201000289 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種模具脫模回復用橡膠系組合物，更詳 、’、田而s，係關於一種用以使除去了硬化性樹脂之成形步驟 中所產生的模具表面之污垢後之模具表面的脫模性得以回 復之模具脫模回復用橡膠系組合物，其特徵在於，使用作 為基材樹脂之特定的未硫化橡膠、及特定的脫模劑。 【先前技術】 利用環氧樹脂成形材料等熱固性樹脂成形材料來使積體 電路等之密封成形物成形時，上述熱固性樹脂成形材料中 所含有之脫模劑滲出至成形物與模具之界面，藉此對切割 部、模穴部、流道部發揮脫模作用。若將此種成形連續進 订數百次以上’則成形材料中所含有之脫模劑或樹脂之低 分子量物等由於在高溫下反覆成形而氧化劣化，逐漸堆積 於模具上，因此引起如下不良情況：成形品之脫模性顯著 變差，或於成形品之表面產生表面粗糙等外觀不良，或於 成形後之印刷步驟中產生不良。 因此’為了避免此種狀況’必須實施清洗，但清洗後雖 然模具表面變乾淨，但另一方面模具表面之脫模劑亦被除 去’因此若剛清洗後立即再進行密封成形則存在模具脫模 性極差之問題。 ' 因此，使用清洗材料後，必須使模具脫模回復樹脂组八 物成形’使模具脫模回復樹脂組合物中之脫模劑轉移至： 具表面，而使脫模性回復。 139397.doc 201000289 另-方面’提出如下方法：使用含有清洗成分之未硫化 橡膠系化合物代替上述熱固性三聚氰胺樹脂成形材料，於 模具中硫化而形成硫化橡膠時，利用清洗成分將存在於模 具表面之脫模劑等之氧化劣化層分解並且與硫化橡膠形成 一體，繼而，將硫化橡膠自模具中取出，藉此清潔模具表 面。又’亦提出丁二烯橡膠/乙烯_丙烯橡膠成分設定成 90/10〜50/50重量份之橡膠系組合物作為未硫化橡膠成分 (例如參照美國專利第4935175號說明書、曰本專利特開平 4-357007 號公報）。 作為該等模具清潔用樹脂，可大致分成轉移型與壓縮型 這兩個類型，轉移型係使用三聚氰胺系樹脂成形材料，壓 知百型係使用二聚氰胺系樹脂成形材料以及橡膠系組合物。 近年來，隨著積體電路等（簡記為IC · LSI(integrated cirCUit/large sca!e integrati〇n ’積體電路/大型積體電路）） 之高積體化、薄型化、表面安裝化，成形品之形狀、結構 向多樣化發展，因此謀求半導體密封材料之高流動化或環 保化。 因此，高流動化型之環氧密封材料中，於通氣孔部分易 於產生樹脂堵塞，若產生該等堵塞，則排氣較差而導致樹 月曰麦彳于不動，因此未填充至模穴部而導致不良，故連續 成形較為困難。因此，為了避免該等狀況，必須實施清 洗，但使用轉移型清洗材料時，由於上述理由樹脂未正常 流動’因此難以除去堵塞於通氣孔之樹脂。 為了消除此種通氣孔之堵塞，而使用壓縮型清洗材料， 139397.doc 201000289 但若使用三聚氰胺系樹脂成形材料，雖缺 分之堵塞’但由於樹脂之流出 ：巧：通氣孔部 \ ^ 了棋具外周附近施加充 为之麼力，因此存在成形物之外周部變脆之傾向，將硬化 後之成形物自核具上除去之作業較為煩雜。相對於此，使 用橡膠系組合物之情形時 '植合物整體-致硬化，可形成 -片薄片狀成形物自模具中脫模’因此作業性得到改善。 然而，就流動性方面而t ’橡膠系組合物較三聚氰胺系樹201000289 VI. Description of the Invention: [Technical Field] The present invention relates to a rubber-based composition for mold release recovery, which is more detailed, and is related to the formation of a cured resin. A rubber-based composition for mold release recovery in which the mold release property of the surface of the mold after the step of the mold is restored is characterized in that a specific unvulcanized rubber as a base resin is used, and a specific mold release is used. Agent. [Previous Art] When a sealing molded article such as an integrated circuit is molded by a thermosetting resin molding material such as an epoxy resin molding material, the release agent contained in the thermosetting resin molding material is oozing out to the interface between the molded article and the mold. The pair of cutting portions, the cavity portions, and the flow path portions exert a mold release action. When the molding is continuously carried out for hundreds of times or more, the release agent or the low molecular weight material of the resin contained in the molding material is oxidatively deteriorated by repeated molding at a high temperature, and is gradually deposited on the mold, thereby causing the following defects. In the case, the mold release property of the molded article is remarkably deteriorated, or the surface of the molded article is poor in appearance such as surface roughness, or is defective in the printing step after molding. Therefore, in order to avoid such a situation, cleaning must be carried out, but although the surface of the mold is cleaned after cleaning, on the other hand, the release agent on the surface of the mold is also removed. Therefore, if the sealing is formed immediately after cleaning, there is a mold release. Very poor sex. Therefore, after the cleaning material is used, the mold must be demolded and returned to the resin group to form the mold release agent to release the release agent from the mold release resin composition to: have a surface to restore the mold release property. 139397.doc 201000289 In another aspect, a method is proposed in which a non-vulcanized rubber-based compound containing a cleaning component is used in place of the above-mentioned thermosetting melamine resin molding material, and when vulcanized in a mold to form a vulcanized rubber, a release agent which is present on the surface of the mold by using a cleaning component is used. The oxidatively degraded layer is decomposed and integrated with the vulcanized rubber, and then the vulcanized rubber is taken out from the mold, thereby cleaning the surface of the mold. Further, a rubber-based composition in which a butadiene rubber/ethylene-propylene rubber component is set to 90/10 to 50/50 parts by weight is also proposed as an unvulcanized rubber component (for example, refer to the specification of U.S. Patent No. 4,935,175, -357007 bulletin). The mold cleaning resin can be roughly classified into two types, a transfer type and a compression type, and a transfer type is a melamine resin molding material, and a melamine resin molding material and a rubber composition are used. . In recent years, with the integration of ICs, LSIs (integrated cirCUit/large sca!, integrative circuits, large-scale integrated circuits, surface mounting, etc.) Since the shape and structure of the molded article are diversified, it is desired to increase the fluidity or environmental protection of the semiconductor sealing material. Therefore, in the highly fluidized epoxy sealing material, resin clogging is apt to occur in the vent portion, and if such clogging occurs, the exhaust gas is poor, and the saplings are not moved, so that they are not filled into the cavity portion. Leading to poor, it is difficult to form continuously. Therefore, in order to avoid such a situation, it is necessary to perform cleaning. However, when a transfer type cleaning material is used, the resin does not flow normally due to the above reasons. Therefore, it is difficult to remove the resin that is clogged in the vent hole. In order to eliminate the clogging of such a vent hole, a compression type cleaning material is used, 139397.doc 201000289. However, if a melamine-based resin molding material is used, the clogging is lacking, but due to the outflow of the resin: the ventilating hole portion is a chess piece. Since the force is applied in the vicinity of the outer periphery, there is a tendency that the outer peripheral portion of the molded article becomes brittle, and the work of removing the hardened molded article from the nuclear device is complicated. On the other hand, in the case where a rubber-based composition is used, 'the whole body of the plant is hardened, and the sheet-like formed product can be released from the mold, and the workability is improved. However, in terms of fluidity, the t' rubber-based composition is more melamine-based than the melamine-based tree.
脂成形材料更差’因此存在對模穴内之填充性較差，無法 除去模穴角落等之污垢之問題點。 又，如 Plastic Dual Inline Package(塑 # 雙列直插封 裝）（以下簡記為PDIP)或Small 0utline Integmed ci㈣叫小 外型積體電路）（以了簡記為SOIC)等之模穴較深之小型封 裝製造用模具，或小型封裝之巾銷數純少特小的封裝製 造用模具中使用橡膠系組合物時，封裝之操作數變多，因 此易於產生硬化後之成形物黏貼於模具之現象。將其除去 時，存在以下問題：薄片狀成形物斷裂，而於模穴内產生 橡膠系組合物殘留之碎屑。若於該等模具中產生碎屑，則 由於模穴數較多，因此除去碎屑處之成形物時需要大量時 間，使得生產性大幅降低。 為了解決上述問題點，而尋求作業性（脫模性）、成形性 優異，脫模回復步驟後之模具脫模性長時間持續，密封成 形品之連續成形次數較多的脫模回復用橡膠系組合物。 專利文獻1 :美國專利第493 5 175號說明書 專利文獻2 :曰本專利特開平〇‘357007號公報 139397.doc 201000289 【發明内容】 如上所述，本發明之課題在於提供一種模具脫模回復用 橡膠系組合物，其可消除作業性（脫模性）雖然良好但會產 生空隙或碎屑之先前模具脫模回復用橡膠系組合物的缺 點，不會產生空隙或碎屑，並且脫模性回復後之模具脫模 性長時間持續，密封成形品之連續成形次數較多。 又，如上所述，本發明之課題在於提供一種模具脫模回 復用橡膠系組合物，其可消除作業性（脫模性）雖然良好但 會產生空隙或碎屑《先前帛具脫模回復用才象膠系組合物的 缺點，並且在如PDIP或S〇IC等之模穴較深之小型封裝製 造用模具、或者小型封裝之中銷數亦較少特小的封裝製造 用模具中亦不會產生空隙或碎屑，且脫模性回復後之模具 脫模性長時間持續，密封成形品之連續成形次數較多。 本發明藉由提供下述⑴、⑺及（3)之壓縮型模具脫模回 復用橡膠糸組合物’而解決上述課題。 (1) 一種壓縮型模具脫模回復用橡膠系組合物，其係將 於硬化性樹脂之成形步驟中所產生的模具表面之污垢除去 後，對模具表面賦予脫模性者，其特徵在於，使用乙烯_ 丙烯橡膠與丁二烯橡膠之調配比例設定成9〇/1 〇〜5〇/5〇重量 份之未硫化橡膠來作為基材樹脂，並且含有金屬皂系脫模 劑、以及選自有機脂肪酸酯系脫模劑、合成蠟脫模劑及脂 肪酸醯胺系脫模劑中之至少丨種脫模劑’上述未硫化橡膠 係硫化硬化後之伸長係數為8〇〜8〇〇%、拉伸強度為3〜1〇 MPa、橡膠硬度（硬度計硬度）為A60〜95、模具溫度175»c 139397.doc 201000289 下之鄉硫化時間（適當硫化點）tc(9〇)為心〇〇秒之值之範 圍的未瓜化橡勝。（以下，稱為第i模具脫模回復用橡膠系 組合物） ⑺-種㈣型模具脫模回復用橡膠系組合物其係將 於硬化性樹腊之成形步驟中所產生的模具表面之污垢除去 後，對模具表面賦予脫模性者，其特徵在於，使用乙稀_ 丙烯橡膠與丁二烯橡膠之調配比例設定成則Q〜5G/5〇重量 份之未硫化橡膠來作為基材樹脂，並且含有金屬皂系脫模 劑、以及選自有機脂肪酸酯系脫模劑、合成樣脫模劑及脂 肪酸醯胺系脫模齊！中之至少！種脫模齊卜上述未硫化橡膠 係硫化硬化後之伸長係數為8〇〜8〇〇%、拉伸強度為3〜ι〇 MPa、橡膠硬度（硬度計硬度）為A6〇〜％、模具溫度 下之9〇%硫化時間（適當硫化點）tc(90)為200〜400秒之值之 範圍的未硫化橡膠。（以下，稱為第2模具脫模回復用橡膠 系組合物） (3 )種壓备目型模具脫模回復用橡勝系組合物，其係將 於硬化性樹脂之成形步驟中所產生的模具表面之污垢除去 後，對模具表面賦予脫模性者，其特徵在於，使用乙烯_ 丙稀橡膠與丁二烯橡膠之調配比例設定成9〇/1 〇〜5〇/5〇重量 伤之未硫化橡膠來作為基材樹脂，並且含有選自金屬皂系 脫模劑、有機脂肪酸酯系脫模劑、合成蠟脫模劑及脂肪酸 醯胺系脫模劑中之至少丨種脫模劑，上述未硫化橡膠係硫 化硬化後之伸長係數為80〜800%、拉伸強度為3〜1〇 Mpa、 橡膠硬度（硬度計硬度）為A60〜95、模具溫度i75°C下之9〇〇/〇 139397.doc 201000289 硫化時間（適當硫化點）tc(9〇)為2〇〇〜4〇〇秒之值之範圍的未 硫化橡膠。（以下’稱為第3模具脫模回復用橡膠系組合物） 本發明之第1、第2及第3模具脫模回復用橡膠系組合物 不僅作業性（脫模性）優異，而且成形性或強度亦優異，進 而不會產生空隙或碎屑’脫模性回復後之模具脫模性長時 間持續，密封成形品之連續成形次數較多。 本發明之第2及第3模具脫模回復用橡膠系組合物尤其適 &於如PDIP或SOIC等之模穴較深之小型封裝製造用模 具’或小型封裝之中銷數亦較少特小之封裝製造用模具的 脫模回復。 【實施方式】 以下，首先對本發明之第i模具脫模回復用橡膠系組合 物加以詳細說明。 本發明中所使用之未硫化橡膠係將乙烯_丙烯橡膠與丁 二烯橡膠混合併用者。The fat-forming material is worse. Therefore, there is a problem that the filling property in the cavity is poor, and the dirt such as the corner of the cavity cannot be removed. In addition, such as the Plastic Dual Inline Package (hereinafter referred to as PDIP) or Small 0utline Integmed ci (four) is a small external integrated circuit) (simply referred to as SOIC), etc. When a rubber-based composition is used in a package manufacturing mold for a package manufacturing mold or a small-sized package, the number of operations of the package is increased, so that the molded product after curing is likely to adhere to the mold. When it is removed, there is a problem that the sheet-like formed product is broken, and crumbs remaining in the rubber-based composition are generated in the cavity. If debris is generated in the molds, since the number of cavities is large, a large amount of time is required to remove the molded articles at the scraps, and the productivity is drastically lowered. In order to solve the above problems, the workability (release property) and the moldability are excellent, and the mold release property after the mold release step is continued for a long period of time, and the rubber for mold release for sealing the molded article is often used. combination. Patent Document 1: U.S. Patent No. 4,935,175, the disclosure of which is incorporated herein by reference. A rubber-based composition which can eliminate the disadvantage of the rubber composition of the previous mold release-recovery which is good in the workability (release property) but which causes voids or chips, does not generate voids or debris, and has mold release property. The mold release property after the recovery is continued for a long time, and the number of continuous molding of the sealed molded article is large. Further, as described above, an object of the present invention is to provide a rubber-based composition for mold release recovery, which is excellent in workability (release property) but which may cause voids or chips. It is not only a disadvantage of a gel-based composition, but also a small-package manufacturing mold such as PDIP or S〇IC, or a package for manufacturing a package having a small number of pins and a small package. The voids or chips are generated, and the mold release property after the mold release recovery is continued for a long time, and the number of times of continuous molding of the sealed molded article is large. The present invention solves the above problems by providing a compression type mold of the following (1), (7) and (3) to release the rubber ruthenium composition. (1) A rubber-based composition for releasing a mold for mold release, which is characterized in that, after removing the dirt on the surface of the mold which is formed in the step of forming the curable resin, the release property is imparted to the surface of the mold. An unvulcanized rubber having a ratio of ethylene propylene rubber to butadiene rubber of 9 〇 /1 〇 5 5 /5 parts by weight is used as a base resin, and contains a metal soap release agent, and is selected from organic At least one of the fatty acid ester-based release agent, the synthetic wax release agent, and the fatty acid amide-based release agent, the elongation coefficient of the unvulcanized rubber after vulcanization and hardening is 8 〇 to 8 〇〇%, and is pulled. The tensile strength is 3~1〇MPa, the rubber hardness (hardness hardness) is A60~95, the mold temperature is 175»c 139397.doc 201000289 The hometown curing time (appropriate curing point) tc(9〇) is palpitations The range of values is not melonized rubber. (Hereinafter, it is called the rubber composition for the i-th mold release recovery) (7) The rubber composition for mold release of the type (four) type mold is the dirt of the mold surface which is generated in the molding step of the curable wax. After the removal, the mold release property is imparted to the surface of the mold, and the unvulcanized rubber having a weight ratio of ethylene to propylene rubber and butadiene rubber is set to be Q to 5 G/5 parts by weight as the base resin. Further, it contains a metal soap-based release agent, and is selected from an organic fatty acid ester-based release agent, a synthetic sample release agent, and a fatty acid amide-based release agent. At least! The release modulus of the above unvulcanized rubber after vulcanization and hardening is 8〇~8〇〇%, the tensile strength is 3~ι〇MPa, the rubber hardness (hardness hardness) is A6〇~%, and the mold temperature is The 9% by weight vulcanization time (appropriate cure point) tc (90) is an unvulcanized rubber in the range of 200 to 400 seconds. (hereinafter, referred to as a rubber composition for second mold release recovery) (3) A rubber-based composition for mold release mold release, which is produced in a molding step of a curable resin. After the dirt on the surface of the mold is removed, the mold release property is imparted to the mold surface, and the blending ratio of ethylene-propylene rubber and butadiene rubber is set to 9 〇/1 〇 5 5 〇 〇 〇 The unvulcanized rubber is used as a base resin, and contains at least one type of release agent selected from the group consisting of a metal soap release agent, an organic fatty acid ester release agent, a synthetic wax release agent, and a fatty acid amide amine release agent. The unvulcanized rubber has an elongation coefficient after vulcanization and hardening of 80 to 800%, a tensile strength of 3 to 1 〇Mpa, a rubber hardness (hardness hardness) of A60 to 95, and a mold temperature of i75 ° C at 9 〇〇/〇. 139397.doc 201000289 vulcanization time (appropriate cure point) tc (9 〇) is an unvulcanized rubber in the range of 2 〇〇 to 4 〇〇 seconds. (The following is a rubber composition for the third mold release-recovery.) The rubber-based composition for the first, second, and third mold release of the present invention is excellent in workability (release property) and formability. The strength is also excellent, and no voids or chips are generated. The mold release property after the mold release recovery is continued for a long time, and the number of continuous molding of the seal molded article is large. The second and third mold release-recovering rubber-based compositions of the present invention are particularly suitable for use in small-sized package manufacturing molds or small packages such as PDIP or SOIC. The mold release of the small package manufacturing mold. [Embodiment] Hereinafter, the rubber composition for the i-th mold release of the present invention will be described in detail. The unvulcanized rubber used in the present invention is a mixture of an ethylene-propylene rubber and a butadiene rubber.
所謂乙烯-丙烯橡膠（以下，有時簡記為EPM(ethylene propylene rubber))，主要係指包含通常之乙烯_丙烯橡膠 (EPM)與乙烯-丙烯-二烯橡膠（以下，有時簡記為EpDM (ethylene propylene diene rubber))兩者。 作為上述EPM，較好的是乙烯與心烯烴（尤其為丙烯）之 共聚合比例以莫耳比計為乙烯/α_烯烴=55/45〜83/17、孟納 黏度（Mooney viscosity)MI^+4(i〇(rc)g5〜3〇〇者，尤其好 的是上述共聚合比例以莫耳比計為乙烯/α_烯烴 = 55/45 〜61/39、孟納黏度 ML1+4(l〇(TC)為 36 〜44 者。 139397.doc 201000289 又，上述epdm係由乙烯盥α_嫌 /、佈焱及具有非共軛雙鍵 之％狀物或非環狀物所構成 再战之一兀共聚物。若加以詳細敍 迷’則係由乙稀與α_稀煙(尤其為丙稀)、及多稀單體所構 成之三元共聚物。 作為上述多烯單體，可列舉：二環戊二稀、5_環辛二 烯、π環十二碳二稀、…·環十二碳三烯、環庚二 烯、1，4-環己二稀、降福二烯、”基降宿烯、2_甲基戊The ethylene-propylene rubber (hereinafter sometimes referred to as EPM (ethylene propylene rubber)) mainly includes ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (hereinafter, abbreviated as EpDM (hereinafter sometimes referred to as EpDM). Ethylene propylene diene rubber)) Both. As the above EPM, it is preferred that the copolymerization ratio of ethylene to a heart olefin (especially propylene) is ethylene/α-olefin = 55/45 to 83/17 in terms of molar ratio, and Mooney viscosity MI^ +4(i〇(rc)g5~3〇〇, especially preferably, the above copolymerization ratio is ethylene/α_olefin = 55/45 ～61/39 in terms of molar ratio, and Mengna viscosity ML1+4 ( L〇(TC) is 36 to 44. 139397.doc 201000289 In addition, the above epdm is composed of ethylene 盥α_ suspect/, cloth and a non-conjugated double bond or acyclic One of the ruthenium copolymers. If it is described in detail, it is a terpolymer composed of ethylene and α-lean smoke (especially propylene) and a plurality of dilute monomers. Listed: dicyclopentadiene, 5-cyclooctadiene, π-cyclododecaxene, ... cyclododecatriene, cycloheptadiene, 1,4-cyclohexanediene, pentadiene "base pentene, 2_methyl pentyl
一烯::，4、i，5-己二烯、I6·庚二烯、甲基-四氫茚、1，4-己 二烯等。此種三元共聚物中之各單體之共聚合比例較好的 是乙烯為30〜80莫耳％，多稀單體為〇1〜2莫耳％，其餘 &烯烴。更好的是乙烯為3〇〜6〇莫耳％。並且，作為上述2 元共聚物即EPDM’較好的是使用孟納黏度MLi + 4(i〇(rc) 為20〜70者。 又，作為上述丁二烯橡膠（以下，有時簡記為BR)，可較 好地使用具有，,4鍵之含量為9〇重量％以上之高順結構， 孟納黏度ML1+4(10(TC )為20〜60、尤其好的是30〜45者。 並且，上述乙烯-丙烯橡膠與丁二烯橡膠之調配比例以 重里比计為90/10〜50/50重量份，較好的是8〇/2〇〜6〇/4〇重 量份。 若乙烯-丙烯橡膠之調配量超過9〇重量份，則模具脫模 性麦差，因此不佳。若丁二稀橡膠之調配量超過5〇重量 伤，則模具脫模性變好，但硫化後之成形物變硬變脆而易 於產生碎屑，因此不佳。 上述未硫化橡膠係硫化硬化後之伸長係數為80〜800%、 I39397.doc 201000289 較好的是1〇〇〜3〇〇%者。若伸長係數為以下，則成形性 變差，因此不佳。 上述未硫化橡膠係硫化硬化後之拉伸強度為3〜1〇 Mpa、 較好的是5〜8 MPa者。若拉伸強度 Mpa以 碎屑，因此不佳。 上述未硫化橡膠係硫化硬化後之橡膠硬度（硬度計硬度） 為A60 95、較好的是A7〇〜9〇者。若橡膠硬度偏離該範 圍’則產生碎屑或空隙，因此不佳。 上述未硫化橡膠係模具溫度175t：下之9〇%硫化時間（適 當硫化點）tc(90)為5〇〜1〇〇秒、較好的是7〇〜1〇〇秒者。若 忱（90)之值在該範圍内，則硫化速度不會過快，可使樹脂 填充至模穴之各個角落，因此可實施脫模回復而不會產生 黏附等不良情況。 本發明之第1模具脫模回復用橡膠系組合物除上述未硫 化橡膠之夕卜3有金屬皂系脫模劑、以及選自有機脂肪酸 酉曰系脫杈劑、合成蠟及脂肪酸醯胺系脫模劑中之至少1種 脫模劑。 作為金屬皂系脫模劑之例，例如可例示硬脂酸鈣、硬脂 酸辞ϋ酸鋅等。作為有機脂肪酸自旨系脫模劑、合成 蠟、脂肪酸醯胺系脫模劑，可例示Lic〇wax 〇p(ciariant Japan股份有限公司製造之褐煤酸部分息化醋）、L〇xi〇i & 78(C〇gniS Japan股份有限公司製造之高分子複合酯）、 L1C〇lub H-4(Clariant japarU5;份有限公司製造之改性烴系 蠟）、Loxiol VPN88l(C〇gnis japan股份有限公司製造之礦 139397.doc -10- 201000289 物油系合成蠟）、Fatty Amide S(花王股份有限公司势造之 脂肪酸醯胺）、Kao Wax EB-P(花王股份有限公 J表造之脂 肪酸醯胺）、Alflow HT-50(日本油脂股份有限公司製、土之 脂肪酸醯胺）等。 金屬皂系脫模劑與其他脫模劑（有機脂肪酸3旨系脫模 劑、合成蠟、脂肪酸醯胺系脫模劑）之比例較好的是·' 10〜3 0 : 70。若其他脫模劑之比例過多，則揸嬙山 π逆項成形性變 差，因此不佳。 金屬皂系脫模劑及其他脫模劑（有機脂肪酸_系脫模 劑、合成蠟、脂肪酸醯胺系脫模劑）之總添加量相對於未 硫化橡膠100重量份，較好的是0.5〜3〇重量份。 若脫模劑之量不足’則模具脫模性下降，若脫模劑之量 過多則模具脫模性良好，但模具脫模回復用橡膠系故人= 熔融時之流動性顯著下降，從而成形性變差，此外脫^。 復步驟後之假射出次數增加，因此不佳。 ' ° 本發明之第1模具脫模回復用橡膠系組合物除上述未访 化橡膠及上述脫模劑之外’可含有填充劑、清洗劑Y清硫 :劑、硫化劑、硫化助劑、硫化促進劑、硫化促進:: 作為填充劑（增強劑），可列舉：二氧化石夕、氧化麵… 酸約、氫氧化铭、氧化鈦等。上述填充劑之使用量相對: 未硫化橡膠100重量份，較好的早 ' 杈好的疋10〜70重量份，更好 30〜60重量份。 疋 作為清洗劑，例如可列舉：覃酿 早乙二乙醇胺、三乙 139397.doc 11 201000289 醇胺、N-甲基二乙醇 二醇二甲喊、二乙_: ，N_二正丁基乙醇胺等胺類，乙 類，㈣類及= 三乙二醇二曱趟等二_ 、上述π洗劑之使用量相對於未# 化橡膠100重量份，# 、未硫 舌β ^ , 較好的疋5〜50重量份’更好的是5〜3〇 重ϊ：份。此外亦可你田田^ j 〇 使用界面活性劑等清洗助劑。 作為硫化劑’例如可 一筮二a'贫 m軋化一第二丁基、過氧化 一第二戊基、過氧化二異丙笨、2,5_二甲基_25 基過氧基）己烷等過氧化_ ，一（第二丁 1，1-雔（第三丁其、k 一烯丙基類有機過氧化物，例如 二、-土過氧基）-3,3,5-三甲基環己烷、1，1、雙（第 二丁基過氧基）環己烷、22雔/ά - d d ^ , ，又（弟二丁基過氧基）辛烷、 4,4-雙（弟三丁基過氣笑 ^甘 土）戊义正丁酯、2,2_雙（第三丁基過 )丁烧等過氧化縮酮類有機過氧化物。通常與過氧化 -稀丙基類比較’過氧化縮_類具有較長的半生期，該等 可依據組合物之設計而單獨使用’亦可將半生期較長者盘 較紐者併用而調整硫化速度。上述硫化劑之使用量相對於 未硫化橡膠1〇0重量份，較好的是Η重量份，更好的是 2〜4重量份。此外亦可#闲 吏用丙烯酸單體或硫等硫化助劑。 作為硫化促進劑，可列舉：例如二苯脈、三苯脈等脈 系，例如甲酸-對甲苯胺縮合物、乙搭-苯胺反應物等酸-胺 糸或醛-氨系，例如2_鲸基笨并嘍。坐、二苯并噻唑基二硫 化物等㈣系等’可使用氧化鐫、氧化錯、石灰等硫化促 進助劑。 本發明之第1模具脫模回復用橡膝系組合物中，除該等 調配物之外，⑲需要例如為了與清洗材料相區別，可使用 139397.doc 201000289 顏料或著色劑。可例示如下 ^ 卜之者色劑.例如氧化鈦、碳 '.、、.、乳化辞、編黃、鐵丹、鐵藍、鐵黑、群青、辞鋇白 _〇P叫、鈦黃、姑藍等無機顏料，例如酿菁系、偶氮 系重氮系、漢薩頁（hansa yell〇w)、啥口丫。定酮紅等有機顏 料，例如笨并噚唑♦、笑 _ 夕、 ^不、酚二唑系、香豆素等之螢光顏 枓，例如墓酉昆系、旋系、偶氮系等之染料。上述顏料或著 色劑之使用量相對於未硫化橡膠1GG重量份，較好的是 〇.〇1〜1重量份左右。 繼而，對本發明之第2模具脫模回復用橡膠系組合物加 以說明。 本發明之第2模具脫模回復用橡膠系組合物除以下方面 外與本發明之第1模具脫模回復用橡膠系組合物相同， 即，作為基材樹脂而使用的未硫化橡膠係模具溫度1 75亡 下之90%硫化時間（適當硫化點）tc(9〇)為2〇〇〜4〇〇秒、較好 的是250〜350秒之未硫化橡膠。 ) 上述tc(90)之值之調整可根據二烯之種類或量、過氧化 物之種類或量、硫化促進劑之種類或量、共交聯劑之種類 或量等進行適當調整。 若上述未硫化橡膠之tc(9〇)之值在2〇〇〜400秒之範圍内， 則硫化速度不會過快，並可使樹脂填充至模穴之各個角 落’因此可實施脫模回復而不會產生黏附等不良情況。 繼而’對本發明之第3模具脫模回復用橡膠系組合物加 以說明。 本發明之第3模具脫模回復用橡膠系組合物除以下方面 139397.doc -13- 201000289 外’與本發明之第2模具脫模回復用橡膠系組合物相同， 即’脫模劑係選自金屬皂系脫模劑、有機脂肪酸酯系脫模 劑、合成蠟脫模劑及脂肪酸醯胺系脫模劑中之至少1種脫 模劑。 作為選自金屬皂系脫模劑、有機脂肪酸酯系脫模劑、合 成蟻脫模劑及脂肪酸醯胺系脫模劑中之至少1種脫模劑之 添加量，相對於未硫化橡膠1〇〇重量份，較好的是1〇〜5〇重 畺伤。若該脫模劑之量不足，則如pDIp或s〇IC等之模穴 較深的小型封裝中’銷數亦較少特小之封裝製造用模具之 模具脫模性下降，若該脫模劑之量過多，則模具脫模性良 好，但模具脫模回復用橡膠系組合物熔融時之流動性顯著 下降而使成形性變差，此外，脫模回復步驟後之假射出次 數增加，因此不佳。 作為本發明之第1、第2及第3模具脫模回復用橡膠系組 合物之製備方法，並無特別限定，可採用眾所周知之方 法。例如，向附有夾套之加壓型捏合機中投入EpM及^汉原 料並開始混練，一面觀察原料之適宜溫度一面繼續混練’，、 直至EPM與BR之混合原料成為年糕狀。並且，於該混合原 料之溫度達到70〜11〇。(：之時間點，添加脫模劑、白碳、胺 基醇系化合物、環狀醯胺化合物、加工處理油、非離子系 界面活性劑、硬脂酸等並混練數分鐘。繼而，添加有機: 氧化物及硫等快速分散後取出，㈣要成形為例如薄片^ 等適當形狀而製成本發明之模具脫模回復用橡膠系袓人 139397.doc 14 201000289 作為此練機構’除上述加壓型捏合機之外，例如可列 舉·班布裏混合機（Banbury mixer)、輥式混合機（r〇U mixer)等。 本發明之第1、第2及第3模具脫模回復用橡膠系組合物 之形悲並無特別限定’若不將經混練之樹脂組合物迅速冷 部’則由於混練時之預熱會促進硫化，而無法獲得穩定之 性旎’因此較好的是可以較短時間容易冷卻之薄片狀。 實施例 以下’列舉實施例等對本發明進行更詳細說明，但本發 明並不受該等實施例等任何限定。 S式驗方法 實％例及比較例中記載之各種物性評價之試驗方法如以 下所述。 [伸長率及拉伸強度] 依據JIS K625 1之拉伸強度及切斷時伸長率之測定方法 進行測定。 <試驗片之製作條件> 使用37T自動壓機，以模具溫度為175t、成形壓力為1〇 MPa(錶壓）、成形時間為5分鐘之條件使未硫化試料成形。 經成形之試驗片尺寸為8〇xl6〇x2 mm之薄片狀，使用3號 °亞鈴對其進行打孔製成測定用試驗片。 [橡膠硬度] 利用依據JIS K6253『硫化橡膠及熱塑性橡膠之硬度試 驗方法』之方法進行測定。 139397.doc -15· 201000289 將上述利用試驗片製作條件所獲得之8〇xl60x2 mm試驗 片重疊3片，使用與橡膠硬度相對應之類型的硬度計，而 測定硬度計硬度。 [硫化速度] 使用依據JIS K6300-2『利用振動式硫化試驗機求出硫化 特性之方法』之方法，在模具溫度為175°C下測定90%硫 化時間（適當硫化點）tc(90)。 [脫模回復試驗] 模具之初始化 進行模具脫模回復用橡膠系組合物之試驗時，必須使試 驗前之模具表面狀態為固定，因此使用市售之三聚氰胺樹 脂系模具清洗材料（NIPPON CARBIDE INDUSTRIES股份 有限公司製造之Nikalet ECR-CL)，藉由轉移成形實施5次 射出之清洗，進而，使用市售之三聚氰胺樹脂系模具清洗 材料（NIPPON CARBIDE INDUSTRIES股份有限公司製造 之Nikalet ECR-SW7320)，藉由壓縮成形實施2次射出之清 洗，從而進行模具清洗。 <成形條件> 模具：實施例1〜8中使用QFP。 實施例9〜12中使用PDIP-8L(8投膠口 -96模穴）。Monoolefin: :, 4, i, 5-hexadiene, I6·heptadiene, methyl-tetrahydroanthracene, 1,4-hexadiene, and the like. The copolymerization ratio of each of the monomers in the terpolymer is preferably from 30 to 80 mol% of ethylene, and the dilute monomer is 〇1 to 2 mol%, and the rest & olefin. More preferably, the ethylene is 3 〇 to 6 〇 mol%. In addition, it is preferable to use the Mona viscosity MLi + 4 (i 〇 (rc) is 20 to 70 as the above-mentioned bipolymer, that is, the above-mentioned butadiene rubber (hereinafter, abbreviated as BR) It is preferable to use a high-cis structure having a content of 4 bonds of 9 〇 or more, and a Mona viscosity ML1+4 (10 (TC ) of 20 to 60, particularly preferably 30 to 45). Further, the blending ratio of the above ethylene-propylene rubber to butadiene rubber is from 90/10 to 50/50 parts by weight, preferably from 8〇/2〇 to 6〇/4 parts by weight, based on the weight ratio. - If the blending amount of propylene rubber exceeds 9 〇 by weight, the mold release property is poor, so it is not good. If the blending amount of butyl rubber is more than 5 〇, the mold release property is improved, but after vulcanization The molded article is hard and brittle and is liable to generate chips, which is not preferable. The above-mentioned unvulcanized rubber has an elongation coefficient after vulcanization and hardening of 80 to 800%, and I39397.doc 201000289 is preferably 1 to 3 % by weight. When the elongation coefficient is less than, the moldability is deteriorated, which is not preferable. The tensile strength of the unvulcanized rubber after vulcanization and hardening is 3 to 1 〇Mpa. Preferably, it is 5 to 8 MPa. If the tensile strength Mpa is detritus, it is not preferable. The rubber hardness (hardness hardness) of the unvulcanized rubber after vulcanization and hardening is A60 95, preferably A7〇~ 9. If the rubber hardness deviates from this range, then crumbs or voids are generated, so it is not good. The above unvulcanized rubber mold temperature is 175t: the next 9〇% vulcanization time (appropriate vulcanization point) tc(90) is 5〇~ 1 〇〇 second, preferably 7 〇 to 1 〇〇 second. If the value of 忱 (90) is within this range, the vulcanization rate is not too fast, and the resin can be filled into every corner of the cavity, so The rubber-based composition for mold release of the first mold of the present invention has a metal soap-based release agent in addition to the above-mentioned unvulcanized rubber, and is selected from the group consisting of organic fatty acid 酉. At least one of a release agent, a synthetic wax, and a fatty acid amide-based release agent. Examples of the metal soap release agent include calcium stearate and zinc stearate. Etc. As a release agent for organic fatty acids, synthetic waxes, fatty acids The amine-based release agent can be exemplified by Lic〇wax 〇p (montanic acid partially vinegar manufactured by ciariant Japan Co., Ltd.), L〇xi〇i & 78 (polymer composite manufactured by C〇gniS Japan Co., Ltd.) Ester), L1C〇lub H-4 (Clariant japarU5; modified hydrocarbon wax manufactured by Co., Ltd.), Loxiol VPN88l (mine produced by C〇gnis japan Co., Ltd. 139397.doc -10- 201000289) ), Fatty Amide S, Kao Wax EB-P (Kao Wax EB-P), Alflow HT-50 (made by Nippon Oil Co., Ltd.) The fatty acid guanamine) and the like. The ratio of the metal soap-based release agent to other mold release agents (organic fatty acid 3-based release agent, synthetic wax, and fatty acid amide-based release agent) is preferably '10 to 30:70. If the ratio of other release agents is too large, the π reverse shape formability of the Laoshan Mountain is deteriorated, which is not preferable. The total addition amount of the metal soap-based release agent and other mold release agents (organic fatty acid-based release agent, synthetic wax, fatty acid amide-based release agent) is preferably 0.5 to 3 with respect to 100 parts by weight of the unvulcanized rubber. 〇 by weight. If the amount of the releasing agent is less than 'the mold release property is lowered, if the amount of the releasing agent is too large, the mold release property is good, but the rubber for the mold release recovery is lowered. The fluidity at the time of melting is remarkably lowered, and the formability is lowered. Change, in addition to off ^. The number of false shots after the step is increased, so it is not good. '° The rubber-based composition for mold release of the first mold of the present invention may contain a filler, a cleaning agent Y sulfur-reducing agent, a vulcanizing agent, a vulcanization aid, etc., in addition to the above-mentioned unvisited rubber and the above-mentioned release agent. Vulcanization accelerator and vulcanization promotion: Examples of the filler (reinforcing agent) include: cerium oxide, oxidized surface, acid, oxyhydroxide, and titanium oxide. The amount of the above filler to be used is relatively 100 parts by weight of the unvulcanized rubber, preferably 10 to 70 parts by weight, more preferably 30 to 60 parts by weight. As a cleaning agent, for example, brewing early ethylenediethanolamine, triethylene 139397.doc 11 201000289 alcohol amine, N-methyldiethanol glycol dimethyl sulfonate, diethyl _:, N-di-n-butylethanolamine Equivalent amines, B, (4) and = triethylene glycol diterpenoids, etc., the use amount of the above π lotion relative to 100 parts by weight of the rubber, #, sulfur-free tongue β ^, preferably疋 5 to 50 parts by weight 'better is 5 to 3 〇 heavy ϊ: portions. In addition, you can also use a cleaning agent such as a surfactant in Tian Tian ^ j 〇. As a vulcanizing agent', for example, a second butyl group, a second pentyl peroxide group, a diisopropyl peroxide group, a 2,5-dimethyl-25-peroxy group can be rolled. Peroxidation such as hexane, _, a (second butyl 1,1-anthracene (third butyl, k-allyl organic peroxide, such as di-o-peroxy)-3,3,5- Trimethylcyclohexane, 1,1, bis(t-butylperoxy)cyclohexane, 22雔/ά-dd ^ , , (di-dibutylperoxy)octane, 4,4 - Bis (dibutyl butyl nitrous oxide ^ gluten) pentyl butyl ketone, 2, 2 bis (t-butyl peroxy) butyl ketone and other peroxide ketal organic peroxides. Usually with peroxide - Compared with the propyl group, the 'peroxidation shrinkage class has a longer half-life period, and these can be used alone according to the design of the composition', and the vulcanization rate can also be adjusted by using the longer half-life period. The amount of use is preferably 0 to 4 parts by weight, more preferably 2 to 4 parts by weight, based on 1 part by weight of the unvulcanized rubber. Further, it may be used as a vulcanization aid such as an acrylic monomer or sulfur. Promoters, for example, for example: a pulse system such as a benzene pulse or a triphenyl hydride, such as a formic acid-p-toluidine condensate or an acetonitrile-aniline reactant, such as an acid-amine oxime or an aldehyde-ammonia system, for example, a 2-whale-based stupid. A vulcanization-promoting aid such as thiazolyl disulfide or the like may be used, and a rubber-promoting auxiliary agent such as cerium oxide, oxidized oxidized or lime may be used. The first rubber mold release composition for mold release of the present invention, in addition to the formulations, 19 needs to be used, for example, in order to distinguish it from the cleaning material, 139397.doc 201000289 pigment or coloring agent can be used. The following can be exemplified by the following toners. For example, titanium oxide, carbon '.,., emulsification, yellow, iron , iron blue, iron black, ultramarine, resignation white _ 〇 P called, titanium yellow, kulan and other inorganic pigments, such as phthalocyanine, azo-diazide, Hansa page (hansa yell〇w), 啥口丫. Organic pigments such as ketone red, such as stupid carbazole ♦, _ _ eve, ^ no, phenol diazole, coumarin, etc., such as tombs, spines, azo The dye or the like is used in an amount of 1 GG by weight of the unvulcanized rubber, preferably 1 to 1 part by weight to the left. Then, the rubber-based composition for mold release of the second mold of the present invention will be described. The rubber composition for mold release of the second mold of the present invention is the same as the rubber for mold release of the first mold of the present invention. The composition is the same, that is, the 90% vulcanization time (appropriate vulcanization point) tc (9 〇) of the unvulcanized rubber-based mold used as the base resin is 1 〇〇 4 4 sec. The unvulcanized rubber is 250 to 350 seconds.) The value of the above tc (90) can be adjusted according to the type or amount of the diene, the type or amount of the peroxide, the type or amount of the vulcanization accelerator, and the co-crosslinking agent. The type or amount is appropriately adjusted. If the value of tc (9〇) of the above unvulcanized rubber is in the range of 2 〇〇 to 400 seconds, the vulcanization rate is not too fast, and the resin can be filled into each corner of the cavity, so that the mold release can be performed. There will be no problems such as adhesion. Next, the rubber composition for releasing the third mold of the present invention will be described. The rubber composition for mold release of the third mold of the present invention is the same as the rubber composition for the second mold release recovery of the present invention except for the following aspects 139,397.doc -13 - 201000289, that is, the release agent is selected. At least one release agent from a metal soap-based release agent, an organic fatty acid ester-based release agent, a synthetic wax release agent, and a fatty acid amide-based release agent. The amount of at least one type of release agent selected from the group consisting of a metal soap release agent, an organic fatty acid ester release agent, a synthetic ant release agent, and a fatty acid amide amine release agent is 1 相对 relative to the unvulcanized rubber. 〇 by weight, preferably 1〇~5〇 heavy bruises. If the amount of the mold release agent is insufficient, the mold release property of the package manufacturing mold in which the number of pins is smaller than that of a small package having a deep cavity such as pDIp or s〇IC is lowered, and if the mold release property is lowered, the mold release property is lowered. When the amount of the agent is too large, the mold release property is good, but the fluidity at the time of melting the rubber composition for mold release recovery is remarkably lowered to deteriorate the moldability, and the number of false shots after the mold release step is increased. Not good. The method for producing the rubber composition for the first, second, and third mold release of the present invention is not particularly limited, and a well-known method can be employed. For example, the EpM and the Han raw material are put into a jacketed press kneader and kneading is started, and the kneading is continued while observing the appropriate temperature of the raw material, until the mixed raw material of the EPM and the BR becomes a rice cake. Further, the temperature of the mixed raw material reached 70 to 11 Torr. (At the time point, add a release agent, white carbon, an amino alcohol-based compound, a cyclic guanamine compound, a processing oil, a nonionic surfactant, stearic acid, etc., and mix for several minutes. Then, add organic : Oxide and sulfur are taken out after rapid dispersion, and (4) are formed into a suitable shape such as a sheet, etc., to form a rubber mold for mold release of the present invention. 139397.doc 14 201000289 As the training mechanism, in addition to the above-mentioned pressurized type In addition to the kneading machine, for example, a Banbury mixer, a roller mixer, or the like, a rubber mixer combination for the first, second, and third mold release of the present invention. The shape of the object is not particularly limited. 'If the resin composition that is kneaded is quickly cooled, the preheating during mixing will promote vulcanization, and it will not be able to obtain stable properties. Therefore, it is better to have a shorter time. The present invention will be described in more detail below by way of examples and the like, but the present invention is not limited to the examples and the like. The method of the invention is described in the % examples and the comparative examples. The test method for evaluation is as follows. [Elongation and tensile strength] The measurement was carried out in accordance with the measurement method of tensile strength and elongation at break in JIS K625 1. <Production conditions of test piece> Automatic pressure using 37T The unvulcanized sample was formed under the conditions of a mold temperature of 175 t, a forming pressure of 1 MPa (gauge pressure), and a forming time of 5 minutes. The formed test piece was in the form of a sheet of 8 〇 x 16 〇 x 2 mm, and was used. The test piece for measurement was punched out on the No. 3 °. [Rubber hardness] The measurement was carried out by the method according to JIS K6253 "Test method for hardness of vulcanized rubber and thermoplastic rubber". 139397.doc -15· 201000289 The 8 〇 xl 60 x 2 mm test piece obtained by the test piece production conditions was overlapped by 3 pieces, and the hardness of the hardness tester was measured using a hardness tester of a type corresponding to the rubber hardness. [Vulcanization speed] Use according to JIS K6300-2 "Using vibration type vulcanization The method of determining the vulcanization characteristics of the testing machine, the 90% vulcanization time (appropriate vulcanization point) tc (90) is measured at a mold temperature of 175 ° C. [Release recovery test] Initial mold When testing the rubber-based composition for mold release recovery, the surface state of the mold before the test must be fixed. Therefore, a commercially available melamine resin-based mold cleaning material (Nikalet ECR-CL manufactured by NIPPON CARBIDE INDUSTRIES Co., Ltd.) is used. The melamine resin-based mold cleaning material (Nikalet ECR-SW7320, manufactured by NIPPON CARBIDE INDUSTRIES Co., Ltd.) was used for the cleaning by the injection molding, and the cleaning was performed twice by compression molding. Thereby the mold cleaning is performed. <Forming Condition> Mold: QFP was used in Examples 1 to 8. PDIP-8L (8-gut-96 cavities) was used in Examples 9 to 12.
模具溫度：175°C/175°C 硬化時間：ECR-CL 300秒 SW7320 180 秒 脫模回復試驗 139397.doc -16- 201000289 用以杈具初始化之清潔結束後，藉由壓縮成形使模具脫 模回復用橡膠系組合物以硬化時間為200秒進行3次射出成 形。其後’使用市售之聯苯系環氧樹脂成形材料 (Sumitomo Bakehte股份有限公司製造之eme-7351T)實施 成形’對脫模性及連續成形性進行評價。 <成形條件> 模具：QFP或 PDIP-8L 模具溫度：175°(：/175。〇 i 硬化時間：100秒 實施例1(本發明之第1模具脫模回復用橡膠系組合物） 向3000 ml之附有夾套之加壓型捏合機中，添加EPDM原 料[孟納黏度ML1+4(l〇〇°C )為23者]1050 g及BR原料[孟納黏 度ML1+4(100 C )為42，1，4順鍵含有率為95重量％者]45〇 g，一面冷卻一面加壓混練約3分鐘後，EpDM與之混合 原料成年糕狀’其溫度約為80。(：。繼而，添加聚氧化烯癸 , 醚系界面活性劑45 g(相對於EPDM與BR之混合原料1〇〇重 量份為3重量份）、硬脂酸15 g(相對於epdm與BR之混合原 料100重量份為1重量份）、白碳63 0 g(相對於EPDM與BR之 混合原料100重量份為42重量份）、加工處理油[商品名PW_ 380;出光興產股份有限公司製造]45 g(相對於EPDM與BR 之混合原料10 0重量份為3重量份）、碳酸妈7 5 g (相對於 EPDM與BR之混合原料1〇〇重量份為5重量份）、氧化鈦75 g(相對於EPDM與BR之混合原料100重量份為5重量份）、氧 化辞75 g(相對於EPDM與BR之混合原料100重量份為5重量 139397.doc -17- 201000289 份）、硬脂酸鋅60 g(相對於EPDM與BR之混合原料100重量 份為4重量份）及Licowax OP(Clariant Japan股份有限公司製 造之褐煤酸部分皂化酯）85 g(相對於EPDM與BR之混合原 料1 00重量份為5.7重量份），並混練約3分鐘。最後添加 1，1-雙（第三丁基過氧基）環己烷48 g(相對於EPDM與BR之 混合原料100重量份為3.2重量份），再繼續混練約1分鐘。 調節此期間混練物之溫度以使其不超過1 〇〇°C。將所獲得 之混練物迅速通過加壓輥，而加工成薄片狀，並冷卻至 2 5°C以下，藉此獲得厚度為6 mm之薄片狀模具脫模回復用 橡膠系組合物A。 所獲得之薄片狀模具脫模回復用橡膠系組合物A之特性 值及脫模回復試驗結果示於表1。根據試驗結果判斷可 知，薄片狀模具脫模回復用橡膠系組合物A表現出良好的 成形性及脫模回復性。 實施例2(本發明之第1模具脫模回復用橡膠系組合物） 於實施例1中，將基材樹脂之調配量變更為EPDM原料 [孟納黏度ML1+4(100°C)為23者]900 g及BR原料[孟納黏度 ?^1^1+4(100°(：)為42，1，4順鍵含有率為95重量％者]600 §， 將加工處理油[商品名PW-380 ;出光興產股份有限公司製 造]之調配量自45 g(相對於EPDM與BR之混合原料100重量 份為3重量份）變更為75 g(相對於EPDM與BR之混合原料 100重量份為5重量份），使用1>〇乂1〇10-78((1；〇§11丨5 13卩&11股 份有限公司製造之高分子複合酯）85 g(相對於EPDM與BR 之混合原料100重量份為5.7重量份）代替Licowax OP 85 139397.doc -18- 201000289 g(相對於EPDM與BR之混合原料1〇〇重量份為57重量份）， 除此之外以同樣之方式，獲得厚度為6職之薄片狀模具脫 模回復用橡膠糸組合物B。 所獲得之薄片狀模具脫模回復用橡膠系組合物B之特性 值及脫模回復試驗結果示於表丨。根據試驗結果判斷可 知，薄片狀模具脫模回復用橡膠系組合物B表現出良好的 成形性及脫模回復性。 實施例3(本發明之第丨模具脫模回復用橡膠系組合物） 於實施例1中，使用硬脂酸鈣60 g(相對於EPDM與BR之 混合原料100重量份為4重量份）代替硬脂酸鋅6〇 g(相對於 EPDM與BR之混合原料100重量份為4重量份），使用 Licolub H_4(Clariant Japan股份有限公司製造之改性烴）85 g(相對於EPDM與BR之混合原料1〇〇重量份為5 7重量份）代 替LiC〇wax 〇p 85 g(相對於之混合原料1〇〇重量 份為5.7重量份），除此之外以同樣之方式，獲得厚度為6 mm之薄片狀模具脫模回復用橡膠系組合物c。 所獲得之薄片狀模具脫模回復用橡膠系組合物C之特性 值及脫模回復試驗結果示於表1。根據試驗結果判斷可 知’薄片狀模具脫模回復用橡膠系組合物C表現出良好的 成形性及脫模回復性。 實施例4(本發明之第丨模具脫模回復用橡膠系組合物） 於實施例1中，將基材樹脂變更為EPDM原料[孟納黏度 MLi + 4(100°C )為23者]825 g及BR原料[孟納黏度ML1+4 (100°C )為42，1，4順鍵含有率為95重量％者]675 g，使用硬 139397.doc •19- 201000289 脂酸鈣60 g(相對於EPDM與BR之混合原料100重量份為4重 量份）代替硬脂酸鋅60 g(相對於EPDM與BR之混合原料100 重量份為4重量份），使用Fatty Amide S(花王股份有限公司 製造之脂肪酸醯胺）85 g(相對於EPDM與BR之混合原料100 重量份為5.7重量份）代替1^〇〇界&乂0?85§(相對於£?0厘與 BR之混合原料100重量份為5.7重量份），除此之外以同樣 之方式，獲得厚度為6 mm之薄片狀模具脫模回復用橡膠系 組合物D。 所獲得之薄片狀模具脫模回復用橡膠系組合物D之特性 值及脫模回復試驗結果示於表1。根據試驗結果判斷可 知，薄片狀模具脫模回復用橡膠系組合物D表現出良好的 成形性及脫模回復性。 比較例1 於實施例1中，將基材樹脂之調配量變更為EPDM原料 [孟納黏度ML1+4(100°C )為23者]600 g及BR原料[孟納黏度 ML1+4(100°C)為42，1,4順鍵含有率為95重量％者]900 g， 除此之外以同樣之方式，獲得厚度為6 mm之薄片狀模具脫 模回復用橡膠系組合物E。 所獲得之薄片狀模具脫模回復用橡膠系組合物E之特性 值及脫模回復試驗結果示於表1。根據試驗結果判斷可 知，薄片狀模具脫模回復用橡膠系組合物E產生空隙，連 續成形性亦不良。 139397.doc •20· 201000289 [表i] 項目 實施例1 實施例2 實施例3 實施例4 比較例1 組合物A 組合物B 組合物C 組合物D 組合物E EPDM 比 70 60 70 55 40 BR比 30 40 30 45 60 伸長率(％) 247 138 243 82 54 拉伸強度(MPa) 4.8 3.9 4.6 4.1 3.8 橡膠硬度 91 92 90 92 92 tc(90)(秒） 63 57 69 56 60 成形性 〇 〇 〇 〇 A 模具脫模性 〇 〇 〇 〇 X 空隙 〇 〇 〇 〇 X 連續成形性 >1000 >1000 >1000 >1000 395 成形性、模具脫模性及空隙之評價基準如下所述。 (表2及表3中亦相同） 成形性之評價基準 〇：未填充之產生率未滿3% △:未填充之產生率為3%以上且未滿10% X :未填充之產生率為10°/❶以上 模具脫模性之評價基準 〇：碎屑之產生率未滿3% △:碎屑之產生率為3%以上且未滿10% X :碎屑之產生率為10°/«以上 空隙之評價基準 〇：空隙之產生率未滿3% △:空隙之產生率為3%以上且未滿10% X:空隙之產生率為10%以上 139397.doc •21 _ 201000289 實施例5(本發明之第2模具脫模回復用橡膠系組合物） 向3 000 ml之附有夾套之加壓型捏合機中，添加epdM原 料[孟納黏度ML1+4( 1 〇〇°C )為23者]1 050 g及BR原料[孟納黏 度ML1+4(100°C )為42，1，4順鍵含有率為95重量％者]450 g ’ 一面冷卻一面加壓混練約3分鐘後，EPDM與BR之混合 原料成年糕狀，其溫度約為8 0 °C。繼而，添加聚氧化烯癸 醚系界面活性劑45 g(相對於EPDM與BR之混合原料1 00重 量份為3重量份）、硬脂酸1 5 g(相對於EPDM與BR之混合原 料100重量份為1重量份）、白碳600 g(相對於EPDM與BR之 混合原料100重量份為40重量份）、加工處理油[商品名PW-3 80;出光興產股份有限公司製造]45 g(相對於EPDM與BR 之混合原料100重量份為3重量份）、碳酸鈣75 g(相對於 EPDM與BR之混合原料100重量份為5重量份）、氧化鈦75 g(相對於EPDM與BR之混合原料100重量份為5重量份）、氧 化辞75 g(相對於EPDM與BR之混合原料1 〇〇重量份為5重量 份）、硬脂酸鋅60 g(相對於EPDM與BR之混合原料1〇〇重量 份為4重量份）及Licowax OP(Clariant Japan股份有限公司製 造之褐煤酸部分皂化酯）85 g(相對於EPDM與BR之混合原 料100重量份為5.7重量份），並混練約3分鐘。最後添加過 氧化二異丙苯48 g(相對於EPDM與BR之混合原料1〇〇重量 份為3 ·2重量份）並繼續混練約1分鐘。調節此期間混練物之 溫度以使其不超過11 〇 X：。將所獲得之混練物迅速通過加 壓輥，而加工成薄片狀，並冷卻至25。(：以下，藉此獲得厚 度為6 mm之薄片狀模具脫模回復用橡膠系組合物F。 139397.doc -22- 201000289 所獲得之薄片狀模具脫模回復用橡膠系組合物F之特性 值及脫模回復試驗結果示於表2。根據試驗結果判斷可 知，薄片狀模具脫模回復用橡膠系組合物F表現出良好的 成形性及脫模回復性。 實施例6(本發明之第2模具脫模回復用橡膠系組合物）Mold temperature: 175 ° C / 175 ° C Hardening time: ECR-CL 300 seconds SW7320 180 seconds release test 139397.doc -16- 201000289 After the cleaning of the cookware initialization, the mold is demolded by compression molding The rubber composition for recovery was subjected to three injection moldings at a curing time of 200 seconds. Then, the commercially available biphenyl-based epoxy resin molding material (eme-7351T manufactured by Sumitomo Bakehte Co., Ltd.) was subjected to molding to evaluate the mold release property and the continuous moldability. <Forming Condition> Mold: QFP or PDIP-8L Mold temperature: 175° (: / 175. 〇i Hardening time: 100 seconds Example 1 (the first rubber mold composition for mold release recovery of the present invention) 3000 ml of jacketed pressurizing kneader, adding EPDM material [Menner viscosity ML1+4 (l〇〇 °C) is 23] 1050 g and BR material [Menna viscosity ML1+4 (100 C) is a 45,1,4 straight-bond content of 95% by weight] 45 〇g, and after mixing and mixing for about 3 minutes while cooling, EpDM is mixed with the raw material into a cake-like temperature of about 80. (: Then, adding polyoxyalkylene oxime, ether surfactant 45 g (3 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR), and 15 g of stearic acid (relative to the mixed raw material of epdm and BR) 100 parts by weight of 1 part by weight), white carbon 63 0 g (42 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), and processed oil [trade name: PW_380; manufactured by Idemitsu Kosan Co., Ltd.] 45 g (3 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR), 7 5 g of carbonic acid mother (5 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR) ), 75 g of titanium oxide (5 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR), and 75 g of oxidized amount (100 parts by weight relative to 100 parts by weight of the mixed raw materials of EPDM and BR 139397.doc -17- 201000289) Parts), 60 g of zinc stearate (4 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) and 85 g of Licowax OP (partially saponified montanic acid ester manufactured by Clariant Japan Co., Ltd.) (relative to EPDM and BR mixed raw material 100 parts by weight of 5.7 parts by weight), and kneaded for about 3 minutes. Finally, 1,1-bis(t-butylperoxy)cyclohexane 48 g (relative to the mixed raw materials of EPDM and BR) 100 parts by weight of 3.2 parts by weight), and then continue to knead for about 1 minute. Adjust the temperature of the kneaded material during this period so as not to exceed 1 〇〇 ° C. The obtained kneaded material is quickly passed through a pressure roller to be processed into a thin sheet. The sheet-like mold release-recovering rubber-based composition A having a thickness of 6 mm was obtained by cooling to a temperature of 25 ° C or less. The obtained sheet-like mold release-recovering rubber-based composition A characteristic value was obtained. And the results of the mold release recovery test are shown in Table 1. According to the test results, it is known The rubber-based composition A for sheet-shaped mold release recovery exhibits good moldability and mold release recovery. Example 2 (the first mold release rubber composition for mold release of the present invention) In the first embodiment, The blending amount of the base resin was changed to EPDM raw material [Menner viscosity ML1+4 (100 °C) was 23] 900 g and BR raw material [Menna viscosity? ^1^1+4 (100° (:) was 42 , 1,4, the content of the key is 95% by weight] 600 §, the processing oil (trade name PW-380; manufactured by Idemitsu Kosan Co., Ltd.) is adjusted from 45 g (relative to the mixture of EPDM and BR) 100 parts by weight of the raw material is changed to 75 g (5 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), and 1>〇乂1〇10-78 is used ((1; 〇§11丨5) 85 卩 &11 Co., Ltd. polymer complex ester) 85 g (5.7 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) instead of Licowax OP 85 139397.doc -18- 201000289 g (relative to EPDM In the same manner, a mixed mold with BR is used in an amount of 57 parts by weight, and in the same manner, a rubber sheet for mold release of a sheet-like mold having a thickness of 6 is obtained. Compound B. The characteristic values of the rubber-based composition B for mold release recovery of the sheet-like mold obtained and the results of the mold release recovery test are shown in Table 丨. According to the results of the test, it was found that the rubber-based composition B for mold release of the flaky mold exhibited good moldability and mold release recovery. Example 3 (The rubber-based composition for mold release of the second mold of the present invention) In Example 1, 60 g of calcium stearate (4 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR) was used instead. 6 〇g of zinc stearate (4 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR), using Licolub H_4 (modified hydrocarbon manufactured by Clariant Japan Co., Ltd.) 85 g (relative to the mixture of EPDM and BR) In the same manner, a thickness of 6 was obtained in the same manner except that 1 part by weight of the raw material was 5 7 parts by weight instead of LiC〇wax 〇p 85 g (relatively 5.7 parts by weight based on 1 part by weight of the mixed raw material). The rubber-based composition c for mold release of the sheet-like mold of mm. The characteristic values of the rubber-based composition C for mold release recovery of the sheet-like mold obtained and the results of the mold release recovery test are shown in Table 1. According to the results of the test, it was found that the rubber-based composition C for sheet-shaped mold release recovery exhibited good moldability and mold release recovery. Example 4 (The rubber-based composition for mold release of the ninth mold of the present invention) In the first embodiment, the base resin was changed to an EPDM material [Monner viscosity MLi + 4 (100 ° C) was 23] 825 g and BR raw materials [Menna viscosity ML1+4 (100 ° C) is 42,1,4 with a 95% by weight content] 675 g, using hard 139397.doc •19- 201000289 calcium sulphate 60 g ( Using 40 parts by weight of the mixed raw material of EPDM and BR in place of 60 g of zinc stearate (4 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR), using Fatty Amide S (Kao Co., Ltd.) The manufactured fatty acid guanamine) is 85 g (5.7 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) instead of 1^〇〇界&乂0?85§ (relative to the mixture of 0.25% and BR) In the same manner as above, a sheet-like mold release-recovering rubber-based composition D having a thickness of 6 mm was obtained in the same manner. The characteristic values of the rubber-based composition D for mold release of the flaky mold obtained and the results of the mold release recovery test are shown in Table 1. According to the results of the test, it was found that the rubber-based composition D for mold release of the flaky mold exhibited good moldability and mold release recovery. Comparative Example 1 In Example 1, the blending amount of the base resin was changed to an EPDM raw material [Menner viscosity ML1+4 (100 ° C) was 23] 600 g and BR raw material [Menner viscosity ML1+4 (100 In the same manner, a rubber-based composition E for mold release of a sheet-like mold having a thickness of 6 mm was obtained in the same manner. The characteristic values of the rubber-based composition E for mold release recovery of the sheet-like mold obtained and the results of the mold release recovery test are shown in Table 1. According to the results of the test, it was found that the rubber-based composition E for mold release recovery of the sheet-like mold produced voids, and the continuous formability was also poor. 139397.doc •20· 201000289 [Table i] Item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Composition A Composition B Composition C Composition D Composition E EPDM ratio 70 60 70 55 40 BR Ratio 30 40 30 45 60 Elongation (%) 247 138 243 82 54 Tensile strength (MPa) 4.8 3.9 4.6 4.1 3.8 Rubber hardness 91 92 90 92 92 tc (90) (seconds) 63 57 69 56 60 Formability〇〇 〇〇A mold release property 〇〇〇〇X void 〇〇〇〇X continuous formability>1000 >1000 >1000 >1000 395 The evaluation criteria of moldability, mold release property, and void were as follows. (The same applies to Table 2 and Table 3.) Evaluation criteria for formability: 未: The rate of unfilling is less than 3% △: The rate of unfilling is 3% or more and less than 10% X: The rate of unfilling is Evaluation criteria for mold release of 10°/❶ or more 〇: The generation rate of debris is less than 3% △: The rate of generation of debris is 3% or more and less than 10% X: The generation rate of debris is 10°/ «Evaluation criteria for the above gaps: The generation rate of voids is less than 3% △: The rate of occurrence of voids is 3% or more and less than 10% X: The incidence of voids is 10% or more 139397.doc •21 _ 201000289 Example 5 (The second rubber mold composition for mold release recovery of the present invention) To 3,000 ml of a jacketed pressure type kneader, epdM raw material is added [Menna viscosity ML1+4 (1 〇〇 °C) ) is 23] 1 050 g and BR raw materials [Menner viscosity ML1+4 (100 ° C) is 42,1, 4, the content of the key is 95% by weight] 450 g 'One side cooling and pressure mixing about 3 After a minute, the mixed raw material of EPDM and BR was in the form of a cake, and the temperature was about 80 °C. Then, 45 g of a polyoxyalkylene ether ether surfactant (3 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR) and 15 g of stearic acid (100 parts by weight of the mixed raw material of EPDM and BR) were added. 1 part by weight), 600 g of white carbon (40 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), and processed oil [trade name: PW-3 80; manufactured by Idemitsu Kosan Co., Ltd.] 45 g (3 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), 75 g of calcium carbonate (5 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), and 75 g of titanium oxide (relative to EPDM and BR) 100 parts by weight of the mixed raw material is 5 parts by weight), 75 g of oxidized word (5 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR), and 60 g of zinc stearate (relative to the mixture of EPDM and BR) 15 parts by weight of the raw material and 4 parts by weight of Licowax OP (partially saponified ester of montanic acid manufactured by Clariant Japan Co., Ltd.) (5.7 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), and kneaded About 3 minutes. Finally, 48 g of dicumyl peroxide (compared to 3 · 2 parts by weight based on 1 part by weight of the mixed raw material of EPDM and BR) was added and kneading was continued for about 1 minute. Adjust the temperature of the kneading material during this period so that it does not exceed 11 〇 X:. The obtained kneaded material was quickly passed through a press roll, processed into a sheet shape, and cooled to 25. (In the following, the rubber-based composition F for mold release of the flaky mold having a thickness of 6 mm was obtained. 139397.doc -22- 201000289 The characteristic value of the rubber-based composition F for mold release of the flaky mold obtained The results of the mold release recovery test are shown in Table 2. From the results of the test, it was found that the rubber-based composition F for mold release of the flaky mold exhibited good moldability and mold release recovery. Example 6 (No. 2 of the present invention) Rubber-based composition for mold release recovery)
於實施例5中，將基材樹脂之調配量變更為EPDM原料 [孟納黏度ML1+4(100°C )為23者]900 g及BR原料[孟納黏度 ML1 + 4(100°C )為42，1,4順鍵含有率為95重量％者]6〇〇 g， 將加工處理油[商品名PW_380 出光興產股份有限公司製 造]之调配量自45 g(相對於EPDM與BR之混合原料1 〇〇重量 份為3重量份）變更為75 g(相對於EPDM與BR之混合原料 1〇〇重量份為5重量份），使用Loxiol G-78(Cognis Japan股 份有限公司製造之高分子複合酯）85 g(相對於^1>〇]^1與BR 之混合原料100重量份為5.7重量份）代替Lic〇wax OP 85 g(相對於EPDM與BR之混合原料100重量份為5 7重量份）， 除此之外以同樣之方式，獲得厚度為6 mm之薄片狀模具脫 模回復用橡膠系組合物G。 所獲得之薄片狀模具脫模回復用橡膠系組合物g之特性 值及脫模回復試驗結果示於表2。根據試驗結果判斷可 知，薄片狀模具脫模回復用橡膠系組合物G表現出良好的 成形性及脫模回復性。 實施例7(本發明之第2模具脫模回復用橡膠系組合物） 於實施例5中，使用過氧化-昱In Example 5, the blending amount of the base resin was changed to EPDM raw material [Menner viscosity ML1+4 (100 ° C) was 23] 900 g and BR raw material [Menner viscosity ML1 + 4 (100 ° C) For the 42,1,4, the content of the singularity of 95% by weight is 6 〇〇g, and the processing oil (trade name PW_380 Idemitsu Kosan Co., Ltd.) is prepared from 45 g (relative to EPDM and BR). 1 part by weight of the mixed raw material was changed to 75 g (5 parts by weight based on 1 part by weight of the mixed raw material of EPDM and BR), and Loxiol G-78 (manufactured by Cognis Japan Co., Ltd.) was used. Molecular complex ester) 85 g (relative to 157 parts by weight of 100 parts by weight of the mixed raw material of ^1) and BR) instead of Lic〇wax OP 85 g (100 parts by weight relative to the mixed raw material of EPDM and BR) In the same manner as above, a rubber-like composition G for sheet-shaped mold release-recovering having a thickness of 6 mm was obtained in the same manner. The characteristic values of the obtained rubber-based composition g for mold release recovery of the sheet-like mold and the results of the mold release recovery test are shown in Table 2. According to the results of the test, it was found that the rubber-based composition G for mold release of the flaky mold exhibited good moldability and mold release recovery. Example 7 (The second rubber mold composition for mold release recovery of the present invention) In Example 5, peroxidation-ruthenium was used.
礼化一異丙本28 g(相對於EPDM 與BR之混合原料⑽重量份為19重量份）及4,4_&第三丁 139397.doc •23- 201000289 基過氧基）戊酸正丁酯20 g(相對於EPDM與BR之混合原料 100重量份為1.3重量份），代替過氧化二異丙苯48 g(相對 於EPDM與BR之混合原料1 〇〇重量份為3.2重量份），使用硬 脂酸鈣60 g(相對於EPDM與BR之混合原料100重量份為4重 量份）代替硬脂酸鋅60 g(相對於EPDM與BR之混合原料1 〇〇 重量份為4重量份），使用Licolub H-4(Clariant Japan股份 有限公司製造之改性烴）85 g(相對於EPDM與BR之混合原 料1 00重量份為5.7重量份）代替Lic〇wax OP 85 g(相對於 EPDM與BR之混合原料100重量份為5.7重量份），除此之外 以同樣之方式，獲得厚度為6 mm之薄片狀模具脫模回復用 橡膠系組合物Η。 所獲得之薄片狀模具脫模回復用橡膠系組合物Η之特性 值及脫模回復試驗結果示於表2。根據試驗結果判斷可 知，薄片狀模具脫模回復用橡膠系組合物Η表現出良好的 成形性及脫模回復性。 實施例8(本發明之第2模具脫模回復用橡膠系組合物） 於實施例5中，使用BR原料[孟納黏度ML1+4(100°C )為 35，1,4順鍵含有率為95重量％者]450 g代替BR原料[孟納 黏度ML1+4(100°C )為42，1，4順鍵含有率為95重量％者]450 g，使用1,1-雙（第三丁基過氧基）環己烷13 g(相對於EPDM 與BR之混合原料100重量份為0.9重量份）及過氧化二異丙 苯35 g(相對於EPDM與BR之混合原料100重量份為2.3重量 份），代替過氧化二異丙苯48 g(相對於EPDM與BR之混合 原料100重量份為3.2重量份），使用硬脂酸鈣60 g(相對於 139397.doc -24- 201000289 EPDM與BR之混合原料100重量份為4重量份）代替硬脂酸 辞60 g(相對於EPDM與BR之混合原料1〇〇重量份為4重量 份），使用Fatty Amide S(花王股份有限公司製造之脂肪酸 酿胺）85 g(相對於EPDM與BR之混合原料1〇〇重量份為5 7重 量份）代替Licowax OP 85 g(相對於EPDM與BR之混合原料 100重量份為5.7重量份），除此之外以同樣之方式獲得厚 度為6 mm之薄片狀模具脫模回復用橡膠系組合物I。 所獲得之薄片狀模具脫模回復用橡膠系組合物I之特性 值及脫模回復試驗結果示於表2。根據試驗結果判斷可 知，薄片狀模具脫模回復用橡膠系組合物I表現出良好的 成形性及脫模回復性。 比較例2 於實施例5中’將基材樹脂之調配量變更為EpDM原料 [孟納黏度ML1+4(l〇(TC )為23者]450 g及BR原料[孟納黏度 ML1 + 4(l〇〇°C)為42’ 1，4順鍵含有率為95重量％者]1050 g， U 除此之外以同樣之方式，獲得厚度為6 mm之薄片狀模具脫 模回復用橡谬系組合物j。 所獲得之薄片狀模具脫模回復用橡膠系組合物j之特性 值及脫模回復試驗結果示於表2。根據試驗結果判斷可 • 知’薄片狀模具脫模回復用橡膠系組合物J產生空隙，連 續成形性亦不良。 139397.doc -25- 201000289 [表2] 項目 實施例5 實施例6 實施例7 實施例8 比較例2 組合物F 組合物G 組合物Η 組合物I 組合物J EPDM 比 70 60 70 70 40 BR比 30 40 30 30 60 伸長率(％) 150 120 184 188 54 拉伸強度(MPa) 5.8 5.2 4.3 4.1 4.4 橡膠硬度 83 87 75 80 92 tc(90)(秒） 329 287 278 267 58 成形性 〇 〇 〇 〇 Δ 模具脫模性 〇 〇 〇 〇 X 空隙 〇 〇 〇 〇 X 連續成形性 >1000 >1000 >1000 >1000 486 實施例9(本發明之第3模具脫模回復用橡膠系組合物） 向3 000 ml之附有夾套之加壓型捏合機中，添加EPDM原 料[孟納黏度ML1+4(100°C )為23者]900 g及BR原料[孟納黏 度ML1+4(100°C )為42，1，4順鍵含有率為95重量％者]600 g，一面冷卻一面加壓混練約3分鐘後，EPDM與BR之混合 原料成年糕狀’其溫度約為8 0 °C。繼而，添加聚氧化稀癸 醚系界面活性劑45 g(相對於EPDM與BR之混合原料1 00重 量份為3重量份）、硬脂酸1 5 g(相對於EPDM與BR之混合原 料100重量份為1重量份）、白碳900 g(相對於EPDM與BR之 混合原料100重量份為60重量份）、氧化鈦75 g(相對於 EPDM與BR之混合原料1 00重量份為5重量份）、碳黑1.5 139397.doc •26- 201000289 g(相對於EPDM與BR之混合原料loo重量份為o.l重量份）、 硬脂酸鋅225 g(相對於EPDM與BR之混合原料1〇〇重量份為 15重1伤）、[〇父1〇1〇-78((3〇§1^】3卩311股份有限公司製造 之高分子複合酯）150 g(相對於EPDM與BR之混合原料100 重量份為10重量份）及Licolub H-4(Clariant Japan股份有限 公司製造之改性烴）150 g(相對於EPDM與BR之混合原料 100重量份為1 0重量份），並混練約3分鐘。最後添加過氧 化二異丙苯1 8 g(相對於EPDM與BR之混合原料1 00重量份 為1 · 2重篁份）’並繼續混練約1分鐘。調節此期間混練物之 溫度以使其不超過110°C。將所獲得之混練物迅速通過加 壓輥，而加工成薄片狀，並冷卻至25。(：以下，藉此獲得厚 度為6 mm之薄片狀模具脫模回復用橡膠系組合物κ。 所獲得之薄片狀模具脫模回復用橡膠系組合物K之特性 值及脫模回復試驗結果示於表3。根據試驗結果判斷可 知，薄片狀模具脫模回復用橡膠系組合物K表現出良好的 成形性及脫模回復性。 實施例1 〇(本發明之第3模具脫模回復用橡膠系組合物） 於實施例9中，將白碳之調配量自900 g(相對於EPDM與 BR之混合原料1〇〇重量份為60重量份）變更為105〇 g(相對 於EPDM與BR之混合原料100重量份為70重量份），使用硬 脂酸鈣225 g(相對於EPDM與BR之混合原料1〇〇重量份為15 重量份）代替硬脂酸辞225 g(相對於EPDM與br之混合原料 100重量份為15重量份），將Loxiol G-78之調配量自150 g(相對於EPDM與BR之混合原料100重量份為丨〇重量份）變 139397.doc -27- 201000289 更為225 g(相對於EPDM與BR之混合原料100重量份為15重 量份）’除此之外以同樣之方式，獲得厚度為6 mm之薄片 狀模具脫模回復用橡膠系組合物L。 所獲得之薄片狀模具脫模回復用橡膠系組合物L之特性 值及脫模回復試驗結果示於表3。根據試驗結果判斷可 知’薄片狀模具脫模回復用橡膠系組合物L表現出良好的 成形性及脫模回復性。 實施例11 (本發明之第3模具脫模回復用橡膠系組合物） 於實施例9中’將基材樹脂之調配量變更為EPDM原料 [孟納黏度ML1+4(100°C )為23者]1050 g及BR原料[孟納黏度 ML1+4(100°C)為42’ 1，4順鍵含有率為95重量％者]450 g， 使用硬脂酸鈣1 50 g(相對於EPDM與BR之混合原料100重量 份為10重量份）代替硬脂酸鋅225 g(相對於EPDM與BR之混 合原料100重量份為15重量份），將Loxiol G-78之調配量自 150 g(相對於EPDM與BR之混合原料100重量份為1〇重量 份）變更為105 g(相對於EPDM與BR之混合原料100重量份 為7重量份）’使用Fatty Amide S(花王股份有限公司製造之 脂肪酸醯胺）45 g(相對於EPDM與BR之混合原料100重量份 為3重量份）代替Licolub H-4 150 g(相對於EPDM與BR之混 合原料100重量份為10重量份），將過氧化二異丙苯之調配 量自18 g(相對於EPDM與BR之混合原料100重量份為1.2重 量份）變更為30 g(相對於EPDM與BR之混合原料1〇〇重量份 為2重量份），除此之外以同樣之方式，獲得厚度為6 mm之 薄片狀模具脫模回復用橡膠系組合物Μ。 139397.doc -28- 201000289 所獲得之薄片狀模具脫模回復用橡膠系組合物Μ之特性 值及脫模回復試驗結果示於表3。根據試驗結果判斷可 知，薄片狀模具脫模回復用橡膠系組合物Μ表現出良好的 成形性及脫模回復性。 實施例12(本發明之第3模具脫模回復用橡膠系組合物） 於實施例9中，使用BR原料[孟納黏度ML1+4(10(TC )為 35，1,4順鍵含有率為95重量％者]450 g代替BR原料[孟納 黏度ML1 + 4(l〇〇C)為42 ’ 1,4順鍵含有率為95重量°/。者]600 g，將白碳之調配量自900 g(相對於EPDM與BR之混合原料 100重量份為60重量份）變更為1050 g(相對於EPDM與BR之 混合原料10 〇重量份為7 0重量份），使用硬脂酸辞1 〇 5 g(相 對於EPDM與BR之混合原料1〇〇重量份為7重量份）及硬脂 酸鈣195 g(相對於EPDM與BR之混合原料100重量份為13重 量份）’代替硬脂酸鋅225 g(相對於EPDM與BR之混合原料 100重量份為15重量份），將Loxiol G-78之調配量自150 g(相對於EPDM與BR之混合原料1〇〇重量份為10重量份）變 更為300 g(相對於EPDM與BR之混合原料100重量份為20重 量份），使用過氧化二異丙苯35 g(相對於EPDM與BR之混 合原料100重量份為2.3重量份）及1，1-雙（第三丁基過氧基） 環己烷13 g(相對於EPDM與BR之混合原料1〇〇重量份為〇.9 重量份），代替過氧化二異丙苯18 g(相對於EPDM與BR之 混合原料100重量份為1.2重量份），除此之外以同樣之方 式’獲得厚度為6 mm之薄片狀模具脫模回復用橡膝系組合 物N。 •29· 139397.doc 201000289 所獲得之薄片狀模具脫模回復用橡膠系組合物N之特性 值及脫模回復試驗結果示於表3。根據試驗結果判斷可 知，薄片狀模具脫模回復用橡膠系組合物N表現出良好的 成形性及脫模回復性。 [表3] 項目 實施例9 實施例10 實施例11 實施例12 組合物K 組合物L 組合物Μ 組合物Ν ΕΙΌΜ 比 60 60 70 60 BR比 40 40 30 40 伸長率(％) 138 116 163 112 拉伸強度(MPa) 5.8 5.1 4.6 5.3 橡膠硬度 85 89 88 89 tc(90)(秒） 329 312 287 283 成形性 〇 〇 〇 〇 模具脫模性 〇 〇 〇 〇 空隙 〇 〇 〇 〇 連續成形體 >1000 >1000 >1000 >1000 產業上之可利用性 藉由使用本發明之模具脫模回復用橡膠系組合物，可獲 得優異之模具脫模回復性，並可防止因近年來環氧密封樹 脂之高功能化及半導體元件之高功能化而引起的於模穴 部、通氣孔部等所產生之黏附。又，由於可長時間維持模 具脫模性，因此表現出優異之連續成形性，從而提昇了生 產性。 139397.doc -30-Lithium-Isopropyl 28 g (19 parts by weight relative to the mixed material of EPDM and BR) and 4,4_&Third 139397.doc •23- 201000289-based peroxy)-n-butyl valerate 20 g (1.3 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), instead of 48 g of dicumyl peroxide (3.2 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR), used 60 g of calcium stearate (4 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) instead of 60 g of zinc stearate (4 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR), Using Licolub H-4 (modified hydrocarbon manufactured by Clariant Japan Co., Ltd.) 85 g (5.7 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) instead of Lic〇wax OP 85 g (relative to EPDM and BR) In the same manner, a rubber-like composition for sheet-like mold release-recovering having a thickness of 6 mm was obtained in the same manner as in the above, except that the amount of the mixed raw material was 5.7 parts by weight. The properties of the obtained rubber-based composition for mold release recovery of the flaky mold and the results of the mold release recovery test are shown in Table 2. According to the results of the test, it was found that the rubber-based composition for the mold release of the flaky mold exhibited good formability and mold release recovery. Example 8 (The second rubber mold composition for mold release recovery of the present invention) In Example 5, a BR raw material [Menner viscosity ML1+4 (100 ° C) was used as a 35, 1, 4 straight bond content ratio. For 95% by weight] 450 g instead of BR material [Menner viscosity ML1+4 (100 ° C) is 42,1,4 with a bond content of 95% by weight] 450 g, using 1,1-double (first Tributylperoxy)cyclohexane 13 g (0.9 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) and 35 g of dicumyl peroxide (100 parts by weight relative to the mixed raw material of EPDM and BR) 2.3 parts by weight), instead of 48 g of dicumyl peroxide (3.2 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR), 60 g of calcium stearate was used (relative to 139397.doc -24-201000289) 100 parts by weight of the mixed raw material of EPDM and BR is 4 parts by weight) instead of stearic acid 60 g (4 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR), using Fatty Amide S (Kao Corporation) 85 g of fatty acid amine produced (compared to 5 7 parts by weight of the mixed raw material of EPDM and BR) instead of Licowax OP 85 g (relative to the mixed raw material of EPDM and BR 100) In an amount of 5.7 parts by weight parts), the same manner except that a thickness of 6 mm to obtain a sheet of rubber-based mold release composition reply I. The characteristic values of the rubber-based composition I for mold release recovery of the sheet-like mold obtained and the results of the mold release recovery test are shown in Table 2. According to the results of the test, it was found that the rubber-based composition I for mold release recovery of the sheet-like mold exhibited good moldability and mold release recovery. Comparative Example 2 In Example 5, 'the amount of the base resin was changed to EpDM material [Menner viscosity ML1+4 (l〇(TC) is 23] 450 g and BR material [Menner viscosity ML1 + 4 ( L〇〇°C) is 42' 1,4, the content of the key is 95% by weight] 1050 g, U In addition, in the same manner, a flaky mold with a thickness of 6 mm is obtained. Composition j. The characteristic values of the rubber-based composition j for mold release recovery of the obtained sheet mold and the results of the mold release recovery test are shown in Table 2. According to the test results, it was judged that the rubber for mold release of the sheet mold was released. The composition J produced voids and the continuous formability was also poor. 139397.doc -25- 201000289 [Table 2] Item Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Composition F Composition G Composition Η Combination Composition I Composition J EPDM ratio 70 60 70 70 40 BR ratio 30 40 30 30 60 Elongation (%) 150 120 184 188 54 Tensile strength (MPa) 5.8 5.2 4.3 4.1 4.4 Rubber hardness 83 87 75 80 92 tc (90 ) (seconds) 329 287 278 267 58 Formability 〇〇〇〇Δ Mold release 〇〇〇〇X void 〇〇〇〇 X continuous formability > 1000 > 1000 > 1000 > 1000 486 Example 9 (3rd mold release rubber composition for mold release) 3 000 ml of jacketed press-type kneading In the machine, add EPDM raw material [Menner viscosity ML1+4 (100 °C) is 23] 900 g and BR raw material [Menna viscosity ML1+4 (100 °C) is 42,1,4 right bond content rate 95% by weight] 600 g, after mixing and mixing for about 3 minutes while cooling, the mixed raw material of EPDM and BR is in the form of a cake. The temperature is about 80 ° C. Then, the polyoxynized ether surfactant is added. 45 g (3 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), 15 g of stearic acid (1 part by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), and 900 g of white carbon ( 100 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), 75 g of titanium oxide (5 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), carbon black 1.5 139397.doc •26-201000289 g (relative to LDP parts by weight of the mixed raw material loo of EPDM and BR), 225 g of zinc stearate (15 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR), [ Master 1〇1〇-78 ((3〇§1^) 3卩311 Co., Ltd. polymer complex ester) 150 g (10 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) and Licolub H-4 (modified hydrocarbon manufactured by Clariant Japan Co., Ltd.) 150 g (10 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), and kneaded for about 3 minutes. Finally, 18 g of dicumyl peroxide (100 parts by weight of the mixed raw material of EPDM and BR was 1 · 2 parts by weight) was added and the kneading was continued for about 1 minute. The temperature of the kneaded material during this period was adjusted so as not to exceed 110 °C. The obtained kneaded material was quickly passed through a press roll, processed into a sheet shape, and cooled to 25. (In the following, the rubber-based composition κ for mold release of the flaky mold having a thickness of 6 mm was obtained. The characteristic value of the rubber-based composition K for mold release of the flaky mold obtained and the test results of the release test were shown. According to the results of the test, it was found that the rubber-based composition K for mold release recovery of the flaky mold exhibited good moldability and mold release recovery. Example 1 〇 (The third mold release rubber for use in the present invention) In the ninth embodiment, the amount of white carbon was changed from 900 g (60 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR) to 105 〇g (relative to EPDM and BR). 100 parts by weight of the mixed raw material is 70 parts by weight, using 225 g of calcium stearate (15 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR) instead of stearic acid 225 g (relative to EPDM and br 100 parts by weight of the mixed raw material is 15 parts by weight), and the amount of the Loxiol G-78 is adjusted from 150 g (100 parts by weight relative to the mixed raw material of EPDM and BR) to 139397.doc -27-201000289 225 g (15 parts by weight relative to 100 parts by weight of the mixed raw materials of EPDM and BR) In the same manner, a rubber-based composition L for mold release of a sheet-like mold having a thickness of 6 mm was obtained in the same manner. The characteristic value of the rubber-based composition L for mold release of the flaky mold obtained was obtained. The results of the mold recovery test are shown in Table 3. According to the results of the test, it was found that the rubber composition L for the mold release of the flaky mold exhibited good moldability and mold release recovery. Example 11 (The third mold of the present invention Rubber-based composition for mold recovery) In Example 9, 'the amount of the base resin was changed to EPDM material [Menner viscosity ML1+4 (100 ° C) was 23] 1050 g and BR material [Menner viscosity] ML1+4 (100 ° C) is 42' 1,4, the content of the cis bond is 95% by weight] 450 g, using calcium stearate 1 50 g (10 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) In lieu of 225 g of zinc stearate (15 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR), the amount of the Loxiol G-78 is from 150 g (100 parts by weight relative to the mixed raw material of EPDM and BR) 1 part by weight) was changed to 105 g (7 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) 45 g of fatty acid decylamine manufactured by Fatty Amide S (3 parts by weight relative to 100 parts by weight of a mixed raw material of EPDM and BR) was used instead of Licolub H-4 150 g (relative to the mixed raw material of EPDM and BR) 100 parts by weight of 10 parts by weight), the amount of dicumyl peroxide changed from 18 g (1.2 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) to 30 g (relative to EPDM and BR) In the same manner, a rubber-like composition for sheet-shaped mold release recovery having a thickness of 6 mm was obtained in the same manner as in the above-mentioned manner. 139397.doc -28- 201000289 The properties of the rubber-based composition for mold release recovery of the flaky mold obtained and the results of the mold release recovery test are shown in Table 3. According to the results of the test, it was found that the rubber-based composition for the mold release of the flaky mold exhibited good formability and mold release recovery. Example 12 (The third rubber mold composition for mold release recovery of the present invention) In Example 9, a BR raw material was used [Menna viscosity ML1+4 (10(TC) was 35, 1, 4 sequential bond content) For 95% by weight] 450 g instead of BR material [Menna viscosity ML1 + 4 (l〇〇C) is 42 ' 1,4 cis bond content rate is 95 weight ° /.] 600 g, white carbon blending The amount is changed from 900 g (60 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR) to 1050 g (70 parts by weight relative to 10 parts by weight of the mixed raw material of EPDM and BR), using stearic acid 1 〇 5 g (7 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR) and 195 g of calcium stearate (13 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) 225 g of zinc citrate (15 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR), and the amount of the Loxiol G-78 is from 150 g (10 parts by weight relative to the mixed raw material of EPDM and BR) The weight part is changed to 300 g (20 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), and 35 g of dicumyl peroxide is used (100 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR). Parts by weight and 1,1-bis(t-butylperoxy)cyclohexane 13 g (1. 9 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR), instead of dioxygen peroxide 18 g of propylbenzene (1.2 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), and in the same manner, a sheet-like mold release-recovering rubber-knee composition N having a thickness of 6 mm was obtained in the same manner. • 29· 139397.doc 201000289 The characteristic values of the rubber-based composition N for mold release of the flaky mold obtained and the results of the release test are shown in Table 3. According to the test results, it is known that the flaky mold is released for mold release. The rubber-based composition N exhibited good formability and mold release recovery. [Table 3] Item Example 9 Example 10 Example 11 Example 12 Composition K Composition L Composition Μ Composition Ν ΕΙΌΜ Ratio 60 60 70 60 BR ratio 40 40 30 40 Elongation (%) 138 116 163 112 Tensile strength (MPa) 5.8 5.1 4.6 5.3 Rubber hardness 85 89 88 89 tc (90) (seconds) 329 312 287 283 Formability〇〇〇〇 Mold release 〇〇〇〇 void 〇〇〇〇 continuous forming >1000 >1000 > 1000 > 1000 Industrial Applicability By using the rubber-based composition for mold release of the mold of the present invention, excellent mold release recovery property can be obtained, and prevention can be prevented in recent years. Adhesion of the cavity portion, the vent portion, and the like due to the high functionality of the epoxy sealing resin and the high functionality of the semiconductor element. Further, since the mold release property can be maintained for a long period of time, excellent continuous formability is exhibited, thereby improving productivity. 139397.doc -30-