TW201800475A - Polycarbonate resin composition, molded body, and carrier tape - Google Patents

Polycarbonate resin composition, molded body, and carrier tape Download PDF

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TW201800475A
TW201800475A TW106105286A TW106105286A TW201800475A TW 201800475 A TW201800475 A TW 201800475A TW 106105286 A TW106105286 A TW 106105286A TW 106105286 A TW106105286 A TW 106105286A TW 201800475 A TW201800475 A TW 201800475A
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mass
polycarbonate resin
parts
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resin composition
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TWI726997B (en
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谷村博之
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住化Pc有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06Unsaturated polyesters

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A polycarbonate resin composition which includes a polycarbonate resin, a polyalkylene terephthalate resin, a carbon material, and a graft copolymer, the graft copolymer having a structure that includes a core and a covering portion that covers at least a portion of the core, the content of the carbon material being 10 to 45 parts by mass with respect to 100 parts by mass of the total of the polycarbonate resin and the polyalkylene terephthalate resin, and the content of the graft copolymer being 0.5 to 35 parts by mass with respect to 100 parts by mass of the total of the polycarbonate resin and the polyalkylene terephthalate resin.

Description

聚碳酸酯樹脂組合物、成形體及承載帶Polycarbonate resin composition, formed body, and carrier tape

本發明係關於一種聚碳酸酯樹脂組合物、成形體及承載帶。The present invention relates to a polycarbonate resin composition, a molded body, and a carrier tape.

積體電路晶片(IC晶片)等電子零件若附著有灰塵或污物則會引發誤動作等故障。因此,於對電子零件進行相關操作時,有時會使用合成樹脂製承載帶作為搬送或保管電子零件之容器,該承載帶係於任意寬度之長條片材上隔開一定間隔地配置有稱為袋狀部之凹部。 於該情形時,電子零件被收容於袋狀部內。並且,經稱為覆帶之膜蓋住而獲得承載帶體。將承載帶體捲成盤狀,於此狀態下搬送、保管等。自承載帶體剝離覆帶後,自袋狀部中取出電子零件而使用。電子零件有時係使用安裝機自動取出。於下述專利文獻1中揭示有一種不會因安裝機之振動而導致電子零件自袋狀部飛彈出之承載帶。 聚碳酸酯樹脂係具有優異之耐熱性、耐衝擊性及尺寸穩定性之工程塑膠,廣泛用於各領域中,作為適於承載帶用途之材料受到關注。然而,聚碳酸酯樹脂之成形體易附著灰塵,要求對此進行改良。對此,自先前以來,為了對含有聚碳酸酯樹脂之聚碳酸酯樹脂組合物賦予抗靜電性或導電性,而使用含有聚碳酸酯樹脂與導電性填料(碳黑、碳纖維、奈米碳管等)之組合物(例如參照下述專利文獻2)。 若為了對樹脂組合物賦予導電性而大量使用導電性填料(碳黑等),則存在熔融混練時或成形時樹脂組合物之加工性明顯降低之情況。又,存在因碳之凝集而導致成形體之表面外觀變差之問題。為了解決該問題,使用有調配熱塑性聚對苯二甲酸烷二醇酯樹脂等之方法(例如參照下述專利文獻3)。 [先前技術文獻] [專利文獻] 專利文獻1:日本專利特開2000-103496號公報 專利文獻2:日本專利特開平10-92225號公報 專利文獻3:日本專利特開昭62-297353號公報 聚碳酸酯樹脂組合物被用於作為要求抗靜電性及防靜電性之容器的電子零件(IC晶片等)之搬送或保管用容器(例如電子零件(IC晶片等)之承載帶)等用途。其中,於電子零件(IC晶片等)之承載帶用途中,近年來,就提高生產性之觀點、及減輕環境負荷(減少廢棄物排出量等)之觀點而言,將成形加工時產生之一定量之邊角材料暫時回收後加以粉碎,繼而將粉碎物送回至擠出機內,經熔融混練後再次成形加工等而再利用。此時,有時會出現因反覆熔融混練所致之樹脂之熱劣化、導電性填料之凝集等原因而導致成形體之導電性明顯降低之問題。Dust or dirt attached to electronic parts such as integrated circuit chips (IC chips) can cause malfunctions such as malfunction. Therefore, when carrying out related operations on electronic parts, a synthetic resin carrier tape is sometimes used as a container for transporting or storing electronic parts. The carrier tape is arranged on a long sheet of any width with a certain interval. It is the concave part of the bag-shaped part. In this case, the electronic components are housed in the bag-shaped portion. Then, a carrier tape body is obtained by covering with a film called a cover tape. The carrier tape is rolled into a disk shape, and the carrier tape is transported and stored in this state. After the cover tape is peeled from the carrier tape body, the electronic components are taken out from the bag-shaped portion and used. Electronic parts are sometimes automatically removed using a mounting machine. The following Patent Document 1 discloses a carrier tape that does not cause electronic components to fly out of a bag-like portion due to vibration of a mounting machine. Polycarbonate resins are engineering plastics with excellent heat resistance, impact resistance, and dimensional stability. They are widely used in various fields and have attracted attention as materials suitable for use in carrier tapes. However, the molded body of polycarbonate resin is prone to dust, and improvement is required. To this end, in order to impart antistatic properties or conductivity to a polycarbonate resin composition containing a polycarbonate resin, a polycarbonate resin and a conductive filler (carbon black, carbon fiber, nano carbon tube) have been used. Etc.) (see, for example, Patent Document 2 below). If a large amount of conductive filler (such as carbon black) is used to impart conductivity to the resin composition, the processability of the resin composition may be significantly reduced during melt-kneading or molding. In addition, there is a problem that the surface appearance of the formed body is deteriorated due to the aggregation of carbon. In order to solve this problem, a method of blending a thermoplastic polyalkylene terephthalate resin or the like is used (for example, refer to Patent Document 3 below). [Prior Art Literature] [Patent Literature] Patent Literature 1: Japanese Patent Laid-Open No. 2000-103496 Patent Literature 2: Japanese Patent Laid-Open No. 10-92225 Patent Literature 3: Japanese Patent Laid-Open No. 62-297353 The carbonate resin composition is used for applications such as containers for transporting or storing electronic parts (such as a carrier tape for electronic parts (IC wafers)) as containers for which antistatic properties and antistatic properties are required. Among them, in the use of carrier tapes for electronic parts (IC wafers, etc.), in recent years, from the viewpoint of improving productivity and the viewpoint of reducing environmental load (reducing the amount of waste, etc.), it will be constant during molding. The amount of the corner material is temporarily recovered and pulverized, and the pulverized material is returned to the extruder, melted and kneaded, and then reshaped and processed for reuse. In this case, there may be a problem that the conductivity of the molded body is significantly lowered due to the thermal degradation of the resin caused by repeated melt-kneading, the aggregation of the conductive filler, and the like.

[發明所欲解決之問題] 本發明之目的在於提供一種即便於經反覆成形之情形時亦可抑制導電性之降低之聚碳酸酯樹脂組合物。又,本發明之目的在於提供一種包含上述樹脂組合物之成形體。進而,本發明之目的在於提供一種包含上述樹脂組合物之承載帶。 [解決問題之技術手段] 本發明者發現,具有具備芯部與被覆該芯部之至少一部分之被覆部的結構之接枝共聚物對於抑制經反覆成形之情形時之導電性之降低有效,並且發現,藉由使用含有聚碳酸酯樹脂、聚對苯二甲酸烷二醇酯樹脂、碳材料及上述接枝共聚物之樹脂組合物,即便於樹脂組合物經反覆成形之情形時亦可抑制導電性之降低。 本發明之聚碳酸酯樹脂組合物含有聚碳酸酯樹脂、聚對苯二甲酸烷二醇酯樹脂、碳材料及接枝共聚物,上述接枝共聚物具有具備芯部與被覆該芯部之至少一部分之被覆部的結構,上述碳材料之含量相對於上述聚碳酸酯樹脂及上述聚對苯二甲酸烷二醇酯樹脂之合計100質量份為10~45質量份,上述接枝共聚物相對於上述聚碳酸酯樹脂及上述聚對苯二甲酸烷二醇酯樹脂之合計100質量份為0.5~35質量份。 本發明之聚碳酸酯樹脂組合物即便於經反覆成形之情形時亦可抑制導電性之降低。例如本發明之聚碳酸酯樹脂組合物即便基於再利用等目的而反覆藉由熔融擠出進行成形,亦可將導電性之降低抑制至極低程度。進而,本發明之聚碳酸酯樹脂組合物不僅可實現成形體之優異外觀,且即便於經反覆成形之情形時亦可抑制導電性之降低。 本發明之聚碳酸酯樹脂組合物較佳為如下態樣:於上述接枝共聚物中,上述芯部包含具有源自含丙烯醯基之單體之結構單元之聚合物,上述被覆部包含具有源自不飽和羧酸酯之結構單元之聚合物。於該情形時,對再利用時之導電性之降低之抑制效果更優異。 本發明之成形體包含上述聚碳酸酯樹脂組合物。本發明之成形體即便於使樹脂組合物反覆成形而獲得成形體之情形時亦可抑制導電性之降低。進而,本發明之成形體不僅可實現成形體之優異外觀,且即便於使樹脂組合物反覆成形而獲得成形體之情形時亦可抑制導電性之降低。 又,本發明者發現,於即便經反覆成形之情形時亦可抑制導電性之降低之上述樹脂組合物適用於承載帶。本發明之承載帶包含上述聚碳酸酯樹脂組合物。本發明之承載帶即便於使樹脂組合物反覆成形而獲得成形體之情形時亦可抑制導電性之降低。進而,藉由本發明之承載帶不僅可實現成形體之優異外觀,且即便於使樹脂組合物反覆成形而獲得成形體之情形時亦可抑制導電性之降低。 [發明之效果] 根據本發明,即便於經反覆成形之情形時亦可抑制導電性之降低。進而,根據本發明,不僅可實現成形體之優異外觀,且即便於經反覆成形之情形時亦可抑制導電性之降低。因此,本發明於實用上之利用價值極高。根據本發明,可提供包含聚碳酸酯樹脂組合物之成形體於電子零件之搬送或保管方面之應用。根據本發明,可提供包含聚碳酸酯樹脂組合物之承載帶於電子零件之搬送或保管方面之應用。[Problems to be Solved by the Invention] An object of the present invention is to provide a polycarbonate resin composition capable of suppressing a decrease in conductivity even when subjected to overmolding. It is another object of the present invention to provide a molded article containing the resin composition. Furthermore, an object of the present invention is to provide a carrier tape including the resin composition. [Technical means to solve the problem] The present inventors have found that a graft copolymer having a structure having a core portion and a coating portion covering at least a part of the core portion is effective in suppressing a decrease in conductivity when subjected to overmolding, and It was found that by using a resin composition containing a polycarbonate resin, a polyalkylene terephthalate resin, a carbon material, and the above-mentioned graft copolymer, it is possible to suppress electrical conductivity even when the resin composition is repeatedly formed. Sexual decline. The polycarbonate resin composition of the present invention contains a polycarbonate resin, a polyalkylene terephthalate resin, a carbon material, and a graft copolymer. The graft copolymer has at least a core portion and at least a core portion covering the core portion. In the structure of a part of the coating portion, the content of the carbon material is 10 to 45 parts by mass based on 100 parts by mass of the polycarbonate resin and the polyalkylene terephthalate resin in total. A total of 100 parts by mass of the polycarbonate resin and the polyalkylene terephthalate resin is 0.5 to 35 parts by mass. The polycarbonate resin composition of the present invention can suppress a decrease in conductivity even when subjected to overmolding. For example, even if the polycarbonate resin composition of the present invention is repeatedly formed by melt extrusion for the purpose of reuse or the like, the reduction in conductivity can be suppressed to a very low level. Furthermore, the polycarbonate resin composition of the present invention can not only achieve an excellent appearance of a molded article, but also suppress a decrease in conductivity even when subjected to overmolding. The polycarbonate resin composition of the present invention is preferably such that, in the graft copolymer, the core portion includes a polymer having a structural unit derived from a monomer containing a propylene fluorene group, and the coating portion includes A polymer derived from the structural unit of an unsaturated carboxylic acid ester. In this case, the effect of suppressing the decrease in conductivity during reuse is more excellent. The molded article of the present invention contains the polycarbonate resin composition. The molded article of the present invention can suppress a decrease in conductivity even when a molded article is obtained by repeatedly molding the resin composition. Furthermore, the molded article of the present invention can not only achieve the excellent appearance of the molded article, but also suppress the decrease in conductivity even when the molded article is obtained by repeatedly molding the resin composition. Moreover, the present inventors have found that the above-mentioned resin composition which can suppress a decrease in conductivity even when subjected to overmolding is suitable for a carrier tape. The carrier tape of the present invention contains the above-mentioned polycarbonate resin composition. The carrier tape of the present invention can suppress a decrease in conductivity even when the resin composition is repeatedly formed to obtain a molded body. Furthermore, the carrier tape of the present invention can not only achieve an excellent appearance of a molded article, but also suppress a decrease in conductivity even when a molded article is obtained by repeatedly molding a resin composition. [Effects of the Invention] According to the present invention, it is possible to suppress a decrease in conductivity even when subjected to overmolding. Furthermore, according to the present invention, not only the excellent appearance of the molded body can be achieved, but also the reduction in conductivity can be suppressed even in the case of overmolding. Therefore, the present invention has extremely high practical use value. According to the present invention, it is possible to provide an application of a molded body containing a polycarbonate resin composition in the transportation or storage of electronic parts. According to the present invention, an application of a carrier tape including a polycarbonate resin composition to the transportation or storage of electronic parts can be provided.

以下,對用以實施本發明之形態進行詳細說明。但本發明並不限定於以下之實施形態。又,有時省略不必要之詳細說明。例如有時省略公知事項之詳細說明、及對實質上同一構成之重複說明。其原因在於避免以下說明過於冗長而便於業者理解。再者,本發明者提供以下說明之目的在於使業者充分理解本發明,而非意欲藉此限定申請專利範圍中所記載之主題。 於本說明書中,作為「承載帶」,例如可列舉用於搬送或保管電子零件(例如記憶微晶片、IC晶片、電阻器、連接器、處理器、電容器、閘陣列、電晶體、二極體、繼電器及LED(Light Emitting Diode,發光二極體))等對象物(構成要素。搬送對象物、保管對象物等)之承載帶。承載帶例如可作為於長條狀之任意寬度之片材上隔開一定間隔地配置有用以收容對象物(電子零件等)之凹部(稱為袋狀部之凹部)的包裝材料(對象物(電子零件等)之包裝材料)使用。亦可於將對象物(電子零件等)收容於凹部後,使稱為覆帶之具有黏著性或熱熔性之膜沿連續設置有袋狀部之方向連續黏著或接著於承載帶之上部,而覆蓋袋狀部之開口面,藉此形成蓋部。 於本說明書中,所謂「(甲基)丙烯酸」意指丙烯酸、及與此對應之甲基丙烯酸中之至少一者。「(甲基)丙烯醯基」等其他類似表達亦同樣。本說明書中,關於組合物中之各成分之含量,於組合物中相當於各成分之物質存在複數個之情形時,只要無特別說明,則意指組合物中所存在之該複數個物質之合計量。以下例示之材料可單獨使用一種,亦可併用兩種以上。 本實施形態之聚碳酸酯樹脂組合物含有聚碳酸酯樹脂、聚對苯二甲酸烷二醇酯樹脂、碳材料及接枝共聚物。上述接枝共聚物具有具備芯部與被覆該芯部之至少一部分之被覆部的結構。上述碳材料之含量相對於上述聚碳酸酯樹脂及上述聚對苯二甲酸烷二醇酯樹脂之合計100質量份為10~45質量份。上述接枝共聚物相對於上述聚碳酸酯樹脂及上述聚對苯二甲酸烷二醇酯樹脂之合計100質量份為0.5~35質量份。本實施形態之聚碳酸酯樹脂組合物可用作導電性聚碳酸酯樹脂組合物。 本實施形態之聚碳酸酯樹脂組合物即便於經反覆成形之情形時亦可抑制導電性之降低。本發明者推測獲得此種效果之原因如下。即,推測於使用具有具備芯部及被覆部之結構之接枝共聚物及碳材料之情形時,碳材料易存在於上述接枝共聚物之表面,碳材料彼此間變得容易接觸。並且,推測藉由於含有聚碳酸酯樹脂及聚對苯二甲酸烷二醇酯樹脂之樹脂組合物中使用特定量之具有具備芯部及被覆部之結構之接枝共聚物及碳材料,而於接枝共聚物之表面上碳材料相互接觸,藉此易形成導電路徑。又,推測藉由接枝共聚物具有具備被覆部之結構,而於含有聚碳酸酯樹脂及聚對苯二甲酸烷二醇酯樹脂之樹脂組合物中接枝共聚物彼此之凝集得到抑制,從而獲得優異之分散性,因此易維持導電路徑。推測基於以上原因,樹脂組合物即便於經反覆成形之情形時亦抑制導電性之降低。 <聚碳酸酯樹脂組合物> ((A)成分:聚碳酸酯樹脂) 作為(A)成分之聚碳酸酯樹脂,可列舉例如利用使各種二羥基二芳基化合物與碳醯氯反應之光氣法、及使二羥基二芳基化合物與碳酸酯(碳酸二苯酯等)反應之酯交換法等所得之聚合物。製造(A)成分時根據需要可使用分子量調節劑、觸媒等。 作為二羥基二芳基化合物,可列舉:雙(4-羥基苯基)甲烷、1,1-雙(4-羥基苯基)乙烷、2,2-雙(4-羥基苯基)丙烷(別名:雙酚A)、2,2-雙(4-羥基苯基)丁烷、2,2-雙(4-羥基苯基)辛烷、雙(4-羥基苯基)苯甲烷、2,2-雙(4-羥基苯基-3-甲基苯基)丙烷、1,1-雙(4-羥基-3-第三丁基苯基)丙烷、2,2-雙(4-羥基-3-溴苯基)丙烷、2,2-雙(4-羥基-3,5-二溴苯基)丙烷、2,2-雙(4-羥基-3,5-二氯苯基)丙烷等雙(羥基芳基)烷烴類;1,1-雙(4-羥基苯基)環戊烷、1,1-雙(4-羥基苯基)環己烷等雙(羥基芳基)環烷烴類;4,4'-二羥基二苯醚、4,4'-二羥基-3,3'-二甲基二苯醚等二羥基二芳基醚類;4,4'-二羥基二苯硫醚等二羥基二芳基硫醚類;4,4'-二羥基二苯基亞碸、4,4'-二羥基-3,3'-二甲基二苯基亞碸等二羥基二芳基亞碸類;4,4'-二羥基二苯碸、4,4'-二羥基-3,3'-二甲基二苯碸等二羥基二芳基碸類等。二羥基二芳基化合物可單獨使用一種,亦可併用兩種以上。 亦可將二羥基二芳基化合物與哌𠯤、二哌啶基對苯二酚、間苯二酚、4,4'-二羥基聯苯等併用。 亦可將二羥基二芳基化合物與3價以上之酚化合物併用。作為3價以上之酚化合物,可列舉:間苯三酚、4,6-二甲基-2,4,6-三(4-羥基苯基)庚烯、2,4,6-三甲基-2,4,6-三(4-羥基苯基)庚烷、1,3,5-三(4-羥基苯基)苯、1,1,1-三(4-羥基苯基)乙烷、2,2-雙[4,4-(4,4'-二羥基二苯基)環己基]丙烷等。 (A)成分之黏度平均分子量就易獲得優異成形性之觀點而言,較佳為10000以上,更佳為15000以上,進而較佳為17000以上,特佳為20000以上。(A)成分之黏度平均分子量就易獲得成形體(片材等)之表面之優異外觀之觀點而言,較佳為100000以下,更佳為35000以下,進而較佳為28000以下,特佳為25000以下。就該等觀點而言,(A)成分之黏度平均分子量較佳為10000~100000,更佳為15000~35000,進而較佳為17000~28000,特佳為20000~25000。 (A)成分之黏度平均分子量可藉由以下程序獲得。首先,使用二氯甲烷作為溶劑而獲得0.5質量%之聚碳酸酯樹脂溶液。繼而,利用坎農-芬斯克型黏度管於溫度20℃下測定比黏度(ηsp )。進而,藉由濃度換算而求出極限黏度[η],根據下述SCHNELL式而可算出黏度平均分子量M。 [η]=1.23×10-4 M0.83 (A)成分之含量以(A)成分與(B)成分之合計量為基準計較佳為下述範圍。(A)成分之含量就易獲得優異成形性之觀點而言,較佳為90質量%以上,更佳為93質量%以上,進而較佳為95質量%以上,特佳為97質量%以上。(A)成分之含量就易獲得成形體(片材等)之表面之優異外觀之觀點而言,較佳為99.94質量%以下,更佳為99.9質量%以下,進而較佳為99.5質量%以下,特佳為99質量%以下。就該等觀點而言,(A)成分之含量較佳為90~99.94質量%,更佳為93~99.9質量%,進而較佳為95~99.5質量%,特佳為97~99質量%。 ((B)成分:聚對苯二甲酸烷二醇酯樹脂) 作為(B)成分之聚對苯二甲酸烷二醇酯樹脂,可列舉:聚對苯二甲酸乙二酯樹脂、聚對苯二甲酸丙二酯樹脂、聚對苯二甲酸丁二酯樹脂等。 根據JIS K7233而測定之(B)成分之固有黏度較佳為下述範圍。上述固有黏度就易獲得優異導電性(較低電阻值。以下同樣)之觀點而言,較佳為0.6以上,更佳為0.7以上,進而較佳為0.9以上,特佳為1.0以上。上述固有黏度就(B)成分相對於其他樹脂成分((A)成分等)之分散性提高之觀點而言,較佳為1.5以下,更佳為1.4以下,進而較佳為1.2以下。就該等觀點而言,上述固有黏度較佳為0.6~1.5,更佳為0.7~1.4,進而較佳為0.9~1.2,特佳為1.0~1.2。 (B)成分之含量以(A)成分與(B)成分之合計量為基準計較佳為下述範圍。(B)成分之含量就易獲得優異導電性之觀點而言,較佳為0.06質量%以上,更佳為0.5質量%以上,進而較佳為1.0質量%以上,特佳為1.5質量%以上,極佳為2.0質量%以上。(B)成分之含量就易獲得成形體之優異外觀之觀點而言,較佳為10質量%以下,更佳為5.0質量%以下,進而較佳為3.0質量%以下。就該等觀點而言,(B)成分之含量較佳為0.06~10質量%,更佳為0.5~5.0質量%,進而較佳為1.0~3.0質量%,特佳為1.5~3.0質量%,極佳為2.0~3.0質量%。 ((C)成分:碳材料) 作為(C)成分之碳材料,可列舉:碳黑、石墨、碳纖維、奈米碳管、奈米碳卷、奈米碳球等。 作為碳黑之分類,可列舉:爐型、乙炔型、科琴型等。其中,就易獲得優異再利用性之觀點而言,較佳為爐型碳黑。 碳黑之比表面積就易獲得優異導電性之觀點而言,較佳為30 m2 /g以上,更佳為40 m2 /g以上,進而較佳為50 m2 /g以上。碳黑之比表面積就易獲得碳黑之優異分散性、成形體(片材等)之表面之優異外觀之觀點而言,較佳為90 m2 /g以下,更佳為75 m2 /g以下,進而較佳為60 m2 /g以下。就該等觀點而言,碳黑之比表面積較佳為30~90 m2 /g,更佳為40~75 m2 /g,進而較佳為50~60 m2 /g。碳黑之比表面積亦可為50~90 m2 /g。 比表面積可依據JIS K6217橡膠用碳黑之基本性能之試驗法進行測定。比表面積係以每單位質量(g)之碳黑之表面積(m2 )表示。比表面積可藉由將經脫氣之碳黑浸漬於液態氮中,測定平衡時碳黑表面所吸附之氮量而獲得。 碳黑之DBP吸油量就易獲得優異導電性之觀點而言,較佳為100 ml/100 g以上,更佳為130 ml/100 g以上,進而較佳為150 ml/100 g以上,特佳為超過150 ml/100 g,極佳為160 ml/100 g以上,極其佳為170 ml/100 g。碳黑之DBP吸油量就易獲得碳黑之優異分散性、成形體(片材等)之表面之優異外觀之觀點而言,較佳為300 ml/100 g以下,更佳為220 ml/100 g以下,進而較佳為200 ml/100 g以下。就該等觀點而言,碳黑之DBP吸油量較佳為100~300 ml/100 g,更佳為130~300 ml/100 g,進而較佳為150~300 ml/100 g,特佳為超過150 ml/100 g且為300 ml/100 g以下,極佳為160~220 ml/100 g,極其佳為170~200 ml/100 g。 DBP(鄰苯二甲酸正二丁酯,Di-butylphthalate)吸油量可依據JIS K6217橡膠用碳黑之基本性能之試驗法進行測定。DBP吸油量與碳黑粒子彼此間之接合力有關,DBP吸油量較大則表示結構較長。 就易獲得優異導電性之觀點,及易獲得碳黑之優異分散性、成形體(片材等)之表面之優異外觀之觀點而言,較佳為碳黑之上述比表面積及上述DBP吸油量兩者滿足上述較佳範圍。例如較佳為比表面積為30~90 m2 /g,且DBP吸油量為100~300 ml/100 g之態樣。 (C)成分之含量相對於(A)成分與(B)成分之合計100質量份為10~45質量份。若(C)成分之含量未達10質量份,則成形體無法獲得充分之導電性。若(C)成分之含量超過45質量份,則黏度增大、成形穩定性降低。(C)成分之含量就易獲得優異導電性之觀點而言,相對於(A)成分與(B)成分之合計100質量份,較佳為13質量份以上,更佳為15質量份以上,進而較佳為17質量份以上,特佳為20質量份以上,極佳為21質量份以上。(C)成分之含量就成形穩定性易提高之觀點而言,相對於(A)成分與(B)成分之合計100質量份,較佳為40質量份以下,更佳為30質量份以下,進而較佳為27質量份以下,特佳為25質量份以下。就該等觀點而言,(C)成分之含量相對於(A)成分與(B)成分之合計100質量份,較佳為10~40質量份,更佳為13~30質量份,進而較佳為15~27質量份,特佳為15~25質量份,極佳為17~25質量份,尤佳為20~25質量份,進而較佳為21~25質量份。 ((D)成分:接枝共聚物) (D)成分之接枝共聚物具有具備芯部(芯材)與被覆該芯部之至少一部分之被覆部的結構。(D)成分亦可具有例如具備核心層(芯部)與包覆該核心層之殼層(被覆部)之核殼型結構。芯部及被覆部可由互不相同之聚合物構成。芯部及被覆部亦可分別具有複數層。被覆部可被覆芯部之一部分,亦可被覆整個芯部。(D)成分可藉由於芯部之構成成分之存在下使被覆部之構成成分反應,而使被覆部之構成成分與芯部之構成成分接枝聚合而獲得。 芯部就進一步抑制再利用時之導電性降低之觀點而言,較佳為包含選自由丙烯酸系橡膠(具有源自含丙烯醯基之單體之結構單元的聚合物)及矽酮系橡膠所組成之群中之至少一種,更佳為包含丙烯酸系橡膠。作為芯部之構成成分,不限於丙烯酸系橡膠及矽酮系橡膠,亦可使用聚丁二烯等。 作為丙烯酸系橡膠,可使用具有源自含丙烯醯基之單體之結構單元作為主結構單元之聚合物。源自含丙烯醯基之單體之結構單元之含量就易獲得優異再利用性之觀點而言,以丙烯酸系橡膠之總質量為基準計,較佳為50~100質量%,更佳為70~100質量%。 作為含丙烯醯基之單體,可使用丙烯酸酯。作為丙烯酸酯,可列舉烷基之碳數為2~8之丙烯酸烷基酯等,可列舉:丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯等。 丙烯酸系橡膠亦可具有源自丙烯酸酯以外之其他成分之結構單元。作為此種成分,就易低價獲得共聚物之觀點而言,較佳為能夠與丙烯酸酯共聚合之乙烯基系單體。 作為能夠與丙烯酸酯共聚合之乙烯基系單體,可列舉:苯乙烯、α-甲基苯乙烯等芳香族乙烯基化合物;甲基丙烯酸甲酯、甲基丙烯酸乙酯等甲基丙烯酸烷基酯;丙烯腈、甲基丙烯腈等不飽和腈;甲基乙烯醚、丁基乙烯醚等乙烯醚;氯乙烯、溴乙烯等鹵化乙烯;偏二氯乙烯、偏二溴乙烯等偏二鹵乙烯;丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、烯丙基縮水甘油醚、乙二醇縮水甘油醚等具有縮水甘油基之乙烯基系單體等。 作為丙烯酸系橡膠,可使用矽酮-丙烯酸系橡膠(具有源自含丙烯醯基之單體(丙烯酸系成分)之結構單元、及源自矽酮成分之結構單元的複合聚合物。例如具有源自丙烯酸烷基酯之結構單元、及聚有機矽氧烷骨架的聚合物)。 作為矽酮系橡膠,可使用聚有機矽氧烷,例如可使用有機矽氧烷鍵之單元達數千以上之作為線性聚合物之聚有機矽氧烷。矽酮系橡膠藉由何種方法製造均可,較佳為利用乳化聚合法所得之橡膠。 作為聚有機矽氧烷,並無特別限制,較佳為具有乙烯基聚合性官能基之聚有機矽氧烷。聚有機矽氧烷可使用二甲基矽氧烷而獲得。二甲基矽氧烷可為鏈狀,亦可為環狀。作為二甲基矽氧烷,可列舉3員環以上之二甲基矽氧烷系環狀體等,較佳為3~7員環之二甲基矽氧烷系環狀體。具體而言,可列舉:六甲基環三矽氧烷、八甲基環四矽氧烷、十甲基環五矽氧烷、十二甲基環六矽氧烷等。二甲基矽氧烷可單獨使用一種,亦可併用兩種以上。 構成(D)成分之被覆部就(D)成分相對於其他樹脂成分((A)成分、(B)成分等)之分散性提高之觀點而言,較佳為包含如下聚合物,該聚合物具有選自由源自不飽和羧酸酯之結構單元、源自乙烯基化合物(不飽和羧酸酯除外)之結構單元、源自順丁烯二醯亞胺化合物之結構單元、源自不飽和二羧酸之結構單元、及源自不飽和二羧酸酸酐之結構單元所組成之群中之至少一種。 作為乙烯基化合物,可列舉:含縮水甘油基之乙烯基化合物、脂肪族乙烯基化合物、芳香族乙烯基化合物、氰化乙烯基化合物等。將相當於含縮水甘油基之乙烯基化合物、且同時相當於脂肪族乙烯基化合物、芳香族乙烯基化合物或氰化乙烯基化合物之化合物歸類為含縮水甘油基之乙烯基化合物。 就(D)成分相對於其他樹脂成分((A)成分、(B)成分等)之分散性提高之觀點而言,較佳為具有選自由源自不飽和羧酸酯之結構單元、源自含縮水甘油基之乙烯基化合物之結構單元、及源自不飽和二羧酸酸酐之結構單元所組成之群中之至少一種的聚合物,更佳為具有源自不飽和羧酸酯之結構單元的聚合物。提供構成被覆部之聚合物之結構單元的化合物可單獨使用一種,亦可併用兩種以上。 作為不飽和羧酸酯,可列舉:不飽和羧酸烷基酯、不飽和羧酸芳基酯等。作為不飽和羧酸酯,可使用(甲基)丙烯酸酯。作為(甲基)丙烯酸酯,可列舉:(甲基)丙烯酸烷基酯、(甲基)丙烯酸芳基酯等。 作為不飽和羧酸烷基酯,就(D)成分相對於其他樹脂成分((A)成分、(B)成分等)之分散性提高之觀點而言,較佳為(甲基)丙烯酸烷基酯。作為(甲基)丙烯酸烷基酯,可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸氯甲酯、(甲基)丙烯酸2-氯乙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2,3,4,5,6-五羥基己酯、(甲基)丙烯酸2,3,4,5-四羥基戊酯、(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸(丙基胺基)乙酯、(甲基)丙烯酸(二甲基胺基)乙酯、(甲基)丙烯酸(乙基胺基)丙酯、(甲基)丙烯酸(苯基胺基)乙酯、(甲基)丙烯酸(環己基胺基)乙酯等。作為(甲基)丙烯酸烷基酯,就(D)成分相對於其他樹脂成分((A)成分、(B)成分等)之分散性提高效果較顯著之觀點而言,較佳為選自由(甲基)丙烯酸甲酯及(甲基)丙烯酸正丁酯所組成之群中之至少一種。 作為不飽和羧酸芳基酯,就(D)成分相對於其他樹脂成分((A)成分、(B)成分等)之分散性提高之觀點而言,較佳為(甲基)丙烯酸芳基酯。作為(甲基)丙烯酸芳基酯,可列舉:(甲基)丙烯酸苯酯、(甲基)丙烯酸二甲基苯酯、(甲基)丙烯酸萘酯等。 作為含縮水甘油基之乙烯基化合物,可列舉:(甲基)丙烯酸縮水甘油酯、伊康酸縮水甘油酯、伊康酸二縮水甘油酯、烯丙基縮水甘油醚、苯乙烯-4-縮水甘油醚、4-縮水甘油基苯乙烯等。作為含縮水甘油基之乙烯基化合物,就耐衝擊性提高效果較顯著之觀點而言,較佳為(甲基)丙烯酸縮水甘油酯。含縮水甘油基之乙烯基化合物可單獨使用一種,亦可併用兩種以上。 作為脂肪族乙烯基化合物,可列舉:乙烯、丙烯、丁二烯等。作為芳香族乙烯基化合物,可列舉:苯乙烯、α-甲基苯乙烯、對胺基苯乙烯、1-乙烯基萘、4-甲基苯乙烯、4-丙基苯乙烯、4-環己基苯乙烯、4-十二烷基苯乙烯、2-乙基-4-苄基苯乙烯、4-(苯基丁基)苯乙烯、鹵化苯乙烯、2-苯乙烯-㗁唑啉等。作為氰化乙烯基化合物,可列舉:丙烯腈、甲基丙烯腈、乙基丙烯腈等。 作為其他乙烯基化合物,可列舉:丙烯醯胺、甲基丙烯醯胺、N-甲基丙烯醯胺、丁氧基甲基丙烯醯胺、N-丙基甲基丙烯醯胺、N-乙烯基二乙基胺、N-乙醯基乙烯基胺、烯丙基胺、甲基烯丙基胺、N-甲基烯丙基胺、2-異丙烯基㗁唑啉、2-乙烯基㗁唑啉等。 作為順丁烯二醯亞胺化合物,可列舉:順丁烯二醯亞胺、N-甲基順丁烯二醯亞胺、N-乙基順丁烯二醯亞胺、N-丙基順丁烯二醯亞胺、N-異丙基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、N-(對溴苯基)順丁烯二醯亞胺、N-(氯苯基)順丁烯二醯亞胺等。作為不飽和二羧酸,可列舉:順丁烯二酸、伊康酸、苯二甲酸等。 作為芯部及被覆部之構成成分之組合,就抑制再利用時之導電性之降低之效果更優異之觀點而言,較佳為具有具備芯部與被覆部之結構之接枝共聚物,上述芯部包含丙烯酸系橡膠(具有源自含丙烯醯基之單體之結構單元之聚合物),上述被覆部包含如下聚合物,該聚合物具有選自由源自不飽和羧酸酯之結構單元及源自乙烯基化合物之結構單元所組成之群中之至少一種。更佳為選自由下述(D-I)成分及下述(D-II)成分所組成之群中之至少一種,進而較佳為(D-II)成分。 (D-I)成分:具有具備芯部與被覆部之核殼型結構之接枝共聚物,上述芯部包含矽酮-丙烯酸系橡膠,上述被覆部包含如下聚合物,該聚合物具有選自由源自不飽和羧酸酯之結構單元及源自乙烯基化合物之結構單元所組成之群中之至少一種。 (D-II)成分:具有具備芯部與被覆部之核殼型結構之接枝共聚物,上述芯部包含丙烯酸系橡膠,上述被覆部包含具有源自不飽和羧酸酯之結構單元之聚合物。 作為(D-I)成分,就抑制再利用時導電性之降低之效果更優異之觀點而言,較佳為具備包含如下聚合物之被覆部,該聚合物具有選自由源自不飽和羧酸烷基酯之結構單元及源自乙烯基化合物之結構單元所組成之群中之至少一種,更佳為具備包含如下聚合物之被覆部,該聚合物具有選自由源自(甲基)丙烯酸甲酯之結構單元及源自含縮水甘油基之乙烯基化合物之結構單元所組成之群中之至少一種。作為(D-I)成分之市售品,可列舉Mitsubishi Rayon股份有限公司製造之Metablen S-2001、Metablen S-2006、Metablen S-2200等。 作為(D-II)成分,就抑制再利用時導電性之降低之效果更優異之觀點而言,較佳為具備包含如下聚合物之被覆部,該聚合物具有源自不飽和羧酸烷基酯之結構單元,更佳為具備包含如下聚合物之被覆部,該聚合物具有源自(甲基)丙烯酸甲酯之結構單元。作為(D-II)成分之市售品,可列舉Rohm and Haas Japan股份有限公司製造之Paraloid BPM-500及Paraloid BPM-515;Mitsubishi Rayon股份有限公司製造之Metablen W-450A及Metablen W-600A等。 (D)成分之含量相對於(A)成分與(B)成分之合計100質量份為0.5~35質量份。若(D)成分之含量未達0.5質量份,則無法獲得充分之再利用性。(D)成分之含量就抑制再利用時導電性之降低之效果更優異之觀點而言,相對於(A)成分與(B)成分之合計100質量份,較佳為1質量份以上,更佳為2質量份以上,進而較佳為5質量份以上,特佳為7質量份以上,極佳為8質量份以上,尤佳為10質量份以上。若(D)成分之含量超過35質量份,無法獲得充分之再利用性,且成形體之外觀變差。(D)成分之含量就抑制再利用時導電性之降低之效果更優異之觀點,及獲得成形體之更優異外觀之觀點而言,相對於(A)成分與(B)成分之合計100質量份,較佳為30質量份以下,更佳為20質量份以下,進而較佳為18質量份以下,特佳為15質量份以下,極佳為12質量份以下。就該等觀點而言,(D)成分之含量相對於(A)成分與(B)成分之合計100質量份,較佳為0.5~30質量份,更佳為1~20質量份,進而較佳為2~20質量份,特佳為5~18質量份,極佳為7~15質量份,尤佳為8~12質量份,進而較佳為10~12質量份。 (其他成分) 本實施形態之聚碳酸酯樹脂組合物根據需要可含有上述成分以外之公知樹脂(聚醯胺樹脂、聚醯亞胺樹脂、聚苯乙烯樹脂、ABS(Acrylonitrile-Butadiene-Styrene,丙烯腈-丁二烯-苯乙烯)樹脂、聚烯烴樹脂(聚乙烯樹脂、聚丙烯樹脂等)、酚樹脂、環氧樹脂等)。 本實施形態之聚碳酸酯樹脂組合物根據需要可含有上述成分以外之公知添加劑。作為此種添加劑,可列舉:抗氧化劑(磷系抗氧化劑、酚系抗氧化劑等)、脫模劑(甘油脂肪酸酯等)、潤滑劑(石蠟、硬酯酸正丁酯、合成蜜蠟、天然蜜蠟、甘油單酯、褐煤酸蠟、聚乙烯蠟、季戊四醇四硬脂酸酯等)、著色劑(氧化鈦、染料、顏料等)、填充劑(碳酸鈣、黏土、二氧化矽、玻璃纖維、玻璃球、玻璃碎片、滑石、雲母、各種晶鬚類等)、流動性改良劑、展佈劑(環氧化大豆油、液態石蠟等)、阻燃劑(溴系化合物、磷系化合物、有機金屬鹽系化合物、矽酮系化合物等)等。 (樹脂組合物之製作方法) 本實施形態之聚碳酸酯樹脂組合物可藉由將構成成分加以混合而獲得。作為本實施形態之聚碳酸酯樹脂組合物之構成成分之混合方法,並無特別限制,例如可列舉使用任意混合機(滾筒混合機、帶式混合機、高速混合機等)混合後,使用擠出機等進行熔融混練之方法。 <成形體及其製造方法> 本實施形態之成形體(成形品)包含本實施形態之聚碳酸酯樹脂組合物。本實施形態之成形體可為膜狀,亦可為平板狀。作為本實施形態之成形體,可列舉:膜、帶、片材等。作為本實施形態之成形體,例如可列舉收容電子零件之容器(例如電子零件之搬送或保管用容器)。 作為本實施形態之成形體,例如可列舉承載帶。本實施形態之承載帶包含本實施形態之聚碳酸酯樹脂組合物。本實施形態之承載帶可為膜狀,亦可為平板狀。本實施形態之承載帶亦可具有能夠收容對象物(電子零件等)之收容部,例如具有於帶之長度方向上隔開間隔而形成之複數個袋狀部(用以收容對象物之凹部)。 作為膜,例如可列舉寬度(膜寬度)為100~1500 mm且厚度為0.05~0.5 mm之成形體。作為帶(承載帶等),例如可列舉寬度(帶寬度)為3~100 mm(較佳為10~50 mm)且厚度為0.05~0.5 mm之成形體。作為片材,例如可列舉寬度(片材寬度)為100~1500 mm且厚度為0.7~10 mm之成形體。 本實施形態之成形體之製造方法具備使本實施形態之聚碳酸酯樹脂組合物成形而獲得成形體之成形步驟。本實施形態之成形體之製造方法可具備複數個成形步驟,例如亦可進而具備使包含本實施形態之聚碳酸酯樹脂組合物之成形體熔融而獲得樹脂組合物之步驟、與使該樹脂組合物成形而獲得成形體之步驟。作為本實施形態之聚碳酸酯樹脂組合物之成形方法,並無特別限制,可使用公知之擠出成形法(T模成形法、壓延成形法等)、射出成形法、射出-壓縮成形法等。 本實施形態之承載帶之製造方法具備使本實施形態之聚碳酸酯樹脂組合物成形而獲得承載帶之成形步驟。本實施形態之承載帶之製造方法亦可具備複數個成形步驟,例如亦可進而具備使本實施形態之聚碳酸酯樹脂組合物熔融而獲得樹脂組合物之步驟、與使該樹脂組合物成形而獲得承載帶之步驟。作為用以對承載帶賦予稱為袋狀部之凹部之成形方法,可列舉:壓空成形法、加壓成形法、真空旋轉成形法等。 以上說明了作為本發明之技術之例示的實施形態。為此提供詳細說明。因而,詳細說明所記載之構成要素中不僅包含用以解決課題之必需構成要素,亦可能包含用以例示上述技術但並非解決課題所必需之構成要素。因此,不該因該等非必需之構成要素記載於詳細說明中,而當即認定該等非必需之構成要素為必需。又,上述實施形態係用以例示本發明之技術者,因此可於申請專利範圍或其均等範圍中進行各種變更、置換、附加、省略等。 [實施例] 以下,藉由實施例對本發明進行說明,但本發明並非限定於該等實施例。 <1.顆粒之製作> 準備表1~3所示含量之調配成分。繼而,使用直徑37 mm之雙軸擠出機(神戶製鋼所股份有限公司製造,KTX-37)於缸體溫度280℃下對上述調配成分進行熔融混練,而獲得各種顆粒。 所使用之調配成分之詳細內容如下所示。 [聚碳酸酯樹脂] A-1:由雙酚A及碳醯氯合成之聚碳酸酯樹脂,Sumika Styron Polycarbonate股份有限公司製造,Calibre 200-13(黏度平均分子量:21000) [聚對苯二甲酸烷二醇酯樹脂] B-1:聚對苯二甲酸丁二酯樹脂,Polyplastics股份有限公司製造,Duranex 600FP(固有黏度:1.0) [碳材料] C-1:爐型碳黑,Cabot公司製造,Vulcan XC-305(比表面積:70 m2 /g,DBP吸油量:130 ml/100 g) C-2:爐型碳黑,三菱化學股份有限公司製造,#3050B(比表面積:50 m2 /g,DBP吸油量:175 ml/100 g) [接枝共聚物] D-1:核殼型接枝共聚物(核心層:矽酮-丙烯酸系橡膠,殼層:具有如下結構單元之聚合物,該結構單元係源自具有源自不飽和羧酸烷基酯之結構單元之聚合物;(D-I)成分),Mitsubishi Rayon股份有限公司製造,Metablen S-2001 D-2:核殼型接枝共聚物(核心層:丙烯酸系橡膠,殼層:具有源自不飽和羧酸烷基酯之結構單元之聚合物;(D-II)成分),Mitsubishi Rayon股份有限公司製造,Metablen W-450A D-3:核殼型接枝共聚物(核心層:聚丁二烯,殼層:具有源自(甲基)丙烯酸烷基酯之結構單元之聚合物),Rohm and Haas Japan股份有限公司製造,Paraloid EXL2603 <2.平板之製造> 利用乾燥機將上述項目1之顆粒於120℃下乾燥4小時。繼而,利用小型射出成形機(日本製鋼所股份有限公司(JSW)製造,J100EII-P),於成形溫度300℃、模具溫度90℃下,獲得尺寸為50 mm×80 mm×厚度2 mm之平板。 <3.導電性之評估> 準備5張上述項目2之平板(反覆造粒次數為零之樣品)。繼而,利用導電性測定器(三菱化學股份有限公司製造,Loresta-GP MCP-T600)測定平板表面之中央附近之表面固有電阻值(Ω/sq.),求出5張之平均值作為導電性之值。 <4.再利用性之評估> 使用上述項目1之顆粒,利用小型單軸擠出機(Tanabe Plastics Machinery股份有限公司製造,VS-40)於擠出溫度300℃、螺桿轉數120 rpm下反覆進行5次造粒。採集經反覆5次造粒後之顆粒,藉由與上述項目2之方法相同之方法獲得平板。藉由與上述項目3相同之方法求出該平板(反覆進行5次造粒後之樣品)之導電性。 作為再利用性之判定,將反覆進行有5次造粒時(反覆造粒次數為5次)之平板之表面固有電阻值未達1×1010 (Ω/sq.)之情形評估為「A」(再利用性良好),將表面固有電阻值為1×1010 (Ω/sq.)以上(表中記載為「≧1×1010 」)之情形評估為「B」(再利用性較差)。 <5.平板外觀之評估> 藉由目視觀察未進行反覆造粒時(反覆造粒次數為零)之平板之表面。將確認無不均之均勻表面之情形評估為「A」,將平板表面確認有不均之情形評估為「B」。 各評估結果如表1~3所示。 [表1]

Figure TW201800475AD00001
[表2]
Figure TW201800475AD00002
[表3]
Figure TW201800475AD00003
如表1及表2所示,實施例中,導電性、再利用性及平板之外觀各項均良好。 另一方面,如表3所示,比較例中,結果各情形時均無法滿足再利用性。 比較例1為碳材料之含量較少之情形,導電性及再利用性較差。 比較例2為碳材料之含量較多之情形,黏度過高,成形其本身較為困難。 比較例3為接枝共聚物之含量較少之情形,再利用性較差。 比較例4為接枝共聚物之含量較多之情形,再利用性及平板之外觀較差。 比較例5為未使用接枝共聚物之情形,導電性、再利用性及平板之外觀較差。 比較例6為碳材料之含量較少之情形,導電性、再利用性及平板之外觀較差。 [產業上之可利用性] 根據本發明,即便於經反覆成形之情形時亦可抑制導電性之降低。例如根據本發明,即便基於再利用等目的而反覆藉由熔融擠出進行成形,亦可將導電性之降低抑制至極低程度。進而,根據本發明,不僅可實現成形體之優異外觀,且即便於經反覆成形之情形時亦可抑制導電性之降低。因此,本發明之工業利用價值極高。Hereinafter, the form for implementing this invention is demonstrated in detail. However, the present invention is not limited to the following embodiments. Moreover, unnecessary detailed description may be omitted in some cases. For example, detailed descriptions of well-known matters and repeated descriptions of substantially the same structure may be omitted. The reason is to avoid the following description being too long and easy for the industry to understand. In addition, the inventor provides the following description for the purpose of fully understanding the present invention, and is not intended to limit the subject matter described in the scope of the patent application. In this specification, as the "carrier tape", for example, it is used to carry or store electronic parts (for example, memory microchips, IC chips, resistors, connectors, processors, capacitors, gate arrays, transistors, diodes, etc.). , Relay and LED (Light Emitting Diode, light emitting diode)) and other objects (constituent elements. Objects to be transported, objects to be stored, etc.). The carrier tape can be used, for example, as a packaging material (object (object) Electronic parts, etc.) packaging materials). After accommodating the object (electronic parts, etc.) in the recessed portion, the adhesive or hot-melt film called a cover tape may be continuously adhered in the direction in which the bag-shaped portion is continuously provided or adhered to the upper portion of the carrier tape. The cover surface is formed by covering the opening surface of the bag-shaped portion. In the present specification, "(meth) acrylic acid" means at least one of acrylic acid and corresponding methacrylic acid. The same applies to other similar expressions such as "(meth) acrylfluorenyl". In this specification, regarding the content of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it means that Total measurement. The materials exemplified below may be used alone or in combination of two or more. The polycarbonate resin composition of this embodiment contains a polycarbonate resin, a polyalkylene terephthalate resin, a carbon material, and a graft copolymer. The graft copolymer has a structure including a core portion and a coating portion covering at least a part of the core portion. The content of the carbon material is 10 to 45 parts by mass based on 100 parts by mass of the total of the polycarbonate resin and the polyalkylene terephthalate resin. The graft copolymer is 0.5 to 35 parts by mass based on 100 parts by mass of the polycarbonate resin and the polyalkylene terephthalate resin in total. The polycarbonate resin composition of this embodiment can be used as a conductive polycarbonate resin composition. The polycarbonate resin composition of this embodiment can suppress a decrease in conductivity even when subjected to overmolding. The inventors speculate that the reason for obtaining such an effect is as follows. That is, when a graft copolymer and a carbon material having a structure having a core portion and a coating portion are used, it is estimated that the carbon material tends to exist on the surface of the above-mentioned graft copolymer, and the carbon materials easily come into contact with each other. In addition, it is presumed that a specific amount of a graft copolymer having a structure including a core portion and a coating portion and a carbon material are used in a resin composition containing a polycarbonate resin and a polyalkylene terephthalate resin. The carbon materials on the surface of the graft copolymer are in contact with each other, thereby easily forming a conductive path. In addition, it is estimated that the graft copolymer has a structure having a coating portion, and aggregation of the graft copolymers in a resin composition containing a polycarbonate resin and a polyalkylene terephthalate resin is suppressed, so that An excellent dispersibility is obtained, so it is easy to maintain a conductive path. It is presumed that for the above reasons, the resin composition suppresses a decrease in conductivity even when subjected to overmolding. <Polycarbonate resin composition> ((A) component: Polycarbonate resin) As a polycarbonate resin of (A) component, the phosgene which makes various dihydroxy diaryl compound and carbochlorine react is mentioned, for example. And polymers obtained by a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate (diphenyl carbonate, etc.). When manufacturing (A) component, a molecular weight regulator, a catalyst, etc. can be used as needed. Examples of the dihydroxydiaryl compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) propane ( Alias: bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) benzenemethane, 2, 2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-third butylphenyl) propane, 2,2-bis (4-hydroxy- 3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, etc. Bis (hydroxyaryl) alkanes; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane and other bis (hydroxyaryl) cycloalkanes ; 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether and other dihydroxydiaryl ethers; 4,4'-dihydroxydiphenylsulfide Ethers and other dihydroxydiaryl sulfides; 4,4'-dihydroxydiphenylsulfene, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfene Alkylidenes; 4,4'-dihydroxydiphenylstilbene, 4,4'-dihydroxy-3,3'-dimethyldiphenylstilbene and the like. The dihydroxydiaryl compound may be used singly or in combination of two or more kinds. A dihydroxydiaryl compound can also be used in combination with piperazine, dipiperidinyl hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl and the like. A dihydroxydiaryl compound may be used in combination with a trivalent or higher phenol compound. Examples of the trivalent or higher phenol compound include resorcinol, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene, and 2,4,6-trimethyl -2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane , 2,2-bis [4,4- (4,4'-dihydroxydiphenyl) cyclohexyl] propane and the like. The viscosity average molecular weight of the component (A) is preferably 10,000 or more, more preferably 15,000 or more, still more preferably 17,000 or more, and particularly preferably 20,000 or more from the viewpoint of easily obtaining excellent moldability. (A) The viscosity average molecular weight of the component is preferably 100,000 or less, more preferably 35,000 or less, still more preferably 28,000 or less, and particularly preferably, from the viewpoint of easily obtaining the excellent appearance of the surface of a molded body (sheet, etc.) Below 25000. From these viewpoints, the viscosity average molecular weight of the component (A) is preferably 10,000 to 100,000, more preferably 15,000 to 35,000, still more preferably 17,000 to 28,000, and particularly preferably 20,000 to 25,000. The viscosity average molecular weight of the component (A) can be obtained by the following procedure. First, a 0.5% by mass polycarbonate resin solution was obtained using methylene chloride as a solvent. Then, a Cannon-Fenske-type viscosity tube was used to measure the specific viscosity (η sp ). Furthermore, the limiting viscosity [η] is obtained by concentration conversion, and the viscosity average molecular weight M can be calculated according to the following SCHNELL formula. [η] = 1.23 × 10 -4 M 0.83 The content of the component (A) is preferably in the following range based on the total amount of the component (A) and the component (B). The content of the component (A) is preferably 90% by mass or more, more preferably 93% by mass or more, more preferably 95% by mass or more, and particularly preferably 97% by mass or more from the viewpoint of easily obtaining excellent moldability. (A) The content of the component is preferably 99.94% by mass or less, more preferably 99.9% by mass or less, and still more preferably 99.5% by mass or less from the viewpoint of easily obtaining an excellent appearance on the surface of a molded body (sheet, etc.). Especially preferred is 99% by mass or less. From these viewpoints, the content of the component (A) is preferably 90 to 99.94% by mass, more preferably 93 to 99.9% by mass, still more preferably 95 to 99.5% by mass, and particularly preferably 97 to 99% by mass. ((B) component: polyalkylene terephthalate resin) Examples of the poly (alkylene terephthalate) resin as (B) include polyethylene terephthalate resin and polyterephthalate Propylene diformate resin, polybutylene terephthalate resin, etc. The intrinsic viscosity of the component (B) measured in accordance with JIS K7233 is preferably in the following range. From the viewpoint of easily obtaining excellent conductivity (lower resistance value; the same applies hereinafter), the inherent viscosity is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.9 or more, and particularly preferably 1.0 or more. From the viewpoint of improving the dispersibility of the component (B) relative to other resin components (such as (A) component), the intrinsic viscosity is preferably 1.5 or less, more preferably 1.4 or less, and even more preferably 1.2 or less. From these viewpoints, the above-mentioned inherent viscosity is preferably 0.6 to 1.5, more preferably 0.7 to 1.4, still more preferably 0.9 to 1.2, and particularly preferably 1.0 to 1.2. The content of the component (B) is preferably the following range based on the total amount of the component (A) and the component (B). (B) The content of the component is preferably 0.06 mass% or more, more preferably 0.5 mass% or more, more preferably 1.0 mass% or more, and particularly preferably 1.5 mass% or more from the viewpoint of easily obtaining excellent conductivity. Excellent is 2.0% by mass or more. The content of the component (B) is preferably 10% by mass or less, more preferably 5.0% by mass or less, and further preferably 3.0% by mass or less from the viewpoint of easily obtaining the excellent appearance of the molded body. From these viewpoints, the content of the component (B) is preferably 0.06 to 10% by mass, more preferably 0.5 to 5.0% by mass, still more preferably 1.0 to 3.0% by mass, and particularly preferably 1.5 to 3.0% by mass. Excellent is 2.0 to 3.0% by mass. ((C) component: carbon material) Examples of the carbon material of (C) component include carbon black, graphite, carbon fiber, nano carbon tube, nano carbon roll, and nano carbon ball. Examples of the classification of carbon black include furnace type, acetylene type, and Ketjen type. Among these, from the viewpoint of easily obtaining excellent recyclability, furnace-type carbon black is preferred. The specific surface area of carbon black is preferably 30 m from the viewpoint of easily obtaining excellent conductivity. 2 / g or more, more preferably 40 m 2 / g or more, more preferably 50 m 2 / g or more. The specific surface area of carbon black is preferably 90 m from the viewpoint of easily obtaining excellent dispersibility of carbon black and excellent appearance of the surface of a molded body (sheet, etc.). 2 / g or less, preferably 75 m 2 / g or less, more preferably 60 m 2 / g or less. From these viewpoints, the specific surface area of carbon black is preferably 30 to 90 m 2 / g, more preferably 40 ~ 75 m 2 / g, more preferably 50 ~ 60 m 2 / g. The specific surface area of carbon black can also be 50 ~ 90 m 2 / g. The specific surface area can be measured in accordance with the test method for the basic properties of carbon black for rubber according to JIS K6217. Specific surface area is the surface area (m) of carbon black per unit mass (g) 2 ). The specific surface area can be obtained by immersing the degassed carbon black in liquid nitrogen and measuring the amount of nitrogen adsorbed on the surface of the carbon black at equilibrium. The DBP oil absorption of carbon black is preferably 100 ml / 100 g or more, more preferably 130 ml / 100 g or more, and further preferably 150 ml / 100 g or more, from the viewpoint of easily obtaining excellent conductivity. It is more than 150 ml / 100 g, more preferably 160 ml / 100 g or more, and very preferably 170 ml / 100 g. The DBP oil absorption of carbon black is preferably 300 ml / 100 g or less, more preferably 220 ml / 100, from the viewpoint of easily obtaining excellent dispersibility of carbon black and excellent appearance of the surface of a molded body (sheet, etc.). g or less, more preferably 200 ml / 100 g or less. From these viewpoints, the DBP oil absorption of carbon black is preferably 100 to 300 ml / 100 g, more preferably 130 to 300 ml / 100 g, and even more preferably 150 to 300 ml / 100 g, and particularly preferably Over 150 ml / 100 g and less than 300 ml / 100 g, very preferably 160 ~ 220 ml / 100 g, and very preferably 170 ~ 200 ml / 100 g. DBP (Di-butylphthalate) oil absorption can be measured according to the basic performance test method of JIS K6217 rubber carbon black. The amount of DBP oil absorption is related to the bonding force between carbon black particles. A larger amount of DBP oil absorption indicates a longer structure. From the viewpoint of easily obtaining excellent electrical conductivity, and from the viewpoint of easily obtaining excellent dispersibility of carbon black and excellent appearance of the surface of a molded body (sheet, etc.), the above-mentioned specific surface area of carbon black and the above-mentioned DBP oil absorption are preferred Both satisfy the above-mentioned preferred ranges. For example, the specific surface area is preferably 30 to 90 m 2 / g, and DBP oil absorption is 100 ~ 300 ml / 100 g. The content of the component (C) is 10 to 45 parts by mass based on 100 parts by mass of the total of the components (A) and (B). If the content of the (C) component is less than 10 parts by mass, the formed body cannot obtain sufficient electrical conductivity. When the content of the (C) component exceeds 45 parts by mass, the viscosity increases and the molding stability decreases. The content of the component (C) is preferably 13 parts by mass or more, and more preferably 15 parts by mass or more with respect to 100 parts by mass of the total of the components (A) and (B) from the viewpoint of easily obtaining excellent conductivity. It is more preferably 17 parts by mass or more, particularly preferably 20 parts by mass or more, and extremely preferably 21 parts by mass or more. The content of the component (C) is from the viewpoint of easy improvement in molding stability, and is preferably 40 parts by mass or less, more preferably 30 parts by mass or less with respect to 100 parts by mass of the total of the components (A) and (B) It is more preferably 27 parts by mass or less, and particularly preferably 25 parts by mass or less. From these viewpoints, the content of the (C) component is preferably 10 to 40 parts by mass, more preferably 13 to 30 parts by mass relative to the total of the (A) component and the (B) component, and more preferably It is preferably 15 to 27 parts by mass, particularly preferably 15 to 25 parts by mass, very preferably 17 to 25 parts by mass, particularly preferably 20 to 25 parts by mass, and still more preferably 21 to 25 parts by mass. ((D) component: Graft copolymer) The graft copolymer of (D) component has a structure which has a core part (core material) and the coating part which coat | covers at least one part of this core part. The component (D) may have, for example, a core-shell structure including a core layer (core portion) and a shell layer (coated portion) covering the core layer. The core portion and the covering portion may be composed of different polymers. The core portion and the covering portion may each have a plurality of layers. The covering portion may cover a part of the core portion, or may cover the entire core portion. (D) A component can be obtained by graft-polymerizing the component of a coating part, and the component of a core part by making the component of a coating part react in the presence of the component of a core part. From the viewpoint of further suppressing a decrease in conductivity during reuse, the core is preferably selected from the group consisting of acrylic rubber (a polymer having a structural unit derived from a monomer containing an acrylic fluorenyl group) and silicone rubber. It is more preferable that at least one of the composition group contains an acrylic rubber. The core component is not limited to acrylic rubber and silicone rubber, and polybutadiene and the like may be used. As the acrylic rubber, a polymer having a structural unit derived from a monomer containing an acrylic fluorenyl group as a main structural unit can be used. The content of the structural unit derived from the propylene fluorenyl group-containing monomer is preferably 50 to 100% by mass, and more preferably 70 from the viewpoint of easily obtaining excellent recyclability based on the total mass of the acrylic rubber. ~ 100% by mass. As the propylene fluorenyl group-containing monomer, an acrylate can be used. Examples of the acrylate include alkyl acrylates having 2 to 8 carbon atoms in the alkyl group, and examples thereof include ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. The acrylic rubber may have a structural unit derived from components other than acrylate. As such a component, a vinyl-based monomer which can be copolymerized with an acrylate is preferable from the viewpoint of obtaining a copolymer easily at a low price. Examples of vinyl-based monomers that can be copolymerized with acrylates include aromatic vinyl compounds such as styrene and α-methylstyrene; and alkyl methacrylates such as methyl methacrylate and ethyl methacrylate. Esters; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride and vinylidene bromide ; Vinyl monomers having glycidyl groups, such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and ethylene glycol glycidyl ether. As the acrylic rubber, a silicone-acrylic rubber (a composite polymer having a structural unit derived from a monomer containing an acrylic fluorenyl group (acrylic component) and a structural unit derived from a silicone component can be used. For example, it has a source From the structural unit of alkyl acrylate, and the polymer of polyorganosiloxane frame). As the silicone-based rubber, polyorganosiloxane can be used, and for example, a polyorganosiloxane that is a linear polymer having an organosiloxane bond unit of thousands or more can be used. The silicone rubber can be produced by any method, and a rubber obtained by an emulsion polymerization method is preferred. The polyorganosiloxane is not particularly limited, but a polyorganosiloxane having a vinyl polymerizable functional group is preferred. Polyorganosiloxane can be obtained using dimethylsiloxane. Dimethylsilane may be chain-shaped or cyclic. Examples of the dimethylsiloxane include a dimethylsiloxane ring having a 3-membered ring or more, and a dimethylsiloxane ring having a 3- to 7-member ring is preferred. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecylcyclohexasiloxane. Dimethylsilane may be used alone or in combination of two or more. The coating portion constituting the (D) component preferably contains the following polymer from the viewpoint of improving the dispersibility of the (D) component relative to other resin components ((A) component, (B) component, etc.) It is selected from structural units derived from unsaturated carboxylic acid esters, structural units derived from vinyl compounds (except unsaturated carboxylic acid esters), structural units derived from maleimide compounds, and unsaturated dicarboxylic acids At least one of a group consisting of a structural unit of a carboxylic acid and a structural unit derived from an unsaturated dicarboxylic acid anhydride. Examples of the vinyl compound include a glycidyl-containing vinyl compound, an aliphatic vinyl compound, an aromatic vinyl compound, and a cyanidated vinyl compound. A compound equivalent to a glycidyl group-containing vinyl compound and also an aliphatic vinyl compound, an aromatic vinyl compound, or a cyanide vinyl compound is classified as a glycidyl group-containing vinyl compound. From the viewpoint of improving the dispersibility of the (D) component with respect to other resin components ((A) component, (B) component, etc.), it is preferred to have a component selected from a structural unit derived from an unsaturated carboxylic acid ester, A polymer having at least one of a structural unit consisting of a glycidyl-containing vinyl compound and a structural unit derived from an unsaturated dicarboxylic acid anhydride, more preferably a structural unit derived from an unsaturated carboxylic acid ester Polymer. The compound which provides the structural unit of the polymer which comprises a coating part may be used individually by 1 type, and may use 2 or more types together. Examples of the unsaturated carboxylic acid ester include an unsaturated carboxylic acid alkyl ester and an unsaturated carboxylic acid aryl ester. As the unsaturated carboxylic acid ester, a (meth) acrylate can be used. Examples of the (meth) acrylate include alkyl (meth) acrylate, aryl (meth) acrylate, and the like. The unsaturated carboxylic acid alkyl ester is preferably a (meth) acrylic acid alkyl group from the viewpoint of improving the dispersibility of the (D) component relative to other resin components ((A) component, (B) component, and the like). ester. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) ) Third butyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Octadecyl ester, benzyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 3-hydroxypropyl ester, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, amine (meth) acrylate Ethyl ester, (propylamino) ethyl (meth) acrylate, (dimethylamino) ethyl (meth) acrylate, (ethylamino) propyl (meth) acrylate, (methyl ) (Phenylamino) ethyl acrylate, (cyclohexylamino) ethyl (meth) acrylate, and the like. As the (meth) acrylic acid alkyl ester, from the viewpoint that the dispersibility improvement effect of the (D) component relative to other resin components ((A) component, (B) component, etc.) is significant, it is preferably selected from ( At least one of the group consisting of methyl (meth) acrylate and n-butyl (meth) acrylate. As the unsaturated carboxylic acid aryl ester, from the viewpoint of improving the dispersibility of the (D) component with respect to other resin components ((A) component, (B) component, etc.), the (meth) acrylic aryl group is preferred. ester. Examples of the aryl (meth) acrylate include phenyl (meth) acrylate, dimethylphenyl (meth) acrylate, and naphthyl (meth) acrylate. Examples of the glycidyl-containing vinyl compound include glycidyl (meth) acrylate, glycidyl iconate, diglycidyl iconate, allyl glycidyl ether, and styrene-4-glycidyl. Glyceryl ether, 4-glycidyl styrene, etc. The glycidyl group-containing vinyl compound is preferably a glycidyl (meth) acrylate from the viewpoint that the effect of improving impact resistance is significant. The glycidyl group-containing vinyl compound may be used alone or in combination of two or more. Examples of the aliphatic vinyl compound include ethylene, propylene, and butadiene. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-aminostyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, and 4-cyclohexyl Styrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, halogenated styrene, 2-styrene-oxazoline, and the like. Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, and ethacrylonitrile. Examples of other vinyl compounds include acrylamide, methacrylamide, N-methacrylamide, butoxymethacrylamide, N-propylmethacrylamide, and N-vinyl Diethylamine, N-Ethyl vinylamine, allylamine, methallylamine, N-methylallylamine, 2-isopropenyloxazoline, 2-vinyloxazole Porphyrin, etc. Examples of the maleimide compounds include maleimide, maleimide, N-methyl maleimide, maleimide, and N-propylimide Butene difluorene imine, N-isopropyl cis butene difluorene imine, N-cyclohexyl cis butene difluorene imine, N-phenylcis butene difluorene imine, N- (p-bromobenzene Group) maleimide, N- (chlorophenyl) maleimide and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, and phthalic acid. As the combination of the constituent components of the core portion and the coating portion, from the viewpoint that the effect of suppressing the decrease in conductivity during reuse is more excellent, a graft copolymer having a structure of the core portion and the coating portion is preferable. The core contains an acrylic rubber (a polymer having a structural unit derived from a monomer containing an acrylic fluorenyl group), and the coating portion includes a polymer selected from a structural unit derived from an unsaturated carboxylic acid ester and Derived from at least one of the group consisting of structural units of a vinyl compound. More preferably, it is at least one selected from the group consisting of the following (DI) component and the following (D-II) component, and still more preferably the (D-II) component. (DI) component: a graft copolymer having a core-shell structure having a core portion and a covering portion, the core portion including a silicone-acrylic rubber, and the covering portion including a polymer selected from the group consisting of At least one of a group consisting of a structural unit of an unsaturated carboxylic acid ester and a structural unit derived from a vinyl compound. (D-II) component: a graft copolymer having a core-shell structure having a core portion and a coating portion, the core portion including an acrylic rubber, and the coating portion including a polymerization unit having a structural unit derived from an unsaturated carboxylic acid ester Thing. As the (DI) component, from the viewpoint that the effect of suppressing the decrease in conductivity at the time of reuse is more excellent, it is preferable to include a coating portion comprising a polymer selected from the group consisting of an alkyl group derived from an unsaturated carboxylic acid. At least one of a group consisting of a structural unit of an ester and a structural unit derived from a vinyl compound, more preferably a coating portion comprising a polymer selected from the group consisting of methyl (meth) acrylate At least one of a structural unit and a group consisting of a structural unit derived from a glycidyl-containing vinyl compound. Examples of commercially available (DI) components include Metablen S-2001, Metablen S-2006, and Metablen S-2200 manufactured by Mitsubishi Rayon Co., Ltd. As the (D-II) component, from the viewpoint that the effect of suppressing the decrease in conductivity at the time of reuse is more excellent, it is preferable to include a coating portion containing a polymer having an unsaturated carboxylic acid alkyl group The structural unit of the ester is more preferably provided with a coating portion comprising a polymer having a structural unit derived from methyl (meth) acrylate. Examples of commercially available (D-II) ingredients include Paraloid BPM-500 and Paraloid BPM-515 manufactured by Rohm and Haas Japan Co., Ltd .; Metablen W-450A and Metablen W-600A manufactured by Mitsubishi Rayon Co., Ltd. . The content of the component (D) is 0.5 to 35 parts by mass based on 100 parts by mass of the total of the components (A) and (B). If the content of the (D) component is less than 0.5 parts by mass, sufficient recyclability cannot be obtained. The content of the (D) component is more preferably 1 part by mass or more relative to 100 parts by mass of the total of the components (A) and (B) from the viewpoint that the effect of suppressing the decrease in conductivity during reuse is more excellent. It is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, particularly preferably 7 parts by mass or more, very preferably 8 parts by mass or more, and even more preferably 10 parts by mass or more. When the content of the (D) component exceeds 35 parts by mass, sufficient recyclability cannot be obtained, and the appearance of the molded article is deteriorated. The content of the component (D) is more excellent in the effect of suppressing the decrease in conductivity at the time of reuse, and a more excellent appearance of the molded body, relative to 100 mass of the total of the components (A) and (B). It is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 18 parts by mass or less, particularly preferably 15 parts by mass or less, and extremely preferably 12 parts by mass or less. From these viewpoints, the content of the (D) component is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total of the components (A) and (B). It is preferably 2 to 20 parts by mass, particularly preferably 5 to 18 parts by mass, very preferably 7 to 15 parts by mass, particularly preferably 8 to 12 parts by mass, and even more preferably 10 to 12 parts by mass. (Other components) The polycarbonate resin composition of the present embodiment may contain a known resin (polyamidamine resin, polyimide resin, polystyrene resin, ABS (Acrylonitrile-Butadiene-Styrene, acrylic) Nitrile-butadiene-styrene) resin, polyolefin resin (polyethylene resin, polypropylene resin, etc.), phenol resin, epoxy resin, etc.). The polycarbonate resin composition of the present embodiment may contain known additives other than the above-mentioned components as necessary. Examples of such additives include antioxidants (phosphorus-based antioxidants, phenol-based antioxidants, etc.), release agents (glycerin fatty acid esters, etc.), lubricants (paraffin wax, n-butyl stearate, synthetic beeswax, Natural beeswax, monoglycerides, montanic acid wax, polyethylene wax, pentaerythritol tetrastearate, etc.), colorants (titanium oxide, dyes, pigments, etc.), fillers (calcium carbonate, clay, silica, glass Fiber, glass ball, glass fragments, talc, mica, various whiskers, etc.), fluidity improver, spreading agent (epoxidized soybean oil, liquid paraffin, etc.), flame retardants (bromine compounds, phosphorus compounds, Organometallic salt compounds, silicone compounds, etc.). (Production method of resin composition) The polycarbonate resin composition of the present embodiment can be obtained by mixing constituent components. The method of mixing the constituent components of the polycarbonate resin composition of the present embodiment is not particularly limited, and examples thereof include mixing using an arbitrary mixer (roller mixer, belt mixer, high-speed mixer, etc.) and then using an extruder. A method of melting and kneading out of the machine. <Molded Article and Manufacturing Method thereof> The molded article (molded article) of this embodiment includes the polycarbonate resin composition of this embodiment. The molded body of this embodiment may be a film shape or a flat plate shape. Examples of the molded body of this embodiment include a film, a tape, and a sheet. Examples of the molded article of the present embodiment include a container (for example, a container for transporting or storing electronic parts) that houses electronic parts. Examples of the molded body of the present embodiment include a carrier tape. The carrier tape of this embodiment contains the polycarbonate resin composition of this embodiment. The carrier tape of this embodiment may be film-shaped or flat. The carrier tape of this embodiment may also include a storage portion capable of accommodating an object (electronic parts, etc.), for example, a plurality of bag-like portions (recesses for accommodating the object) formed at intervals in the length direction of the belt. . Examples of the film include a molded body having a width (film width) of 100 to 1500 mm and a thickness of 0.05 to 0.5 mm. Examples of the belt (bearing belt) include a molded body having a width (band width) of 3 to 100 mm (preferably 10 to 50 mm) and a thickness of 0.05 to 0.5 mm. Examples of the sheet include a molded body having a width (sheet width) of 100 to 1500 mm and a thickness of 0.7 to 10 mm. The method for producing a molded body according to this embodiment includes a molding step of forming a polycarbonate resin composition according to this embodiment to obtain a molded body. The method for producing a molded body of this embodiment may include a plurality of molding steps. For example, it may further include a step of melting a molded body containing the polycarbonate resin composition of this embodiment to obtain a resin composition, and combining the resin with the resin. A step of forming a product to obtain a molded body. The method for forming the polycarbonate resin composition of the present embodiment is not particularly limited, and known extrusion molding methods (T-die molding method, calender molding method, etc.), injection molding methods, injection-compression molding methods, and the like can be used. . The manufacturing method of the carrier tape of this embodiment has the shaping | molding process which shape | molds the polycarbonate resin composition of this embodiment, and obtains a carrier tape. The manufacturing method of the carrier tape of this embodiment may further include a plurality of forming steps. For example, it may further include a step of melting the polycarbonate resin composition of this embodiment to obtain a resin composition, and forming the resin composition into Steps to obtain a carrier tape. Examples of the forming method for providing a recessed portion called a bag-shaped portion to the carrier tape include a pressure forming method, a pressure forming method, and a vacuum rotation forming method. The embodiments described above as examples of the technology of the present invention have been described. Provide detailed instructions for this. Therefore, the constituent elements described in the detailed description include not only constituent elements necessary to solve the problem, but also constituent elements used to illustrate the above-mentioned technology but not necessary to solve the problem. Therefore, the non-essential constituents should not be recorded in the detailed description, but the non-essential constituents should be immediately recognized as necessary. In addition, the above-mentioned embodiment is exemplified by those skilled in the present invention, and thus various changes, substitutions, additions, omissions, etc. can be made within the scope of the patent application or its equivalent scope. [Examples] Hereinafter, the present invention will be described by examples, but the present invention is not limited to these examples. <1. Preparation of granules> Prepare the blending ingredients with the contents shown in Tables 1 to 3. Then, the above-mentioned blending ingredients were melt-kneaded at a cylinder temperature of 280 ° C. using a twin-screw extruder (manufactured by Kobe Steel Co., Ltd., KTX-37) with a diameter of 37 mm to obtain various pellets. The details of the ingredients used are shown below. [Polycarbonate resin] A-1: Polycarbonate resin synthesized from bisphenol A and carbochloride, manufactured by Sumika Styron Polycarbonate Co., Ltd., Calibre 200-13 (viscosity average molecular weight: 21000) [polyterephthalic acid Alkanediol Ester Resin] B-1: Polybutylene terephthalate resin, manufactured by Polyplastics Co., Ltd., Duranex 600FP (inherent viscosity: 1.0) [Carbon material] C-1: Furnace carbon black, manufactured by Cabot , Vulcan XC-305 (specific surface area: 70 m 2 / g, DBP oil absorption: 130 ml / 100 g) C-2: furnace carbon black, manufactured by Mitsubishi Chemical Corporation, # 3050B (specific surface area: 50 m 2 / g, DBP oil absorption: 175 ml / 100 g) [Graft copolymer] D-1: Core-shell type graft copolymer (core layer: silicone-acrylic rubber, shell layer: polymerization with the following structural units The structural unit is derived from a polymer having a structural unit derived from an unsaturated carboxylic acid alkyl ester; (DI) component), manufactured by Mitsubishi Rayon Co., Ltd., Metablen S-2001 D-2: core-shell type connection Branch copolymer (core layer: acrylic rubber, shell layer: polymer having a structural unit derived from an unsaturated carboxylic acid alkyl ester; (D-II) component), Mitsubishi Rayon Co., Ltd., Metablen W-450A D-3: Core-shell type graft copolymer (core layer: polybutadiene, shell layer: polymer having a structural unit derived from an alkyl (meth) acrylate), manufactured by Rohm and Haas Japan Co., Ltd. , Paraloid EXL2603 <2. Manufacturing of flat plates> The granules of the above item 1 were dried at 120 ° C for 4 hours using a dryer. Next, a small injection molding machine (J100EII-P, manufactured by Japan Steel Manufacturing Corporation (JSW)) was used to obtain a flat plate having a size of 50 mm × 80 mm × thickness 2 mm at a molding temperature of 300 ° C and a mold temperature of 90 ° C. . <3. Evaluation of electrical conductivity> Five plates of the above item 2 were prepared (samples with zero repeated granulation times). Then, the surface specific resistance value (Ω / sq.) Near the center of the surface of the flat plate was measured by a conductivity measuring device (Loresta-GP MCP-T600, manufactured by Mitsubishi Chemical Corporation), and the average value of 5 sheets was determined as conductivity Value. <4. Evaluation of reusability> The pellets of item 1 were used, and repeated using a small uniaxial extruder (manufactured by Tanabe Plastics Machinery Co., Ltd., VS-40) at an extrusion temperature of 300 ° C and a screw revolution of 120 rpm. Granulation was performed 5 times. Collect the granules after repeated 5 times of granulation, and obtain a flat plate by the same method as the method of item 2 above. The conductivity of the flat plate (the sample after 5 times of granulation) was obtained by the same method as the item 3 above. As a judgment of recyclability, the surface inherent resistance value of the flat plate when the granulation was repeated 5 times (the number of repeated granulation was 5 times) did not reach 1 × 10. 10 (Ω / sq.) Is evaluated as "A" (good recyclability), and the surface specific resistance value is 1 × 10 10 (Ω / sq.) Or more (recorded as "≧ 1 × 10 10 ”) Was evaluated as“ B ”(poor reusability). <5. Evaluation of flat plate appearance> The surface of the flat plate when repeated granulation was not performed (the number of repeated granulation was zero) was visually observed. A case where a uniform surface with no unevenness was confirmed was evaluated as "A", and a case where a plate surface was confirmed with unevenness was evaluated as "B". The evaluation results are shown in Tables 1-3. [Table 1]
Figure TW201800475AD00001
[Table 2]
Figure TW201800475AD00002
[table 3]
Figure TW201800475AD00003
As shown in Tables 1 and 2, in the examples, all of the electrical conductivity, recyclability, and appearance of the flat plate were good. On the other hand, as shown in Table 3, in the comparative example, the reusability was not satisfied in each case. Comparative Example 1 is a case where the content of the carbon material is small, and the conductivity and recyclability are poor. Comparative Example 2 is a case where the content of the carbon material is large, the viscosity is too high, and forming itself is difficult. Comparative Example 3 is a case where the content of the graft copolymer is small, and the recyclability is poor. Comparative Example 4 is a case where the content of the graft copolymer is large, and the recyclability and the appearance of the flat plate are poor. Comparative Example 5 is a case where the graft copolymer is not used, and the conductivity, recyclability, and appearance of the flat plate are poor. Comparative Example 6 is a case where the content of the carbon material is small, and the conductivity, recyclability, and appearance of the flat plate are poor. [Industrial Applicability] According to the present invention, it is possible to suppress a decrease in conductivity even in the case of repeated molding. For example, according to the present invention, even if the molding is repeatedly performed by melt extrusion for the purpose of reuse or the like, the reduction in conductivity can be suppressed to a very low level. Furthermore, according to the present invention, not only the excellent appearance of the molded body can be achieved, but also the reduction in conductivity can be suppressed even in the case of overmolding. Therefore, the industrial utilization value of the present invention is extremely high.

no

Claims (4)

一種聚碳酸酯樹脂組合物,其含有聚碳酸酯樹脂、聚對苯二甲酸烷二醇酯樹脂、碳材料及接枝共聚物, 上述接枝共聚物具有具備芯部與被覆該芯部之至少一部分之被覆部的結構, 上述碳材料之含量相對於上述聚碳酸酯樹脂及上述聚對苯二甲酸烷二醇酯樹脂之合計100質量份為10~45質量份, 上述接枝共聚物相對於上述聚碳酸酯樹脂及上述聚對苯二甲酸烷二醇酯樹脂之合計100質量份為0.5~35質量份。A polycarbonate resin composition comprising a polycarbonate resin, a polyalkylene terephthalate resin, a carbon material, and a graft copolymer. The graft copolymer has at least a core portion and at least a core portion covering the core portion. In the structure of a part of the coating portion, the content of the carbon material is 10 to 45 parts by mass based on 100 parts by mass of the polycarbonate resin and the polyalkylene terephthalate resin in total, and the graft copolymer is contained in A total of 100 parts by mass of the polycarbonate resin and the polyalkylene terephthalate resin is 0.5 to 35 parts by mass. 如請求項1之聚碳酸酯樹脂組合物,其中於上述接枝共聚物中,上述芯部包含具有源自含丙烯醯基之單體之結構單元之聚合物,上述被覆部包含具有源自不飽和羧酸酯之結構單元之聚合物。The polycarbonate resin composition according to claim 1, wherein in the graft copolymer, the core includes a polymer having a structural unit derived from a monomer containing a propylene fluorene group, and the coating portion includes a polymer having Polymers of structural units of saturated carboxylic acid esters. 一種成形體,其包含如請求項1或2之聚碳酸酯樹脂組合物。A formed article comprising the polycarbonate resin composition as claimed in claim 1 or 2. 一種承載帶,其包含如請求項1或2之聚碳酸酯樹脂組合物。A carrier tape comprising a polycarbonate resin composition as claimed in claim 1 or 2.
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