200831657 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種抗靜電性組合物。更詳細而言，本發 明係關於一種於聚烯烴中添加有高分子型抗靜電劑之抗靜 電性組合物及其成形品。 【先前技術】 k 聚丙烯、聚乙烯係通用樹脂，其等使用於汽車、機械零 件、各15、包裝、建材、生活用品等各種產業領域中。該 攀 ㈣脂係非導電性物質，因此用於須要抗靜電性用途時， 則對該等樹脂添加界面活性劑等抗靜電劑使之具有抗靜電 性。 作為樹脂中添加有抗靜電劑之樹脂組合物，例如於專利 文獻1中揭示有包括離子性鹽（A)、與至少i種聚合物及/或 彈性體（B)的抗靜電性聚合物組合物，上述離子性鹽含 有具有1個以上烯丙基之氮鑌陽離子、與弱配位性陰離 子0 又，於專利文獻2中揭示有於含有樹脂及/或彈性體之組 一 中刀放有έ有具有氟基及石黃醯基之陰離子之鹽而成 . 的抗靜電性組合物。 • 然而，該等方法未必能夠使聚丙烯、聚乙烯具有充分抗 靜電性能。 專利文獻1:曰本專利特開2005-350579號公報 專利文獻2 :日本專利特開2006-137790號公報 本發明係鑒於上述問題研製而成者，其目的在於提供一 125417.doc 200831657 種具有充分之抗靜電性能的抗靜電性組合物及由其獲得之 成品。 【發明内容】 根據本發明，可提供以下抗靜電性組合物等。 , h —種抗靜電性組合物，其含有炫融流動速率未達 2.5(g/1〇min)之聚烯烴、與高分子型抗靜電劑。 2·如1所述之抗靜電性組合物，其中上述聚烯烴與高分子 φ 型抗靜電劑之總量中上述聚烯烴所佔之含量為95〜60 _%，上述高分子型抗靜電劑所佔之含量為5〜40 wt%。 3· 一種薄片或薄膜，其由如上述所述之抗靜電性組合 物構成。 4·如3所述之薄片或薄膜，其厚度為1〇 μηι以上。 5. —種積層體，其含有如上述3或4所述之薄片或薄膜。 6. —種成形品，其由如上述3〜5中任一項所述之薄片、薄 膜或積層體構成。 # 根據本發明，可提供一種具有較高抗靜電性能之抗靜電 性組合物及由其獲得之成形品。 【實施方式】 • 以下，具體說明本發明之抗靜電性組合物。 - 本發明之抗靜電性組合物之特徵在於包括熔融流動速率 (MFR，Melt Flow Rate)未達 2.5(g/1〇 min)之聚嫦烴、與高 分子型抗靜電劑。本發明中使用之聚烯烴較之先前使用之 聚烯烴，MFR較低。本發明者發現本發明藉由使用mfr較 低之聚烯烴與高分子型抗靜電劑，可大幅度提高組合物之 125417.doc 200831657 抗靜電性能。 再者，本發明中所謂MFR係於230°C、荷重2.16 kg之條 件下測定的測定值（g/10 min)。 本發明中使用之聚烯烴，若MFR未達2.5則並無特別限 制，使用工業上市售者亦無問題。較好的是聚烯烴為聚丙 烯、聚乙烯。聚烯烴之MFR較好的是於0.3〜1.6之範圍内。 ^ 聚丙烯包括聚丙烯單聚物、以及聚丙烯共聚物（嵌段、 無規、接枝）等。例如可使用普瑞曼聚合物股份有限公司 _ 製之 E110G(MFR=0.3)或 E105GM(MFR=0.5)。聚乙烯包括 聚乙烯單聚物、聚乙烯共聚物（嵌段、無規、接枝）、低密 度聚乙烯、以及高密度聚乙烯等。例如可使用普瑞曼聚合 物股份有限公司製之HE30(MFR=0.3)。 當混合使用聚丙烯與聚乙烯時，例如使聚丙烯：聚乙烯 =20〜80 · 80〜20 〇 本發明中使用之高分子型抗靜電劑中，除了包括高分子 φ 型抗靜電劑外，亦包括於高分子型抗靜電劑中添加有離子 性化合物的離子傳導性高分子型抗靜電劑。 高分子型抗靜電劑例如為分子内使PEO • (polyoxyethylene，聚氧化乙烯）鏈為導電性單元之高分子 ^ 化合物，具體而言，存在有聚乙二醇曱基丙烯酸酯共聚 物、聚醚I旨醯胺（PEEA，polyetheresteramide)、聚醚i旨醯 胺-酸亞胺（PEAI，polyether ester amide-imide)、聚氧化乙 烯-聚氧化丙烯（PEO-PPO，polyoxyethylene-polypropyleneoxide) 共聚物等。 125417.doc 200831657 L可列舉《聚烯煙系篏段共聚物、以及聚環氧烧系 /、聚物或環氧乙i環氧丙烧,丙基縮水甘油㈣共聚 物0 ，發明中使用之高分子型抗靜電劑，較好的是使用高分 型抗靜電劑。 化合物之離子傳導性高分子 離=導性高分子型抗靜電劑係藉由u離子等沿高分子 ==徑移動而發揮抗靜電性者。離子傳導性高分子 主抗静笔劑含有離子性鹽與高分子型抗靜電劑。 作為離子性鹽，較好的是例如含有具有1個以上稀丙基 子、：弱配位性陰離子的離子性鹽。該離子性 高離子傳導率。1離子移動率亦較大，因此具有較 作為氮鑌陽離子’可列舉脂肪族氮鑌陽離子、不飽和環 式虱鎬陽離子、以及芳香族氮鑌陽離子。 丙^㈣氮鏽陽離子中’較好的是四級錄，尤其好的是稀 丙基以外之炫基碳數為卜18的四級烧基胺。 ，與作為不飽和環錢鏽陽離子及芳香族氮鑌陽離子， 鑌、噠嗪鑌、物，鑌、咪唾鑌、w Γ麵…惡唾鑽、以及三唾鏽。更好的是該等不飽和 衣式鼠鏽陽離子及芳香族氮鑌陽離子的四級錄。 作為本發明之離子性鹽中使用之弱配位性陰離子 :少包㈣高氣化炫基續酸基之弱配位性氣有機陰： bf4、或pf6即可。所謂高氟化院基續酿基，係指所有 1254I7.doc 200831657 非氟奴化鍵取代基，與直接鍵接磺醯基之碳原子以外之石山 鍵接的全氟烷烴磺醯基或部分氟化烷烴磺醯基。 再者，離子性鹽可使用眾所周知之方法（例如渡邊正義 等「離子性液體之功能創造與應用」N.T.S(2004》製造。 又，作為其他離子性鹽，可列舉具備具有氟基及磺醯基 之陰離子的鹽’該鹽於溶解於水中之狀態下使用。 含有具有氟基及磺醯基之陰離子之鹽，含有選自雙（氟 烷基磺醯基）醯亞胺離子、三（氟烷基磺醯基）甲基離子、氟 烷基磺酸離子組成之群中至少1個陰離子、與選自鹼金 屬、2A族元素、過渡金屬、兩性金屬組成之群中至少^固 陽離子。 較好的是含有由上述陰離子及陽離子構成之鹽中之雙 (氟烷基磺醯基）醯亞胺離子、三（氟烷基磺醯基）甲基離 子、以及氟烧基石頁酸離子。具體而言，較好的是雙（三I 甲烧磺醯基）蕴亞胺鋰Li(CF3S02)2N、雙（三氟曱烷磺醯基） 醯亞胺鉀K(CF3S〇2)2N、雙（三氟甲烷磺醯基）醯亞胺鈉 Na(CF3S〇2)2N、三（三氟甲烷磺醯基）甲基鋰Li (CF3S〇2)3C、三（三氟甲烷磺醯基）甲基鉀k(cf3S02)3C、三 (三氟甲烷磺醯基）甲基鈉Na(CF3S02)3C、三氟曱磺酸鋰 Li(CF3S〇3)、三氟曱磺酸鉀K(CF3S03)、以及三氟甲磺酸 鈉 Na(CF3S03)。 其中，可列舉雙（三氟曱烷磺醯基）醯亞胺鋰、及三（三氟 曱烷磺醯基）甲基化物、三氟甲磺酸鋰。尤其好的是雙（三 氣甲烧石頁S&基）酿亞胺鐘及三氣甲績酸链。 125417.doc -10- 200831657 又’較好的是’相對於i 〇〇質量份之聚烯烴，離子性鹽 之添加5為0 · 〇 1〜3 〇質量份左右。 作為本發明中使用之離子傳導性高分子型抗靜電劑的市 售品’可列舉三光化學工業股份有限公司製之sank〇n〇1 TBX-25或該TBX-310等。該等係聚醚/聚烯烴嵌段共聚物 與鋰離子鹽化合物組合而成之抗靜電劑。200831657 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to an antistatic composition. More specifically, the present invention relates to an antistatic composition to which a polymer type antistatic agent is added to a polyolefin, and a molded article thereof. [Prior Art] k Polypropylene and polyethylene-based general-purpose resins are used in various industrial fields such as automobiles, machine parts, and 15, packaging, building materials, and daily necessities. This climbing (4) is a non-conductive substance, and therefore, when it is used for antistatic use, an antistatic agent such as a surfactant is added to the resin to have antistatic properties. As a resin composition to which an antistatic agent is added as a resin, for example, Patent Document 1 discloses an antistatic polymer combination including an ionic salt (A) and at least one polymer and/or an elastomer (B). The ionic salt contains a nitrogen sulfonium cation having one or more allyl groups and a weakly complex anion 0. In Patent Document 2, a group of resins and/or elastomers is disclosed. An antistatic composition comprising a salt of an anion having a fluorine group and a scutane group. • However, these methods do not necessarily provide sufficient antistatic properties for polypropylene and polyethylene. The present invention has been developed in view of the above problems, and its object is to provide a kind of 125417.doc 200831657 which is sufficient for the present invention. Antistatic composition of antistatic properties and finished products obtained therefrom. SUMMARY OF THE INVENTION According to the present invention, the following antistatic composition and the like can be provided. , h — an antistatic composition comprising a polyolefin having a flow rate of less than 2.5 (g/1 〇 min) and a polymeric antistatic agent. 2. The antistatic composition according to 1, wherein the content of the polyolefin in the total amount of the polyolefin and the polymer φ type antistatic agent is 95 to 60% by weight, and the polymer type antistatic agent The content is 5 to 40 wt%. 3. A sheet or film comprising the antistatic composition as described above. 4. The sheet or film according to 3, which has a thickness of 1 〇 μηι or more. 5. A laminate comprising the sheet or film of the above 3 or 4. A molded article comprising the sheet, the film or the laminate according to any one of the above 3 to 5. According to the present invention, an antistatic composition having a high antistatic property and a molded article obtained therefrom can be provided. [Embodiment] Hereinafter, the antistatic composition of the present invention will be specifically described. - The antistatic composition of the present invention is characterized by comprising a polyfluorene hydrocarbon having a melt flow rate (MFR, Melt Flow Rate) of less than 2.5 (g/1 〇 min), and a high molecular type antistatic agent. The polyolefin used in the present invention has a lower MFR than the polyolefin previously used. The present inventors have found that the present invention can greatly improve the antistatic property of the composition by using a polyolefin having a low mfr and a polymeric antistatic agent. Further, in the present invention, the MFR is a measured value (g/10 min) measured at 230 ° C and a load of 2.16 kg. The polyolefin used in the present invention is not particularly limited if the MFR is less than 2.5, and there is no problem in using the industrial market. Preferably, the polyolefin is polypropylene or polyethylene. The MFR of the polyolefin is preferably in the range of from 0.3 to 1.6. ^ Polypropylene includes polypropylene monomer, and polypropylene copolymer (block, random, graft) and the like. For example, E110G (MFR = 0.3) or E105GM (MFR = 0.5) of Preman Polymer Co., Ltd. can be used. Polyethylene includes polyethylene monopolymer, polyethylene copolymer (block, random, graft), low density polyethylene, and high density polyethylene. For example, HE30 (MFR = 0.3) manufactured by Preman Polymer Co., Ltd. can be used. When polypropylene and polyethylene are used in combination, for example, polypropylene: polyethylene = 20 to 80 · 80 to 20 〇 In the polymer type antistatic agent used in the present invention, in addition to the polymer φ type antistatic agent, An ion conductive polymer type antistatic agent to which an ionic compound is added to a polymer type antistatic agent is also included. The polymer type antistatic agent is, for example, a polymer compound in which a PEO (polyoxyethylene) chain is a conductive unit in a molecule, and specifically, a polyethylene glycol methacrylate copolymer or a polyether is present. I intends to use PEEA (polyetheresteramide), polyether i, a polyether ester amide-imide (PEAI), a polyoxyethylene-polypropylene oxide (PEO-PPO) copolymer, and the like. 125417.doc 200831657 L can be exemplified by the "polymethene oxime copolymer", and the polyepoxy-based/polymer or epoxy propylene oxide, propyl glycidyl (tetra) copolymer 0, used in the invention. As the polymer type antistatic agent, it is preferred to use a high-type antistatic agent. Ion-conducting polymer of the compound. The conductive polymer-type antistatic agent exhibits antistatic properties by moving along the polymer == diameter by u ions or the like. Ion Conductive Polymer The main anti-static agent contains an ionic salt and a polymeric antistatic agent. The ionic salt preferably contains, for example, an ionic salt having one or more dilute propyl groups and a weakly coordinating anion. The ionic high ionic conductivity. Since the ion mobility is also large, the aliphatic ruthenium cation, the unsaturated cyclic ruthenium cation, and the aromatic ruthenium cation are mentioned. Among the propylene (4) nitrogen rust cations, 'fourth grade is preferred, and particularly preferred is a quaternary alkylamine having a singular carbon number other than the dilute propyl group. And as unsaturated ring rust cations and aromatic nitrogen sulfonium cations, hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, w Γ ... ... ... ... ... ... ... ... ... ... ... More preferred are the four grades of such unsaturated styling rust cations and aromatic hydrazine cations. The weakly coordinating anion used in the ionic salt of the present invention is as follows: (4) a weakly coordinated gas organic cation of a highly vaporized leuco acid group: bf4 or pf6. The so-called high-fluorination base-based continuation base refers to all non-fluorinated bond substituents of 1254I7.doc 200831657, and perfluoroalkanesulfonyl or partially fluorinated with a rock-bonded bond other than the carbon atom directly bonded to the sulfonate group. Alkanesulfonyl. Further, the ionic salt can be produced by a well-known method (for example, "Creating and Applying Function of Ionic Liquids", such as Watanabe Justice, NTS (2004). Further, as other ionic salts, there are provided fluorine-containing groups and sulfonyl groups. The salt of the anion is used in a state of being dissolved in water. A salt containing an anion having a fluorine group and a sulfonyl group, which is selected from the group consisting of bis(fluoroalkylsulfonyl)phosphonium ion and tris(fluoroalkane) At least one anion of the group consisting of a methyl sulfonyl group and a fluoroalkyl sulfonate ion, and at least one cation selected from the group consisting of an alkali metal, a Group 2A element, a transition metal, and an amphoteric metal. Is a bis(fluoroalkylsulfonyl)phosphonium ion, a tris(fluoroalkylsulfonyl)methyl ion, and a fluoroalkyl sulphate ion in a salt composed of the above anions and cations. In other words, it is preferred that bis(tris-trimethylsulfonyl) lithium imide lithium Li(CF3S02)2N, bis(trifluorodecanesulfonyl) phthalimide potassium K (CF3S〇2) 2N, double ( Trifluoromethanesulfonyl) sulfoximine sodium Na(CF3S〇2)2N, tris (trifluoromethyl) Sulfomethyl)methyllithium Li (CF3S〇2)3C, tris(trifluoromethanesulfonyl)methyl potassium k(cf3S02)3C, tris(trifluoromethanesulfonyl)methyl sodium Na(CF3S02)3C Lithium trifluorosulfonate Li (CF3S〇3), potassium trifluoromethanesulfonate K (CF3S03), and sodium triflate Na(CF3S03). Among them, bis(trifluorodecanesulfonyl) Lithium quinone iodide, and tris(trifluorodecanesulfonyl) methide, lithium trifluoromethanesulfonate. Especially good is bis (three gas calcined stone page S & base) brewed imine clock and three 125417.doc -10- 200831657 And 'better' is that relative to the mass of the i 〇〇 mass of polyolefin, the addition of ionic salt 5 is 0 · 〇 1~3 〇 parts by mass. The commercially available product of the ion-conductive polymer type antistatic agent used in the present invention is exemplified by Sank〇n〇1 TBX-25 manufactured by Sanko Chemical Industry Co., Ltd., or the TBX-310, etc. An antistatic agent composed of a polyolefin block copolymer and a lithium ion salt compound.
於本發明中’較好的是使用上述離子傳導性高分子型抗 靜電劑’但亦可併用其他高分子型抗靜電劑（例如 peleStat2〇3、三洋化成製）等。 進而’於本發明中，亦可併用高分子型抗靜電劑以外之 抗靜電劑’例如低分子型界面活性劑（例如elecon PP720A、大日製化製）等。 本發明之抗靜電性組合物中，相對於聚烯烴與高分子型 抗靜電劑之總量，聚烯烴所佔之含量較好的是95 wt%以 I 3尤其好的是60〜95 wt%，而高分子型抗靜電劑所佔之 各里車又好的是4〇〜5 wt%。t樹脂含量超過％赠。時，存在 表面電阻值變大之情形，當樹脂含量未達60 wt%時，存在 無法獲得原本具有之樹脂特性的情形。 發明之抗靜f性組合物中，於不影響本發明目的之襄 内’，可添加聚烯烴以外的樹脂或各種添加劑等。 、_丁二蝉·苯乙烯）樹脂等。 定二：為添加劑’可列舉結晶成核劑、抗氧化劑、熱_ ’、外線吸收劑、阻燃劑、阻燃助劑、著色劑、彥 125417.doc 200831657 料、抗菌抗黴劑、耐光劑、可塑劑、填充料等眾所周知之 添加劑。 本發明之抗靜電性組合物既可實質性含有聚稀烴及高分 子型抗靜電劑’又’亦可僅由該等成分組成。所謂「實質 性」’係指上述組合物僅由聚烯烴及高分子型抗靜電劑組 成’且除該等成分以外，亦可包含上述眾所周知之添加 劑0 不發明之抗靜電 成分簡單混合之混合物、或藉由二軸混練機等擠出機將上 述成分熔融混練並使其顆粒化者，作為各種成形品原料。 例如，可將上述混合物或顆粒投入擠出成形機、射出成 形機等:加工為薄片或薄膜、或者各種抗靜電性零件等。 又，可藉由共擠出法等而獲得積層體。 多僅其表面部分具有抗靜電性即可。因此靜: =^_言’較好的是製成積層構造’並形成僅於表 面層S有本發明之抗靜電性組合物的層。 藉由真空成形等眾所周知 積層體，藉此可製造電子零件用托盤==片、薄膜、 層Π之=乂發明之抗靜電性組合物之薄片厚度(於積 時，為含有抗靜電性組合物之表面層厚 又#乂妤的是10叫1以上。當厚产夫、* ln 以控制多層擠出之情形。 又未達1〇㈣，存在難 本而言，過於厚有時亦不佳^仁就成 存方y子度尤其好的是1〇 125417.doc -12- 200831657 μιη〜2 mm 〇 [實施例] 以下，藉由實施例，更具體地說明本發明。又，實施例 中使用之各原料如下所示。 再者，MFR係於230它、荷重2.16 kg之條件下測定的值 (g/10 min) 〇 ⑴聚丙烯 E110G(均聚丙烯）：普瑞曼聚合物製、MFR=0.3 E105GM(均聚丙烯）··普瑞曼聚合物製、MFR=0·5 E200GV(均聚丙烯）：普瑞曼聚合物製、MFR=1.6 E3 3 0GV(均聚丙烯）：普瑞曼聚合物製、MFR=2.4 E3 04GP(均聚丙烯）··普瑞曼聚合物製、MFR=2.8 F704NT(均聚丙烯）：普瑞曼聚合物製、MFR=8.3 E2000GV(均聚丙烯）：普瑞曼聚合物製、MFR=18 F704NT(均聚丙烯）：普瑞曼聚合物製、MFR=8.1 (2) 聚乙烯 HE3 0(低密度聚乙烯）：普瑞曼聚合物製、MFR=0.3 (3) 離子傳導性高分子型抗靜電劑 TBX-25 ：三光化學工業股份有限公司製、商品名 sankonol 實施例1 使用單軸擠出機，藉由共擠出法製造2層薄片。 表面層原料使用作為聚丙烯之E110G(85 wt%)、與作為 抗靜電劑之TBX-25(15 wt%)經乾摻合者。又，基材層原料 125417.doc -13- 200831657 使用作為聚丙烯之E105GM(100 wt%)。薄片成形時之條件 如下所示。 •加熱器設定溫度：200〜240°C •薄片冷卻溫度：60°C •薄片牵引速度：2 m/min •薄片厚度（整體厚度）：〇·4 mm 表1表示所使用之聚丙烯種類、聚丙烯與抗靜電劑之添 加比例、薄片表層厚度及其表面内在電阻值。In the present invention, it is preferred to use the above-mentioned ion-conductive polymer type antistatic agent, but other polymer type antistatic agents (for example, peleStat2〇3, manufactured by Sanyo Chemicals Co., Ltd.) may be used in combination. Further, in the present invention, an antistatic agent other than the polymer type antistatic agent may be used in combination, for example, a low molecular type surfactant (for example, elecon PP720A, manufactured by Dainippon Co., Ltd.). In the antistatic composition of the present invention, the content of the polyolefin is preferably 95% by weight, particularly preferably 60 to 95% by weight, based on the total amount of the polyolefin and the polymeric antistatic agent. And the polymer antistatic agent occupies a good 4 to 5 wt% of each car. t resin content exceeds %. In the case where the surface resistance value becomes large, when the resin content is less than 60% by weight, there is a case where the resin property originally possessed cannot be obtained. In the anti-static composition of the invention, a resin other than polyolefin or various additives may be added to the inside of the composition which does not impair the object of the present invention. , _ butyl styrene styrene resin, and the like. Ding 2: as an additive, it can be exemplified by crystal nucleating agent, antioxidant, heat _ ', external absorbent, flame retardant, flame retardant, coloring agent, Yan 125417.doc 200831657 material, antibacterial antifungal agent, light stabilizer Well-known additives such as plasticizers and fillers. The antistatic composition of the present invention may substantially contain a polyolefin and a high molecular type antistatic agent, and may also be composed only of such components. The term "substantial" means that the above composition is composed only of a polyolefin and a polymeric antistatic agent, and in addition to the components, may also comprise a mixture of the above-mentioned well-known additives 0 which is not simply mixed with an antistatic component. Alternatively, the above components may be melt-kneaded and granulated by an extruder such as a two-axis kneader as a raw material of various molded articles. For example, the above mixture or granules may be put into an extrusion molding machine, an injection molding machine or the like: processed into a sheet or a film, or various antistatic members or the like. Further, a laminate can be obtained by a co-extrusion method or the like. Most of the surface portions only have antistatic properties. Therefore, it is preferable that the static: =^_言' is a layered structure' and forms a layer having the antistatic composition of the present invention only in the surface layer S. By using a well-known laminated body such as vacuum forming, it is possible to manufacture a sheet for an electronic component==sheet, film, layer 乂=乂, the thickness of the sheet of the antistatic composition of the invention (in the case of product, it is an antistatic composition) The thickness of the surface layer is #乂妤1 is 10 or more. When the thick production, * ln to control the multi-layer extrusion. Not up to 1 〇 (4), in the case of difficulty, too thick and sometimes not good The present invention is particularly preferably 1 〇 125417.doc -12- 200831657 μιη〜2 mm 实施 [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples. Further, in the embodiment The raw materials used are as follows: Further, MFR is a value measured under conditions of 230 and a load of 2.16 kg (g/10 min) 〇 (1) Polypropylene E110G (homopolypropylene): manufactured by Preman Polymer, MFR=0.3 E105GM (homopolypropylene)··Premman polymer, MFR=0·5 E200GV (homopolypropylene): made of Preman polymer, MFR=1.6 E3 3 0GV (homopolypropylene): Made by Reman polymer, MFR=2.4 E3 04GP (homopolypropylene)··Premman polymer, MFR=2.8 F704NT (homopolypropylene): Preman's polymerization Material, MFR=8.3 E2000GV (homopolypropylene): made of Preman polymer, MFR=18 F704NT (homopolypropylene): made of Preman polymer, MFR=8.1 (2) Polyethylene HE3 0 (low density) Polyethylene): Premarin polymer, MFR=0.3 (3) Ion-conductive polymer type antistatic agent TBX-25: manufactured by Sanko Chemical Industry Co., Ltd., trade name sankonol Example 1 Single-axis extruder A two-layer sheet was produced by a co-extrusion method. The surface layer material was used as a blend of E110G (85 wt%) of polypropylene and TBX-25 (15 wt%) as an antistatic agent. Raw material material 125417.doc -13- 200831657 E105GM (100 wt%) is used as polypropylene. The conditions for sheet forming are as follows: • Heater setting temperature: 200~240 °C • Sheet cooling temperature: 60 °C • Sheet pulling speed: 2 m/min • Sheet thickness (integral thickness): 〇·4 mm Table 1 shows the type of polypropylene used, the ratio of polypropylene to antistatic agent, the thickness of the sheet surface and the intrinsic resistance of the surface. .
又，表面内在電阻值係根據JIS(Japanese Industrial Standard，日本工業標準）K6911，對樣品形狀製成11 cmxll cm，且於製造後於 23°C、50% RH(Relative Humidity，相對濕度）之條件下存放12小時以上之試料進行 測定的值。 [表1] 聚丙烯(PP) 添加比例(wt%) PP/TBX25 表面層厚度 (m) 表面内在電阻值 (Ω) 等級名 MFR(g/10min) 實施例1 E110G 0.3 85/15 50 3.0 x10s 實施例2 E105GM 0.5 85/15 50 l.OxlO8 實施例3 E200GV 1.6 85/15 50 l.lxlO9 實施例4 E330GV 2.4 85/15 50 2.6χ109 比較例1 E304GP 2.8 85/15 60 7.3 χΙΟ10 比較例2 F704NT 8.3 85/15 50 1.8χ10π 比較例3 E2000GV 18 85/15 50 1.5χ1012 實施例5 E110G 0.3 90/10 42 1.5x10 s 實施例6 E1I0G 0.3 80/20 45 2.8χ108 實施例7 E110G 0.3 70/30 42 1.5χ108 實施例8 E110G 0.3 60/40 50 Ι.ΙχΙΟ8 實施例9 E110G 0.3 60/40 137 7.3χ107 實施例10 E110G 0.3 60/40 170 5.2χ107 實施例11 E110G 0.3 95/5 20 2.1χ1010 實施例12 E110G 0.3 90/10 20 2.3χ109 125417.doc -14- 200831657 實施例2 - 4比較例1 - 3 除使用表m示之聚丙稀外，以與實施例】相同方式製造 2層薄片並加以評價。結果示於表1。 根據實施例1-4及比較例1-3之結果，求出表面層之聚丙 稀之MFR與表面層之表面内在電阻值的關係。結果示於圖 1。又，表面内在電阻之值（縱軸）中，1〇Ε+χ表示ΐχΐ〇χ。 例如’ 1.0Ε+08表示ΐχίο8。圖2、圖3中亦相同。 根據該圖，可確認薄片之表面内在電阻值較大依存於聚 丙烯之MFR，於MFR未達2.5之區域内出現臨界性變化。 實施例5-8 如表1所示，除了變更聚丙烯（E110G)與抗靜電劑（ΤΒΧ_ 25)之添加比例以外，以與實施例1相同之方式製造2層薄 片並加以評價。結果示於表1。 實施例9、1 0 如表1所示，除了變更薄片表面層厚度外’以與實施例1 相同之方式製造2層薄片並加以評價。結果示於表i。 實施例11、12 如表1所示，除了變更聚丙烯（E110G)與抗靜電劑（ΤΒχ_ 25)之添加比例、及薄片表面層厚度外，以與實施例i相同 之方式製造2層薄片並加以評價。結果示於表1。 實施例13 -17 如表2所示，除了使用聚丙烯與聚乙烯、或聚乙烯代替 ♦丙稀作為樹脂外，以與實施例i相同之方式製造2;薄片 並加以評價。結果示於表2。 125417.doc -15 - 200831657 [表2] 成分及添加比例 厚度 (μιη) 表面内在電阻值 (Ω) 實施例13 El 10G/HE30/TBX25=25/60/l 5 73 4.5χ10δ 實施例14 Ell 0G/HE30/TBX25=45/40/l 5 53 5.4x10s 實施例15 E110G/HE30/TBX25=60/25/l 5 51 5.8χ108 實施例16 HE30/TBX25=85/15 50 2·〇χ108 實施例17 HE30/TBX25=85/15 50 2.8x10 s 實施例18Further, the intrinsic resistance value of the surface is 11 cm x 11 cm in accordance with JIS (Japanese Industrial Standard) K6911, and is 23 ° C, 50% RH (Relative Humidity) after manufacture. The value of the sample that was stored for 12 hours or more was measured. [Table 1] Polypropylene (PP) Addition ratio (wt%) PP/TBX25 Surface layer thickness (m) Surface intrinsic resistance value (Ω) Grade name MFR (g/10 min) Example 1 E110G 0.3 85/15 50 3.0 x10s Example 2 E105GM 0.5 85/15 50 l.OxlO8 Example 3 E200GV 1.6 85/15 50 l.lxlO9 Example 4 E330GV 2.4 85/15 50 2.6χ109 Comparative Example 1 E304GP 2.8 85/15 60 7.3 χΙΟ10 Comparative Example 2 F704NT 8.3 85/15 50 1.8χ10π Comparative Example 3 E2000GV 18 85/15 50 1.5χ1012 Example 5 E110G 0.3 90/10 42 1.5x10 s Example 6 E1I0G 0.3 80/20 45 2.8χ108 Example 7 E110G 0.3 70/30 42 1.5χ108 Example 8 E110G 0.3 60/40 50 Ι.ΙχΙΟ8 Example 9 E110G 0.3 60/40 137 7.3χ107 Example 10 E110G 0.3 60/40 170 5.2χ107 Example 11 E110G 0.3 95/5 20 2.1χ1010 Example 12 E110G 0.3 90/10 20 2.3χ109 125417.doc -14- 200831657 Example 2 - 4 Comparative Example 1 - 3 A 2-layer sheet was produced and evaluated in the same manner as in Example except that the polypropylene shown in Table m was used. The results are shown in Table 1. From the results of Examples 1-4 and Comparative Examples 1-3, the relationship between the MFR of the surface layer of polypropylene and the intrinsic resistance value of the surface layer was determined. The results are shown in Figure 1. Further, in the value of the internal resistance of the surface (vertical axis), 1 〇Ε + χ represents ΐχΐ〇χ. For example, '1.0Ε+08 means ΐχίο8. The same applies to Figures 2 and 3. According to the figure, it was confirmed that the intrinsic resistance value of the surface of the sheet largely depends on the MFR of the polypropylene, and a critical change occurs in the region where the MFR is less than 2.5. [Example 5-8] As shown in Table 1, a two-layer sheet was produced and evaluated in the same manner as in Example 1 except that the ratio of addition of polypropylene (E110G) to antistatic agent (?25) was changed. The results are shown in Table 1. [Examples 9 and 10] As shown in Table 1, a two-layered sheet was produced and evaluated in the same manner as in Example 1 except that the thickness of the surface layer of the sheet was changed. The results are shown in Table i. Examples 11 and 12 As shown in Table 1, a 2-layer sheet was produced in the same manner as in Example i except that the addition ratio of the polypropylene (E110G) to the antistatic agent (ΤΒχ_25) and the thickness of the surface layer of the sheet were changed. To be evaluated. The results are shown in Table 1. Example 13-17 As shown in Table 2, 2 sheets were produced and evaluated in the same manner as in Example i except that polypropylene and polyethylene, or polyethylene was used instead of propylene as the resin. The results are shown in Table 2. 125417.doc -15 - 200831657 [Table 2] Composition and addition ratio thickness (μιη) Surface intrinsic resistance value (Ω) Example 13 El 10G/HE30/TBX25=25/60/l 5 73 4.5χ10δ Example 14 Ell 0G /HE30/TBX25=45/40/l 5 53 5.4x10s Example 15 E110G/HE30/TBX25=60/25/l 5 51 5.8χ108 Example 16 HE30/TBX25=85/15 50 2·〇χ108 Example 17 HE30/TBX25=85/15 50 2.8x10 s Example 18
對2層薄片之表面層厚度與表面内在電阻值的關係加以 評價。 具體而言，除了將薄片表面層厚度變更為10 μπι、130 μιη及160 μπι外，以與實施例1相同之方式製造2層薄片。 同樣，除了將聚丙烯變更為E105GM，並將薄片表面層 厚度變更為10 μπι、120 μιη及150 μιη外，以與實施例1相同 之方式製造2層薄片。 又，表面層厚度之控制，可藉由使薄片牽引速度固定不 變，並調整擠出機之旋轉數而進行。 對所得薄片，分析薄片之表面層厚度與表面内在電阻值 的關係。結果示於表3及圖2。 [表3] 表面層厚度 (μιη) 表面内在電阻值(Ω) E110G E105GM 10 l.SxlO9 3·7χ109 50 3.〇χ10δ 1·〇χ109 120 2,8χ109 130 2.8χ|〇δ 150 2·1χ109 160 2.8χ10δ 125417.doc -16- 200831657 實施例19 ▲變更表面層之膜厚(5〇㈣、13〇 _及16〇㈣，而評價 抗靜電劑之添加量與表面内在電阻值的關係。 、具體而言，對各膜厚除了使抗靜電劑(ΤΒχ25)之添加量 為15 Wt%、20 Wt❶/°、30 wt%及4〇 wt%以外，以與實施例i 相同之方式製造2層薄片。 圖3表示根據薄片評價結果所得之抗靜電劑添加量與表 面内在電阻值的關係。 實施例20 除了使表面層厚度為60 μηι外，u與實施例i相同之方式 製造2層薄片並加以評價。表面内在電阻值為4.3X108 (Ω/sq) 〇 /進而自薄片巾取出11 cmx 11⑽之樣品並加以製造 後’於23C、5G%RH之條件下存放12小時以上。自該樣品 之大致中央取出薄片，由四氧化釕進行染色固定後，藉由 冷凍薄片切片機使其薄片化。藉由透過型電子顯微鏡肝 曰立製作所製），觀察經薄化後之樣品於丁D方向及 —方向的口面，亚加以拍攝。如圖从之剖面模式圖所 不可知抗靜電劑分布於表面層之整個厚度上，進而密集 於中央‘刀。即’層内存在疏密分布。圖5之照片(x5000) 拍攝有抗靜電劑所密集之中央部分。 實施例21 除了使聚丙烯（El l〇G)與抗靜電劑（ΤΒχ_25)之添加比例 為6〇: 40,並使表面層厚度為〜外，以與實施例^相同 125417.doc -17· 200831657 表面内在電阻值為 之方式襄造2層薄片並加以評價 6.6xl〇7(Q/Sq) 〇 I、:施例20相同之方式，觀察拍攝薄片剖面。如圖4B 1厂拉式圖所不’可知抗靜電劑分布於表面層之整個严 度上，進而密集於中央部分。雖與實施例20㈣，於層： 存在疏密分布，但抗靜電劑於中央部分之㈣程度高於實 施例20。圖6之照片(χ5〇〇〇)拍攝有抗靜電劑密集之中央部 分。The relationship between the thickness of the surface layer of the two-layer sheet and the intrinsic resistance value of the surface was evaluated. Specifically, a two-layer sheet was produced in the same manner as in Example 1 except that the thickness of the sheet surface layer was changed to 10 μm, 130 μm, and 160 μm. Similarly, a two-layer sheet was produced in the same manner as in Example 1 except that the polypropylene was changed to E105GM and the thickness of the surface layer of the sheet was changed to 10 μm, 120 μm, and 150 μm. Further, the control of the thickness of the surface layer can be carried out by fixing the sheet pulling speed constant and adjusting the number of rotations of the extruder. With respect to the obtained sheet, the relationship between the thickness of the surface layer of the sheet and the intrinsic resistance value of the sheet was analyzed. The results are shown in Table 3 and Figure 2. [Table 3] Surface layer thickness (μιη) Surface intrinsic resistance value (Ω) E110G E105GM 10 l.SxlO9 3·7χ109 50 3.〇χ10δ 1·〇χ109 120 2,8χ109 130 2.8χ|〇δ 150 2·1χ109 160 2.8χ10δ 125417.doc -16- 200831657 Example 19 ▲Change the film thickness of the surface layer (5 〇 (4), 13 〇 _ and 16 〇 (4), and evaluate the relationship between the amount of the antistatic agent added and the intrinsic resistance value of the surface. In the same manner as in Example i, a 2-layer sheet was produced in the same manner as in Example i except that the amount of the antistatic agent (ΤΒχ25) was 15 Wt%, 20 Wt❶/°, 30 wt%, and 4% by weight. Fig. 3 shows the relationship between the amount of the antistatic agent added and the intrinsic resistance of the surface obtained from the evaluation results of the sheet. Example 20 A 2-layer sheet was produced in the same manner as in Example i except that the surface layer thickness was 60 μηι. Evaluation: The surface internal resistance value is 4.3X108 (Ω/sq) 〇 / and then the sample of 11 cmx 11 (10) is taken out from the sheet towel and manufactured and stored under conditions of 23 C, 5 G % RH for more than 12 hours. The center is taken out of the sheet and dyed and fixed by ruthenium tetroxide. Freezing microtome it exfoliated by said transmission electron microscope stand liver Seisakusho), the observed sample was thinned to direction D and D - orofacial direction to capture acrylic. As can be seen from the section pattern diagram, the antistatic agent is distributed over the entire thickness of the surface layer and is densely concentrated in the center. That is, there is a dense distribution in the layer. Photograph of Figure 5 (x5000) Photographed with a dense central portion of the antistatic agent. Example 21 The addition ratio of polypropylene (El l〇G) to antistatic agent (ΤΒχ_25) was 6〇: 40, and the thickness of the surface layer was ~, as in the case of Example ^, 125417.doc -17· 200831657 The intrinsic resistance value of the surface was measured in two layers and evaluated in the same manner as in 6.6xl〇7(Q/Sq) 〇I,: Example 20, and the cross section of the photographed sheet was observed. As shown in Fig. 4B, the pull-down diagram of the factory shows that the antistatic agent is distributed over the entire severity of the surface layer and is densely concentrated in the central portion. Although in the case of Example 20 (d), there is a dense distribution in the layer: the level of the antistatic agent in the central portion is higher than that in the embodiment 20. The photograph of Fig. 6 (χ5〇〇〇) was photographed with a dense central portion of the antistatic agent.
比較例4 除了使用MFR較两之均聚丙婦（請術)作為聚丙烯，並 使表面層厚度為70，外’以與實施例"目同之方式製造2 層薄片並加以評價。表面内在電阻值為29xiGii(—)。 之剖面模式圖所示，可知技籍帝 j知彳几^电劑僅分布於表面層厚度約 2 〇 μηι之整個表面部分上，而光 而亚非如實施例20、2 1之疏密 分布。圖7之照片（χ5〇〇〇)拍摄右4人士 ^ V 攝有包含表面層之表面部分的 一部分。 以與實施例20相同之方式’觀察拍攝薄片剖面。如圖 根據圖4_7’可知相比比較例4,實施例2〇、21之薄片剖 面具有抗靜電劑密集於中央部分之特異構造。 實施例22 自實施例1中製成之2層薄片中取出9 emx9⑽樣品，並 使用延伸裝置（BRUCK職公司製），於溫度15代、預熱 時間60秒、速度6 m/分鐘之延伸條件下，分別以2〜 3x2 3x3、4x3的延伸倍數延伸。冷卻時間為⑺秒。對各 125417.doc -18- 200831657 測疋延伸别後之表面内在電阻值。結果示於表*中Comparative Example 4 A 2-layer sheet was produced and evaluated in the same manner as in the Example except that the MFR was used as the polypropylene and the surface layer thickness was 70. The intrinsic resistance value of the surface is 29 xiGii (-). As shown in the cross-sectional pattern diagram, it is known that the electrophoresis is only distributed over the entire surface portion of the surface layer thickness of about 2 〇μηι, and the light and sub-distribution is as dense as the embodiment 20, 2 1 . . Photograph of Figure 7 (χ5〇〇〇) is taken by the right 4 people ^ V has a part of the surface part containing the surface layer. The photographed sheet section was observed in the same manner as in Example 20. As can be seen from Fig. 4-7', in comparison with Comparative Example 4, the sheet profiles of Examples 2 and 21 have a specific structure in which an antistatic agent is densely concentrated in the central portion. Example 22 A 9 emx9 (10) sample was taken out from the 2-layer sheet prepared in Example 1, and an extension device (manufactured by BRUCK Co., Ltd.) was used, and the elongation condition was 15 generations, a preheating time of 60 seconds, and a speed of 6 m/min. Next, the extension is extended by 2~3x2 3x3 and 4x3 respectively. The cooling time is (7) seconds. For each 125417.doc -18- 200831657, the intrinsic resistance value of the surface after extension is measured. The results are shown in Table *
[產業上之可利用性] 性=明之抗靜f性組合物例如可較佳用於托盤等抗靜電 子f借费要求抗靜電性之汽車用零件、家電設備零件、電 備办件V # f子材料製造設備、電池構件、資訊辦公設 貨t ·通訊設備、外殼零件、光學機械構件、家用百 楚上 建材，地板材料、以及包裝流通構件 寺0尤其適用於JC、 • . σ 、電日日體、LSI(Large-scale ::::料大型積體電路)等電子零件之盛載盤等容器及 【圖式簡單說明】 之關係 圖，表面層之聚丙稀之MFR與表面内在電阻值 的不思圖。 係薄片之表面層厚度與表面内在電阻值之關係的示 思圖。 立^係抗靜電劑之添加量與表面内在電阻值之關係的示 思圖。 圖4A係實施例20中製造之薄片剖面的模式圖。 _系實施例21中製造之薄片剖面的模式圖。 125417.doc -19· 200831657 圖4C係比較例4中製造之薄片 圖5係實施例20中製造之薄片 圖。 圖6係實施例21中製造之薄片 圖。 圖7係比較例4中製造之薄片 圖。 【主要元件符號說明】 ^ MD、TD 方向 剖面的模式圖。 剖面之顯微鏡照片的示意 剖面之顯微鏡照片的示意 剖面之顯微鏡照片的示意[Industrial Applicability] The anti-static composition of the present invention can be preferably used, for example, for antistatic articles such as trays, and for automotive parts, household electrical appliances, and electrical equipment. f sub-material manufacturing equipment, battery components, information office equipment t · communication equipment, housing parts, optical mechanical components, household building materials, flooring materials, and packaging distribution components Temple 0 is especially suitable for JC, • σ, electricity A diagram of a container such as a carrier for electronic components such as a Japanese-made body, an LSI (Large-scale::: large-scale integrated circuit), and a simple diagram of the drawing, the MFR of the surface layer and the intrinsic resistance of the surface. The value is not thought of. A diagram showing the relationship between the thickness of the surface layer of the sheet and the intrinsic resistance value of the surface. A diagram showing the relationship between the amount of antistatic agent added and the intrinsic resistance of the surface. Fig. 4A is a schematic view showing a cross section of a sheet produced in Example 20. _ is a schematic view of a cross section of a sheet produced in Example 21. 125417.doc -19· 200831657 Fig. 4C is a sheet produced in Comparative Example 4. Fig. 5 is a sheet view produced in Example 20. Fig. 6 is a sheet view produced in Example 21. Fig. 7 is a sheet view produced in Comparative Example 4. [Explanation of main component symbols] ^ Pattern diagram of MD, TD direction profile. Schematic diagram of the microscopic photograph of the section Schematic of the micrograph of the section
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