TW200930757A - Mold cleaning rubber compositon - Google Patents

Mold cleaning rubber compositon Download PDF

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Publication number
TW200930757A
TW200930757A TW97141649A TW97141649A TW200930757A TW 200930757 A TW200930757 A TW 200930757A TW 97141649 A TW97141649 A TW 97141649A TW 97141649 A TW97141649 A TW 97141649A TW 200930757 A TW200930757 A TW 200930757A
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TW
Taiwan
Prior art keywords
rubber
mold
cleaning
weight
parts
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TW97141649A
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Chinese (zh)
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TWI428384B (en
Inventor
Hiroaki Nomura
Kiyohito Hiromitsu
Osamu Sunago
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Nippon Carbide Kogyo Kk
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Publication of TW200930757A publication Critical patent/TW200930757A/en
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Publication of TWI428384B publication Critical patent/TWI428384B/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/70—Maintenance
    • B29C33/72—Cleaning
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2021/00—Use of unspecified rubbers as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This invention provides a mold cleaning rubber composition for removing soiling on the surface of a mold produced in a curable resin molding process. An unvulcanized rubber is used as a base material resin. The unvulcanied rubber comprises an ethylene-propylene rubber and a butadiene rubber at a mixing ratio of 90/10 to 50/50 on the basis of parts by weight. After the vulcanization curing of the unvulcanized rubber, the elongation is 80 to 800%, the tensile strength is 3 to 10 MPa, and the rubber hardness (durometer hardness) is A60 to 95. The 90% vulcanization time (proper vulcanization point) tc (90) at a mold temperature of 175 DEG C is 50 to 100 sec or 200 to 400 sec. When the mold cleaning rubber composition is used for cleaning for molds for the production of small-size packages having a large cavity depth, for example, PDIP or SOIC, and molds for the production of small packages, particularly small packages with a small number of pins, preferably, the mold cleaning rubber composition contains a release agent in addition to the unvulcanized rubber having a tc (90) value of 200 to 400 sec.

Description

200930757 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種模具清潔用橡膠系組合物，詳細而言 係關於一種用以將硬化性樹脂之成形步驟中所產生的模具 表面之污垢去除的模具清潔用樹脂組合物，其特徵在於： . 基材樹脂係使用特定之未硫化橡膠。 【先前技術】 先前，利用環氧樹脂等熱硬化性樹脂來進行積體電路等 〇 t密封成形物的成形時，如下情況較多：若持續長時間成 形’則模具内部表面會受污染，若在此狀態下繼續持續進 行成形’則密封成形物之表面會受污染，或密封成形物會 附著於模具上，導致成形作業無法繼續進行。因此，必須 對模具進行定期清潔’提出有每使成形材料成形數百次 (shot)而以數次之比例使模具清潔用樹脂成形來進行模具 '月潔的方法’例如’於日本專利特公昭52-788號公報中揭 $有藉由使包含胺基系樹脂、有機質基材及/或無機質基 #⑽模劑之模具清潔用樹脂組合物成形來清潔模具的方 法。 ' 另一方面，提出有如下方法：當使用含有清洗成分之未BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-based composition for mold cleaning, and more particularly to a method for removing dirt on a mold surface generated in a forming step of a curable resin. The resin composition for mold cleaning is characterized in that: The base resin is a specific unvulcanized rubber. [Prior Art] When a molded article such as an integrated circuit is molded by a thermosetting resin such as an epoxy resin, the following is often the case: if the molding is continued for a long time, the inner surface of the mold may be contaminated. When the molding is continued in this state, the surface of the sealed molded article may be contaminated, or the sealed molded article may adhere to the mold, and the forming operation may not proceed. Therefore, it is necessary to perform regular cleaning of the mold, and a method of forming a mold for cleaning the resin for a mold cleaning process by a number of times to form a mold for a mold cleaning is proposed. For example, in Japanese Patent Special Publication No. JP-A-52-788 discloses a method of cleaning a mold by molding a resin composition for mold cleaning comprising an amine-based resin, an organic substrate, and/or an inorganic matrix #10. On the other hand, the following method is proposed: when using a cleaning component

Kb橡料、化合物來代替上述熱硬化性三聚氰胺樹脂成形 材料’於模具中使其硫化而進行硫化橡膠化時，將存在於 模具表面之脫模劑等的氧化劣化層利用清洗成分進行分 解同時與硫化橡膠一體化，繼而將硫化橡膠自模具中取 出，藉此對模具表面進行清潔。又，作為未硫化橡膠成 135644.doc 200930757 分，亦提出有丁二烯橡膠/乙烯-丙 90/10〜50/50重量份之橡 成分經設定為 開昭03_227308號公報，n $ & …曰本專利特 報）。 “日本專㈣開平仙而號公 作為模具之清潔材料，可大致分為 種類型，轉移型中侦用Λ 主/、堙縮型此2 用—聚氰胺系樹脂成形材料，壓縮型 中使用三聚氰胺系樹脂成 '' 成1材科以及橡膠系清潔材料。When a Kb rubber material or a compound is used in place of the above-mentioned thermosetting melamine resin molding material to be vulcanized and vulcanized in a mold, the oxidative degradation layer such as a release agent existing on the surface of the mold is decomposed by a cleaning component and vulcanized rubber. Integration, and then the vulcanized rubber is removed from the mold to clean the surface of the mold. Further, as an unvulcanized rubber, 135644.doc 200930757, it is also proposed that a rubber component having a butadiene rubber/ethylene-propylene content of 90/10 to 50/50 parts by weight is set to open. 03_227308, n $ & This patent special report). "Japan's special (four) Kaiping Xian and No. gong as a cleaning material for molds, can be roughly divided into types, transfer type of medium detection Λ main /, contraction type 2 - melamine resin molding material, used in compression type The melamine-based resin is made into a material and a rubber-based cleaning material.

❹❹

，㈣著_f路等（簡記4IC 化、薄型化、表面封裝仆士以〇 ； ° ^ ° 不斷推進，因此，❹ 之形狀、結構之多樣化 ，虽業者謀求半導體密封材料之高流動化 及環境對應化。 因此，高流動化型環氧密封材容易產生通氣孔部分之樹 月曰堵塞，且右產生該等之堵塞，則排氣性差，樹脂不流 動’、因此會由於在模腔部產生未填充而變得不良使得連 續成形困冑。因此’為避免該等狀況而必須實施清潔，但 :轉移U材料之情況，由於上述原因而造成樹脂無法 正常流動，因此難以除去通氣孔中所堵塞之樹脂。 為了消除如上所述之通氣孔堵塞而使用壓縮型清潔材 料，右使用二聚氰胺系樹脂成形材料，則雖消除通氣孔部 刀之堵塞，但模具外周附近會由於樹脂之流出而無法充分 施加壓力，因此有成形物之外周部變脆之傾向，將硬化後 之成形物自模具上除去之作業煩雜。針對此而使用橡膠系 清潔材料之情形時，清潔材料整體一樣地硬化而製成1片 之片狀成形物’可自模具t脫模，因此作業性得到改善。 135644.doc 200930757 然而，於流動性方面，橡膠系清潔材料比三聚氰胺系樹脂 成形材料差’故有對模腔内之填充性差，模腔角隅等之污 垢無法除去之問題。 又，於如Plastic Dual Inline Package(塑勝雙列直插封 裝，以下簡記為PDIP)或Small 〇mIine Integrated Circuit (小外形積體電路，以下簡記為s〇IC)等般模腔深之小型封 裝製造用模具、或小型封裝中銷數少的尤其小之封裝製造 用模具中使用橡膠系清潔材料之情形時，封裝之取數變 多，因此容易產生硬化後之成形物貼附於模具上之現象。 將其除去時’存在片狀成形物斷裂，產生橡膝系清潔材料 殘留於模腔内之碎屑的問題。若該等之模具内產生碎屑， 則由於模腔數多，故除去碎屑部位之成形物需要大量時 間。 為了解決上述問題’而謀求一種作業性（脫模性）、成形 性優異而不會於模腔角隅部產生未填充者’或者由於有延(4) _f road, etc. (abbreviation 4IC, thinning, surface-encapsulated servants; ^ ° ° continuous advancement, therefore, the shape and structure of ❹ are diversified, although the industry seeks high fluidity of semiconductor sealing materials and Therefore, the highly fluidized epoxy sealing material tends to cause clogging of the vent hole portion, and if the right clogging occurs, the venting property is poor, and the resin does not flow, so it is due to the cavity portion. It is unfilled and becomes poor, which makes continuous forming difficult. Therefore, it is necessary to perform cleaning in order to avoid such conditions. However, when the U material is transferred, the resin cannot flow normally due to the above reasons, so it is difficult to remove the vent hole. In order to eliminate the clogging of the vent hole as described above, a compression type cleaning material is used, and when the melamine resin molding material is used right, the clogging of the vent hole is eliminated, but the resin is discharged near the outer periphery of the mold. However, the pressure cannot be sufficiently applied, so that the peripheral portion of the molded article tends to become brittle, and the work of removing the hardened molded article from the mold is troublesome. In the case where a rubber-based cleaning material is used in this case, the cleaning material is hardened as a whole to form a sheet-like formed product' which can be released from the mold t, so workability is improved. 135644.doc 200930757 However, in the flow In terms of properties, rubber-based cleaning materials are inferior to melamine-based resin molding materials, so there is a problem that the filling property in the cavity is poor, and the dirt such as cavity angles cannot be removed. Also, such as the Plastic Dual Inline Package In-line package, the following is a brief description of PDIP) or Small 〇mIine Integrated Circuit (small outline integrated circuit, hereinafter referred to as s〇IC), such as a mold cavity for small package manufacturing, or a small package with a small number of pins. In the case where a rubber-based cleaning material is used in a small package manufacturing mold, the number of packages is increased, so that the molded product after curing tends to adhere to the mold. When it is removed, the sheet-like formed product is broken. , the problem of debris remaining in the cavity of the rubber knee cleaning material. If debris is generated in the mold, since the number of cavities is large, the debris is removed. A large amount of time is required for the molded article. In order to solve the above problem, an workability (release property) and moldability are obtained, and an unfilled portion is not generated in the cavity corner portion or due to delay

伸強度冋而不會於模具脫模時產生碎屑等現象的橡膝系 清潔材料。 X 專利文獻1:日本專利特公昭52_788號公報 專利文獻2 :日本專利特開昭63-227308號公報 專利文獻3:日本專利特開平〇4_357〇〇7號公報 【發明内容】 本發明之課題在於提供—種橡膠系清潔材料，其係如上 所述作業陡(脫模性)良好，但消除產生空隙或碎屑之 知橡膠系清潔材料的缺點而不會產生空隙或碎屑。 135644.doc 200930757 ’其作 ’或者 的習知 的模腔 尤其小 又，本發明之課題在於提供__種橡㈣清潔材科 業性（脫模性）良好，但不僅消除會產生空隙或碎屬 不會產生空隙’但作業性（脫模性）差而會產生碎屬 橡膠系清潔材料之缺點，並且於如PDIp*s〇ic等 冰之小型封裝製造用模具、或小型封裝中銷數少的 之封裝製造用模具中亦不會產生空隙或碎屑。 本發明係藉由提供下述⑴、⑺以及（3)之模具清潔用橡 膠系組合物而解決上述課題者。 ❹A rubber knee-cleaning material that stretches in strength without causing debris or the like when the mold is released. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Provided is a rubber-based cleaning material which is excellent in workability (release property) as described above, but which eliminates the disadvantage of a rubber-based cleaning material which generates voids or chips without generating voids or debris. 135644.doc 200930757 The conventional cavity of 'the work' or the like is particularly small, and the object of the present invention is to provide a good cleaning property (release property) of the rubber (four) cleaning material, but not only eliminate voids or breakage It is a defect that does not cause voids, but the workability (release property) is poor, and the rubber-based cleaning material is generated, and the number of pins is small in a small package manufacturing mold such as PDIp*s〇ic or ice. There are also no voids or debris in the mold for manufacturing the package. The present invention solves the above problems by providing the rubber-based composition for mold cleaning of the following (1), (7) and (3). ❹

(1)一種模具清潔用橡膠系組合物，其係用以將硬化性 樹脂之成形步驟中所產生的模具表面之污垢去除者，其特 徵在於：基材樹脂係使用乙烯_丙烯橡膠與丁二烯橡膠之 調配比例經設定為90/10〜50/50重量份之未硫化橡膠，並且 該未硫化橡膠的經硫化硬化後之延伸率為8〇〜8〇〇%、拉伸 強度為3〜10 MPa、橡膠硬度（硬度計硬度）為A6〇〜95、175 C之模具溫度下之90%硫化時間（適當硫化點）tc(9〇)為 50〜100秒之值的範圍。（以下’稱為第1模具清潔用橡膠系 組合物） (2) —種模具清潔用橡膠系組合物，其係用以將硬化性 樹脂之成形步驟中所產生的模具表面之污垢去除者，其特 徵在於：基材樹脂係使用乙婦-丙稀橡膠與丁二稀橡膠之 調配比例經設定為90/10〜50/50重量份之未硫化橡膠，並且 該未硫化橡膠的經硫化硬化後之延伸率為80〜800%、拉伸 強度為3〜10 MPa、橡膠硬度（硬度計硬度）為A60〜95、175 。(：之模具溫度下之90%硫化時間（適當硫化點）tc(9〇)為 135644.doc 9- 200930757 200〜400秒之值的範圍。（以下，稱為第2模具清潔用橡膠 系組合物） (3) —種模具清潔用橡膠系組合物，其係用以將硬化性 樹脂之成形步驟中所產生的模具表面之污垢去除者，其特 徵在於：基材樹脂係使用乙烯-丙烯橡膠與丁二烯橡膠之 調配比例經設定為90/10-50/50重量份之未硫化橡膠，且該 未硫化橡膠係經硫化硬化後之延伸率為8〇〜8〇〇%之範圍、 拉伸強度為3〜10 MPa、橡膠硬度（硬度計硬度）為A60〜95、 1 75 °C之模具溫度下之90%硫化時間（適當硫化點）tc(9〇)為 200〜400秒之值的範圍者，並且該模具清潔用橡膠系組合 物含有至少1種脫模劑。（以下，稱為第3模具清潔用橡膠 系組合物） 本發明之第1、第2以及第3模具清潔用橡膠系組合物係 不僅作業性（脫模性）優異’成形性及強度亦優異，並且不 會產生空隙或碎屑者。 本發明之第1、第2以及第3模具清潔用橡膠系組合物係 如下橡膠系組合物：用作基材樹脂之未硫化橡膠係硫化硬 化後之延伸率為80〜800%之範圍、拉伸強度為3〜1〇 Mpa、 橡膠硬度（硬度計硬度）為A6〇〜95、175它之模具溫度下之 90%硫化時間（適當硫化點）tc(9〇)為5〇〜1〇〇秒或者2〇〇〜4〇〇 秒之值的範圍者，結果容易實施通氣孔部分之清潔，進 而，橡膠系清潔材料之特徵即作業性（剝離性）得以維持， 並且成形性及強度亦優異。 又，本發明之第3模具清潔用橡膠系組合物係藉由含有 135644.doc •10- 200930757 至少1種脫模劑，而適用於如PDIP4S〇IC等般模腔深之 型封裝製造用模具、或小型封裝中銷數少的尤其小之封裝 製造用模具之清潔的橡膠系組合物。 【實施方式】 以下，首先對本發明之第丨模具清潔用橡膠系組合物加 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。 所謂乙烯-丙烯橡膠（以下有時簡記為EPM)，係包括通常 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)此兩者之含義。 作為上述EPM，較好的是乙烯與…烯烴（尤其係丙烯）之 共聚合比例以莫耳比計為乙烯/α_烯烴=55/45〜83/17，且孟 納黏度ML1+4(100C)為5〜300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，且孟納黏度 ML1+4(l〇〇°C )為 36〜44者。 又，上述EPDM係由乙烯、α_稀烴、與具有非共耗雙鍵 之環狀物或者非環狀物所形成的三元共聚物。詳細而言， 係由乙烯、α-烯烴（尤其係丙烯）、與聚烯單體所形成之三 元共聚物。 作為上述聚烯早體’可列舉：二環戊二烯；5環辛二 烯，1，7-環十二烷二烯；1，5,9-環十二烷三烯；ι，4-環庚二 烯；1，4-環己二烯；降葙二烯；亞甲基降葙烯；2_甲基戊 二烯-1，4、1，5-己二烯；1,6-庚二烯；曱基四氫茚；1>4•己 135644.doc -11 - 200930757 -烯等。上述三元共聚物中之各單體之共聚合比例較好的 是乙料30〜8G莫耳％，聚科體极卜2莫耳％，立餘為 ㈣烴。更好的是乙烯為3〇〜⑽耳％。並且，作為上述三 元共聚物即EPDM，較好的县# Λ 平又野的疋使用孟納黏度^^丨+4(1〇〇t；) 為2 0〜7 0者。 又，作為上述丁二烯橡膠（以下簡記為BR),適宜使用具 有反式Μ鍵之含量為9〇重量％以上之高順式結構，且孟;内 黏度ML1+4(10(TC)為20〜60、尤其為3〇〜45者。 並且，上述乙烯-丙烯橡膠與丁二烯橡膠之調配比例以 重量比计為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-丙烯橡膠經調配為超過9〇重量份，則模具脫模 性變差，清潔作業時間變長，故欠佳。若丁二烯橡膠經調 配為超過50重量份，則模具脫模性變好，但硫化後之成形 物變硬變脆’故容易產生碎屑，因此欠佳。 上述未硫化橡膠係硫化硬化後之延伸率為8〇〜8〇〇%、較 好的是100〜300°/。者。若延伸率達到8〇%以下，則成形性變 差，故欠佳。 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。若拉伸強度達到3 MPa以下，則容 易產生碎屑，故欠佳。 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A70〜90者。若橡膠硬度脫離該範 圍，則容易產生碎屑或空隙，故欠佳。 135644.doc •12- 200930757 上述未硫化橡膠係175t之模具溫度下之9〇%硫化時間 (適當硫化點）tc(90)為50〜100秒、較好的是7〇〜1〇〇秒者。 若叫9〇)之值為該範圍心則硫化速度不會過快，可使樹 脂填充至模腔之角肖，可不產生黏附等不良情況而實施清 潔。又，與習知之橡膠系清潔材料相比，可於效率良好之 硬化時間内進行清潔，因此可減少_之清潔時間。 本發明之橡膠系組合物除了含有上述未硫化橡膠以外，(1) A rubber-based composition for cleaning a mold for removing dirt on a surface of a mold which is formed in a step of forming a curable resin, characterized in that the base resin is made of ethylene-propylene rubber and diced The blending ratio of the olefin rubber is set to 90/10 to 50/50 parts by weight of the unvulcanized rubber, and the elongation of the unvulcanized rubber after vulcanization and hardening is 8 〇 to 8 〇〇%, and the tensile strength is 3 to 10 MPa. The rubber hardness (hardness hardness) is a range of values of 50 to 100 seconds at a mold temperature of A6 〇 95 and 175 C at a mold temperature of 90% vulcanization time (appropriate cure point) tc (9 〇). (hereinafter referred to as "the rubber composition for the first mold cleaning") (2) A rubber-based composition for cleaning a mold for removing dirt on the surface of the mold generated in the step of forming the curable resin, The method is characterized in that: the base resin is an unvulcanized rubber set to a ratio of 90/10 to 50/50 parts by weight, and the vulcanized hardened extension of the unvulcanized rubber is used. The ratio was 80 to 800%, the tensile strength was 3 to 10 MPa, and the rubber hardness (hardness hardness) was A60 to 95, 175. (: 90% vulcanization time at the mold temperature (appropriate vulcanization point) tc (9 〇) is a range of values of 135644.doc 9-200930757 200 to 400 seconds. (hereinafter, referred to as a second rubber mold for mold cleaning) (3) A rubber-based composition for cleaning a mold for removing dirt on a surface of a mold which is formed in a step of forming a curable resin, characterized in that the base resin is made of ethylene-propylene rubber The blending ratio with the butadiene rubber is set to 90/10-50/50 parts by weight of the unvulcanized rubber, and the elongation ratio of the unvulcanized rubber after vulcanization hardening is in the range of 8 〇 to 8 〇〇%, and the tensile strength A range of values of 200 to 400 seconds for a mold hardness of 3 to 10 MPa and a rubber hardness (hardness hardness) of A60 to 95 and a mold temperature of 1 75 ° C at a mold temperature of 90% (suitable vulcanization point) tc (9 〇) In addition, the rubber composition for mold cleaning contains at least one type of release agent. (hereinafter, referred to as a third rubber composition for cleaning a mold) The first, second, and third mold cleaning rubbers of the present invention The composition is excellent not only in workability (release property) but also in formability and The rubber composition of the first, second, and third mold cleanings of the present invention is a rubber-based composition: an unvulcanized rubber which is used as a base resin, and is vulcanized and hardened. The subsequent elongation is in the range of 80 to 800%, the tensile strength is 3 to 1 〇Mpa, the rubber hardness (hardness hardness) is A6 〇 95, 175, and 90% of the vulcanization time at the mold temperature (appropriate curing point) When tc (9 〇) is in the range of 5 〇 to 1 〇〇 second or 2 〇〇 to 4 〇〇 seconds, the vent hole portion is easily cleaned, and the rubber-based cleaning material is characterized by workability ( The peeling property is maintained, and the moldability and the strength are also excellent. The third rubber composition for mold cleaning of the present invention is suitable for use as long as it contains at least one release agent of 135644.doc •10-200930757. A mold-like mold for manufacturing a cavity cavity type such as PDIP4S〇IC, or a rubber-based composition for cleaning a package for manufacturing a package having a small number of pins in a small package. [Embodiment] Hereinafter, the first aspect of the present invention will be described. Mould cleaning rubber system The composition is described in detail. The unvulcanized rubber used in the present invention is a mixture of an ethylene-propylene rubber and a butadiene rubber. The ethylene-propylene rubber (hereinafter sometimes abbreviated as EPM) includes a usual ethylene-propylene. The meaning of both rubber (EPM) and ethylene-propylene-diene rubber (hereinafter sometimes abbreviated as EPDM). As the above EPM, it is preferred that the copolymerization ratio of ethylene to olefin (especially propylene) is in the molar ratio. The ratio is ethylene/α_olefin = 55/45 to 83/17, and the Mona viscosity ML1+4 (100C) is 5 to 300. Particularly preferably, the above copolymerization ratio is ethylene/α in terms of molar ratio. _ olefin = 55/45~61/39, and the Manner viscosity ML1+4 (l 〇〇 ° C) is 36~44. Further, the EPDM is a terpolymer formed of ethylene, an α-dilute hydrocarbon, and a cyclic or acyclic substance having a non-covalent double bond. More specifically, it is a terpolymer formed of ethylene, an α-olefin (especially propylene), and a polyolefin monomer. Examples of the above polyene precursors include dicyclopentadiene; 5-cyclooctadiene, 1,7-cyclododecadiene; 1,5,9-cyclododecanetriene; and i. Cycloheptadiene; 1,4-cyclohexadiene; norbornadiene; methylene norbornene; 2-methylpentadiene-1,4,1,5-hexadiene; 1,6- Heptadiene; mercapto tetrahydroanthracene; 1 > 4 • 135644.doc -11 - 200930757 - alkene and the like. The copolymerization ratio of each monomer in the above terpolymer is preferably from 30 to 8 Gmol% of the binder, 2 mol% of the polyorganism, and the remainder is (tetra) hydrocarbon. More preferably, the ethylene is 3 〇 ~ (10) ear %. Further, as the above-mentioned terpolymer, that is, EPDM, a good county #Λ平和野疋 uses Mengna viscosity ^^丨+4(1〇〇t;) as 2 0~7 0. Further, as the butadiene rubber (hereinafter abbreviated as BR), a high cis structure having a content of a trans-ruthenium bond of 9 〇 by weight or more is preferably used, and the internal viscosity ML1+4 (10 (TC) is 20 to 60, especially 3 to 45. Further, the ratio of the above ethylene-propylene rubber to butadiene rubber is 90/10 to 50/50 parts by weight, preferably 8〇/2 by weight. 〇~6〇/4〇 parts by weight. If the ethylene-propylene rubber is blended to more than 9 parts by weight, the mold release property is deteriorated, and the cleaning operation time becomes long, which is not preferable. If the butadiene rubber is blended as When the amount is more than 50 parts by weight, the mold release property is improved, but the molded product after vulcanization becomes hard and brittle, so that chipping is liable to occur, which is unsatisfactory. The elongation of the unvulcanized rubber after vulcanization and hardening is 8 〇 to 8 〇. 〇%, preferably 100 to 300 ° /. If the elongation is 8 % or less, the moldability is deteriorated, which is not preferable. The tensile strength of the unvulcanized rubber after vulcanization and hardening is 3 to 1 Torr. MPa, preferably 5 to 8 MPa. If the tensile strength is less than 3 MPa, it is prone to chipping, which is not preferable. The rubber hardness (hardness tester hardness) after vulcanization and hardening of the rubber is A60 to 95, preferably A70 to 90. If the rubber hardness is out of this range, it is liable to generate chips or voids, which is not preferable. 135644.doc • 12- 200930757 The 9未% vulcanization time (appropriate vulcanization point) tc(90) at the mold temperature of 175t of the above unvulcanized rubber is 50~100 seconds, preferably 7〇~1〇〇 seconds. The value of the range is such that the vulcanization rate is not too fast, and the resin can be filled to the corner of the cavity, and the cleaning can be performed without causing adhesion or the like. Further, compared with the conventional rubber-based cleaning material, it can be cleaned in an efficient hardening time, thereby reducing the cleaning time. The rubber-based composition of the present invention contains, in addition to the above-mentioned unvulcanized rubber,

可含有填充劑、清洗劑、清洗助劑、硫化劑、硫化助劑、 硫化促進劑、硫化促進助劑等。 作為填充劑（補強劑），可列舉：二氧化石夕、氧化銘、碳 弓氫氧化Is、氧化鈦等。上述填充劑之使用量相對於 未硫化橡膠1GG重量份’較好的是1G〜7〇重量份，更好的是 30〜60重量份。 作為清洗劑，例如可列舉：單乙醇胺、二乙醇胺、三乙 醇胺：N-甲基二乙醇胺、N，N•二正丁基乙醇胺等胺類；乙 醇一曱醚、-乙二醇二甲醚、三乙二醇二曱醚等二醇醚 米坐類以及咪唾琳類。上述清洗劑之使用量相對於未 硫化橡膠1 〇〇重詈伦 曰 重伤，較好的是5〜50重量份，更好的是 5〜30重董份。除此以外可使用界面活性劑等清洗助劑。 作為硫化劑’可列舉：例如二第三丁基過氧化物、二第 二戍一基過氧化物、過氧化二異丙苯、2,5_二甲基_2,5_二 基過氧化）-己燒等二婦丙基過氧化物類有機過氧化 物；例如雙（第三丁基過氧化）33,5三甲基環己規、 ’i雙（第二丁基過氧化）環己烧、2,2-雙（第三丁基過氧化） 135644.doc •13- 200930757 辛烧、4,4-雙（第三丁基過氧化）戊酸正丁酯、2,2_雙（第三 丁基過氧化）丁烷等過氧化縮酮類有機過氧化物。一般而 5，與一烯丙基過氧化物類相比，過氧化縮酿j類具有較長 之半衰期，該等可根據組合物之設計而單獨使用，亦可將 半衰期較長者與較短者併用來調整硫化速度。上述硫化劑 之使用量相對於未硫化橡膠100重量份，較好的是丨〜6重量 份，更好的是2〜4重量份。除此以外可使用丙烯酸單體或 硫等硫化助劑。 作為硫化促進劑，可列舉：例如二苯胍、三苯胍等胍 系，例如甲醛-對甲苯胺縮合物、乙醛_笨胺反應物等醛-胺 系或醛-氨系；例如2-巯基苯并噻唑、二硫化二苯并噻唑等 噻唑系等’可使用氧化鎂、氧化鉛、石灰等硫化促進助 劑。 本發明之橡膠系組合物中除了該等調配物以外可視需 要而併用：例如紅丹、鐵藍、鐵黑、群青、碳黑、鋅鋇 鈦黃H㈣黃、^丫 „定_紅等無機或有機顏料 類；例如硬脂酸鋅、肉豆M酸鋅、硬脂酸銘、硬脂酸舞等 金屬皂系潤滑劑；例如硬脂酸丁醋、月桂酸丁醋、硬脂酸 硬脂醋等脂肪酸自旨系潤滑劑；例如亞乙基雙硬脂醯胺、芬 醯胺油醯胺、硬脂醯胺、山蓊醯胺等醯胺系潤滑劑等。 其次，對本發明之第2模具清潔用橡膠系組合物加以說 明。 本發月之第2模具清潔用橡膠系組合物，除了用作基材 t曰之未硫化橡膠係175 c之模具溫度下之硫化時間 135644.doc 14 200930757 (適當硫化點）tc(9〇)為200〜4〇〇秒、較好的是25〇〜35〇秒之 未硫化橡膠以外，與本發明之第丨模具清潔用橡膠系組合 物相同。 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 或量等來適當調整。 若上述未硫化橡膠之tc(9〇)之值為2〇〇〜4〇〇秒之範圍内， 則硫化速度不會過快，鎖模時橡膠系組合物緩慢追隨模具 & 形狀，因此可使樹脂填充至模腔之角隅而不會產生空隙。 又，可不產生由於未填充或空隙之產生所引起的黏附等不 良情況而實施清潔。 繼而’對本發明之第3模具清潔用橡膠系組合物加以說 明。 本發明之第3模具清潔用橡膠系組合物係使本發明之第2 模具清潔用橡膠系組合物中含有至少1種脫模劑而形成 者。 作為上述脫模劑，可列舉：金屬皂系脫模劑、脂肪酸酯 系脫模劑、合成蠟、脂肪酸醯胺系脫模劑等。 作為金屬皂系脫模劑之例’例如可例示硬脂酸鈣、硬脂 酸辞、肉豆蔻酸鋅等。作為脂肪酸酯系脫模劑、合成壤、 脂肪酸醯胺系脫模劑，可例示：Lic〇wax OP (Clariant JaPan股份有限公司製造’褐煤酸部分皂化酯）、L〇xiol G_ 78 (Cognis japan股份有限公司製造，高分子複合醋）、 Licolub H-4 (Clariant Japan股份有限公司製造，改質烴）、 135644.doc -15- 200930757It may contain a filler, a cleaning agent, a cleaning aid, a vulcanizing agent, a vulcanization aid, a vulcanization accelerator, a vulcanization accelerating aid, and the like. Examples of the filler (reinforcing agent) include: cerium oxide, oxidized iron, carbon hydride, and titanium oxide. The amount of the filler to be used is preferably 1 G to 7 parts by weight, more preferably 30 to 60 parts by weight, per 1 part by weight of the unvulcanized rubber. Examples of the cleaning agent include amines such as monoethanolamine, diethanolamine, triethanolamine: N-methyldiethanolamine, N,N•di-n-butylethanolamine; ethanol monoterpene ether, ethylene glycol dimethyl ether, Glycol ethers such as triethylene glycol dioxime are used in the class of rice glycols. The amount of the above-mentioned cleaning agent used is relatively heavy, and is preferably 5 to 50 parts by weight, more preferably 5 to 30 parts by weight, relative to the unvulcanized rubber. In addition to this, a cleaning aid such as a surfactant can be used. Examples of the vulcanizing agent include, for example, di-tert-butyl peroxide, di-second-yl-based peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-diyl peroxidation. )-dipropyl propyl peroxide organic peroxide such as hexane; for example, bis(t-butylperoxy) 33,5 trimethylcyclohexane, 'i bis (second butyl peroxy) ring Benzene, 2,2-bis(t-butylperoxy) 135644.doc •13- 200930757 octyl, 4,4-bis(t-butylperoxy) n-butyl valerate, 2,2_double Peroxy ketal organic peroxides such as (t-butyl peroxy) butane. In general, 5, compared with monoallyl peroxides, the peroxidation shrinkage class j has a longer half-life, which can be used alone depending on the design of the composition, and can also have a longer half-life and a shorter one. And used to adjust the vulcanization rate. The amount of the vulcanizing agent to be used is preferably from 丨 6 parts by weight, more preferably from 2 to 4 parts by weight, per 100 parts by weight of the unvulcanized rubber. In addition to this, a vulcanization aid such as an acrylic monomer or sulfur can be used. Examples of the vulcanization accelerator include an anthracene system such as diphenylguanidine or triphenylsulfonium, and an aldehyde-amine system or an aldehyde-ammonia system such as a formaldehyde-p-toluidine condensate or an acetaldehyde-thromamine reactant; for example, 2- A sulfazole-promoting aid such as magnesium oxide, lead oxide or lime can be used as a thiazole system such as mercaptobenzothiazole or dibenzothiazole disulfide. In addition to the formulations, the rubber-based composition of the present invention may be used in combination with, for example, red dan, iron blue, iron black, ultramarine blue, carbon black, zinc bismuth titanium yellow H (tetra) yellow, 丫 定 _ red, etc. Organic pigments; for example, metal soaps such as zinc stearate, zinc mash, stearic acid, stearic acid, etc.; for example, butyl sulphate, butyl laurate, stearic acid The fatty acid is intended to be a lubricant; for example, a guanamine-based lubricant such as ethylene bis-lipidamine, melamine amide, stearylamine or behenamide, etc. Next, the second mold of the present invention The rubber composition for cleaning is described in the second rubber mold composition for cleaning of the mold of the present month, except for the vulcanization time of the unvulcanized rubber system 175 c used as the substrate t 135644.doc 14 200930757 (suitable The vulcanization point tc (9 〇) is the same as the rubber-based composition for the second mold cleaning of the present invention, except that the unvulcanized rubber is preferably 200 to 4 sec., preferably 25 〇 to 35 sec. The value of the adjustment can be based on the type or amount of the diene, the type or amount of the peroxide, The type or amount of the accelerator, the type or amount of the co-crosslinking agent, etc. are appropriately adjusted. If the value of the unvulcanized rubber tc (9 〇) is in the range of 2 〇〇 to 4 〇〇 seconds, the vulcanization rate is not It will be too fast, and the rubber-based composition will slowly follow the shape of the mold when clamping, so that the resin can be filled into the corner of the cavity without voids. Moreover, adhesion due to unfilled or voids may not occur. In the third step, the rubber composition for mold cleaning according to the present invention is the second rubber mold composition for cleaning the mold of the present invention. The release agent is formed by at least one type of release agent. Examples of the release agent include a metal soap release agent, a fatty acid ester release agent, a synthetic wax, a fatty acid amide amine release agent, and the like. Examples of the soap-based release agent include, for example, calcium stearate, stearic acid, zinc myristate, etc. Examples of the fatty acid ester-based release agent, synthetic soil, and fatty acid amide-based release agent are as follows: Lic〇wax OP (Clariant JaPan Co., Ltd. manufactures 'sulphuric acid partially saponified ester), L〇xiol G_78 (manufactured by Cognis japan Co., Ltd., polymer compound vinegar), Licolub H-4 (manufactured by Clariant Japan Co., Ltd., modified hydrocarbon), 135644 .doc -15- 200930757

Loxiol VPN881 (Cognis Japan股份有限公司製造’礦物油 系合成蠟）、Fatty Amide S(花王股份有限公司製造，脂肪 酸醯胺）、Kao Wax EB-P(花王股份有限公司製造，脂肪酸 醯胺）、Alflow HT-50(日本油脂股份有限公司製造，脂肪 酸醯胺）等。 該等脫模劑相對於未硫化橡膠100重量份，較好的是調 配3〜15重量份，較好的是5〜1〇重量份。 若脫模劑之量不足，則於如PDip或SOIC等般模腔深之Loxiol VPN881 (Mineral Oil Synthetic Wax manufactured by Cognis Japan Co., Ltd.), Fatty Amide S (manufactured by Kao Co., Ltd., fatty acid decylamine), Kao Wax EB-P (manufactured by Kao Co., Ltd., fatty acid guanamine), Alflow HT-50 (manufactured by Nippon Oil & Fat Co., Ltd., fatty acid guanamine). The release agent is preferably formulated in an amount of from 3 to 15 parts by weight, preferably from 5 to 1 part by weight, based on 100 parts by weight of the unvulcanized rubber. If the amount of the release agent is insufficient, it is deep in the cavity like PDip or SOIC.

小型封裝中，銷數少的尤其小之封裝製造用模具中，模具 上所配置之模腔數變多，因此模具脫模性相對降低。若脫 模劑之量過多，則模具脫模性雖良好，但清潔性變差，故 欠佳。 作為本發明之第丨及第2模具清潔用橡膠系組合物之製備 方法’並無特別限定，可採用公知之方法。例如，於附有 夾套之加壓型捏合機中投入職及时原料開始混練，一 面觀察適宜原料之溫度’ -面持續混練直至聰與BR之混 合原料成為年糕狀。並且 於該混合原料之溫度達到 70〜100 C之時刻，添加白碳、 胺基醇系化合物、環狀醯胺 化〇物、加工處理油、非離子系界面活性劑、硬脂酸等， 混練數为鐘。繼而添加右機 加有機過氧化物以及硫等吏苴 分散後取出1需要而 I、迅逮 ^ ^ qπ如片狀等適當之形狀，從 而裝成本發明之模具清潔用橡膠系組合物。 本發明之第3模具清潔用换挪么 w m 膠系組合物之製備，例如若 於上述本發明之第2模具清 右 、'、用橡膠系組合物之製備方法 135644.doc 200930757 中’將上述脫模劑與其他添加劑一併添加於^1>]^與811之、尾 合原料中即可。 作為混練手段’除上述加壓型捏合機以外，例如可列舉 班布裏混合機、輥磨機等。In a small-sized package, in a mold for manufacturing a package having a small number of pins, the number of cavities disposed on the mold is increased, so that the mold release property is relatively lowered. If the amount of the releasing agent is too large, the mold release property is good, but the cleanability is deteriorated, which is not preferable. The method for producing the rubber composition of the second and second mold cleanings of the present invention is not particularly limited, and a known method can be employed. For example, in a pressurized kneading machine with a jacket, the raw materials are put into time and mixed, and the temperature of the suitable raw materials is observed. The surface is continuously kneaded until the mixed raw materials of Cong and BR become a cake. Further, when the temperature of the mixed raw material reaches 70 to 100 C, white carbon, an amino alcohol-based compound, a cyclic amide-containing hydrazine, a processing oil, a nonionic surfactant, stearic acid, or the like is added, and kneading is performed. The number is a clock. Then, the right-hand machine is added with an organic peroxide, sulfur, and the like. After dispersing, a suitable rubber-like composition for mold cleaning of the present invention is prepared by taking out an appropriate shape such as a sheet or the like. In the third mold cleaning method of the present invention, the preparation of the wm gel composition is, for example, the above-mentioned second mold clearing of the present invention, and the preparation method of the rubber-based composition 135644.doc 200930757 The release agent may be added together with other additives in the raw materials of the mixture of ^1 and 811. As the kneading means, in addition to the above-mentioned pressurizing type kneader, for example, a Banbury mixer, a roll mill, or the like can be mentioned.

本發明之第1、第2及第3模具清潔用橡膠系組合物之形 態並無特別限疋’經混練之樹脂組合物若不迅速冷卻，則 會由於混練時之預熱而促進硫化’從而無法獲得穩定之性 能，因此作為本發明之模具清潔用橡膠系組合物之形態， 較好的是可在短時間内容易冷卻之片狀。 實施例 以下列舉實施例等來對本發明加以更詳細之說明，本發 明並不受該等實施例等之任何限定。 試驗方法 實施例以及比較例中所記載之各種物性評價之試驗方法 如下。_ [延伸率及拉伸強度] 依據JIS K6251中之拉伸強度以及切斷時延伸之測定方 法進行測定》 <試驗片之製作條件> 使用37T自動壓機，於模具溫度、成形壓為⑺ MPa(計示壓力）、成料間為5分鐘之條件下使未硫化試料 成形。所成形之試驗片尺寸為8〇χ16〇χ2 mm之片狀，將其 以3號啞鈴進行打孔而製成測定用之試驗片。 [橡膠硬度] 135644.doc •17· 200930757 利用依據JIS K6253『硫化橡膠及熱塑性橡膠之硬度試 驗方法』的方法進行測定。 將3片以上述試驗片製作條件而獲得之6〇x2 mm試 驗·片重整’使用符合橡膠硬度之類型的硬度計來測定硬度 計硬度。 [硫化速度] 利用依據JIS K63 00-2『利用振動式硫化試驗機的硫化特 性之求出方法』的方法，於l75°c之模具溫度下測定9〇0/〇 硫化時間（適當硫化點）tc(9〇)。 [清潔性試驗] 使用市售之聯苯系環氧樹脂成形材料（住友電木股份有 限公司製造，EME-735 1T)，於PDIP-14L(8罐-48模腔）之模 具中藉由500次之成形而實現模具之受污染。使用該受污 染之模具’使模具清潔用樹脂組合物反覆成形直至模具表 面經清潔乾淨，藉此進行評價。於實施例9〜12中，以 PDIP-8L(8罐-96模腔）之模具加以評價。 實施例1(本發明之第丨模具清潔用橡膠系組合物） 於3000 ml的附有夾套之加壓型捏合機中添加1〇5〇呂之 £卩〇]^原料[孟納黏度1^1^+4(1〇〇。(：）為23者]、與45()§之811 原料[孟納黏度ML1+4(l〇〇°c )為42且1，4順式鍵含有率為95 重量％者]，一面冷卻一面加壓混練約3分鐘，則£1>〇厘與 BR之混合原料成為年糕狀，其溫度達到約8〇它^繼而添 加150 g(相對於1〇〇重量份之ePDM與BR之混合原料而為1〇 重量份）之單乙醇胺、75 g(相對於1〇〇重量份之]£1>£)1^與311 135644.doc 18 200930757 〇原料而為5重量份）之聚環氧烷癸醚系界面活性劑、 1、5 g(相對於！⑽重量份之EpD_⑽之混合原料而為】重量 份）之硬脂酸、750 g(相對於100重量份之之混 σ原料而為50重量份）之白碳、75 g(相對於丨⑻重量份之 EPDM與BR之混合原料而為5重量份）之碳酸鈣' 75 §(相對 於重量份之EPDM與BR之混合原料而為5重量份）之氧 化鈦以及75 g(相對於1〇〇重量份之卯1)]^與BR之混合原料 而為5重量份）之氧化鋅，混練約3分鐘。最後添加48 g(相 對於100重量份之EPDM與BR之混合原料而為3 2重量份）之 l’l-雙（第三丁基過氧化）環己烷，繼績混練約丨分鐘。此期 間之混練物溫度經調節為不超過1〇(rc。使所獲得之混練 物迅速通過加壓輥，加工成片狀，同時冷卻至25t>c以下， 藉此獲得厚度為ό mm之片狀模具清潔用橡膠系組合物a。 將所獲付之片狀模具清潔用橡膠系組合物A之特性值以 及清潔性試驗結果示於表1中。根據試驗結果而判明，片 狀模具清潔用橡膠系組合物A表現出良好之清潔性。 實施例2(本發明之第丨模具清潔用橡膠系組合物） 於實施例1中，將基材樹脂之調配量變更為900 g之 EPDM原料[孟納黏度ML1+4(l〇〇°C )為23者]以及600 g之BR 原料[孟納黏度ML1+4(l〇(TC )為42且1，4順式鍵含有率為95 重量％者]’除此以外，以相同之方式獲得厚度為6 mm之 片狀模具清潔用橡膠系組合物B。 將所獲得之片狀模具清潔用橡膠系組合物B之特性值以 及清潔性5式驗結果不於表1中D根據試驗結果而判明，片 135644.doc •19· 200930757 狀模具清潔用橡膠系組合物B表現出良好之清潔性。 實施例3(本發明之第1模具清潔用橡膠系組合物） 於實施例1中，使用450 g(相對於100重量份之EpDM與 BR之混合原料而為3〇重量份）之（±)_丨_胺基_2_丙醇，來代 替150 g(相對於丨00重量份之ePDM與BR之混合原料而為i 〇 重量份）之單乙醇胺，除此以外，以相同之方式獲得厚度 為6 mm之片狀模具清潔用橡膠系組合物C。 將所獲得之片狀模具清潔用橡膠系組合物C之特性值以 及清潔性試驗結果示於表i中。根據試驗結果而判明，片 狀模具清潔用橡膠系組合物C表現出良好之清潔性。 實施例4(本發明之第丨模具清潔用橡膠系組合物） 於實施例1中’將基材樹脂變更為825 g<EPDM原料[孟 納黏度ML+4( 100X：)為23者]以及675 g之BR原料[孟納黏度 ML1+4(i〇〇°c)為35且1，4順式鍵含有率為95重量。/。者]，又， 將白碳之調配量由750 g(相對於1〇〇重量份之EPDM與8尺之 混合原料而為50重量份）變更為450 g(相對於1〇〇重量份之 EPDM與BR之混合原料而為30重量份），除此以外，以相 同之方式獲得厚度為6 mm之片狀模具清潔用橡膠系組合物 D。 將所獲得之片狀模具清潔用橡膠系組合物D之特性值以 及清潔性試驗結果示於表1中。根據試驗結果而判明，片 狀模具清潔用橡膠系組合物D表現出良好之清潔性。 比較例1 於實施例1中，將基材樹脂之調配量變更為6〇〇 g之 135644.doc •20- 200930757 EPDM原料[孟納黏度MLi+4(100°C )為23者]以及900 g<BR 原料[孟納黏度ML1+4(100°C )為42且1，4順式鍵含有率為95 重量％者]，除此以外，以相同之方式獲得厚度為6 mm之 片狀模具清潔用橡膠系組合物E。 將所獲得之片狀模具清潔用橡膠系組合物E之特性值以 • 及清潔性試驗結果示於表1中。根據試驗結果而判明，於 • 模腔部中產生未填充或對模具之切削等，必須有大量之清 潔作業時間。又，清潔性亦不良，清潔完畢之前必須有較 © 多成形次數。 [表1] 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 30 BR比 30 40 30 45 70 延伸率(°/〇) 270 150 253 98 59 拉伸強度(MPa) 5.2 4.1 4.9 4.3 4.1 橡膠硬度 90 91 90 91 92 tc(90)(秒） 60 56 67 54 58 成形性 〇 〇 〇 〇 Δ 模具脫模性 〇 〇 〇 〇 X 清潔完畢 次數 4 4 4 4 8 成形性之評價基1 1 〇：未填充之產生率小於3% △:未填充之產生率為3%以上且小於1〇% X :未填充之產生率為10%以上 模具脫模性之評價基準 〇：碎屑之產生率小於3% △:碎屑之產生率為3%以上且小於ι〇〇/0 X :碎屑之JL生率為10%以上 實施例5(本發明之第2模具清潔用橡膠系組合物）The form of the rubber composition for cleaning the first, second, and third molds of the present invention is not particularly limited. If the resin composition that has been kneaded is not rapidly cooled, the vulcanization is promoted by the preheating during kneading. In the form of the rubber composition for mold cleaning of the present invention, it is preferably in the form of a sheet which can be easily cooled in a short period of time. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples and the like, and the present invention is not limited by the examples and the like. Test method The test methods for various physical property evaluations described in the examples and the comparative examples are as follows. _ [Elongation and tensile strength] Measured according to the measurement method of tensile strength and elongation at break in JIS K6251. <Production conditions of test piece> Using a 37T automatic press, the mold temperature and molding pressure were (7) An unvulcanized sample was formed under the conditions of MPa (measured pressure) and a mixture of materials for 5 minutes. The formed test piece had a sheet size of 8 〇χ 16 〇χ 2 mm, and was punched with a No. 3 dumbbell to prepare a test piece for measurement. [Rubber hardness] 135644.doc •17· 200930757 The measurement was carried out by the method according to JIS K6253 “Test method for hardness of vulcanized rubber and thermoplastic rubber”. Three sheets of 6 〇 x 2 mm test pieces were obtained by the above test piece production conditions. The hardness of the durometer was measured using a durometer of a rubber hardness type. [Vulcanization rate] Using a method according to JIS K63 00-2 "Method for determining the vulcanization characteristics of a vibration type vulcanization tester", the 9 〇 0 / 〇 vulcanization time (appropriate vulcanization point) is measured at a mold temperature of 175 ° C. Tc (9〇). [Cleaning test] A commercially available biphenyl-based epoxy resin molding material (manufactured by Sumitomo Bakelite Co., Ltd., EME-735 1T) was used in a mold of PDIP-14L (8-can-48 cavity) by 500. The formation of the second is to achieve contamination of the mold. The mold for cleaning the mold was subjected to repeated use until the surface of the mold was cleaned by using the contaminated mold. In Examples 9 to 12, evaluation was carried out using a mold of PDIP-8L (8 cans - 96 cavity). Example 1 (The ninth mold cleaning rubber composition of the present invention) In a 3000 ml jacketed press type kneader, 1 〇 5 〇 之 卩〇 ^ ^ ^ ^ 孟 孟 孟 孟 孟 孟 孟 孟^1^+4(1〇〇.(:) is 23], and 45()§ 811 raw material [Menna viscosity ML1+4(l〇〇°c) is 42 and 1,4 cis bond contains The rate is 95% by weight], and the mixture is pressurized and kneaded for about 3 minutes while cooling, and then the mixture of 〇 与 and BR becomes a cake, and the temperature reaches about 8 〇. Then, 150 g is added (relative to 1 〇). 〇 parts by weight of the mixed raw materials of ePDM and BR are 1 part by weight of monoethanolamine, 75 g (relative to 1 part by weight) of £1> £)1^ and 311 135644.doc 18 200930757 5 parts by weight of the polyalkylene oxide oxime ether surfactant, 1, 5 g (relative to (10) parts by weight of the mixed raw material of EpD_(10), stearic acid, 750 g (relative to 100) 50 parts by weight of white carbon, 75 g (5 parts by weight relative to 丨 (8) parts by weight of a mixed raw material of EPDM and BR) of calcium carbonate '75 § (relative to parts by weight) Mix of EPDM and BR Material and 5 parts by weight) of titanium oxide and 75 g (1〇〇 parts by weight with respect to the d 1)] ^ zinc oxide mixed feed of BR and 5 parts by weight), the kneaded for about 3 minutes. Finally, 48 g (32 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR) of l'l-bis(t-butylperoxy)cyclohexane was added, and the mixture was kneaded for about several minutes. The temperature of the kneaded material during this period is adjusted to not more than 1 〇 (rc. The obtained kneaded material is quickly passed through a pressure roller, processed into a sheet shape, and cooled to 25 t > c, thereby obtaining a sheet having a thickness of ό mm. The rubber-based composition a for cleaning the mold was shown in Table 1. The characteristic values of the rubber-based composition A for cleaning the sheet-like mold and the cleaning test results are shown in Table 1. According to the test results, it was found that the sheet mold was cleaned. The rubber composition A showed good cleanability. Example 2 (The rubber composition for mold cleaning of the present invention) In the first embodiment, the amount of the base resin was changed to 900 g of the EPDM raw material. Mengna viscosity ML1+4 (l〇〇°C) is 23] and 600 g of BR material [Menna viscosity ML1+4 (l〇(TC) is 42 and 1,4 cis bond content is 95 weight In the same manner, the rubber-based composition B for sheet mold cleaning having a thickness of 6 mm was obtained in the same manner. The characteristic value and cleanability of the rubber-based composition B for cleaning the sheet-like mold obtained were obtained. The test results are not determined according to the test results in Table 1, D, 135644.doc •19· 20093075 The rubber composition B for the 7-mold mold cleaning showed good cleanability. Example 3 (The first rubber composition for mold cleaning of the present invention) In Example 1, 450 g (relative to 100 parts by weight) was used. A mixture of EpDM and BR is 3 parts by weight of (±) 丨 胺 胺 胺 _2 _ _ _ , 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 相对 相对 相对 相对 相对 相对 丨 丨 丨 丨 丨 丨 丨In the same manner, a rubber composition C for sheet mold cleaning having a thickness of 6 mm was obtained in the same manner as in the case of the monoethanolamine in the same manner. The characteristic value of the obtained rubber-based composition C for sheet mold cleaning and The results of the cleaning test are shown in Table 1. According to the test results, the rubber composition C for sheet mold cleaning showed good cleanability. Example 4 (The rubber composition for cleaning the third mold of the present invention) In Example 1, 'the base resin was changed to 825 g< EPDM raw material [Menner viscosity ML+4 (100X:) was 23] and 675 g of BR raw material [Menner viscosity ML1+4 (i〇〇°) c) is 35 and the 1,4 cis bond content is 95% by weight. In addition, the white carbon is adjusted by 750 g ( 50 parts by weight based on 1 part by weight of the mixture of EPDM and 8 feet of the raw material is changed to 450 g (30 parts by weight based on 1 part by weight of the mixed raw material of EPDM and BR). The sheet-like mold cleaning rubber composition D having a thickness of 6 mm was obtained in the same manner. The characteristic values and the cleaning test results of the obtained rubber-based composition D for sheet mold cleaning are shown in Table 1. According to the test results, it was found that the rubber composition D for sheet mold cleaning showed good cleanability. Comparative Example 1 In Example 1, the amount of the base resin was changed to 6 〇〇g of 135644.doc • 20-200930757 EPDM raw material [Menner viscosity MLi+4 (100 ° C) was 23] and 900 g<BR raw material [Monner viscosity ML1+4 (100 ° C) is 42 and 1,4 cis bond content is 95% by weight], except that a sheet having a thickness of 6 mm is obtained in the same manner. Rubber-based composition E for mold cleaning. The characteristic values of the obtained rubber-based composition E for sheet mold cleaning were shown in Table 1 and the results of the cleaning test. According to the test results, it is necessary to have a large amount of cleaning work time, such as unfilled or cut to the mold in the cavity portion. Moreover, the cleanliness is also poor, and there must be more than 100 times of forming before cleaning. [Table 1] 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 30 BR ratio 30 40 30 45 70 Extension Rate (°/〇) 270 150 253 98 59 Tensile strength (MPa) 5.2 4.1 4.9 4.3 4.1 Rubber hardness 90 91 90 91 92 tc(90) (seconds) 60 56 67 54 58 Formability 〇〇〇〇Δ Mold off Moulding 〇〇〇〇X Cleaning times 4 4 4 4 8 Evaluation of formability 1 1 〇: The rate of unfilling is less than 3% △: The rate of unfilling is 3% or more and less than 1〇% X : The unfilled production rate is 10% or more. The evaluation criteria of the mold release property 〇: the generation rate of the chips is less than 3% △: The generation rate of the chips is 3% or more and less than ι〇〇/0 X : JL of the chips The growth rate is 10% or more. Example 5 (the second rubber composition for mold cleaning of the present invention)

於實施例1中，使用48 g(相對於100重量份之EPDM與BR 135644.doc -21 - 200930757 之混合原料而為3.2重量份）之過氧化二異丙苯，來代替48 g(相對於1 〇〇重量份之EPDM與BR之混合原料而為3 2重量 份)之1’!-雙(第三丁基過氧化)環己烷，並且將混練物溫度 調節為不超過11(rc ’除此以外，以相同之方式獲得厚度 為6 mm之片狀模具清潔用橡膠系組合物 將所獲得之片狀模具清潔用橡膠系組合物F之特性值以 . 騎潔性試驗結果示於表2中。根據試驗結果而判明，片 &模具清潔轉膠系組合物F表現出良好之成形性以及清 © 潔性。 實施例6 (本發明之第2模具清潔用橡膠系組合物） 於實施例5中，將基材樹脂之調配量變更為层之 EPDM原料[孟納黏度ML丨wore )為23者]以及_ §之时 原料[孟納黏度MLl+4(100〇c )為42且14順式鍵含有率為95 重量％者]’除此以外，以相同之方式獲得厚度為6山爪之 片狀模具清潔用橡膠系組合物G。 泛 將所獲得之片狀模具清潔用橡膠系組合物G之特性值以 及清潔性試驗結果示於表2中。根據試驗結果而判明，片 狀模具清潔用橡膠系組合物G表現出良好之成形性以及清 潔性。 實施例7(本發明之第2模具清潔用橡膠系組合物） 於實施例5中，使用300 g(相對於100重量份之砂〇1^與 BR之混合原料而為2〇重量份）之（±)1_胺基_2·丙醇，來代 替150 g(相對於100重量份iEpDM與811之混合原料而為w 重量伤）之單乙醇胺，並且使用28 g(相對於1〇〇重量份之 135644.doc •22· 200930757 EPDM與BR之混合原料而為i 9重量份）之過氧化二異兩苯 以及2二g(相對於！ 〇〇重量份之EpDM與狀之混合原料而為 1.3重量份）之4,4·雙（第三丁基過氧化）戊酸正丁酯，來代替 48 g(相對於】00重量份之卿職抓之混合原料而為3 2重 量份）之過氧化二異丙苯，除此以夕卜，以相同之方式獲得 厚度為6 mm之片狀模具清潔用橡膠系組合物H。 將所獲得之片狀模具清潔用#膠系组合物H之特性值以 及清潔性試驗結果示於表2中。根據試驗結果而判明，片 狀模具清潔用橡膠系組合物H表現出良好之成形性以及 潔性。 實施例8(本發明之第2模具清潔用橡膠系組合物） 於實施例5中，將450 g之BR原料[孟納黏度MLi + 4(1〇〇t) 為42且1，4順式鍵含有率為95重量％者]變更為45〇吕之8&原 料[孟納黏度ML1+4(l〇〇°c )為35且1，4順式鍵含有率為％重 量％者]，又，將48 g(相對於100重量份之EpDM與BR之混 合原料而為3.2重量份）之過氧化二異丙苯變更為13 g(相對 於1〇〇重量份之EPDM與BR之混合原料而為〇 9重量份）之 U-雙（第三丁基過氧化）環己烷以及35 g(相對於1〇〇重量份 之EPDM與BR之混合原料而為2.3重量份）之過氧化二異丙 苯，除此以外，以相同之方式獲得厚度為6 mm之片狀模具 清潔用橡膠系組合物I。 將所獲得之片狀模具清潔用橡膠系組合物I之特性值以 及清潔性試驗結果示於表2中。根據試驗結果而判明，片 狀模具/青潔用橡膠系組合物I表現出良好之成形性以及清 135644.doc -23- 200930757 潔性。 比較例2 於實施例5中，將基材樹脂之調配量變更為600 g之 EPDM原料[孟納黏度MLi+4(100°C )為23者]以及900 g之BR 原料[孟納黏度ML1+4(100°C )為42且1，4順式鍵含有率為95 重量％者]，除此以外，以相同之方式獲得厚度為6 mm之 • 片狀模具清潔用橡膠系組合物J。 將所獲得之片狀模具清潔用橡膠系組合物J之特性值以 © 及清潔性試驗結果示於表2中。根據試驗結果而判明，於 模腔部產生未填充或對模具之切削等，必須有大量之清潔 作業時間。又，清潔性亦不良，清潔完畢之前必須有較多 成形次數。 [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 4伸率(％) 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） 329 297 278 267 58 成形性 〇 〇 〇 〇 Δ 模具脫模性 r 〇 〇 〇 〇 X 空隙 〇 〇 〇 〇 X 清潔完畢次數 Γ 4 4 4 4 8 〇：空隙之產生率小於3% △:空隙之產生率為3%以上且小於ι〇〇/0 X :空隙之產生率為10%以上 實施例9(本發明之第3模具清潔用橡膠系組合物） 於3000 ml的附有夾套之加壓型捏合機中添加1050 g之 135644.doc •24· 200930757 EPDM原料[孟納黏度ML1+4(i〇〇°c )為23者]、與45〇 g之BR 原料[孟納黏度ML1+4(100°C )為42且1，4順式鍵含有率為95 重量％者]，一面冷卻一面加壓混練約3分鐘，則EPDM與 BR之混合原料成為年糕狀’且其溫度達到約8〇。〇。繼而 添加150 g(相對於1〇〇重量份之EPDM與BR之混合原料而為 ‘ 10重量份）之單乙醇胺、75 g(相對於100重量份之EPDM與 BR之混合原料而為5重量份）之聚環氧烷癸醚系界面活性In Example 1, 48 g (3.2 parts by weight of a mixed raw material of 100 parts by weight of EPDM and BR 135644.doc -21 - 200930757) of dicumyl peroxide was used instead of 48 g (relative to 48 g). 1 part by weight of the mixed raw material of EPDM and BR is 32 parts by weight of 1'!-bis(t-butylperoxy)cyclohexane, and the temperature of the kneaded material is adjusted to not exceed 11 (rc ' In the same manner, the rubber-based composition for sheet-like mold cleaning having a thickness of 6 mm was obtained in the same manner, and the characteristic values of the rubber-based composition F for sheet-like mold cleaning obtained were shown in the table. 2. According to the test results, it was found that the sheet & mold cleaning gel composition F exhibited good formability and cleansing property. Example 6 (The second mold cleaning rubber composition of the present invention) In Example 5, the amount of the base resin was changed to a layer of EPDM raw material [Menner viscosity ML丨wore) of 23] and _ § when the raw material [Menner viscosity MLl+4 (100〇c) was 42 And the 14 cis bond content rate is 95% by weight]' In addition, a film having a thickness of 6 claws is obtained in the same manner. The mold cleaning rubber composition G. The characteristic values of the rubber composition G for sheet mold cleaning obtained and the results of the cleaning test are shown in Table 2. According to the test results, it was found that the rubber composition G for sheet mold cleaning exhibited good formability and cleanability. Example 7 (Second mold cleaning rubber composition of the present invention) In Example 5, 300 g (2 parts by weight based on 100 parts by weight of the mixed material of the sand and the BR) was used. (±) 1-amino-2-propanol instead of 150 g (w weight damage relative to 100 parts by weight of iEpDM and 811 mixed material), and 28 g (relative to 1 〇〇 weight) 135644.doc •22· 200930757 The mixed raw material of EPDM and BR is i 9 parts by weight of diiso-biphenyl peroxide and 2 gg (relative to the mixture of EpDM and the weight of the material) 1.3 parts by weight of 4,4·bis(t-butylperoxy)-n-butyl valerate instead of 48 g (32 parts by weight relative to 00 parts by weight of the mixed raw material) In the same manner as above, a sheet-like mold cleaning rubber composition H having a thickness of 6 mm was obtained in the same manner. The characteristic values of the obtained gel-form composition for cleaning the sheet-like mold H and the results of the cleaning test are shown in Table 2. According to the test results, it was found that the rubber-based composition H for sheet mold cleaning exhibited good formability and cleanability. Example 8 (Second mold cleaning rubber composition of the present invention) In Example 5, 450 g of BR raw material [Menna viscosity MLi + 4 (1〇〇t) was 42 and 1,4 cis The bond content is 95% by weight] changed to 45 〇 之 8 & raw material [Menner viscosity ML1+4 (l〇〇°c) is 35 and 1,4 cis bond content is % by weight], Further, 48 g (3.2 parts by weight based on 100 parts by weight of the mixed raw material of EpDM and BR) of dicumyl peroxide was changed to 13 g (relative to 1 part by weight of the mixed raw material of EPDM and BR) And 9 parts by weight of U-bis(t-butylperoxy)cyclohexane and 35 g (2.3 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR) A sheet-like mold cleaning rubber composition I having a thickness of 6 mm was obtained in the same manner except for cumene. The characteristic values of the obtained rubber-based composition I for sheet mold cleaning and the results of the cleaning test are shown in Table 2. According to the test results, it was found that the sheet-like mold/green rubber composition I exhibited good formability and cleanness of 135644.doc -23-200930757. Comparative Example 2 In Example 5, the amount of the base resin was changed to 600 g of EPDM raw material [Menner viscosity MLi+4 (100 ° C) was 23] and 900 g of BR raw material [Menner viscosity ML1 A rubber mold composition for sheet mold cleaning J having a thickness of 6 mm was obtained in the same manner, except that the ratio of +4 (100 ° C ) was 42 and the 1,4- cis bond content was 95% by weight. . The characteristic values of the obtained rubber-based composition J for sheet mold cleaning were shown in Table 2 as a result of © and the cleaning test results. According to the test results, it is found that there is a large amount of cleaning work time in the cavity portion which is not filled or cut into the mold. Moreover, the cleanliness is also poor, and there must be more forming times before cleaning. [Table 2] Item Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Composition F Composition G Composition Η Composition I Composition J epdm ratio 70 60 70 70 40 BR ratio 30 40 30 30 60 4 Extensibility (%) 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) 329 297 278 267 58 Formability 〇〇〇〇 Δ Mold release Sex r 〇〇〇〇X Void 〇〇〇〇X Number of cleanings completed Γ 4 4 4 4 8 〇: The generation rate of voids is less than 3% △: The generation rate of voids is 3% or more and less than ι〇〇/0 X : The void generation rate was 10% or more. Example 9 (the third mold cleaning rubber composition of the present invention) was added to a 3000 ml jacketed press type kneader to add 1050 g of 135644.doc •24· 200930757 EPDM raw material [Menner viscosity ML1+4(i〇〇°c) is 23], and 45〇g of BR raw material [Menner viscosity ML1+4 (100 °C) is 42 and 1,4 cis bond When the content is 95% by weight, the mixture is pressurized and kneaded for about 3 minutes while cooling, and the mixed raw material of EPDM and BR becomes a cake-like shape and the temperature thereof reaches about 8 Torr. Hey. Then, 150 g (10 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR) of monoethanolamine, 75 g (5 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) is added. Polyalkylene oxide oxime ether interface activity

劑、15 g(相對於100重量份之EPdm與BR之混合原料而為1 〇 重量份）之硬脂酸、650 g(相對於100重量份之EPDM與BR 之混合原料而為43重量份）之白碳、75 g(相對於100重量份 之EPDM與BR之混合原料而為5重量份）之碳酸約、75 g(相 對於100重量份之EPDM與BR之混合原料而為5重量份）之 氧化鈦、75 g(相對於100重量份之EPDM與BR之混合原料 而為5重量份）之氧化鋅、75 g(相對於100重量份之EPDM與 BR之混合原料而為5重量份）之Loxiol G-78 (Cognis Japan 股份有限公司製造之高分子複合酯）、以及75 g(相對於100 〇 重量份之EPDM與BR之混合原料而為5重量份）之Licolub H-4 (Clariant Japan股份有限公司製造之改質烴），混練約3 • 分鐘。最後添加48 g(相對於100重量份之EPDM與BR之混 合原料而為3.2重量份）之過氧化二異丙苯，繼續混練約1分 鐘。此期間之混練物溫度經調節為不超過110°C。使所獲 得之混練物迅速通過加壓輥，加工成片狀，同時冷卻至25 °C以下，藉此獲得厚度為6 mm之片狀模具清潔用橡膠系組 合物K。 135644.doc • 25- 200930757 將所獲得之片狀模具清潔用橡膠系組合物κ之特性值以 及清潔性試驗結果示於表3中。根據試驗結果而判明，片 狀模具清潔用橡膠系組合物κ表現出良好之成形性以及清 潔性。 實施例10(本發明之第3模具清潔用橡膠系組合物） 於實施例9中，使用900 g之EPDM原料[孟納黏度 ML1+4(100 °C )為8者]，來代替EPDM原料[孟納黏度 ML1+4(100°C)為23者]，並且將BR原料[孟納黏度MLi+4(1〇〇 ΟAnd 15 g (1 part by weight relative to 100 parts by weight of the mixed raw material of EPdm and BR) of stearic acid, 650 g (43 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) White carbon, 75 g (5 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR), about 75 g (5 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) Titanium oxide, 75 g (5 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), 75 g (5 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR) Lixiol G-78 (polymer complex ester manufactured by Cognis Japan Co., Ltd.) and 75 g (5 parts by weight relative to 100 parts by weight of a mixed raw material of EPDM and BR) Licolub H-4 (Clariant Japan) The modified hydrocarbon produced by the company, mixed for about 3 minutes. Finally, 48 g (3.2 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR) of dicumyl peroxide was added, and kneading was continued for about 1 minute. The temperature of the kneaded material during this period was adjusted to not exceed 110 °C. The kneaded material obtained was quickly passed through a pressure roll, processed into a sheet shape, and cooled to 25 ° C or lower, whereby a rubber composition K for sheet-like mold cleaning having a thickness of 6 mm was obtained. 135644.doc • 25-200930757 The characteristic values of the obtained rubber-based composition for sheet mold cleaning κ and the results of the cleaning test are shown in Table 3. According to the test results, it was found that the rubber composition κ for cleaning a sheet mold exhibited good formability and cleanability. Example 10 (The third rubber mold composition for mold cleaning of the present invention) In Example 9, 900 g of EPDM raw material [Monner viscosity ML1+4 (100 °C) was used as a substitute for EPDM raw material) [Menner viscosity ML1+4 (100 °C) is 23], and the BR material [Menna viscosity MLi+4 (1〇〇Ο)

C)為42且1，4順式鍵含有率為95重量％者]之調配量變更為 600 g，將Loxiol G-78之調配量變更為30 g(相對於1〇〇重量 份之EPDM與BR之混合原料而為2重量份），且將Lie〇lub H-4之調配量變更為丨5 g(相對於丨〇〇重量份之EpDM與br之 混合原料而為1重量份），新添加丨5 g(相對於丨〇〇重量份之 EPDM與BR之混合原料而為丨重量份）之硬脂酸鋅，除此以 外’以相同之方式獲得厚度為6mm片狀模具清潔用橡踢系 組合物L。 將所獲得之片狀模具清潔用橡膠系組合物L之特性值以 及清潔性試驗結果示於表3中。根據試驗結果而判明，片 =具清潔用橡㈣組合物L表現出良好之成形性以及清 實施例11 於實施例9中’將白碳之調配量 重量份之咖_BR之混 重g(相對於100 ㈣之調配量變更為45… 為7重量份”將―1 變更為45 g(相對於崎量份之卿 135644.doc • 26 - 200930757 之混合原料而為3重量份）’使用30 g(相對於100重量份之 EPDM與BR之混合原料而為2重量份）之Fatty Amide S(花王 股份有限公司製造’脂肪酸醯胺）’來代替使用75 S(相對 於100重量份之EPDM與BR之混合原料而為5重量份）之 Licolub H-4，進而新添加75 g(相對於100重量份之EPDM '與BR之混合原料而為5重量份）之硬脂酸鋅，並且使用48 . g(相對於100重量份之EPDM與BR之混合原料而為3.2重量 份）之2,5-二甲基-2,5-二第三丁基過氧化己烷，來代替48 〇 g(相對於100重量份之EPDM與BR之混合原料而為3.2重量 份）之過氧化二異丙苯，除此以外’以相同之方式獲得厚 度為6 mm片狀模具清潔用橡膠系組合物Μ。 將所獲得之片狀模具清潔用橡膠系組合物Μ之特性值以 及清潔性試驗結果示於表3中。根據試驗結果而判明，片 狀模具清潔用橡膠系組合物Μ表現出良好之成形性以及清 潔性。 實施例12 於實施例10中，將600 g之BR原料[孟納黏度ML1+4(100 °C )為42且1，4順式鍵含有率為95重量％者]變更為600 g之 . BR原料[孟納黏度ML1+4(100°C )為35且1，4順式鍵含有率為 95重量％者]，又，將65 0 g(相對於100重量份之EPDM與BR 之混合原料而為43重量份）之白碳變更為700 g(相對於1〇〇 重量份之EPDM與BR之混合原料而為47重量份）之白碳， 將30 g(相對於100重量份之EPDM與BR之混合原料而為2重 量份）之硬脂酸鋅變更為5 g(相對於100重量份之EPDM與 135644.doc -27· 200930757 BR之混合原料而為5重量份）之硬脂酸鋅’將30 g(相對於 100重量份之EPDM與BR之混合原料而為2重量份）之Loxiol G-78變更為60 g(相對於100重量份之EPDM與BR之混合原 料而為4重量份）之Loxiol G-78，並且使用48 g(相對於100 重量份之EPDM與BR之混合原料而為3.2重量份）之二（第三 •丁基過氧化）-間二異丙苯，來代替48 g(相對於1〇〇重量份 ，之EPDM與BR之混合原料而為3.2重量份）之過氧化二異丙 苯，除此以外，以相同之方式獲得厚度為6 mm之片狀模具 Ο 清潔用橡膠系組合物N。 將所獲得之片狀模具清潔用橡膠系組合物N之特性值以 及清潔性試驗結果示於表3中。根據試驗結果而判明，片 狀模具清潔用橡膠系組合物N表現出良好之成形性以及清 潔性。 [表3] 項目 實施例9 實施例10 實施例11 實施例12 鈹合物K 組合物L 組合物Μ 組合物Ν EPDM 比 70 60 70 60 BR比 30 40 30 90 延伸率(％) 138 128 157 140 拉伸強度(MPa) 7.0 6.2 8,3 7.2 橡膠硬度 87 84 80 84 tc(90)(秒） 306 328 319 328 成形性 〇— ~〇~ 〇 〇 模具脫模性 〇 〇 〇 〇 清潔完畢 次數 4 4 4 4 上之可利用性 產業 如上所述，利用使用有未硫化橡膠之模具清潔用橡膠系 組合物，該未硫化橡膠係乙烯-丙烯橡膠與丁二烯橡膠之 135644.doc •28· 200930757 調配比例經設定為90/10〜50/50重晋a本 .α . 里篁伤者，並且其硫化硬化 後之延伸率顯示為80〜8〇〇%’拉伸強度顯示為3〜i〇 Mpa， 橡膠硬度（硬度計硬度）顯示為A6〇〜95，175〇c之模具溫度 下之90%硫化時間（適當硫化點）tc(9〇)顯示為5〇〜1〇〇秒或= 200〜400秒之值；藉此作業性（剝離性）良好，並且不會產 生碎屑或空隙，不僅可易於去除模腔或流道、澆口之污 垢’並且可易於取出通氣孔或模具分區之污垢。 本發明之模具清潔用橡膠系組合物中，尤其是本發明之 第3模具清潔用橡膠系組合物由於含有脫模劑，故適用於 如PDIP或SOIC等般模腔深之小型封裝製造用模具、或小 型封裝中銷數少的尤其小之封裝製造用模具的清潔。 135644.doc 29-C) is 42 and the cis bond content is 95% by weight. The amount of the formulation is changed to 600 g, and the amount of the Loxiol G-78 is changed to 30 g (relative to 1 part by weight of EPDM and 2 parts by weight of the mixed raw material of BR, and the amount of Lie〇lub H-4 is changed to 丨5 g (1 part by weight relative to the mixed raw material of EpDM and br), new Adding 5 g of zinc stearate (parts by weight of the mixed raw material of EPDM and BR to the weight of the niobium), in addition to the same way, a 6 mm thick sheet-shaped mold cleaning rubber is obtained in the same manner. Composition L. The characteristic values of the rubber composition L for sheet mold cleaning obtained and the results of the cleaning test are shown in Table 3. According to the test results, it was found that the sheet = cleansing rubber (IV) composition L exhibited good formability and clearing Example 11 in Example 9 'mixing the amount of white carbon to the weight of the coffee_BR mixture g ( Change the ratio to 100 (4) to 45... to 7 parts by weight" Change "1" to 45 g (3 parts by weight compared to the mixed raw material of 5.7644.doc • 26 - 200930757) Instead of using 75 S (with respect to 100 parts by weight of EPDM), g (2 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) of Fatty Amide S (manufactured by Kao Co., Ltd.) 5 parts by weight of the mixed raw material of BR, Licolub H-4, and then 75 g (5 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM 'and BR) of zinc stearate, and 48 is used. g (3.2 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, instead of 48 〇g ( 3.2 parts by weight of dicumyl peroxide relative to 100 parts by weight of the mixed raw material of EPDM and BR, except In the manner of obtaining a rubber composition for cleaning a sheet-like mold having a thickness of 6 mm, the characteristic values of the obtained rubber-based composition for cleaning a sheet-like mold and the results of the cleaning test are shown in Table 3. It was found that the rubber composition for sheet mold cleaning showed good formability and cleanability. Example 12 In Example 10, 600 g of BR material [Menner viscosity ML1+4 (100 ° C) was 42 and 1,4 cis bond content is 95% by weight] changed to 600 g. BR material [Menner viscosity ML1+4 (100 ° C) is 35 and 1,4 cis bond content rate is 95 weight %), in addition, changing the white carbon of 65 0 g (43 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) to 700 g (compared to 1 part by weight of the mixture of EPDM and BR) 7 parts by weight of white carbon of the raw material, 30 g (2 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) of zinc stearate was changed to 5 g (relative to 100 parts by weight of EPDM) And 5 parts by weight of zinc silicate's mixed with 135644.doc -27· 200930757 BR, 30 g (relative to 100 parts by weight of EPDM and BR) 2 parts by weight of the mixed raw material of Loxiol G-78 was changed to 60 g (4 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) of Loxiol G-78, and 48 g (relative to 100) was used. In parts by weight of the mixed raw material of EPDM and BR, 3.2 parts by weight of the second (third • butyl peroxy)-m-isopropylbenzene, instead of 48 g (relative to 1 part by weight, EPDM and BR) A sheet-like mold 清洁 cleaning rubber-based composition N having a thickness of 6 mm was obtained in the same manner except that the raw material was mixed with 3.2 parts by weight of dicumyl peroxide. The characteristic values of the rubber composition N for sheet mold cleaning and the results of the cleaning test are shown in Table 3. According to the test results, it was found that the rubber composition N for sheet mold cleaning exhibited good formability and cleanability. [Table 3] Item Example 9 Example 10 Example 11 Example 12 Composition K Composition L Composition Μ Composition Ν EPDM ratio 70 60 70 60 BR ratio 30 40 30 90 Elongation (%) 138 128 157 140 Tensile strength (MPa) 7.0 6.2 8,3 7.2 Rubber hardness 87 84 80 84 tc(90) (seconds) 306 328 319 328 Formability 〇 - ~〇~ 〇〇 mold release 〇〇〇〇 cleaning completion 4 4 4 4 The above-mentioned usability industry utilizes a rubber-based composition for mold cleaning using an unvulcanized rubber, which is 135644.doc •28· 200930757 of an unvulcanized rubber-based ethylene-propylene rubber and butadiene rubber. The ratio is set to 90/10~50/50 to re-introduction. A. Injury, and the elongation after vulcanization and hardening is shown as 80~8〇〇%' tensile strength is shown as 3~i〇Mpa , rubber hardness (hardness tester hardness) is shown as A6 〇 ~ 95, 175 〇 c at the mold temperature 90% vulcanization time (appropriate cure point) tc (9 〇) is displayed as 5 〇 ~ 1 〇〇 seconds or = 200 ~ 400 seconds; this workability (peelability) is good, and no debris or voids are generated, not only Easy to remove the mold cavity or runner, gates of dirt 'and can be easily removed dirt vent or partition of the mold. In the rubber-based composition for cleaning a mold of the present invention, the third rubber composition for cleaning a mold of the present invention is preferably used for a mold for manufacturing a small-sized package such as PDIP or SOIC. Or the cleaning of a particularly small package manufacturing mold with a small number of pins in a small package. 135644.doc 29-

Claims (1)

200930757 十、申請專利範圍： 1. 一種模具清潔用橡膠系組合物，其係用以將硬化性樹脂 之成形步驟中所產生的模具表面之污垢去除者，其特徵 在於：基材樹脂係使用乙稀-丙烤橡膠與丁二稀橡膠之調 配比例經設定為90/H)〜50/50重量份之未硫化橡膠，並且 ‘ 該未硫化橡膠的經硫化硬化後之延伸率為8〇〜8〇〇%、拉 .伸強度為3〜10 MPa、橡膠硬度（硬度計硬度）為A6〇〜 且175 C之模具溫度下之90%硫化時間（適當硫化 〇 點）tc(90)為50〜1〇〇秒之值的範圍。 2· 一種模具清潔用橡膠系組合物，其係用以將硬化性樹脂 之成形步驟中所產生的模具表面之污垢去除者，其特徵 在於.基材樹脂係使用乙烯-丙烯橡膠與丁二烯橡膠之調 配比例經設定為90/10〜50/50重量份之未硫化橡膠，並 且，該未硫化橡穋的經硫化硬化後之延伸率為 80〜800%、拉伸強度為3〜10 MPa、橡膠硬度（硬度計硬 度）為A60〜95、且1751之模具溫度下之90%硫化時間（適 ® 當硫化點）tc(90)為200〜400秒之值的範圍。 3. —種模具清潔用橡膠系組合物，其係用以將硬化性樹脂 之成形步驟中所產生的模具表面之污垢去除者，其特徵 在於：基材樹脂係使用乙烯-丙烯橡膠與丁二烯橡膠之調 配比例經設定為90/10〜50/50重量份之未硫化橡膠，且該 未硫化橡膠係經硫化硬化後之延伸率為8〇〜800%、拉伸 強度為3〜10 MPa、橡膠硬度（硬度計硬度）為A60〜95、且 175°C之模具溫度下之90%硫化時間（適當硫化點）tc(90) 135644.doc 200930757 · 為200〜400秒之值的範圍者，並且該模具清潔用橡膠系 組合物含有至少1種脫模劑。 4.如請求項3之模具清潔用橡膠系組合物，其中上述基材 樹脂與上述脫模劑之調配比例係相對於1〇〇重量份之基 材樹脂，脫模劑為3〜15重量份。 * 5.如請求項1至4中任一項之模具清潔用橡膠系組合物，其 ， 令上述乙烯-丙烯橡膠與丁二烯橡膠之調配比例係經設定 為80/20〜60/40重量份。 〇 如叻求項1至4中任-項之模具清潔用橡膠系組合物，其 為壓縮型。 «•月求項1至4中任一項之模具清潔用橡膠系組合物，其 進而含有填充劑、清洗劑、清洗助劑、硫化劑、硫化助 劑、硫化促進劑、硫化促進助劑中之至少丨種。 8. 一種模具清潔方法，其係使用如請求項1至4中任-項之 模具清潔用橡膠系組合物。 ❹ 135644.doc 200930757 七、 指定代表囷： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 八、 本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無）200930757 X. Patent Application Range: 1. A rubber-based composition for mold cleaning, which is used for removing dirt on a surface of a mold generated in a forming step of a curable resin, characterized in that a substrate resin is used. The blending ratio of the dilute-propylene-baked rubber to the butyl rubber is set to 90/H) to 50/50 parts by weight of the unvulcanized rubber, and the elongation of the unvulcanized rubber after vulcanization and hardening is 8〇~8〇〇. %, tensile strength is 3~10 MPa, rubber hardness (hardness hardness) is A6〇~ and 90% vulcanization time at the mold temperature of 175 C (suitable vulcanization point) tc(90) is 50~1〇 The range of values for leap seconds. 2. A rubber-based composition for cleaning a mold, which is used for removing dirt on a surface of a mold which is formed in a step of forming a curable resin, wherein the base resin is made of ethylene-propylene rubber and butadiene. The ratio of the rubber is set to 90/10 to 50/50 parts by weight of the unvulcanized rubber, and the elongation of the unvulcanized rubber after vulcanization and hardening is 80 to 800%, and the tensile strength is 3 to 10 MPa. The rubber hardness (hardness hardness) is A60 to 95, and the 90% vulcanization time (suitable for vulcanization point) tc (90) at a mold temperature of 1751 is in the range of 200 to 400 seconds. 3. A rubber-based composition for cleaning a mold for removing dirt on a surface of a mold which is formed in a step of forming a curable resin, characterized in that the base resin is made of ethylene-propylene rubber and diced The blending ratio of the olefin rubber is set to 90/10 to 50/50 parts by weight of the unvulcanized rubber, and the unvulcanized rubber has an elongation after vulcanization and hardening of 8 〇 to 800%, a tensile strength of 3 to 10 MPa, and rubber. Hardness (hardness hardness) is A60 to 95, and 90% vulcanization time at a mold temperature of 175 ° C (appropriate cure point) tc (90) 135644.doc 200930757 · is a range of values of 200 to 400 seconds, and The rubber composition for mold cleaning contains at least one release agent. 4. The rubber-based composition for mold cleaning according to claim 3, wherein the ratio of the base resin to the release agent is from 3 to 15 parts by weight based on 1 part by weight of the base resin. . The rubber-based composition for mold cleaning according to any one of claims 1 to 4, wherein the ratio of the ethylene-propylene rubber to the butadiene rubber is set to 80/20 to 60/40 by weight. Share. The rubber-based composition for mold cleaning according to any one of Items 1 to 4, which is a compression type. The rubber-based composition for mold cleaning according to any one of the items 1 to 4, further comprising a filler, a cleaning agent, a cleaning aid, a vulcanizing agent, a vulcanization aid, a vulcanization accelerator, and a vulcanization accelerator At least one species. A mold cleaning method using the rubber-based composition for mold cleaning according to any one of claims 1 to 4. 135 135644.doc 200930757 VII. Designated representative 囷: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: VIII. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: (none) 135644.doc135644.doc
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