的清潔作 用。 此外’當含有水以及有機溶劑且相對於1 〇〇份數用作基 材之合成橡膠及合成樹脂中之至少一者，將水之含量設定 為特定比率時，可獲得更優良的清潔作用。 【實施方式】 下文將詳細地闡述本發明實施例。 使用用作基材之合成橡膠及合成樹脂中之至少一者、鹼 金屬鹽及驗金屬氫氧化物中之至少—者及水及有機溶劑中 之至少一者作為基本組份來獲得本發明模具清潔組合物。 合成橡膠係所謂的未硫化橡膠且其實例包括乙烯_α烯 烴橡膠（例如天然橡膠（NR)、丁二烯橡膠（BR)、腈橡膠 (NBR)及乙烯-丙烯橡膠（EpR))、苯乙烯丁二烯橡膠 (SBR)、聚異戊二烯橡膠（IR)、丁基橡膠（iir)、聚矽氧橡 膠（Q)及I化橡膠（FKM)。其可單獨使用或其兩者或更多者 可組合使用。在本發明中，乙烯·α_烯烴橡膠包括乙烯 烯烴-多烯烴橡膠，例如乙烯_丙烯-多烯烴橡膠（EpDM)。 使該等未硫化橡膠在模具中硫化以形成硫化橡膠。 在上述合成橡膠中，考慮到使用模具模製時之弱污染性 質及硫化時之淡氣味’較佳單獨或以混合物形式使用 149716.doc 201107462 EPR(包括 EPDM)及BR。 然後，本文將詳細闡述上述EPDM。EPDM係由乙稀、α_ 烯烴（尤其丙烯）及如下文所例示之多烯烴單體構成的三元 共聚物。可能提及以下作為多稀烴單體：二環戍二稀、 1，5-環辛二稀、1,1-環辛二烯、1，6-環十二二烯、17•環十 二二烯、1，5,9-環十二三烯、1,4-環庚二烯、14環己二 烯、降冰片二烯（norb〇rnadiene)、亞甲基降冰片婦、2甲 基-1,4-戊二烯、1，5-己二烯、l，6-庚二烯、甲基四氫茚、 1，4-己二烯及諸如此類。 關於上述EPDM中相應單體之共聚比率，較佳者係三元 共聚物，其中乙烯為30至80 mol0/。，多烯烴單體為〇1至2〇 mol%且其餘部分係α_烯烴。更佳地，乙烯為3〇至⑼ mol%。 作為上述BR，i，2_聚丁二烯及M_聚丁二稀可單獨或以 組合使用之混合物形式使用。 合成樹脂之實例包括聚醯胺樹脂（例如耐綸（Nyi〇n) 6及 耐綸66)、聚酯樹脂（例如聚對苯二甲酸乙二酯及聚對苯二 :酸丁二酯）、聚碳酸酯樹脂、聚芳酯樹脂、氣乙烯樹 脂、氣化氣乙烯樹脂、&乙烯樹脂 '氣化聚乙烯樹脂、氣 化聚丙烯樹脂、聚丙烯樹脂、聚苯乙烯樹脂、丙烯腈_苯 乙烯樹脂、二氣亞乙烯樹脂、乙酸乙稀酿樹脂、聚丙；酸 酯樹脂、聚醯亞胺樹脂、丁二烯樹脂 '聚縮醛樹脂、離聚 物樹脂、乙稀-氯乙烯共聚物樹脂、乙烯_乙酸乙稀㈣ 物樹脂、乙稀乙酸乙烯m烯接枝聚合樹脂1伸苯 149716.doc 201107462 基樹脂、聚颯樹脂、甲基丙烯酸系樹脂、丙烯酸系物-氟 碳樹脂、丙烯酸系物_聚矽氧寡聚物、聚矽氧樹脂、含環 氧聚矽氧-丙烯酸系樹脂、乙烯基脂樹脂、呋喃樹脂、酚 系樹脂、二聚氰胺樹脂、胍胺樹脂、脲樹脂、聚胺基曱酸 醋樹脂、二丙婦酸系物-鄰苯二甲酸酯樹脂（diacrylic phthalate resin)、酮類樹脂、環氧樹脂、二甲苯樹脂、馬 來酸樹脂、苯氧樹脂、苯并二氫吡喃樹脂、聚乙烯醇縮甲 其可單獨使用或其兩者或 醛樹脂及聚乙烯醇縮丁醛樹脂。 更多者可組合使h在㈣合成樹脂中，考慮到在使用模 具模製時之低污染’適宜地，使用聚乙稀樹脂、環氧樹脂 及二聚鼠胺樹脂。 在包括合成橡膠及合成樹脂中之至少一人 成橡膠或合成樹脂可單獨使用或合成橡膠及合成樹脂可: 合使用或其複數種可組合使用。其中，考慮到模具清潔處 理之簡易性，適宜地，使用合成橡膠、聚乙烯樹脂、環氧 樹脂及三聚氰胺樹脂，而言，較佳使用上述合成橡 膠。在上述合成橡膠中，較佳單獨使用職，或較佳使用 EPR與BR之混合物。 若使用EPR與BR之混合物作為基材，則EpR(x)與服⑺ 之此σ & (x/y)較佳設定為乂/广丨⑼川至⑽/川丨重量比）之範 圍内。尤佳係，70/30至3〇/7〇之範圍。亦即，在模製作 業期間去除橡膠模製物件時’當兩種材料之混合比中之 EPR小於20(ER大於8_，模製物件強度會降低，從而導 致易於發生諸如破裂等不便並因此往往難以自模具實施去 149716.doc n 201107462 除作業。 包括合成橡膠及合成樹脂中之至少一者之基材在自模具 分離以去除污染時較佳呈固化狀態。在熱塑性樹脂或諸如 此類之情形中，用於達成上述固化狀態之固化方法包括藉 由加熱固化、藉由冷卻固化及諸如此類。舉例而言，在藉 由加熱固化之情形中，使用固化劑。 上述固化劑可係能夠固化基材之固化劑，且其實例包括 用於合成橡膠及聚乙烯樹脂之有機過氧化物及諸如此類。 在環氧樹脂之情形中，可能提及酚類化合物 '胺基化合 物、咪唑、酸酐基固化劑、有機磷酸化合物及諸如此類。 上述有機過氧化物之實例包括諸如以下之有機過氧化 物.1，1-雙（第三丁基過氧基）_3,3,5•三甲基環己烷、1，1_雙 (第三丁基過氧基）環己烷、第三丁基過氧基馬來酸、過氧 油酸第三丁基酯、過氡基_3,3,5-三曱基己酸第三丁基酯、 過氧化環己酮、過氧基芳基碳酸第三丁基酯、過氧基異丙 基碳酸第三丁基醋、2,5_二甲基_2,5_二（苯甲酿基過氧基) 己烷、2,2-雙（第三丁基過氧基）辛烷、過氧基乙酸第三丁 基酉曰、2,2-雙（第二丁基過氧基）丁烷、過氧基苯甲酸第三 丁基S曰、4,4-雙(第三丁基過氧基)戊酸正丁基酯、過氧基 間苯二甲酸二-第三丁基酯、過氧化甲基乙基_、過氧化 二異丙苯、2,5-二甲基_2,5·二(第三丁基過氧基)己烷、 «，《’-雙（第三丁基過氧基·間·異丙基）笨、過氧化第三丁基 異丙苯、過氧化氫二異丙苯、二第三丁基過氧化物及J·· 二曱基-2,5-二（第三丁基過氧基）己烷_3。 149716.doc 201107462 酚類化合物之實例包括對苯二酚、間苯二酚及兒茶酚， 其係單裱雙官能酚；雙酚A、雙酚F、萘二酚及雙酚，其為 多環雙官能酚；及多官能酚，例如其_化物及經烷基取代 之化合物。 胺基化合物之實例包括N，N_苄基二甲基胺、2_(二甲基 胺基甲基）盼、2,4,6-參（二曱基胺基甲基）酴、四甲基脈、 三乙醇胺、N，N’-二甲基六氫0比嗪、二氮雜二環[2 2·2] 辛烷、1，8-二氮雜二環[54 〇]_7_十一烯、丨，5_二氮雜二環 [4.4·0]_5_壬烯、六亞曱基四胺、吡啶、甲基吡啶、六氫吡 啶、吡咯啶、二甲基環己基胺、二甲基己基胺、環己基 胺、一異丁基胺、二正丁基胺、二苯胺、Ν甲基苯胺、三 正丙基胺、三正辛基胺、三正τ基胺、三苯胺、氯化四甲 鍵、溴化四甲銨、碘化四甲銨、三乙四胺、二胺基二苯甲 燒、二胺基二苯醚、雙氰胺、鄰甲苯雙胍、脉基腺及二甲 基脲。 味唾之實例包括咪唾、2_乙基口米。坐、2_乙基m米 唑、2-甲基咪唑、2_苯基咪唑、2十一烷基咪唑 '卜苄基_ 甲基味唑、2-十七烷基咪唑、4,5_二笨基。米唑、2-甲基 咪唑啉、2-苯基咪唑啉、2_十一烷基咪唑啉、2_十七烷基 咪峻啉、2-異丙基咪啥、2,4_二甲基咪唑、2_苯基冰甲基 咪嗤、2_乙基味㈣、2_苯基_4_甲基咪唾琳、苯并咪吐： 1-氰基乙基味唾及2,4_二胺基_6_[2,·甲基咪唾基⑽乙基_ s-三嗓。 酸針基固化劑之實例包括諸如鄰苯二甲酸針、六氫鄰苯 149716.doc •11· 201107462 -甲馱酐、苯均四酸二酐及二苯曱酮四羧酸酐等酸酐。 有機磷酸化合物之實例包括六甲基磷三酿胺、磷酸三 (二氣兩基）醋、磷酸三（氣两基）醋、亞磷酸三苯基醋磷 酸二甲基酯、膦酸苯基酯、三苯基膦、三正丁基膦、二苯 基膦有機磷化合物及其函化物。 該等固化劑可單獨使用或者可以其兩者或更多者之任一 組合使用。 固化劑之混合量可進行適當設定，但在（例如）合成橡膠 之情形中，相對於100重量份數（下文簡稱為「份數」）之合 成橡膠，該量較佳設定為1至3重量份數之範圍内。 此外，固化劑不僅具有熱固化合成橡膠及合成樹脂之功 能’而且亦可發揮模具清潔劑之功能，且因此可根據需要 在本發明模具清潔組合物中進行混合以達成除固化劑以外 之目的。將固化劑在此一情形中之混合量相對於100份數 合成橡滕及合成樹脂中之至少一者設定為較佳5至60份 數、尤佳5至25份數。 關於欲混合於基材中的鹼金屬鹽及鹼金屬氫氧化物中之 至少一者，可能提及驗金屬鹽、諸如經、鈉、钟、铷及铯 等金屬之鹽。 此一鹼金屬鹽之實例包括硼酸鹽、填酸（例如磷酸、偏 磷酸、連二磷酸、亞磷酸（膦酸）、次亞磷酸（次膦酸）、焦 磷酸、三偏磷酸、四偏磷酸及焦亞磷酸）鹽、碳酸鹽、硫 酸鹽、硝酸鹽、鹽酸鹽及有機酸（例如丙烯酸、己二酸、 抗壞血酸、天冬胺酸、胺基苯甲酸、海藻酸、苯曱酸、油 149716.doc •12· 201107462 酸、甲酸、檸檬酸、乙醇酸、葡萄糖酸'麩胺酸'肉桂 酸、琥珀酸、乙酸、水楊酸、草酸、酒石酸、對曱苯磺 酸、菸酸、乳酸、尿酸、經函素取代之乙酸、鄰苯二甲 酸、苯續酸、丙二酸、丁酸及蘋果酸）鹽。 在鹼金屬鹽係多元酸鹽之情形中，可利用該酸之部分鹼 金屬鹽。舉例而言，在三元磷酸鹽之情形中，該鹽可係以 下中之任一者：具有1個金屬離子及2個氫之一級鹽、具有 2個金屬離子及1個氫之二級鹽及具有3個金屬離子之三級 鹽。此外’其可係酸性鹽、鹼性鹽及中性鹽中之任一者。 其中’自對模具的腐钱性角度來看，驗性鹽或中性鹽較 佳。此外’作為鹼金屬鹽，自水中溶解性角度來看，較佳 使用水合物。 驗金屬氫氧化物之實例包括氫氧化鈉及氫氧化鉀。 該等鹼金屬鹽及鹼金屬氫氧化物可單獨使用或其兩者或 更多者可組合使用。 相對於10 0份數用作基材之合成橡膠及合成樹脂中之至 少一者’鹼金屬鹽及鹼金屬氫氧化物中之至少一者之含旦 設定為較佳0.1至10份數之範圍内、尤佳0‘丨至5份數。亦 即’當混合量太小時’模具表面上所形成污染物之去除性 質會顯著降低’且往往難以完全去除模具污染。另— ’、 乃—方 面，當混合量太大時’鹼金屬鹽及鹼金屬氫氧化物易於沉 澱在模具表面上且因此反而使得模具易於受到污染。 接下來’可適專地使用自來水、藉由去除雜質所獲得之 R〇水（藉助逆滲透膜處理之水）、離子交換水及諸如此類作 149716.doc -13- 201107462 為欲混合於本發明中之水。 相對於100份數用作基材之合成橡膠及合成樹脂中之至 少一者，水之混合量設定為較佳3至3 0份數之範圍内、尤 佳5至20份數。亦即’當混合量太小時，模具表面上所形 成污染物之去除性質會顯著降低，且往往難以完全去除模 具污染。反之，當混合量太大時，不會改良清潔效果且混 合所需要勞力會增加並往往徒勞無益。 接下來，使用各種有機溶劑作為欲用於本發明中之有機 溶劑且舉例而言，在使用鹼金屬鹽之情形中，自溶解性角S 149716. doc ^ 201107462 , at least one of the compounds and at least one of water and an organic solvent as a basic component. Therefore, even contaminants formed for repetitive molding operations, particularly those formed on the surface of the mold during repeated molding operations, are difficult to sufficiently clean with any conventional cleaning composition (the molding operation is used in thermosetting). The resin composition contains no dentate environment-friendly resin molding material with wrong, halogen and environmentally-acceptable substances, which are represented by water, and the action of water or organic solvent can cause dissolution and decomposition of pollutants and by alkali The simultaneous presence of at least one of the metal salt and the alkali metal hydroxide can also exhibit excellent cleaning/removal effects by synergistic effects of promoting the dissolution and decomposition of the π dye. Therefore, contaminants formed on the surface of the mold are adhered to and bonded to the mold cleaning composition and thus the mold surface can be cleaned by using the mold cleaning composition of the present invention to effectively remove contaminants from the mold. For example, the contaminants on the surface of the semiconductor component encapsulating mold (where the epoxy resin composition has been subjected to repetitive molding) are combined with the molded article including the mold cleaning composition and the impurities are effectively removed from the mold. Thereby, the mold is effectively cleaned. Therefore, a semiconductor device formed using a mold cleaned with the cleaning composition of the present invention is obtained, which is an excellent product which does not have any problem in appearance. Further, after the mold cleaning material including the mold cleaning composition of the present invention is placed on the mold plane of the open mold, 'the mold surface is formed by clamping the mold to sandwich the mold cleaning material and heating and pressurizing the mold. The contaminant is combined with the mold cleaning material and then the mold cleaning material is removed by stripping the contaminant from the mold, thereby cleaning the mold surface. Specifically, when at least one of synthetic rubber-based ethylene-propylene rubber and butadiene rubber I49716.doc 201107462, the mold cleaning process becomes easy and thus the cleaning workability is improved. Further, when at least one of the alkali metal salt and the alkali metal hydroxide is set to a specific ratio with respect to at least one of the synthetic rubber and the synthetic resin used as the substrate in 100 parts by weight, more Excellent cleaning effect. Further, when at least one of synthetic rubber and synthetic resin containing water and an organic solvent and used as a base material with respect to 1 part by weight is set to a specific ratio, a more excellent cleaning action can be obtained. [Embodiment] Hereinafter, embodiments of the invention will be described in detail. The mold of the present invention is obtained by using at least one of at least one of a synthetic rubber and a synthetic resin used as a substrate, at least one of an alkali metal salt and a metal hydroxide, and at least one of water and an organic solvent as a basic component. Clean the composition. Synthetic rubber is a so-called unvulcanized rubber and examples thereof include ethylene-alpha olefin rubber (for example, natural rubber (NR), butadiene rubber (BR), nitrile rubber (NBR), and ethylene-propylene rubber (EpR)), styrene Diene rubber (SBR), polyisoprene rubber (IR), butyl rubber (iir), polyoxymethylene rubber (Q) and rubberized rubber (FKM). They may be used singly or in combination of two or more. In the present invention, the ethylene·α-olefin rubber includes an ethylene olefin-polyene rubber such as ethylene-propylene-polyene rubber (EpDM). The unvulcanized rubber is vulcanized in a mold to form a vulcanized rubber. In the above synthetic rubber, it is considered that the weakly polluting property at the time of molding using a mold and the light odor at the time of vulcanization are preferably used singly or in the form of a mixture 149716.doc 201107462 EPR (including EPDM) and BR. Then, this article will elaborate on the above EPDM. EPDM is a terpolymer composed of ethylene, an α-olefin (especially propylene) and a multiolefin monomer as exemplified below. The following may be mentioned as polybasic hydrocarbon monomers: bicyclic quinone dilute, 1,5-cyclooctadiene, 1,1-cyclooctadiene, 1,6-cyclododecene, 17•ring twelve Diene, 1,5,9-cyclododecatriene, 1,4-cycloheptadiene, 14 cyclohexadiene, norbornadiene (norb〇rnadiene), methylene norbornene, 2 methyl -1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, methyltetrahydroanthracene, 1,4-hexadiene, and the like. With respect to the copolymerization ratio of the corresponding monomers in the above EPDM, a ternary copolymer is preferable in which ethylene is 30 to 80 mol0/. The multiolefin monomer is 〇1 to 2〇 mol% and the remainder is α-olefin. More preferably, the ethylene is from 3 Å to (9) mol%. As the above BR, i, 2_polybutadiene and M_polybutadiene may be used singly or in the form of a mixture used in combination. Examples of the synthetic resin include polyamine resins (for example, nylon (Nyi〇n) 6 and nylon 66), polyester resins (for example, polyethylene terephthalate and polyparaphenylene: butylene diester), Polycarbonate resin, polyarylate resin, gas vinyl resin, gasification gas vinyl resin, & vinyl resin 'gasified polyethylene resin, gasified polypropylene resin, polypropylene resin, polystyrene resin, acrylonitrile benzene Vinyl resin, diethylene vinyl resin, ethyl acetate resin, polypropylene; acid ester resin, polyimide resin, butadiene resin 'polyacetal resin, ionomer resin, ethylene-vinyl chloride copolymer resin Ethylene-ethylene acetate (IV) resin, ethylene vinyl acetate mene graft polymer resin 1 benzene 147716.doc 201107462 base resin, polyfluorene resin, methacrylic resin, acrylic resin - fluorocarbon resin, acrylic _polyoxyl oligomer, polyoxyn epoxide, epoxy-containing polyoxy-acrylic resin, vinyl ester resin, furan resin, phenolic resin, melamine resin, guanamine resin, urea resin, Polyamine phthalic acid vinegar resin -diacrylic phthalate resin, ketone resin, epoxy resin, xylene resin, maleic acid resin, phenoxy resin, benzodihydropyran resin, polyvinyl alcohol Used alone or both or an aldehyde resin and a polyvinyl butyral resin. Further, it is possible to combine h in (4) a synthetic resin in consideration of low contamination when molding with a mold. Suitably, a polyethylene resin, an epoxy resin, and a dimeric murine amine resin are used. At least one of the synthetic rubber and the synthetic resin may be used alone or as a synthetic rubber or a synthetic resin: it may be used in combination or a plurality of them may be used in combination. Among them, in view of the ease of mold cleaning treatment, and suitably, synthetic rubber, polyethylene resin, epoxy resin, and melamine resin are used, the above synthetic rubber is preferably used. Among the above synthetic rubbers, it is preferred to use them alone, or a mixture of EPR and BR is preferably used. If a mixture of EPR and BR is used as the substrate, the σ & (x/y) of EpR(x) and (7) is preferably set within the range of 乂/广丨(9)川至(10)/川丨) . Especially good, 70/30 to 3〇/7〇. That is, when the rubber molded article is removed during the molding operation, 'the EPR of the mixing ratio of the two materials is less than 20 (ER is greater than 8 mm, the strength of the molded article is lowered, thereby causing inconvenience such as cracking and thus tends to be often It is difficult to perform from the mold to 149716.doc n 201107462. In addition to the operation, the substrate including at least one of synthetic rubber and synthetic resin is preferably cured when separated from the mold to remove contamination. In the case of a thermoplastic resin or the like, The curing method for achieving the above-mentioned cured state includes curing by heating, curing by cooling, and the like. For example, in the case of curing by heating, a curing agent is used. The curing agent may cure the substrate. And examples thereof include organic peroxides for synthetic rubbers and polyethylene resins, and the like. In the case of epoxy resins, mention may be made of phenolic compounds 'amine-based compounds, imidazoles, acid anhydride-based curing agents, organic phosphoric acid Compounds and the like. Examples of the above organic peroxides include organic peroxides such as the following. (t-butylperoxy)_3,3,5•trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, tert-butylperoxymaleic acid , tert-butyl peroxy oleate, tert-butyl 3,3,5-tridecylhexanoate, cyclohexanone peroxide, tert-butyl peroxyaryl carbonate, Peroxyisopropyl propylene carbonate, tert-butyl vinegar, 2,5-dimethyl-2,5-di(benzolic peroxy)hexane, 2,2-bis(t-butylperoxy) Base) octane, tert-butyl hydrazine peroxyacetate, 2,2-bis(t-butylperoxy)butane, tert-butyl sulfonium peroxybenzoate, 4,4-bis (first) Tributylperoxy)n-butyl valerate, di-t-butyl peroxy isophthalate, methylethyl peroxide, dicumyl peroxide, 2,5-dimethyl Base 2,5·di(t-butylperoxy)hexane, «, '-bis(t-butylperoxy-m-isopropyl) stupid, peroxylated tert-butylisopropyl Benzene, dicumyl hydroperoxide, di-tert-butyl peroxide, and J.-dimercapto-2,5-di(t-butylperoxy)hexane_3. 149716.doc 201107462 Phenol Compound Examples include hydroquinone, resorcinol and catechol, which are monoterpene bifunctional phenols; bisphenol A, bisphenol F, naphthalenediol and bisphenol, which are polycyclic bifunctional phenols; and polyfunctional Phenol, for example, a compound thereof and an alkyl-substituted compound. Examples of the amine compound include N,N-benzyldimethylamine, 2-(dimethylaminomethyl), 2,4,6-para (didecylaminomethyl) hydrazine, tetramethyl nucleus, triethanolamine, N,N'-dimethylhexahydro 0-pyrazine, diazabicyclo[2 2·2] octane, 1,8 -diazabicyclo[54 〇]_7_undecene, anthracene, 5-diazabicyclo[4.4.0]_5_nonene, hexamethylenetetramine, pyridine, picoline, hexahydro Pyridine, pyrrolidine, dimethylcyclohexylamine, dimethylhexylamine, cyclohexylamine, monoisobutylamine, di-n-butylamine, diphenylamine, decylmethylaniline, tri-n-propylamine, three-positive Octylamine, tri-n-t-t-amine, triphenylamine, tetramethyl bond, tetramethylammonium bromide, tetramethylammonium iodide, triethylenetetramine, diaminobenzophenone, diaminodiphenyl ether , dicyandiamide, o-toluene biguanide, vascular base gland and dimethyl urea. Examples of taste saliva include sodium saliva, 2-ethylidene. Sit, 2_ethylm-mazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole 'bubenzyl-methylimidazole, 2-heptadecylimidazole, 4,5_two stupid base. Mizozol, 2-methylimidazoline, 2-phenylimidazoline, 2-epydecyl imidazoline, 2-peptadecylamidophene, 2-isopropylpyridinium, 2,4-dimethyl Imidazole, 2_phenyl glacial methyl oxime, 2_ethyl odor (tetra), 2 phenyl _4_methyl methine, benzopyrazine: 1-cyanoethyl savory saliva and 2,4 _Diamine _6_[2,·Methyl-meridino (10)ethyl _ s-triterpene. Examples of the acid-based curing agent include acid anhydrides such as phthalic acid needles, hexahydro-o-benzene 149716.doc •11·201107462-formaldehyde anhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic anhydride. Examples of the organic phosphoric acid compound include hexamethylphosphoric triamide, tris(dioxadiyl) vinegar, tris(p-diyl) vinegar, dimethyl triphenyl citrate dimethyl ester, and phenyl phosphonate. , triphenylphosphine, tri-n-butylphosphine, diphenylphosphine organophosphorus compound and its complex. These curing agents may be used singly or in combination of two or more thereof. The compounding amount of the curing agent can be appropriately set, but in the case of, for example, a synthetic rubber, the amount is preferably set to 1 to 3 by weight with respect to 100 parts by weight (hereinafter simply referred to as "parts") of the synthetic rubber. Within the range of parts. Further, the curing agent not only functions as a thermosetting synthetic rubber and a synthetic resin but also functions as a mold cleaner, and thus can be mixed in the mold cleaning composition of the present invention as needed to achieve the purpose other than the curing agent. The compounding amount of the curing agent in this case is preferably from 5 to 60 parts, particularly preferably from 5 to 25 parts, based on at least one of 100 parts of synthetic rubber and synthetic resin. With regard to at least one of an alkali metal salt and an alkali metal hydroxide to be mixed in a substrate, a metal salt such as a salt of a metal such as sodium, cesium, strontium or barium may be mentioned. Examples of the alkali metal salt include borate, acid (for example, phosphoric acid, metaphosphoric acid, hypophosphorous acid, phosphorous acid (phosphonic acid), hypophosphorous acid (phosphinic acid), pyrophosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid And pyrophosphoric acid) salts, carbonates, sulfates, nitrates, hydrochlorides and organic acids (eg acrylic acid, adipic acid, ascorbic acid, aspartic acid, aminobenzoic acid, alginic acid, benzoic acid, oil) 149716.doc •12· 201107462 Acid, formic acid, citric acid, glycolic acid, gluconic acid 'glutamic acid' cinnamic acid, succinic acid, acetic acid, salicylic acid, oxalic acid, tartaric acid, p-toluenesulfonic acid, nicotinic acid, lactic acid , acetic acid, phthalic acid, benzoic acid, malonic acid, butyric acid and malic acid substituted by uric acid. In the case of an alkali metal salt polybasic acid salt, a part of the alkali metal salt of the acid can be utilized. For example, in the case of a ternary phosphate, the salt may be any one of the following: a primary salt having one metal ion and two hydrogen salts, a secondary salt having two metal ions and one hydrogen And a tertiary salt having three metal ions. Further, it may be any of an acidic salt, a basic salt and a neutral salt. Among them, the test salt or neutral salt is better from the point of view of the rot of the mold. Further, as the alkali metal salt, a hydrate is preferably used from the viewpoint of solubility in water. Examples of metal hydroxides include sodium hydroxide and potassium hydroxide. These alkali metal salts and alkali metal hydroxides may be used singly or in combination of two or more. The denier of at least one of the alkali metal salt and the alkali metal hydroxide relative to at least one of the synthetic rubber and the synthetic resin used as the substrate is set to preferably in the range of 0.1 to 10 parts. Inside, especially good 0'丨 to 5 copies. That is, when the amount of the mixture is too small, the removal property of the contaminants formed on the surface of the mold is remarkably lowered' and it is often difficult to completely remove the mold contamination. Further, ', on the other hand, when the amount of the mixture is too large, the alkali metal salt and the alkali metal hydroxide are liable to precipitate on the surface of the mold and thus the mold is easily contaminated. Next, it is suitable to use tap water, R 〇 water obtained by removing impurities (water treated by reverse osmosis membrane), ion exchange water, and the like as 149716.doc -13- 201107462 for mixing in the present invention. Water. The mixing amount of water is preferably in the range of preferably 3 to 30 parts, particularly preferably 5 to 20 parts, based on at least one of 100 parts of the synthetic rubber and the synthetic resin used as the substrate. That is, when the mixing amount is too small, the removal property of the contaminants formed on the surface of the mold is remarkably lowered, and it is often difficult to completely remove the mold contamination. Conversely, when the amount of mixing is too large, the cleaning effect is not improved and the labor required for mixing increases and is often useless. Next, various organic solvents are used as the organic solvent to be used in the present invention and, for example, in the case of using an alkali metal salt, the self-solvent angle
甲酸酯及諸如此類。 乙醇、1-丙醇、2-丙醇、^Formate and the like. Ethanol, 1-propanol, 2-propanol, ^
乙一醇單乙基醚、乙二醇單丙 醇基溶劑之實例包括甲醇、 丁醇、2-丁醇、異丁醇 戊醇、2-甲基-1-丁醇、 醇、新戊醇、1-己醇、2 乙基-1-丁醇、1-庚醇、2_庚醇 環己醇、2-f基環己醇、3_甲 乙二醇、乙二醇單甲基醚、 149716.doc 201107462 基謎、乙二醇單丁基醚、二乙二醇、二乙二醇單甲基醚、 二乙二醇單乙基輕、二乙二醇單丙基趟、二乙二醇單丁基 醚、三乙二醇、甲二醇單甲基醚、三乙二醇單乙基醚、四 乙二醇、聚乙二醇（重量平均分子量為200至4〇〇)、12丙 二酵、1，3-丙二醇.、1，2-丁二醇、ι，3_ 丁二醇、丨，4_ 丁二 醇、2,3-丁二醇、；ι，5-戊二醇、甘油、丙二醇及二丙二 醇。 酮基溶劑之實例包括丙酮、甲基乙基酮、2_戊酮、3_戍 酮、2-己酮、甲基異丁基酿j、2_庚酮、‘庚酮、二異丁基 酮故己酮、甲基環己_、佛爾洞（phorone)及異佛爾酮。 醚基溶劑之實例包括二丙基醚、二異丙基醚、二丁基 醚、二己基謎、苯曱醚、苯***、二噁烷、四氫呋喃、縮 醛、乙二醇二甲基醚、乙二醇二乙基醚、二乙二醇二甲基 醚及乙二醇二乙基醚。 此外，除上述有機溶劑以外，亦可使 煙、紛、縮酸、脂肪酸、酸軒、醋化合物、氮化合物、 化。物（單乙醇胺等）及硫化合物（二甲基亞颯等）等溶劑 ”有兩個或更多個官能團之溶劑（酯及醚、醇及醚等）。 等溶劑可單獨使用或其兩者或更多者可組合使用(例如 胺基洛知自身之组合、醯胺基溶劑與除酿胺基溶劑以 t + y n ) H其他溶劑亦可與該等溶劑組合 牛例而。作為無機溶劑或諸如此類，彳混合氨。 一在本’X明中，在使用鹼金屬鹽之情形中，自鹼金屬鹽 溶解性角度來看’較佳與水組合使用，其已於上文中: 149716.doc 15 201107462 機溶劑一同予以例示^在上述鹼金屬鹽作為水合物（其中 結合有結晶水）使用之情形中，除由於藉由對水實施正向 混合可提高溶解速度以彳，由於含有來自結晶水之微量水 而改良溶解性，因此自可操作性角度來看使用水較佳。 在清潔模具時，上述有機溶劑較佳為液體且另外在加熱 模具時，其尤佳為無揮發性之液體。舉例而言，較佳使用 多元醇及多元醇烷基醚。具體而言，由於通常大約在 180C之模具溫度下使用用於半導體器件模製之模具，其 中使用熱固性樹脂組合物作為囊封材料，因此較佳使用沸 點為180。(：或更高之溶劑作為欲用於此一情形中之溶劑。 沸點為180。(：或更高之溶劑包括乙二醇單丁基醚（沸點： 188 C )、丙一醇（沸點：i 87〇c )、二丙二醇曱基醚（沸點： 190C)及二乙二醇單曱基醚（沸點：194。〇）。 相對於100份數用作基材之合成橡膠及合成樹脂中之至 ^ 者’上述有機溶劑之混合量（組合使用相應溶劑之情 形中的全部有機溶劑之總量）設定為較佳3至3〇份數之範圍 内、尤佳5至20份數。亦即，當混合量太小時，模具表面 上所形成污染物之去除性質會顯著降低，且往往難以完全 去除模具污染。反之，當混合量太大時，不會改良清潔效 果且混合所需要勞力會增加並往往徒勞無益。 除作為基本組份上述相應混合組份以外，亦可根據需要 向本發明模具清潔組合物中適當地混入脫模劑、增強劑及 諸如此類。 脫模劑之實例包括長鏈脂肪酸，例如硬脂酸及二十二烷 149716.doc -16- 201107462 酸；長鏈脂肪酸之金屬鹽，例如硬脂酸辞及硬脂酸飼；醋 蠟，例如巴西棕橺蠟、褐煤酸蠟及褐煤酸之部分皂化酯； 長鏈脂肪酸醯胺’例如硬脂基乙二胺；及石蠟，例如聚乙 稀螺· °其可單獨使用或其兩者或更多者可組合使用。 相對於100份數用作基材之合成橡膠及合成樹脂中之至 少一者，脫模劑之含量設定為較佳5至20份數之範圍内、 更佳8至16份數。亦即，當脫模劑含量太小時，難以獲得 足夠脫模效果。反之，當脫模劑含量太大時，清潔能力會 降低且在整新後使用模具製造模製物件時模製物件之外觀 亦往往會變差。 增強劑之實例包括無機填充劑，例如二氧化矽粉、滑石 粉、氧化鋁、碳酸鈣、氫氧化鋁及氧化鈦。其可單獨使用 或其兩者或更多者可組合使用。較佳使用平均粒徑為約 〇.〇1 μΓΠ至100 μιη之填充劑作為增強劑。 相對於100份數用作基材之合成橡膠及合成樹脂中之至 ’者，增強劑之含量設定為較佳10至5 0份數之範圍内、 尤佳15至4〇份數。亦即，#增強劑之含量太小時，機械強 度往往會因增強能力降低而降低。反之，當增強劑之含量 太大時，組合物變得易碎且機械強度亦往往會降低。 此外，除上述添加劑以夕卜’亦可根據需要向向本發明模 具清潔組合物中適當地混入軟化劑（例如芳香油或環烷 油）、硫化劑（例如硫）及硫化促進劑、老化抑制劑、鋅華及 諸如此類。 本發明模具清潔組合物可（例如）如下來製造。亦即，可Examples of the ethyl alcohol monoethyl ether and ethylene glycol monopropyl alcohol-based solvent include methanol, butanol, 2-butanol, isobutanol pentanol, 2-methyl-1-butanol, alcohol, neopentyl alcohol, 1-hexanol, 2 ethyl-1-butanol, 1-heptanol, 2-heptanol cyclohexanol, 2-f-cyclohexanol, 3-methyl glycol, ethylene glycol monomethyl ether, 149716 .doc 201107462 Base, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl light, diethylene glycol monopropyl hydrazine, diethylene glycol Monobutyl ether, triethylene glycol, dimethyl glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol, polyethylene glycol (weight average molecular weight 200 to 4 〇〇), 12 propyl Di-fermentation, 1,3-propanediol, 1,2-butanediol, iota, 3-butanediol, hydrazine, 4-butanediol, 2,3-butanediol, ι, 5-pentanediol, glycerol , propylene glycol and dipropylene glycol. Examples of the ketone-based solvent include acetone, methyl ethyl ketone, 2-pentanone, 3-ketone, 2-hexanone, methyl isobutyl, j-h-heptanone, 'heptanone, diisobutylene Ketones are ketone, methylcyclohexyl, phorone and isophorone. Examples of the ether-based solvent include dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl mystery, phenyl ether, phenethyl ether, dioxane, tetrahydrofuran, acetal, ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol dimethyl ether and ethylene glycol diethyl ether. Further, in addition to the above organic solvent, it is also possible to use a smoke, a condensate, a fatty acid, a fatty acid, an acid hydrazine, a vinegar compound, and a nitrogen compound. a solvent (such as monoethanolamine or the like) and a sulfur compound (such as dimethyl sulfoxide) may have two or more functional groups of solvents (esters and ethers, alcohols, ethers, etc.), etc. Solvents may be used alone or both. Or more may be used in combination (for example, a combination of an amine amide, a guanamine-based solvent and a demineral-based solvent as t + yn ) H other solvents may also be combined with such solvents as an inorganic solvent or In this case, in the case of the use of an alkali metal salt, it is preferably used in combination with water from the viewpoint of solubility of an alkali metal salt, which is already mentioned above: 149716.doc 15 201107462 The solvent of the machine is exemplified together. In the case where the above alkali metal salt is used as a hydrate (in which crystallization water is combined), the dissolution rate is increased by the forward mixing of water, since it contains crystallization water. The water is used to improve the solubility, so that it is preferable to use water from the viewpoint of workability. When the mold is cleaned, the above organic solvent is preferably a liquid and, in addition, when heating the mold, it is preferably a non-volatile liquid. In particular, it is preferred to use a polyol and a polyol alkyl ether. Specifically, since a mold for molding a semiconductor device is usually used at a mold temperature of about 180 C, in which a thermosetting resin composition is used as an encapsulating material, It is preferred to use a solvent having a boiling point of 180. (or higher) as a solvent to be used in this case. The boiling point is 180. (: or higher solvent includes ethylene glycol monobutyl ether (boiling point: 188 C) , propanol (boiling point: i 87〇c), dipropylene glycol decyl ether (boiling point: 190C) and diethylene glycol monodecyl ether (boiling point: 194. 〇). Used as a substrate relative to 100 parts. The amount of the above organic solvent in the synthetic rubber and the synthetic resin (the total amount of all the organic solvents in the case where the corresponding solvent is used in combination) is set to preferably in the range of 3 to 3 parts, particularly preferably 5 Up to 20 parts. That is, when the mixing amount is too small, the removal properties of the contaminants formed on the surface of the mold are significantly reduced, and it is often difficult to completely remove the mold contamination. Conversely, when the mixing amount is too large, the cleaning effect is not improved. And mixing needs The force may increase and is often useless. In addition to the above-mentioned corresponding mixed components as a basic component, a mold release agent, a reinforcing agent, and the like may be appropriately mixed into the mold cleaning composition of the present invention as needed. Examples of the release agent include Long-chain fatty acids, such as stearic acid and behenic acid 149716.doc -16- 201107462 acid; metal salts of long-chain fatty acids, such as stearic acid and stearic acid; vinegar wax, such as Brazilian brown wax, lignite A partially saponified ester of acid wax and montanic acid; a long chain fatty acid guanamine such as stearyl ethylene diamine; and a paraffin wax such as polyethylene snail, which may be used singly or in combination of two or more thereof. The content of the releasing agent is set to preferably in the range of 5 to 20 parts, more preferably 8 to 16 parts, relative to at least one of 100 parts of the synthetic rubber and the synthetic resin used as the substrate. That is, when the release agent content is too small, it is difficult to obtain a sufficient release effect. On the other hand, when the content of the releasing agent is too large, the cleaning ability is lowered and the appearance of the molded article tends to be deteriorated when the molded article is manufactured using the mold after the refreshing. Examples of the reinforcing agent include inorganic fillers such as cerium oxide powder, talc, alumina, calcium carbonate, aluminum hydroxide, and titanium oxide. They may be used singly or in combination of two or more thereof. A filler having an average particle diameter of from about ΓΠ1 μΓΠ to 100 μηη is preferably used as the reinforcing agent. The content of the reinforcing agent is set to preferably in the range of 10 to 50 parts, particularly preferably 15 to 4 parts, based on 100 parts by weight of the synthetic rubber and the synthetic resin used as the substrate. That is, when the content of the #enhancer is too small, the mechanical strength tends to decrease due to a decrease in the reinforcing ability. On the other hand, when the content of the reinforcing agent is too large, the composition becomes brittle and the mechanical strength tends to decrease. Further, in addition to the above additives, a softening agent (for example, an aromatic oil or a naphthenic oil), a vulcanizing agent (for example, sulfur), a vulcanization accelerator, and aging suppression may be appropriately mixed into the mold cleaning composition of the present invention as needed. Agents, zinc and the like. The mold cleaning composition of the present invention can be manufactured, for example, as follows. That is,
S 149716.doc -17· 201107462 藉由使用Banbury混合機、捏合機、輥式混合機1出機 或諸如此類對包括上述相應基本組份在内的相應混合組份 實施機械捏合來製造該組合物。 由此製^•之本發明模m组合物可作為模具清潔材料 提供給模具清潔，該材料形成為粉末形狀、片狀形狀、薄 片狀形狀或條帶狀形狀。該薄片之厚度在作為片狀形狀使 用之情开》中一般設定為3 mm至1 〇 mm。 本發明模具清潔組合物較佳設定為淺色，例如白色或接 近白色之灰色。藉由如上進行設定，達到以下效果：在模 具清潔後可容易地目測確認污染物已自模具去除並黏附至 杈具清潔組合物且可容易地確認模具清潔之情況。 在使用自本發明模具清潔組合物獲得的模具清潔材料 時，在基材係合成橡膠之情形中，通常較佳在將該組合物 模製成薄片狀形狀後再使用。此外，在基材係（例如）合成 樹脂之情形中，較佳在使熱固性三聚氰胺樹脂形成為粉末 形狀或片狀形狀後再使用。 藉由使用形成為薄片狀形狀的本發明模具清潔組合物來 ’月’糸模具之方法係通過將該組合物置於用於半導體器件模 製之模具中來實施。舉例而言，在基材係合成橡膠之情形 中’上述薄片當然呈未硫化狀態，並且將其置於模具中並 隨後熱硫化以使污染物整體上黏附至該薄片。隨後，藉由 自模具去除硫化薄片來實施模具之清潔。 在基材係合成橡膠之情形中使用薄片狀模具清潔組合物 之模具清潔方法將在下文中以事件順序加以詳細地闡述。 149716.doc 201107462 潔模具清潔組合物之薄片狀模具清 _二:::::::材料置於形成一上 具以將H且线上模具及下模 :將缚片狀模具清潔材料填充至由上部模具令形成之凹 =下部模具中形成之凹陷所形成的模穴中，並 =吏其與模具表面塵力接觸。在此情形下，合成橡膠 L 橡膠）藉由模製熱而熱硫化為硫化橡黟且此時，模 人V成的脫模劑之氧化降解層及諸如此類與硫化橡膠結 在起此時，在一些情形中，模穴周圍的毛刺亦與 ㈣勝結合在一起。隨後，在預定時期後開啟上部模具與 下Ρ模八並自上下模具剝離已變成硫化橡膠之薄片狀模 具清潔材料，藉此剝離與上下模具表面之薄片狀模具清潔 材料結合的氧化降解層及諸如此類(污染物”由此實施 模具清潔。 將薄片狀模具清潔材才斗夾於中間&實施壓縮才莫製及加熱 之條件可端視基材之種類及諸如此類來進行適當的設定。 舉例而言，在合成橡膠之情形中，條件較佳設定為16〇t 至190 C及1分鐘至5分鐘之範圍内且在使用熱固性樹脂作 為合成樹脂之情形中，條件較佳設定為l6(rc至l9(rc及i 分鐘至5分鐘之範圍内。 欲使用本發明模具清潔組合物之模具之一個實例係（例 如）用於半導體器件模製之模具，其中藉由使用熱固性樹 脂组合物實施重複性模製。 1497l6.doc -19- 201107462 在用於半導體器件板製之模具（其係使用本發明模具清 泳組合物之模具之一個實例）中，欲用作模製樹脂材料之 熱固性樹脂組合物之實例包括含有環氧樹脂作為主要組份 之環氧樹脂組合物。 作為熱固性樹脂組合物，一般將固化劑及若需要諸如無 機填充劑及固化促進劑等添加劑與用作主要成份之環氧樹 脂一起進行適當地混合。 因此，由於利用本發明模具清潔組合物清潔之模具不含 污木物且恢復至模具表面之初始狀態，因此一般將脫模劑 塗佈於模具表面上，之後使用熱固性樹脂組合物作為模具 材料來模製半導體封裝。舉例而言，在模製含有褐煤酸蠟 作為脫模劑之模製材料之情形中，較佳塗佈褐煤酸蠟。此 外，在模製含有巴西棕櫊蠟作為脫模劑之模製材料之情形 中，較佳塗佈巴西棕櫚蠟。作為在模具表面上塗佈脫模劑 之方法’較佳使用含有脫模劑之未硫化橡膠組合物，其— 旦製得即隨後形成為薄片狀形狀。舉例而言，可能提及可 藉由混合脫模劑與闡述於上文中之未硫化橡膠來獲得之薄 片。以與使用薄片狀模具清潔組合物之清潔過程相同之方 式將由含有脫模劑之未硫化橡膠組合物形成之薄片安放在 模具中並進行加熱，藉此將其中所含脫模劑塗佈於模具表 面上。吾人s忍為未硫化橡膠組合物中之脫模劑在熱硫化期 間熔化並擠出至模具表面而在表面上形成均勻脫模劑膜。 可將上述脫模劑在未硫化橡膠組合物中之含量相對於 wo份數橡膠材料之比率設定為較佳15至35份數、尤佳 149716.doc -20· 201107462 至30份數。當脫模劑之含量小於 ^ ^ 、5伤數時，不展示足夠的 脫才旲效果。虽其含量超過35粉童 時’其將過量塗佈於模旦 表面上，從而造成藉由使用·.主 '知 3田便用π泳及整新後模具獲 物件外觀劣化。 又于Ν棋衣 實例 下文將闡述貫例以及比較實 罕貰例然而，本發明並不受限 於該等實例。 首先’製備構成模具清潔組合物之相應組份。 υ BR: [丁二婦橡膠：由職公司製造，则！（順式_ 1，4鍵：95%)] 2) R [乙稀_丙烯·二埽橡膠：由Mitsui Chemicals公 司裳过EPT 4045](乙婦含量：54 m〇1%，c婦組份含 量：8.1 mol%)] 3) 滑石粉：平均粒徑為9 4) 二氧化矽粉：平均粒徑為9 μηι 5) 氧化鈦：平均粒徑為〇 25 μιη 6) 西棕櫚蠛.巴西棕搁1號（由Nikko Rika公司製造） 7) 味°坐· 2,4-二胺基_6_[2i_甲基咪唑基（丨，)]乙基_s•三嗓 8) 有機過氧化物：4,4_雙（第三丁基過氧基）戊酸正丁酯 9) 水·離子交換水 10) PEG ·聚乙二醇（由N〇F公司製造編號2〇();重量 平均分子量為200) 11) PG .丙二醇（沸點：187°C ) 12) DGMM:二乙二醇單甲基鍵（沸點：194<t) 149716.doc -21 · 201107462 貫例1至8 ’比較實例1至2 下文所述表1至2中所展示之組份係以表中所展示之比率 進行此合’且各混合物係使用捏合輥來捏合。隨後，使用 札頭親使捏合混合物形成為薄片狀形狀（厚度為5 nrn)以製 以期望薄片狀模具清潔組合物（模具清潔材料）》 實例9 藉由以下方式來獲得粉末形狀模具清潔組合物（模具清 '糸材料）.藉由喷霧將1份數作為清潔組份之K3P〇4& 4份數 水黏附至100份數產物（藉由磨碎市售模具清潔用熱固性三 永鼠胺树月曰（由Nipp0n Carbide Industries公司製造， Nikalet ECR-T)來獲得）。 比較實例3 使用市售模具清潔用熱固性三聚氰胺樹脂（由Nippon Carbide Industrie司製造，職心ECR t)來形成片狀模 具清潔組合物（模具清潔材料）。 使用每一由此獲得的以下實例及比較實例之模具清潔組 合物(模具清潔材料)來評價模具上所形成污染物之去除性 質。亦即，使用環境友好型環氧樹脂（由Niu〇 Denk〇公司 製造’ GE-747G)作為囊封材料來實施重複性模製，且在模 製用模具（其表面在800次模製後已受到污染）中使用每一上 述模具清潔組合物(模具清潔材料)來實施清潔模製”遺 後，自模具取出藉由清潔模製所形成之模製物件並目視呼 價模具表面上污染物之去除性f。在評價中，將能夠達成 污染物完全去除之模製作業數為5次或更少之情形評價為 149716.doc -22- 201107462 良」且將去除污染物所需模製作業為6次或更多之 評價為「差」。 慣形 在實m至8及比較⑴之產物的評價中，用模製用模且 夾緊每一薄片狀模具清潔組合物（模具清潔材料）並在175^ 下實施5分鐘熱模製。另—方面，在實例9之試樣之評價中 使用粉末形狀模具清潔組合物(模具清潔材料)實施轉移模 製’且在比較實例3之試樣之評價令使用片狀模具清潔組 合物（模具清潔材料）實施轉移模製，隨後在175。(：下熱模製 3分鐘。 上述評價結果展示於下述表1及2中。S 149716.doc -17· 201107462 The composition is produced by mechanical kneading of a corresponding mixing component including the above respective basic components by using a Banbury mixer, a kneader, a roll mixer 1 or the like. The mold composition of the present invention thus obtained can be supplied to the mold cleaning as a mold cleaning material which is formed into a powder shape, a sheet shape, a sheet shape or a strip shape. The thickness of the sheet is generally set to 3 mm to 1 mm in the case of use as a sheet shape. The mold cleaning composition of the present invention is preferably set to a light color such as white or gray adjacent to white. By setting as above, the following effects are achieved: after the mold is cleaned, it can be easily visually confirmed that the contaminant has been removed from the mold and adhered to the cookware cleaning composition and the mold cleaning can be easily confirmed. In the case of using the mold cleaning material obtained from the mold cleaning composition of the present invention, in the case of the base material-based synthetic rubber, it is generally preferred to use the composition after molding into a sheet-like shape. Further, in the case of a substrate such as a synthetic resin, it is preferred to use the thermosetting melamine resin in a powder shape or a sheet shape. The method of using the mold cleaning composition of the present invention formed into a sheet-like shape to form a "moon" mold is carried out by placing the composition in a mold for molding a semiconductor device. For example, in the case where the substrate is a synthetic rubber, the above-mentioned sheet is of course in an unvulcanized state, and it is placed in a mold and then thermally vulcanized to adhere the contaminants to the sheet as a whole. Subsequently, the cleaning of the mold is carried out by removing the vulcanized flakes from the mold. The mold cleaning method using the flaky mold cleaning composition in the case where the substrate is a synthetic rubber will be explained in detail below in the order of events. 149716.doc 201107462 Thin mold cleaning of the cleaning mold cleaning composition _ 2::::::: The material is placed on the upper part to form the H and the upper mold and the lower mold: the sealing sheet mold cleaning material is filled to The recess formed by the upper mold is in the cavity formed by the depression formed in the lower mold, and is in contact with the surface of the mold. In this case, the synthetic rubber L rubber) is thermally vulcanized to vulcanized rubber by molding heat and at this time, the oxidative degradation layer of the release agent of the mold V and the like are bonded to the vulcanized rubber at this time, in some cases. In the case, the burrs around the cavity are also combined with (4) wins. Subsequently, the upper mold and the lower mold are opened after a predetermined period of time, and the sheet-like mold cleaning material which has been converted into vulcanized rubber is peeled off from the upper and lower molds, thereby peeling off the oxidative degradation layer combined with the sheet-like mold cleaning material of the upper and lower mold surfaces, and the like ( The contaminant is thus cleaned by the mold. The sheet-like mold cleaning material is clamped in the middle & the conditions for performing the compression and heating can be appropriately set depending on the kind of the substrate and the like. For example, In the case of a synthetic rubber, the conditions are preferably set in the range of 16 〇t to 190 C and 1 minute to 5 minutes, and in the case of using a thermosetting resin as the synthetic resin, the condition is preferably set to 16 (rc to 1 9 ( Rc and i minutes to 5 minutes. One example of a mold to which the mold cleaning composition of the present invention is to be used is, for example, a mold for molding a semiconductor device in which repetitive molding is carried out by using a thermosetting resin composition. 1497l6.doc -19- 201107462 In a mold for a semiconductor device board, which is one of the molds using the mold cleaning composition of the present invention In the example, an example of a thermosetting resin composition to be used as a molding resin material includes an epoxy resin composition containing an epoxy resin as a main component. As a thermosetting resin composition, a curing agent and, if necessary, an inorganic filling are generally required. The additive such as the agent and the curing accelerator is appropriately mixed with the epoxy resin used as the main component. Therefore, since the mold cleaned by the mold cleaning composition of the present invention does not contain the stain and returns to the initial state of the mold surface, The release agent is generally applied to the surface of the mold, and then the semiconductor package is molded using the thermosetting resin composition as a mold material. For example, in the case of molding a molding material containing montanic acid wax as a release agent, Preferably, the montanic acid wax is coated. Further, in the case of molding a molding material containing Brazilian palm wax as a releasing agent, it is preferred to apply carnauba wax as a method of applying a releasing agent on the surface of the mold. 'It is preferred to use an unvulcanized rubber composition containing a release agent, which is then formed into a sheet-like shape. For example, A sheet which can be obtained by mixing a release agent with the unvulcanized rubber described above can be mentioned. It is formed of an unvulcanized rubber composition containing a release agent in the same manner as the cleaning process using a flaky mold cleaning composition. The sheet is placed in a mold and heated to apply the release agent contained therein to the surface of the mold. The release agent in the unvulcanized rubber composition is melted and extruded to the surface of the mold during hot vulcanization. A uniform release agent film is formed on the surface. The ratio of the above-mentioned release agent in the unvulcanized rubber composition to the ratio of the parts of the rubber material can be set to preferably 15 to 35 parts, particularly preferably 149716.doc -20 · 201107462 to 30 parts. When the content of the release agent is less than ^ ^, 5 damages, it does not show enough effect. Although the content exceeds 35 powders, it will be excessively applied to the surface of the die, resulting in deterioration of the appearance of the article by using the π swimming and refining the mold after use. Further examples of the rugby game will be exemplified below, as well as comparative examples. However, the invention is not limited to the examples. First, the corresponding components constituting the mold cleaning composition are prepared. υ BR: [Ding Erfu Rubber: Made by the company, then! (cis _ 1, 4 bond: 95%)] 2) R [Ethylene propylene / bismuth rubber: EPT 4045 by Mitsui Chemicals Co., Ltd.] (European content: 54 m 〇 1%, c female component Content: 8.1 mol%)] 3) Talc powder: average particle size is 9 4) cerium oxide powder: average particle size 9 μηι 5) titanium oxide: average particle size 〇25 μιη 6) West Palm 蠛. Brazilian brown No. 1 (manufactured by Nikko Rika) 7) Taste · 2,4-diamino _6_[2i_methylimidazolyl (丨,)]ethyl _s•三嗓8) Organic peroxide : 4,4_bis(t-butylperoxy)-n-butyl valerate 9) Water·ion exchange water 10) PEG·polyethylene glycol (manufactured by N〇F company No. 2〇(); weight average Molecular weight is 200) 11) PG. Propylene glycol (boiling point: 187 ° C) 12) DGMM: diethylene glycol monomethyl bond (boiling point: 194 < t) 149716.doc -21 · 201107462 Example 1 to 8 'Comparative example 1 to 2 The components shown in Tables 1 to 2 described below were subjected to this combination at the ratios shown in the table, and each of the mixtures was kneaded using a kneading roll. Subsequently, the kneading mixture was formed into a sheet-like shape (thickness of 5 nrn) using a zipper to prepare a desired flaky mold cleaning composition (mold cleaning material). Example 9 A powder-shaped mold cleaning composition was obtained by the following manner. (Mold clear '糸 material). Adhere 1 part of the K3P〇4&4 parts water as a cleaning component to 100 parts of the product by spraying (by grinding the commercially available mold for cleaning with thermosetting triamcinamide) Shuyue (obtained by Nipp0n Carbide Industries, Nikalet ECR-T). Comparative Example 3 A sheet mold cleaning composition (mold cleaning material) was formed using a commercially available mold cleaning thermosetting melamine resin (manufactured by Nippon Carbide Industrie Co., Ltd., ECR t). The mold cleaning composition (mold cleaning material) of each of the following examples and comparative examples thus obtained was used to evaluate the removal property of the contaminants formed on the mold. That is, an environmentally-friendly epoxy resin (manufactured by Niu 〇 Denk Co., Ltd. 'GE-747G) was used as an encapsulating material to carry out repetitive molding, and in a molding mold (the surface of which has been molded after 800 times) In each case, each of the above-mentioned mold cleaning compositions (mold cleaning materials) is used to carry out the cleaning molding. After that, the molded articles formed by the cleaning molding are taken out from the mold and the contaminants on the surface of the mold are visually observed. Removability f. In the evaluation, the number of molding operations capable of achieving complete removal of contaminants is 5 or less, and the evaluation is 149716.doc -22-201107462 Good and the molding operation required to remove contaminants is The evaluation of 6 or more times was "poor". Inertial shape In the evaluation of the products of the solids m to 8 and the comparison (1), each of the sheet-like mold cleaning compositions (mold cleaning materials) was clamped by a molding mold and subjected to hot molding at 175 ° for 5 minutes. On the other hand, in the evaluation of the sample of Example 9, the powder-shaped mold cleaning composition (mold cleaning material) was used to carry out transfer molding' and the evaluation of the sample in Comparative Example 3 was carried out using the sheet-shaped mold cleaning composition (mold) The cleaning material) was subjected to transfer molding, followed by 175. (: The next hot molding was carried out for 3 minutes. The above evaluation results are shown in Tables 1 and 2 below.
149716.doc149716.doc
S •23- 201107462 表2 (份數） 比較實例 1 2 3 BR 50 70 - EPR 50 30 - 滑石粉 - - - 二氧化矽粉 40 30 - 氧化鈦 - - - 巴西棕橺蠟 - 10 口米0坐 10 10 - 有機過氧化物 2 2 - 熱固性三聚氰胺 樹脂 - 100 K3P04nH20 - - - Na3P0412H20 - - - KCOOH - - - KOH - - - NaOH - 水 15 15 - 清潔性質 差 差 差 根據上述結果，在比較實例之試樣中將模具之清潔性質 評價為「差」，該等試樣並非含有鹼金屬鹽及鹼金屬氫氧 化物中之至少一者（作為清潔組份）與水二者之情形，而在 所有關於模具之清潔性質的實例之試樣中均獲得「良」之 評價。 囊封材料之改變（1) 此外，關於用於模製之模具，其中使用環境友好型環氧 樹脂GE-103 0(亦由Nitto Denko公司製造）替代環境友好型 環氧樹脂（由Nitto Denko公司製造，GE-7470)作為囊封材 料以與上文相同之方式重複地實施模製（800次），使用實例 1至9及比較實例1至3之每一模具清潔組合物（模具清潔材 149716.doc -24- 201107462 料）以與上文相同之方式目視評價模具上所形成污染物之 去除性質。結果’在比較實例之試樣之情形中，將模且之 清潔性質評價為「差」，而在所有關於模具之清潔性質的 實例之§式樣中均獲得「良」之評價，如上文所述。 囊封材料之改變（2) 此外，關於用於模製之模具，其中使用環境友好型環氧 樹脂GE-100(亦由Nitt0 Denk〇公司製造）替代環境友好型環 氧樹脂（由Nitto Denko公司製造，GE-7470)作為囊封材料 以與上文相同之方式重複地實施模製（8〇〇次），使用實例五 至9及比較實例丨至3之每一模具清潔組合物（模具清潔材料） 以與上文相同之方式目視評價模具上所形成污染物之去除 性質。結果，在比較實例之試樣之情形中，將模具之清潔 性質評價為「差」，而在所有關於模具之清潔性質的實例 之試樣中均獲得「良」之評價，如上文所述。 只例10至1 8，比較實例4及5 下文所述表3至4中所展示之組份係以表中所展示之比率 進仃此合，且各混合物係使用捏合輥來捏合。隨後，使用 ^頌觀❹合混合物形成為薄片狀形狀（厚度為5 mm)以製 &』望薄片狀模具清潔組合物（模具清潔材料）。 實例19 絮^ ;由以下方式來獲得粉末形狀模具清潔組合物（模具清 數/料）.藉由噴霧將1份數作為清潔劑組份之KJO4、3份 磨碎為有隹機'合劑之PEG及1份數水黏附至1 〇〇份數產物（藉由 市13模具清潔用熱固性三聚氰胺樹脂（由Nippon s 1497l6.d〇c -25- 201107462S •23- 201107462 Table 2 (Parts) Comparative Example 1 2 3 BR 50 70 - EPR 50 30 - Talc powder - - - Ceria powder 40 30 - Titanium oxide - - - Brazil palm wax - 10 mouth rice 0 Sitting 10 10 - Organic peroxide 2 2 - Thermosetting melamine resin - 100 K3P04nH20 - - - Na3P0412H20 - - - KCOOH - - - KOH - - - NaOH - Water 15 15 - Difference in cleaning properties difference according to the above results, in the comparative example In the sample, the cleaning properties of the mold were evaluated as "poor", and the samples did not contain at least one of an alkali metal salt and an alkali metal hydroxide (as a cleaning component) and water, and All the samples of the examples regarding the cleaning properties of the mold were evaluated as "good". Change in encapsulation material (1) In addition, regarding molds used for molding, environmentally friendly epoxy resin GE-103 0 (also manufactured by Nitto Denko) was used instead of environmentally friendly epoxy resin (by Nitto Denko Manufacture, GE-7470) was repeatedly molded as an encapsulating material in the same manner as above (800 times), using each of the mold cleaning compositions of Examples 1 to 9 and Comparative Examples 1 to 3 (mold cleaning material 149716) .doc -24- 201107462) The removal properties of the contaminants formed on the mold were visually evaluated in the same manner as above. Results 'In the case of the sample of the comparative example, the cleaning property of the mold was evaluated as "poor", and the evaluation of "good" was obtained in all the examples of the cleaning properties of the mold, as described above. . Change in encapsulation material (2) In addition, regarding the mold used for molding, an environmentally friendly epoxy resin GE-100 (also manufactured by Nitt0 Denk〇 Co., Ltd.) was used instead of the environmentally friendly epoxy resin (by Nitto Denko Co., Ltd.). Manufacture, GE-7470) was repeatedly molded as an encapsulating material in the same manner as above (8 times), using each of the mold cleaning compositions of Examples 5 to 9 and Comparative Examples 丨 to 3 (mold cleaning) Materials) The removal properties of the contaminants formed on the mold were visually evaluated in the same manner as above. As a result, in the case of the sample of the comparative example, the cleaning property of the mold was evaluated as "poor", and the evaluation of "good" was obtained in all the samples regarding the cleaning properties of the mold, as described above. Examples 10 to 18, Comparative Examples 4 and 5 The components shown in Tables 3 to 4 described below were fed at the ratios shown in the table, and each of the mixtures was kneaded using a kneading roll. Subsequently, a mixture of the mixture was formed into a sheet-like shape (thickness: 5 mm) to prepare a sheet-like mold cleaning composition (mold cleaning material). Example 19 Flocs; A powder-shaped mold cleaning composition (mold count/material) was obtained by the following method: 1 part of KJO4, 3 parts as a detergent component was ground into a masher's mixture by spraying. PEG and 1 part water adhered to 1 〇〇 parts of the product (with the city 13 mold cleaning thermosetting melamine resin (by Nippon s 1497l6.d〇c -25- 201107462
Carbide Industries 公司製造，Nikalet ECRT)來獲得）。 比較實例6(*與上述比較實例3相同） 使用市售杈具清潔用熱固性三聚氰胺樹脂(由Nippon Carbide Industries公司製造，職_ ecr t)來形成片狀模 具清潔組合物（模具清潔材料）。 使用每由此獲知的以下實例及比較實例之模具清潔組 合物（模具清潔材料）來評價模具上所形成污染物之去除性 質。亦即，使用環境友好型環氧樹脂（由Nitt〇 Denk〇公司 製’ GE-747G)作為囊封材料來實施重複性模製，且在模 製用模具（其表面在_次模製後已受到污染）中使用每一上 ㈣具清潔組合物（模具清潔材料）來實施清潔模製。隨 後，自模具取出藉由清潔模製所形成之模製物件並目視評 價模具表面上污染物之去除性質。在評價中，將能夠達成 污染物70王去除之杈製作業數為3次或更少之情形評價為 良且將去除污染物所需模製作業為4次或更多之情形評價 為差。 在只例10至18及比較4及5之試樣的評價中，將每一薄片 狀模U組合物（模具清潔材料）失於模製用模具中間且 在下實施5分鐘熱模製。另一方面，在實例19之試樣 之評價中使用粉末形狀模具清潔組合物（模具清潔材料）實 也轉移換衣’且在比較實例6之試樣之評價中使用片狀模 具清潔組合物（模具清潔材料）實施轉移模製，隨後在175。〇 下熱模製3分鐘。 上述評價結果展示於下述表3及4中。 H9716.doc -26- 201107462 表3 (份數） 實例 10 11 12 13 14 15 16 17 18 19 BR 50 70 50 70 50 50 50 50 50 EPR 50 30 50 30 50 50 50 50 50 - 滑石粉 - - - 55 55 - - - - 二氧化矽粉 40 40 40 - - 40 40 40 - 氧化鈦 5 5 5 5 5 - - 5 5 - 巴西棕橺蠟 - - - - - - 10 - - 口米唾 - - - - 10 - - - - 有機過氧化物 2 2 2 2 2 2 2 2 2 - 熱固性三聚氰 胺樹脂 100 Κ3Ρ04·ηΗ20 2 - _ - - - - 5 - 1 Na3P04-12H20 - 2 - - - 2 2 - 5 - KCOOH - - 10 - - - - - - - KOH - - - 0.2 - - - - - - NaOH - - - - 0.2 - - - - 水 5 5 10 5 2 2 5 5 1 PEG - - 10 3 PG - 5 - - - 8 - 20 - - DGMM 5 5 5 8 - 25 - 清潔性質 良* 良 良 良 良 良 良 良 良 良 清潔性質為良，但由於未混合水，故將組合物均質化需要一點時間。 149716.doc 27- 201107462 表4 (份數） 比較實例 4 5 6 BR 50 70 - EPR 50 30 滑石粉 - 二氧化矽粉 40 30 - 氧化鈦 - - - 巴西棕櫚蠟 - 10 - °米°坐 10 10 - 有機過氧化物 2 2 - 熱固性三聚氰胺樹脂 - - 100 Κ3Ρ〇4 ηΗ20 - - Na3P0412H20 - - - KCOOH - - KOH - - NaOH - 水 15 15 - PEG - - PG - - - DGMM - 5 清潔性質 差 差 差 根據上述結果，在比較實例中將模具之清潔性質評價為 「差」，其中不含有驗金屬鹽及驗金屬氫氧化物中之至少 一者作為清潔組份，而在所有關於模具之清潔性質的實例 之試樣中均獲得「良」之評價，該等試樣含有基材；鹼金 屬鹽及鹼金屬氫氧化物中之至少一者；及有機溶劑或有機 溶劑及水。 囊封材料之改變（1) 此外，關於用於模製之模具，其中使用環境友好型環氧 樹脂GE-103 0(亦由Nitto Denko公司製造）替代環境友好型 環氧樹脂（由Nitto Denko公司製造，GE-7470)作為囊封材 149716.doc -28- 201107462 料以與上文相同之方式重複地實施模製（800次），使用實例 10至19及比較實例4至6之每一模具清潔組合物（模具清潔 材料）以與上文相同之方式目才見評價模具上所形成污= 之去除性質。結果，在比較實例之試樣之情形中將模具 之清潔性質評價為「差而在所有關於模具之清潔：質 的實例之試樣令均獲得「良」之評價，如上文所述。 囊封材料之改變（2) 此外，關於用於模製之模具，其中使用環境友好型環氧 樹脂GE_ 1 〇〇(亦由Nitt〇 Denk〇公司製造）替代環境友好型環 氧樹脂（由Nitto Denko公司製造，GE-7470)作為囊封材料 以與上文相同之方式重複地實施模製（8〇〇次），使用實例⑺ 至19及比較實例4至6之每一模具清潔組合物（模具清潔材 料）以與上文相同之方式目視評價模具上所形成污染物之 去除性質。結果，在比較實例之試樣之情形中，將模具之 清潔性質評價為「差」，而在所有關於模具之清潔性質的 實例之試樣中均獲得「良」之評價，如上文所述。 儘笞已參照具體實施例詳細地闡述了本發明，但熟習此 項技術者將明瞭，其中可作出各種改變及修改，此並不背 離本發明之精神及範圍。 附帶而言，本申請案係基於以下專利：2〇〇9年7月17曰 提出申請的日本專利申請案第2〇〇9_16933〇號及2〇〇9年7月 17曰提出申请的第2009-169331號，且其内容以引用方式 併入本發明中。 本發明模具清潔組合物係用於熱固性樹脂模製材料之各 s 149716.doc -29- 201107462 種模製模具之清潔、整新及諸如此類，例 < ，欲在藉助重 複性樹脂囊封模製半導體元件時使用的用於模製之模具， 5玄模製係藉由使用環氧樹脂模製材料實施注射模製或轉移 模製來達成。 149716.docMade by Carbide Industries, Nikalet ECRT). Comparative Example 6 (* is the same as Comparative Example 3 above) A commercially available cooker cleaning thermosetting melamine resin (manufactured by Nippon Carbide Industries, Inc., _ecr t) was used to form a sheet-like mold cleaning composition (mold cleaning material). The mold cleaning composition (mold cleaning material) of each of the following examples and comparative examples thus known was used to evaluate the removal property of the contaminants formed on the mold. That is, an environmentally-friendly epoxy resin ("GE-747G" manufactured by Nitt(R) Denk Co., Ltd.) was used as an encapsulating material to carry out repetitive molding, and in the mold for molding (the surface of which has been molded after _ times molding) Each of the upper (four) cleaning compositions (mold cleaning materials) is used for cleaning molding. Subsequently, the molded article formed by the cleaning molding was taken out from the mold and the removal property of the contaminant on the surface of the mold was visually evaluated. In the evaluation, the case where the number of tanning operations for removing the contaminant 70 was 3 or less was evaluated as good, and the case where the molding operation required to remove the contaminant was 4 or more was evaluated as poor. In the evaluation of only the samples of Examples 10 to 18 and Comparatives 4 and 5, each of the sheet-like mold U composition (mold cleaning material) was lost in the middle of the mold for molding and hot-molded for 5 minutes. On the other hand, in the evaluation of the sample of Example 19, the powder-shaped mold cleaning composition (mold cleaning material) was also used to transfer the coating, and the sheet-like mold cleaning composition was used in the evaluation of the sample of Comparative Example 6 ( Mold cleaning material) was subjected to transfer molding, followed by 175. 〇 Heat molded for 3 minutes. The above evaluation results are shown in Tables 3 and 4 below. H9716.doc -26- 201107462 Table 3 (parts) Example 10 11 12 13 14 15 16 17 18 19 BR 50 70 50 70 50 50 50 50 50 EPR 50 30 50 30 50 50 50 50 50 - Talc - - - 55 55 - - - - Ceria powder 40 40 40 - - 40 40 40 - Titanium oxide 5 5 5 5 5 - - 5 5 - Brazilian palm wax - - - - - - 10 - - Mouth saliva - - - - 10 - - - - Organic peroxide 2 2 2 2 2 2 2 2 2 - Thermosetting melamine resin 100 Κ3Ρ04·ηΗ20 2 - _ - - - - 5 - 1 Na3P04-12H20 - 2 - - - 2 2 - 5 - KCOOH - - 10 - - - - - - - KOH - - - 0.2 - - - - - - NaOH - - - - 0.2 - - - - Water 5 5 10 5 2 2 5 5 1 PEG - - 10 3 PG - 5 - - - 8 - 20 - - DGMM 5 5 5 8 - 25 - Good cleaning properties * Good, good, good, good, good, clean, but because of the unmixed water, it takes a little time to homogenize the composition. 149716.doc 27- 201107462 Table 4 (parts) Comparative Example 4 5 6 BR 50 70 - EPR 50 30 Talc powder - Ceria powder 40 30 - Titanium oxide - - - Carnauba wax - 10 - ° m ° 10 10 - Organic peroxide 2 2 - Thermosetting melamine resin - - 100 Κ3Ρ〇4 ηΗ20 - - Na3P0412H20 - - - KCOOH - - KOH - - NaOH - Water 15 15 - PEG - - PG - - - DGMM - 5 Poor cleaning properties Difference According to the above results, in the comparative example, the cleaning property of the mold was evaluated as "poor", in which at least one of the metal salt and the metal hydroxide was not contained as a cleaning component, and in all the cleaning of the mold The samples of the examples of the properties were evaluated as "good", and the samples contained a substrate; at least one of an alkali metal salt and an alkali metal hydroxide; and an organic solvent or an organic solvent and water. Change in encapsulation material (1) In addition, regarding molds used for molding, environmentally friendly epoxy resin GE-103 0 (also manufactured by Nitto Denko) was used instead of environmentally friendly epoxy resin (by Nitto Denko Manufacture, GE-7470) as a sealing material 149716.doc -28- 201107462 The molding was repeated (800 times) in the same manner as above, using each of the molds of Examples 10 to 19 and Comparative Examples 4 to 6. The cleaning composition (mold cleaning material) was evaluated in the same manner as above to evaluate the removal property of the stain formed on the mold. As a result, in the case of the sample of the comparative example, the cleaning property of the mold was evaluated as "poor and all the samples relating to the cleaning of the mold: the quality of the sample were evaluated as "good" as described above. Change in encapsulation material (2) In addition, regarding the mold used for molding, an environmentally friendly epoxy resin GE_ 1 〇〇 (also manufactured by Nitt 〇 Denk〇) was used instead of the environmentally friendly epoxy resin (by Nitto). Molded by Denko, GE-7470) was repeatedly molded as an encapsulating material in the same manner as above (8 times), using each of the mold cleaning compositions of Examples (7) to 19 and Comparative Examples 4 to 6 ( Mold cleaning material) The removal properties of the contaminants formed on the mold were visually evaluated in the same manner as above. As a result, in the case of the sample of the comparative example, the cleaning property of the mold was evaluated as "poor", and the evaluation of "good" was obtained in all the samples regarding the cleaning properties of the mold, as described above. The present invention has been described in detail with reference to the specific embodiments thereof, and it is to be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. Incidentally, the present application is based on the following patents: Japanese Patent Application No. 2〇〇9_16933〇 filed on July 17th, 2009, and No. 2009 filed on July 17th, 2009. No. 169,331, the contents of which are incorporated herein by reference. The mold cleaning composition of the present invention is used for cleaning, refurbishing, and the like of various molding molds of thermosetting resin molding materials, for example, to be molded by means of repetitive resin encapsulation. The mold for molding used in the semiconductor element is realized by performing injection molding or transfer molding using an epoxy resin molding material. 149716.doc