201114579 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種收納電子機器等之殼體，更詳細而 言’係關於一種將包含具有特定結構之聚碳酸酯-聚有機 石夕氧烷共聚物之聚碳酸酯樹脂組合物成形所得的薄壁且抗 ' 跌落衝擊性、流動性及耐熱性優異之攜帶型電子機器殼 體。 【先前技術】 攜帶型個人電腦、個人數位助理（PDA，Pers〇nal以以⑷BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a housing for housing an electronic device or the like, and more particularly to a polycarbonate-polyorgano-oxygen alkane having a specific structure. A portable electronic device case having a thin wall and excellent in drop impact resistance, fluidity, and heat resistance obtained by molding a polycarbonate resin composition of a copolymer. [Prior Art] Portable personal computer, personal digital assistant (PDA, Pers〇nal to (4)
Assistant)、行動電話、攜帶播放器、電池外殼等攜帶型電 子機器之殼體多使用樹脂材料進行製造。 假設攜帶中不慎跌落電子機器之情形，為保護内部之電 子機器，必需保證殼體之耐衝擊性，以避免殼體產生龜 或破裂。 < 然而，由於樹脂材料之衝擊強度及熱變形溫度等熱特性 劣於金屬材料’故而進行了如下提高機械特性及熱特性等 之嘗試：增加殼體等成形品之厚度，或使用將樹脂 此摻合而成之合金材料，或於塑膠材料中填充無機填料< 有機填料而使之成為纖維強化塑膠。 ’3 工而言係非 之領域，_ 通常，殼體之高強度化對塑膠材料之成形加 常困難之技術’尤其於量產性優異之射出成形 直迫切要求樹脂材料之改良。 因而’選定樹脂材料時考慮到耐衝擊 強度大之材料。 性而尤其期望 衝擊 149464.doc 201114579 進而’於射出成形中，成形品内容易產生由於分子 應變或冷卻應變所引起之殘留應力，因此於使用熱變形溫 度低之材料之情形時’於溫度高之使用環境下殘留應力得 到釋放而有殼體變形之危險性…期望熱變形溫度高之 材料。 作為订動電②殼體用之樹脂組合物，已知有為提高衝擊 強度而於聚碳酸酿中添加有橡膠成分者（例如，參照專利 文獻1)。 头具有一甲基矽氧烷單元之重複數η為100〜400， 具體而言η為150〜350之聚二甲基石夕氧烷(簡， Pdydimethylsil0xane)部分之聚碳酸酯_聚二甲基矽氧烷共 聚物與玻璃纖維混合時，耐衝擊性之下降較小，且於重複 數η為1〇〇以下之情形時難以獲得該效果，但並無關於消除 玻璃纖維之影響時對耐衝擊性造成影響之pDMs結構或重 複數之揭示，且實施例中亦未見該重複數對衝擊強度造成 之影響（例如，參照專利文獻2)。 又，已公知二甲基矽氧烷單元之重複數n為4〇〜6〇，真體 而言η為49之聚碳酸醋_聚二曱基矽氧烷共聚物表現出良好 的低溫衝擊特性（例如，參照專利文獻3)。 進而，已知：獲得具有二甲基矽氧烷單元之重複數η為 5〇之PDMS部分的透明聚碳酸醋_聚二甲基矽氧烷共聚物之 方法（例如，參照專利文獻4);具有二甲基矽氧烷單元之重 ^數η為〇〜20之PDMS部分的透明且具有阻燃性之聚碳酸 西曰聚一甲基矽氧烷共聚物（例如，參照專利文獻5);及包 I49464.doc 201114579 含具有矽氧烧單元之重複數η為2〜500，具體而言η為30或 150之PDMS部分的聚碳酸酯-聚二甲基矽氧烷共聚物之阻 燃性樹脂組合物（例如，參照專利文獻6)。 然而’可薄壁化且抗跌落衝擊性、流動性及耐熱性優異 之攜帶型電子機器殼體用之聚碳酸酯樹脂組合物尚未為人 所知。 先前技術文獻 專利文獻 專利文獻1:曰本專利特開2006-176612號公報 專利文獻2:日本專利第266231〇號 專利文獻3:曰本專利特表2〇〇6_523243號公報 專利文獻4:曰本專利特表2〇〇5_535761號公報 專利文獻5:日本專利特表2〇〇5_519177號公報 專利文獻6:曰本專利特開平8_8162〇號公報 【發明内容】 發明所欲解決之問題 本發明係為解決上述先前技術之問題而完成者，其目的 在於提i、種薄壁且抗跌落衝擊性、流動性及耐熱性優異 之攜帶型1子機器殼冑，該攜帶$電子機器殼體係將包含 具有特定結構之聚碳酸酯_聚有機矽氧烷共聚物之聚碳酸 酯樹脂組合物成形所得。 解決問題之技術手段 本發月者為達成上述目的而反覆進行銳意研究，結果發 現藉由將包含具有特定結構之聚碳酸醋.聚有機石夕氧烧共 149464.doc 201114579 聚物之聚碳酸酯樹脂組合物成形，可達成該目的。 本發明係基於上述知識見解所完成者。 即，本發明提供： ι_一種攜帶型電子機器殼體，其特徵在於：其係將聚碳 酸酯樹脂組合物成形所得者，該聚碳酸酯樹脂組合物包含 聚碳酸酯-聚有機石夕氧烧共聚物0〜1〇〇質量份以及（A_ 1)以外之芳香族聚碳酸酯（A-2)0〜90質量份，使合計量成為 1〇〇質量份；上述聚碳酸酯_聚有機矽氧烷共聚物（Α_υ之黏 度平均分子量為13000〜26000 ’且包含通式⑴所示之結構 單元及通式（II)所示之結構單元，其中包含通式（π)所示之 結構單元之聚有機矽氧烧嵌段部分之含量為丨〜3 〇質量％， 且邊通式（II)之結構單元之平均重複單元數為川〜丨〇〇〇 ; [化1]The housing of a portable electronic device such as an assistant, a mobile phone, a portable player, and a battery case is often manufactured using a resin material. Assuming that the electronic device is accidentally dropped during carrying, in order to protect the internal electronic machine, it is necessary to ensure the impact resistance of the casing to avoid the turtle or crack in the casing. < However, since the thermal properties such as impact strength and heat distortion temperature of the resin material are inferior to those of the metal material, attempts have been made to improve mechanical properties and thermal properties as follows: increase the thickness of a molded article such as a casing, or use a resin. The alloy material is blended, or the plastic material is filled with an inorganic filler < an organic filler to make it a fiber reinforced plastic. In the case of '3', it is a problem that the strength of the casing is often difficult to form a plastic material. In particular, injection molding with excellent mass productivity is urgently required to improve the resin material. Therefore, a material having a large impact strength is considered in selecting a resin material. In particular, it is expected that the impact is 149464.doc 201114579. Further, in the injection molding, residual stress due to molecular strain or cooling strain is likely to occur in the molded article, so when the material having a low heat distortion temperature is used, the temperature is high. The residual stress is released in the use environment and there is a risk of deformation of the casing... a material having a high heat distortion temperature is desired. As a resin composition for the electric 2 housing, a rubber component is added to the polycarbonate for the purpose of improving the impact strength (for example, see Patent Document 1). a polycarbonate having a repeating number η of a monomethyl oxane unit of 100 to 400, specifically a polydimethyl oxa oxane (PTY dimethyl oxalate) having a η of 150 to 350 _ polydimethyl When the siloxane coupling is mixed with the glass fiber, the impact resistance is small, and it is difficult to obtain the effect when the number of repetitions η is 1 Torr or less, but there is no impact resistance when the influence of the glass fiber is eliminated. The structure of the pDMs or the number of repetitions of the influence is revealed, and the influence of the number of repetitions on the impact strength is not seen in the examples (for example, refer to Patent Document 2). Further, it is known that the number of repetitions n of the dimethyloxane unit is 4 〇 6 6 〇, and the polycarbonate _ polydidecyl decane copolymer having a η of 49 exhibits good low-temperature impact characteristics. (For example, refer to Patent Document 3). Further, a method of obtaining a transparent polycarbonate-polydimethyloxane copolymer having a PDMS moiety having a repeating number η of dimethyl oxoxane unit of 5 Å is known (for example, refer to Patent Document 4); A transparent and flame-retardant poly(p-indene polymethyl methoxide) copolymer having a weight fraction η of dimethyl methoxy oxane unit of PD 20 is (for example, refer to Patent Document 5); And package I49464.doc 201114579 flame retardancy of a polycarbonate-polydimethylsiloxane derivative having a PDMS moiety having a repeating number η of from 2 to 500, specifically η of 30 or 150 Resin composition (for example, refer to Patent Document 6). However, a polycarbonate resin composition for a portable electronic device casing which is thinner and which is excellent in drop impact resistance, fluidity and heat resistance is not known. PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1: Patent Publication No. 2006-176612 Patent Document 2: Japanese Patent No. 266231 No. Patent Document 3: Japanese Patent Laid-Open Publication No. Hei. No. 6-523243 Patent Document 4: transcript Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Hei. No. Hei. A person who solves the problems of the prior art mentioned above, and whose object is to provide a portable 1 sub-machine casing that is thin and resistant to drop impact, fluidity, and heat resistance, and the portable electronic device housing system will have A polycarbonate resin composition of a polycarbonate-polyorganosiloxane coupling of a specific structure is obtained by molding. Technical means for solving the problem The present inventors have repeatedly conducted intensive research to achieve the above-mentioned purpose, and as a result, it has been found that a polycarbonate comprising a polycarbonate having a specific structure, a polyorganism, and a 149464.doc 201114579 polymer. This can be achieved by molding the resin composition. The present invention has been completed based on the above knowledge findings. That is, the present invention provides: ι_ a portable electronic device casing characterized in that it is obtained by molding a polycarbonate resin composition comprising polycarbonate-polyorgano-oxygen 0 to 1 part by mass of the copolymer and 0 to 90 parts by mass of the aromatic polycarbonate (A-2) other than (A-1), the total amount is 1 part by mass; the above polycarbonate_polyorganic a siloxane copolymer having a viscosity average molecular weight of 13,000 to 26,000 Å and comprising a structural unit represented by the formula (1) and a structural unit represented by the formula (II), wherein the structural unit represented by the formula (π) is contained The content of the polyorgano-oxygen-burning block portion is 丨~3 〇 mass%, and the average repeating unit number of the structural unit of the formula (II) is chuan~丨〇〇〇; [Chemical 1]
[式中，R1及R2分別獨立表示碳數丨〜6之烷基或烷氧基，χ 表示單鍵、碳數1〜8之伸烷基、碳數2〜8之亞烷基、碳數 5〜15之伸環烧基、碳數5〜15之亞環烷基、_s•…s〇_、_s〇2_ 、-Ο-或-CO-，R3及R4分別獨立表示氫原子、鹵素原子或 可具有取代基之烷基或芳基，3及13分別獨立表示〇〜4之整 數]; 149464.doc 201114579 其係藉由射出成形 2.如上述1之攜帶型電子機器殼體 而成形； 3.如上述2之攜帶型電子機器殼體，該攜帶型電 殼體之厚度為0.5〜1.5 mm; 益 4·如上述2或3之攜帶型電子機器殼體，其中該攜帶型電 子機器殼體之攜帶型電子機器為行動電話。 發明之效果 根據本發明，藉由將包含具有特定結構之聚碳酸醋-聚 有機石夕氧烧共聚物之聚碳酸§旨樹脂組合物成形，可不犧牲 :碳酸醋所具有之流動性，而大幅度提高衝擊強度，從而 提供薄壁抗跌落衝擊性、流動性及耐熱性優異之攜帶型 電子機器框體。 【實施方式】 本發明之搞帶型電子機器殼體之特徵在於：其係聚碳酸 酉曰樹脂組合物成形所得者，該聚碳酸酯樹脂組合物包含聚 碳酸酯-聚有機矽氧烷共聚物（A_1)1〇〜1〇〇f量份以及（A」） ，外之芳香族聚碳酸酯（A_2)〇〜90質量份，使合計量成為 100質量份；上述聚碳酸酯_聚有機矽氧烷共聚物（A」）之黏 度平均分子量為13000〜26000，且包含通式⑴所示之結構 單元及通式（II)所示之結構單元，其中包含通式（11)所示之 結構單元之聚有機矽氧烷嵌段部分之含量為丨〜3 〇質量％， 且及通式（II)之結構單元之平均重複單元數為〜1 〇〇〇。 149464.doc 201114579 [化2]Wherein R1 and R2 each independently represent an alkyl group or alkoxy group having a carbon number of 丨6, and χ represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylene group having 2 to 8 carbon atoms, and a carbon number; 5 to 15 of a cycloalkyl group, a cycloalkylene group having a carbon number of 5 to 15, _s•...s〇_, _s〇2_, -Ο- or -CO-, and R3 and R4 each independently represent a hydrogen atom or a halogen atom. Or an alkyl or aryl group which may have a substituent, and 3 and 13 each independently represent an integer of 〇~4; 149464.doc 201114579 which is formed by injection molding 2. The portable electronic device casing of the above 1; 3. The portable electronic device casing of the above 2, wherein the portable electrical casing has a thickness of 0.5 to 1.5 mm; and the portable electronic casing of the portable electronic casing of the above 2 or 3, wherein the portable electronic casing The portable electronic device is a mobile phone. EFFECTS OF THE INVENTION According to the present invention, by forming a polycarbonate composition containing a polycarbonate-polyorgano oxysulfide copolymer having a specific structure, it is possible to eliminate the liquidity of carbonated vinegar without sacrificing The range is increased in impact strength, thereby providing a portable electronic machine frame having excellent thin wall drop resistance, fluidity, and heat resistance. [Embodiment] The tape-type electronic device casing of the present invention is characterized in that it is obtained by molding a polycarbonate resin composition comprising a polycarbonate-polyorganosiloxane copolymer. (A_1) 1〇~1〇〇f parts and (A"), the outer aromatic polycarbonate (A_2) 〇~90 parts by mass, the total amount is 100 parts by mass; the above polycarbonate _ polyorgano The oxyalkylene copolymer (A") has a viscosity average molecular weight of 13,000 to 26,000, and comprises a structural unit represented by the general formula (1) and a structural unit represented by the general formula (II), wherein the structure represented by the general formula (11) is contained. The content of the polyorganosiloxane block portion of the unit is 丨3 to 3% by mass, and the average repeating unit number of the structural unit of the formula (II) is 〜1 〇〇〇. 149464.doc 201114579 [Chemical 2]
[式中’ R1及R2分別獨立表示碳數1〜6之烷基或烷氧基，χ 表示單鍵、碳數1〜8之伸烧基、碳數2〜8之亞烧基、碳數 5〜〗5之伸環烷基、碳數5〜15之亞環烷基、-s-、-SO-、 •S〇2_、-0-或-CO-，R3及R4分別獨立表示氫原子、鹵素原 子或可具有取代基之烷基或芳基，3及b分別獨立表示〇〜4 之整數] 包含通式（II)所示之結構單元之聚有機矽氧烷嵌段部分 之含置較佳為1〜20質量％，若未達丨〇質量％，則抗跌落衝 擊強度之提高效果不充分，若超過3〇質量％，則耐熱性之 下降變大。 ^ 又，通式（II)之結構單元之平均重複單元數較佳為 ?:700 ’更佳為8〇〜5〇〇 ’若未達7〇，則抗跌落衝擊強度之 提问效果不充分’若超過1〇〇〇 ’則製造聚二甲基矽氧烷_ 聚碳酸酯共聚物(Α·υ時之操作性變困難，經濟性差。 通节為表現出抗跌落衝擊性，聚碳酸酯·聚有 ==黏度平均分子量越大越有效，但若黏 平勻刀子I夂大，則難以 成形為如攜帶型電子機器殼體 涛璧構件。 149464.doc 201114579 藉由提高成形溫度，可降低樹脂組合物之黏度，但於此 情形時’除成形週期變長、經濟性差以外，若過度提高溫 度，則由於樹脂組合物之熱劣化而降低生產穩定性。 因此，聚碳酸酯-聚有機矽氧烷共聚物（A — 丨）之黏度平均 分子量較佳為14000〜23000 ’更佳為15000〜22000。 黏度平均分子量若未達13000，則成形品之強度不充 分，若超過26000，則共聚物之黏度變大，因此除製造時 之生產性下降以外，薄壁之成形亦變得困難。 本發明之聚峡酸酯樹脂組合物係以合計量成為i 〇〇質量 份之方式包含成分（A-1)與成分（A_2)的組合物，聚碳酸酯_ 聚有機矽氧烷共聚物（A-1)之含量較佳為My 〇〇質量份， 更佳為60〜95質量份’（Α_ι)以外之芳香族聚碳酸酯（八义之 3 i較佳為50〜0質量份，更佳為4〇〜5質量份。 聚碳酸醋_聚有機矽氧烷共聚物（Α-i)之含量若未達10質 篁伤，則製造成分(A-ι)時必需使包含通式(π)所示之結構 單元之聚有機石夕氧院嵌段部分之含量為3〇質4%以上於 此情形時，製造成分⑹）時之聚合步驟中反應之均句性 降低，且聚合物之清洗步驟中聚合物與清洗水之分離性牵 化二因此成分⑹)之生產性大幅度降低。 ^ 右（A-1)以外之方香族聚碳酸酿之含量超過質量 份，則成分（A-D之含量未達1〇質量份就上述原因而言 欠佳。 以下 明。 就聚碳酸酯-聚有機 矽氧烷共聚物（A-1)進行說 149464.doc 201114579 本發明中所㈣之聚碳㈣.聚有機魏烧共聚物之點 度平均分子量為13_〜26刚，其係使通式⑴所示之二元 酚及通式⑺所示之聚有機矽氧烷與二氣化羰、碳酸醋、或 氣:酸S旨進行共聚合而得者，其中包含通式（„)所示之結 構單元之聚有機矽氧烷嵌段部分之比例為卜3〇質量。/。， [化3][wherein R1 and R2 each independently represent an alkyl group or alkoxy group having 1 to 6 carbon atoms, and χ represents a single bond, a stretching group having 1 to 8 carbon atoms, a alkylene group having 2 to 8 carbon atoms, and a carbon number. 5~〗 5 of the cycloalkylene group, a cycloalkylene group having a carbon number of 5 to 15, -s-, -SO-, ?S〇2_, -0- or -CO-, and R3 and R4 each independently represent a hydrogen atom a halogen atom or an alkyl group or an aryl group which may have a substituent, and 3 and b each independently represent an integer of 〇4 to 4; and a polyorganosiloxane mixture containing a structural unit represented by the general formula (II) When the amount is less than 5% by mass, the effect of improving the drop impact strength is insufficient. When the amount is more than 3% by mass, the decrease in heat resistance is large. ^ Further, the average repeating unit number of the structural unit of the general formula (II) is preferably ?: 700 'more preferably 8 〇 ~ 5 〇〇 'If it is less than 7 〇, the effect of the anti-drop impact strength is insufficient. When it exceeds 1 〇〇〇', a polydimethyl methoxy oxane-polycarbonate copolymer is produced (the operability of Α·υ becomes difficult, and the economy is poor. The pass is a drop impact resistance, polycarbonate· It is more effective to accumulate == viscosity average molecular weight, but if the viscosity of the knife is large, it is difficult to form into a portable electronic device shell. 149464.doc 201114579 Reducing the resin composition by increasing the forming temperature The viscosity of the material, but in this case, 'when the molding cycle becomes long and the economy is poor, if the temperature is excessively increased, the production stability is lowered due to thermal deterioration of the resin composition. Therefore, polycarbonate-polyorganosiloxane The viscosity average molecular weight of the copolymer (A - 丨) is preferably from 14,000 to 23,000 ', more preferably from 15,000 to 22,000. If the viscosity average molecular weight is less than 13,000, the strength of the molded article is insufficient, and if it exceeds 26,000, the viscosity of the copolymer is Become bigger, In addition to the decrease in the productivity at the time of the production, the formation of the thin wall is also difficult. The poly-gorcoate resin composition of the present invention contains the component (A-1) and the component in such a manner that the total amount is i 〇〇 by mass. The composition of (A_2), the content of the polycarbonate_polyorganosiloxane copolymer (A-1) is preferably My 〇〇 by mass, more preferably 60 to 95 parts by mass of aromatics other than Α_ι The polycarbonate (the yoke 3 i is preferably 50 to 0 parts by mass, more preferably 4 〇 to 5 parts by mass. The content of the polycarbonate _ polyorganosiloxane copolymer (Α-i) is less than 10 In the case of a quality flaw, when the component (A-ι) is produced, it is necessary to make the content of the polyorganismite block portion containing the structural unit represented by the general formula (π) 3 enamel 4% or more. When the component (6) is produced, the uniformity of the reaction in the polymerization step is lowered, and the separation between the polymer and the washing water in the washing step of the polymer is reduced, so that the productivity of the component (6)) is greatly lowered. ^ When the content of the aromatic polycarbonate other than the right (A-1) exceeds the mass part, the content of the component (the content of AD is less than 1 part by mass is not good for the above reasons. The following is clear. The organooxane copolymer (A-1) is said to be 149464.doc 201114579. The polycarbene (IV) of the invention (IV) has a dot average molecular weight of 13 to 26, which is obtained by the formula (1). The dihydric phenol shown and the polyorganosiloxane having the formula (7) and the di-vaporized carbonyl, carbonated vinegar, or gas: acid S are obtained by copolymerization, and the formula („) is included. The proportion of the polyorganosiloxane block portion of the structural unit is the mass of the material. /, [Chemical 3]
[通式（1)中，X、R1〜R2及與通式⑴相同，〇為有機矽 氧烷結構單元之平均重複單元數，表示7〇〜1〇〇〇之整數。 通式⑺中，R3、V、^及以分別獨立表示氫原子或可具有 取代基之烷基或芳基，γ表示鹵素、_R7〇H、R7C〇〇h、 -R7NH2、-COOH或-SH，R7表示直鏈、支鏈或環狀亞烷 基、經芳基取代之亞烷基、環上可具有烷氧基之經芳基取 代之伸烧基、芳基，m表示〇或1]。 又’本發明之聚碳酸酯樹脂組合物中，聚碳酸酯-聚有 機矽氧烷共聚物（A-1)之原料中所使用之通式（1)所示之二 元酚有多種，尤佳為2,2-雙（4-羥基苯基）丙烷[通稱：雙酚 A] 〇 作為雙酚A以外之雙酚，例如可列舉：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）丁 炫、2,2-雙（4-羥基苯基）辛烷、雙（4-羥基苯基）苯基甲烷、 149464.doc •10- 201114579 雙（4-經基苯基）二苯甲烧、2,2_雙（4_羥基_3甲基苯基）丙 炫、雙（4-經基苯基）萘基甲⑥雙…經基_第三丁基苯 基）丙烧2,2_雙（4_羥基_3_溴笨基）丙炫、2,2-雙（4-羥基_ 3,5-四甲基苯基)丙烷、2,2_雙⑷羥基_3_氯笨基)丙烷、以 雙(4-羥基-3,5·二氯苯基)丙烷、2,雙(4_羥基_3,5_二溴苯 基）丙烧等雙（經基芳基）烧烴類，^^雙。-羥基苯基）環戊 炫、U·雙（心經基苯基）環己烷、川,4經基苯基）_ 3’5’5-三甲基環己院、2,2_雙⑷經基苯基）降福院、以_雙 (4-羥基苯基）環十二烷等雙（羥基芳基）環烷烴類，4,4，_二羥 基苯ϋ 4,4 輕基_3,3·-二甲基苯鍵等二經基芳基驗類， 4,4’-二羥基二苯硫醚、4,二羥基_3,3，_二甲基^苯硫醚等 二羥基二芳基硫醚類，4,4，·二羥基二苯亞砜、4,4、二羥基· 3’3’-二甲基二苯亞砜等二羥基二芳基亞颯類，ί二羥基 一苯砜4,4-_·基_3,3i_二曱基二苯硬等二經基二芳基硬 類’ M-一羥基二笨等二羥基二苯類’ 99_雙⑷羥基苯基） 苐、9,9-雙(4_羥基_3_甲基苯細等二羥基二芳基第類， 雙（4-經基苯基）金剛院、^-雙⑷經基苯基）金剛烧、η 雙（4-經基苯基）金_、U_雙（❺基苯基）_5,7_二甲基金 ㈣等二㈣二芳基金剛烧類’ 4,4t_n，3_伸苯基雙㈠·甲基 乙又基）]雙紛、1G，1G-雙（4_經基苯基）·9·蒽_ '丨，5_雙（4_經 基苯硫基）-2,3-二氧五烯等。 該等一 7L酚可分別單獨使用，亦可將兩種以上混合使 用0 若例示通式（2)所示之聚有機矽氧烷，例如可列舉： 149464.doc 201114579 [化4]In the formula (1), X, R1 to R2 are the same as those of the formula (1), and hydrazine is an average repeating unit number of the structural unit of the organic siloxane, and represents an integer of 7 〇 to 1 〇〇〇. In the formula (7), R3, V, and each independently represent a hydrogen atom or an alkyl group or an aryl group which may have a substituent, and γ represents a halogen, _R7〇H, R7C〇〇h, -R7NH2, -COOH or -SH And R7 represents a linear, branched or cyclic alkylene group, an aryl group-substituted alkylene group, an aryl group-substituted stretching group or an aryl group which may have an alkoxy group in the ring, and m represents hydrazine or 1] . Further, in the polycarbonate resin composition of the present invention, the dihydric phenol represented by the formula (1) used in the raw material of the polycarbonate-polyorganosiloxane copolymer (A-1) is various, in particular Preferably, 2,2-bis(4-hydroxyphenyl)propane [general name: bisphenol A] ruthenium as a bisphenol other than bisphenol A, for example, bis(4-hydroxyphenyl)methane, 1,1- Bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butan, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)benzene Methane, 149464.doc •10- 201114579 bis(4-phenylphenyl)benzophenone, 2,2_bis(4-hydroxy-3-methylphenyl)propane, bis(4-phenylbenzene) ))naphthylmethyl 6 bis(transalkyl)-tert-butylphenyl)propane 2,2_bis(4-hydroxy-3-indolyl)propane, 2,2-bis(4-hydroxy-3 , 5-tetramethylphenyl)propane, 2,2-bis(4)hydroxy-3-methyl-phenyl)propane, bis(4-hydroxy-3,5·dichlorophenyl)propane, 2,bis (4 Bis(ylaryl)-burning hydrocarbons such as _hydroxy-3,5-dibromophenyl)propane, etc., ^^ double. -hydroxyphenyl)cyclopentene, U·bis(perphenophenyl)cyclohexane, Chuan, 4-Phenylphenyl)_3'5'5-trimethylcyclohexan, 2,2_bis (4) Benzyl) ruthenium, bis(hydroxyaryl)cycloalkane such as bis(4-hydroxyphenyl)cyclododecane, 4,4,-dihydroxybenzoquinone 4,4 light base_3 , 3·-dimethylbenzene bond and other diaryl aryl groups, 4,4′-dihydroxydiphenyl sulfide, 4, dihydroxy-3,3,_dimethyl benzene sulfide Diaryl thioethers, dihydroxydiaryl sulfoxides such as 4,4,-dihydroxydiphenyl sulfoxide, 4,4, dihydroxy-3'3'-dimethyldiphenyl sulfoxide, ί二Hydroxy-phenylsulfone 4,4-_.yl_3,3i-dimercaptodiphenyl hard di-diyldiaryl hard type 'M-monohydroxy diphenyl dihydroxy diphenyl '99_bis(4)hydroxyl Phenyl) ruthenium, 9,9-bis (4-hydroxy-3-methylbenzene fine dihydroxydiaryl), bis(4-phenylphenyl)-Golden, ^-bis(4)-phenyl )Astragalus, η bis(4-phenylphenyl) gold _, U_ bis(nonylphenyl)_5,7_dimethyl fund (four), etc. Two (four) diaryl fund just burning class '4,4t_n,3_ Phenyl bis(a)·methylethyl keyl)] double, 1G, 1 G-bis(4_ mercaptophenyl)·9·蒽_ '丨, 5_bis(4-cysophenylthio)-2,3-dioxypentene, and the like. These 7L phenols may be used singly or in combination of two or more. If the polyorganosiloxane is represented by the formula (2), for example, 149464.doc 201114579 [Chem. 4]
[上述通式（3)〜（11)中，R3、R4、R5及R6與通式（1)同樣地， 分別獨立表示氫原子、_素原子或可具有取代基之烧基或 方基’R8表示烷基、烯基、芳基或芳烷基，n表示有機矽 氧烧^構單π之平均重複單元數Hi麵之整數，。表 示正整數]等。 之各易度而言，較佳為式 ’進而就獲取之容易度而 該等聚有機矽氧烷中，就聚合 (3)所示之酚改質聚有機矽氧烷 149464.doc •12- 201114579 言’較佳為作為式（4)所示之化合物中之—種 (鄰經基苯基）丙基]聚二甲基錢燒 '或者作為式（5)所示 之化合物中之一錄沾 _ 的(Χ，ω-雙[3_(4·羥基_3_曱氧基苯基）丙基 聚一甲基石夕氧燒。 =式(2)所不之聚有機矽氧烷可藉由使具有烯烴性不飽 和被-碳鍵之盼類，較佳為乙稀基苯紛、稀丙基苯齡、丁 香紛、及異丙稀基笨料，於具有特^之聚合度η之聚有 機矽氡烷鏈之末端進行氫矽烷化反應而容易製造。 本心月之4奴酸醋樹脂組合物中，（八_ 1)以外之芳香族 聚碳酸酯(Α-2)係使用藉由以下等先前之芳香族聚碳酸醋 之製造法而獲得者：界面聚合法，於對反應呈惰性之有機 溶劑及鹼性水溶液之存在下，使二元酚系化合物及二氣化 羰進行反應後，添加三級胺或四級銨鹽等聚合觸媒使之聚 合；或吡啶法’使二元酚系化合物溶解於吡啶或者吡啶與 惰性溶劑之混合溶液中，導入二氯化羰而直接製造。 上述反應時，視.需要而使用末端終止劑、分子量調節 劑、及支化劑等。 作為用於製造芳香族聚碳酸酯（Α-2)之二元酚系化合 物，例如可列舉：2,2-雙（4-羥基苯基）丙烷[=雙酚Α]、雙 (4-經基苯基）甲烷、ι，ΐ-雙（4-羥基苯基）乙烷、2,2-雙（4-經 基笨基）丁烷、2,2-雙（4-羥基苯基）辛烷、雙（4-羥基笨基）笨 基甲烷、雙（4-羥基苯基）二苯甲烷、2,2-雙（4-羥基-3-甲基 苯基）丙烷、雙（4-羥基苯基）萘基甲烷、1,1-雙（4-羥基-3-第 二丁基苯基）丙烧、2,2-雙（4-經基-3-溴苯基）丙烧、2,2-雙 149464.doc 201114579 (4-羥基-3,5-二甲基笨基）丙烷、2,2_雙（4_羥基_3_氣苯基）丙 烧、2,2-雙（4-經基-3,5-二氯苯基）丙炫、2,2-雙（4-羥基·3,5_ 二溴苯基）丙烧等雙（經基芳基）烧烴類，1，丨_雙（4_經基苯 基）環戊烷、1，1-雙（4-羥基苯基）環己烷、l，i_雙（4_羥基苯 基）-3,5,5-三曱基環己烧、2,2-雙（4-羥基苯基）降褚院、lsl_ 雙（4-羥基苯基）環十二烷等雙（羥基芳基）環烷烴類，4,4,_二 羥基苯基醚、4,4’-二羥基-3,3·-二曱基苯基醚等二羥基芳基 醚類，4,4’-二羥基二苯硫醚、4,4，-二羥基_3,3，-二曱基二苯 硫驗等二羥基二芳基硫醚類，4,4，-二羥基二苯亞砜、4,4ι_ 一經基-3,3二曱基二苯亞；ε風等二經基二芳基亞石風類，4,4'_ 二經基二苯石風、4,4’-二羥基-3，3’-二曱基二苯颯等二羥基二 芳基砜類，4,4’-二羥基二苯等二羥基二苯類，9,9_雙（4_羥 基苯基）苐、9,9-雙（4-羥基-3-甲基苯基）苐等二羥基二芳基 第類’雙（4-羥基苯基）金剛烷、ι，3_雙（4-羥基苯基）金剛 烷、2,2-雙（4-羥基苯基）金剛烷、13 —雙（4_羥基苯基）_5,7_ 一曱基金剛烧等二經基二芳基金剛烧，類，4,4，-[ 1，3-伸苯基 雙（1-甲基乙又基）]雙酚、10,10-雙（4-羥基苯基）_9_蒽酮、 及1，5-雙（4-羥基苯硫基）-2,3-二氧五烯等。 該等二元酚可分別單獨使用，亦可將兩種以上混合使 用。 製造芳香族聚碳酸酯（Α-2)時，通常使用末端終止劑或 分子量調節劑。 作為分子量調節劑，只要係通常用於聚碳酸酯樹脂之聚 合者，則可使用各種分子量調節劑。 149464.doc - ]4 - 201114579 具體而a，作為一元酚，例如可列舉：苯酚，鄰正丁基 笨酚間正丁基苯齡，對正丁基苯齡，鄰異丁基苯酚，間 異丁基絲’對異丁基絲，鄰第三了基鋒，間第三丁 基苯盼’對第二丁基苯紛’鄰正戊基苯紛，間正戊基苯 盼’對正戊基苯盼，鄰正己基笨酚，間正己基苯酴，對正 己基苯酚，對第三辛基苯酚，鄰環己基苯酚，間環己基苯 酚’對ί衣己基笨酚’鄰苯基笨酚，間笨基笨酚，對苯基笨 酴，鄰正壬基笨紛，間壬基苯*，對正壬基㈣，鄰異丙 苯基苯酚，間異丙苯基苯酚，對異丙苯基苯酚，鄰萘基苯 酉分，間蔡基苯驗，對萘基苯齡，2,5_二_第三丁基苯盼， 2’4 一-第二丁基苯酚，3,5_二_第三丁基苯酚，2,5_二異丙 苯基苯酚’ 3,5-二異丙笨基苯酚，對曱酚，溴苯酚’三溴 苯盼於鄰位、間位或對位具有平均碳數12〜35之直鍵狀 或支鏈狀燒基之單;1¾基苯盼，9_(4•經基苯基）_9_(4曱氧基 苯基）第、9-(4·經基-3-甲基苯基）-9-(4_甲氧基-3-甲基苯基） 第、及4-(1-金剛烷基）笨酚等。 泫等元酚中，較佳為使用對第三丁基苯酚，對異丙苯 基苯酚’及對苯基苯酚等。 當然亦可將兩種以上之化合物併用。 進而相對於上述二元酚系化合物，可以〇 〇丨〜3莫耳 尤-為G.1〜1』莫耳％之範圍併用支化劑而形成支化聚 作為支化劑，可使用 碳醗酯 烧 4,4’_[ W4-[H4-經基苯基）小甲基乙基]苯基]乙叉 雙酴、《心"-三（4·經基苯基•三異丙基苯、… 149464.doc 15- 201114579 基-α-(4’-羥基苯基）乙基]-4-[α’，α·-雙（4"-經基苯基）乙美] 苯、苯三酚、偏苯三甲酸、及靛紅雙（鄰甲酚）等具有3個以 上官能基之化合物。 本發明所使用之聚板酸酿樹脂組合物中，可視需要而奶 配先前聚碳酸酯樹脂組合物中公知之各種添加劑類。該等 添加劑可列舉補強材料、填充劑、穩定劑、抗氧化劑、紫 外線吸收齊卜抗靜電劑、潤滑劑、脫模劑、染料、顏料、 此外之阻燃劑及耐衝擊性改良用之彈性體等。 本發明所使用之聚碳酸s旨樹脂組合物可藉由調配上述之 各成刀（Α·1)、（A-2)、視需要之公知添加劑類進行混練 而獲得。 之方法來進行，例如使 班布襄混合機、轉鼓 雙螺桿擠出機、雙向捏 該調配、混練可利用通常所使用 用帶型摻合機、亨舍爾混合機、 (dmm tumbler)、單螺桿擠出機、 合機、及多螺桿擠出機等之方法。 阶，皿及逋常選自250〜320。(：炙範圓。 所得之聚碳酸酯樹脂組合 物之成形時，可採用先前公知 之各種成形方法，例如： 擠出成形法、吹塑成形法法、射出I缩成形法、 泡成彤、、夫笼，k /擠壓成形法、真空成形法及發 / ，父佳為於模具溫度60°C以上、較佳為 8〇〜下進行射出成形。 上較佳為 此時’射出成形中夕& t 度，較佳為·〜33〇t。溫度通常為280〜36〇°C之程 又，作為射出成形方法，為防止外觀之凹痕或輕量化’ 149464.doc 201114579 可採用氣體注入成形。 本發明之將包含具有特定結構之聚碳酸酯-聚有機矽氧 烷共聚物之聚碳酸酯樹脂組合物成形而得之攜帶型電子機 器殼體之厚度為0.5〜1.5 mm，較佳為〇.6〜14 mm，更佳為 0·6~1.3 mm。 又，本發明之攜帶型電子機器殼體可用於攜帶型個人電 腦、個人數位助理（pda)、行動電話、攜帶播放器、電池 外殼專攜帶型電子機器’尤佳為行動電話。 實施例 以下，藉由實施例及比較例對本發明進一步進行詳細說 明’但本發明不受該等例之任何限定。 [聚碳酸酯-聚二曱基矽氧烷共聚物（PC/PDMS共聚物）之製 造例1] 聚碳酸酯低聚物之製造 於5.6質量％氫氧化鈉水溶液中，相對於之後溶解之雙酚 A(BPA)而添加200〇ppm之連二亞硫酸鈉，然後於其中溶解 BPA以使BPA濃度達到13.5質量。/❶，從而製備BPA之氫氧化 納水溶液。 將該BPA之氫氧化鈉水溶液以4〇升/hr、二氣甲烷以15升/ hr之流量，且將二氯化羰以4·〇 kg/hr之流量連續通入内徑 為6 mm、管長為30 m之管型反應器中。 管型反應器具有套管部分’使冷卻水通過套管，將反應 液之溫度保持在40°C以下。 將自管型反應器出來之反應液連續導入具有後掠翼的容 149464.doc •17- 201114579 積40升之附擋板之槽型反應器中，向其中進而以2·8升/hr 添加BPA之氫氧化鈉水溶液，以O.O7升/hr添加25質量％氫 氧化鈉水溶液，以17升/hr添加水，且以0.64升/hr添加1質 量％三乙胺水溶液，而進行反應。 將自槽型反應器中溢出之反應液連續抽出，藉由靜置而 分離去除水相，採集二氯甲烷相。 如此而得之聚碳酸酯低聚物之濃度為329 g/L，氣甲酸酯 基之濃度為0.74 mol/L。 聚碳酸酯-聚二甲基矽氧烷共聚物之製造 於具有隔板、槳型攪拌翼及冷卻用套管之5〇 L槽型反應 器中’加入上述所製造之聚碳酸酯低聚物溶液1 5 L、二氯 甲烷9.0 L、二曱基矽氧烷單元之重複數為9〇之烯丙基笨酚 末端改質聚二甲基矽氧烷（PDMS)343 g及三乙胺88 於攪拌下向其中添加6.4質量％氫氧化鈉水溶液1389 g，使 聚奴酸酯低聚物與烯丙基苯酚末端改質pDMs反應1 〇分 鐘。 於該聚合液中添加對第三丁基苯酚（pTBp)之二氣甲烷溶 液（於二氣曱烷2.0 L中溶解PTBp m g而得者）、BPA之氫 氧化納水溶液（於將Na〇H 577 g與連二亞硫酸Μ』§溶解 於水8.4 L中所得之水溶液中溶解ΒρΑ ι〇ΐ2呂而得者），進 行50分鐘聚合反應。 添加10 L二氣甲院以進行稀釋，㈣1()分鐘後，分離 包含聚碳酸酯-聚二甲基矽氧户 7軋烷共聚物之有機相與包含過 剩之BPA及Na0H之水才目，單離出有機相。 149464.doc 201114579 將如此而得之聚碳酸酯-聚二甲基矽氧烷共聚物之二氣 甲烷溶液，相對於該溶液而依序以15體積％之0.03 mol/L 之NaOH水溶液、0.2莫耳/L鹽酸進行清洗，繼而以純水反 覆清洗直至清洗後水相中之導電率達到0·01 pS/m以下為 止。 將經清洗而得之聚碳酸酯-聚二曱基矽氧烷共聚物之二 氣曱烷溶液進行濃縮、粉碎，將所得之薄片於減壓下以 120°C乾燥。 所得之聚碳酸酯-聚二曱基矽氧烷共聚物的藉由核磁共 振（NMR，Nuclear Magnetic Resonance)而求得 PDMS 之殘 基量（PDMS共聚量）為5.6質量％，依據ISO 1628-4(1999)而 測定之黏度數為51.2，黏度平均分子量Mv=l93 00。 [聚碳酸酯-聚二甲基矽氧烷共聚物（PC/PDMS共聚物）之製 造例2〜9] 將末端改質PDMS(烯丙基苯酚末端改質PDMS或丁香酚 末端改質PDMS)之種類、二曱基矽氧烷單元之重複數、末 端改質PDMS之使用量、PTBP之使用量設為如表1所述， 製造聚碳酸酯-聚二甲基矽氧烷共聚物。 將所得之聚碳酸酯-聚二甲基矽氧烷共聚物之PDMS殘基 量（PDMS共聚量）、黏度數、黏度平均分子量Mv示於表1。 149464.doc -19- 201114579 【1^】 製造例 Os 〇 222 [154.1 I 00 ΓΟ 44.8 16500 oo 〇 222 I 154.1 I 00 cn 44.8 | 16500 〇 1—Η 360 I 165.6 I ο 42.5 15500 〇 300 246 I 150.6 I 45.3 16700 〇 222 I 154.1 I 卜 rn 44.5 | 16400 寸 〇 343 I 126.3 I 50.9 | 19200 m 〇 § 276 1 128.6 I 卜 50.9 | 19200 (N 〇 1—Η 276 1 128.6 I <〇· 寸· 50.3 18900 T~H 〇 343 1126-3 tri 51.2 19300 00 s 念S 紫x 丁香酚 末端改質PDMS 二甲基矽氧烷單元之 重複數 末端改質PDMS(g) οΓ PQ Η Ρη PDMS殘基量(WT%) 黏度數 黏度平均分子量 末端改質PDMS 使用量 PC/PDMS 共聚物 149464.doc -20- 201114579 實施例1〜7及比較例1〜3 將製造例1〜9中製造之聚碳酸酯-聚二曱基矽氧烷共聚物 (PC/PDMS共聚物）、FN1500(商品名，出光興產（股）製造， 末端基具有對第三丁基苯酚之BPA聚碳酸酯，黏度數為 39.2，黏度平均分子量 Mv=14500)、Tarflon FN1700A(商品 名，出光興產（股）製造，末端基具有對第三丁基苯酚之 BPA聚碳酸酯，黏度數為47.1，黏度平均分子量Mv= 1 75 00)、Tarflon FN2700A(商品名，出光興產（股）製造，末 端基具有對第三丁基苯酚之BPA聚碳酸酯，黏度數為 69.6，黏度平均分子量Mv=27500)、IRGAFOS168(商品 名，（股）ADEKA製造）’以表2所述之質量份進行摻合，使 用附通氣孔之40 ηιιηφ之單軸擠出機，於樹脂溫度280eC下 進行造粒而獲得顆粒物。 又，僅比較例3中樹脂溫度為3001。 將所得之顆粒物於120°C下乾燥8小時後，使用射出成形 機，於成形溫度280°C '模具溫度80°C下進行射出成形而 獲得試驗片。 使用顆粒物或經射出成形而得之試驗片，進行以下之測 定。 將結果示於表2。 (1)熔融流動性MFR(熔融流動速率，Melt Flow Rate) 依據JIS K7210，於280°C、2_16 kg之荷重下，測定自直 徑2 mm、長度8 mm之模頭中流出之熔融樹脂量（§/1〇分 鐘）。 I49464.doc -21· 201114579 (2) Q 值（流動值）[單元：10.2mL/sec] 使用高架式流變儀，依據JIS K7210，於280°C、15.7 河〜之壓力下，測定自直徑1 mm、長度1 〇 mm之噴嘴中流 出之溶融樹脂量（mL/sec)。 Q值係表示單位時間之流出量，其數值越高，表示流動 性越好。 (3) HDT(熱變形溫度，Heat Deflection Temperature) 依據ASTM D648，於0.45 MPa之壓力下進行測定。 HDT係表示耐熱性之標準。 [行動電話模型之成形] 使用上述所得之顆粒物，於下述條件下藉由射出成形而 獲得圖1之尺寸說明圖所示之成形品（50 mmx88 mm，深度 4.5 mm，厚度 1.2 mm)。 再者，對比較例3已嘗試射出成形’但於3〇〇〜32(rc之料 紅度下黏度變高，無法填充，故而無法獲得成形品。 進而，將料缸溫度提高至36(rc以嘗試進行成形，但無 法獲得成形品’將料缸溫度提高至38(Γ(：時，開始出現由 樹脂組合物之劣化引起之著色，故而中止成形。 成形條件 射出成形機：日精樹脂工業股份有限公司製造，電動射 出成形機ES-1000，80噸[In the above formulae (3) to (11), R3, R4, R5 and R6 each independently represent a hydrogen atom, a _-atom atom or a calcination group or a aryl group which may have a substituent, as in the formula (1). R8 represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group, and n represents an integer of the Hi repeating number of the average repeating unit number of the organic oxime. Indicates a positive integer] and so on. In terms of the ease of use, it is preferred that the formula 'and the ease of obtaining the polyorganosiloxane, the phenol-modified polyorganosiloxane shown in the polymerization (3) 149464.doc • 12- 201114579 It is preferred to use one of the compounds of formula (4) (o-phenylphenyl)propyl]polydimethyl ketone or one of the compounds of formula (5). Χ 的 Χ Χ ω ω ω ω ω ω ω ω = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = By having an olefinic unsaturated-carbon bond, preferably ethylene benzene, propyl benzoate, clove, and isopropyl dilute, having a polymerization degree η The end of the polyorganodecane chain is hydroformylated and easily produced. In the fourth vinegar resin composition of the present month, the aromatic polycarbonate (Α-2) other than (eight-1) is used. Obtained by the following method for producing an aromatic polycarbonate: an interfacial polymerization method, in which a dihydric phenolic compound and a gasification are carried out in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution After the reaction, a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added to polymerize it; or a pyridine method is used to dissolve the dihydric phenol compound in a mixed solution of pyridine or pyridine and an inert solvent to introduce carbonyl dichloride. In the above reaction, a terminal terminator, a molecular weight modifier, a branching agent, etc. are used as needed. Examples of the dihydric phenol compound used for producing the aromatic polycarbonate (Α-2) include : 2,2-bis(4-hydroxyphenyl)propane [=bisphenolphthalein], bis(4-phenylphenyl)methane, iota, bis-(4-hydroxyphenyl)ethane, 2,2 - bis(4-pyridyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenyl, methane (bis-hydroxyphenyl)diphenyl Methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxy-3-t-butylbenzene) Propylene, 2,2-bis(4-carbazhen-3-bromophenyl)propane, 2,2-bis 149464.doc 201114579 (4-hydroxy-3,5-dimethylphenyl)propane , 2,2_bis(4-hydroxy-3-indolyl)propane, 2,2-bis(4-carbazhen-3,5-dichloro Bis(cycloaryl)-fired hydrocarbons such as propyl, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 1, 丨_bis(4-cyanophenyl) Cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,i-bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexene, 2,2- Bis(4-hydroxyphenyl) brothel, bis(hydroxyaryl)cycloalkane such as lsl_bis(4-hydroxyphenyl)cyclododecane, 4,4,-dihydroxyphenyl ether, 4,4 Dihydroxyaryl ethers such as '-dihydroxy-3,3·-didecylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4,-dihydroxy-3,3,-di Dihydroxydiaryl sulfides such as fluorenyldiphenyl sulfide, 4,4,-dihydroxydiphenyl sulfoxide, 4,4ι_mono-based-3,3-didecyldiphenylene; Diaryl sulfite, 4,4'-di-dibenzopyrene, 4,4'-dihydroxy-3,3'-dimercaptodiphenyl hydrazine, etc., 4 , dihydroxy diphenyl such as 4'-dihydroxydiphenyl, dihydroxyl of 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene Diaryl type 'bis(4-hydroxyphenyl)adamantane, iota, 3_bis(4-hydroxyphenyl) Ranane, 2,2-bis(4-hydroxyphenyl)adamantane, 13-bis(4-hydroxyphenyl)_5,7_one 曱 fund just burned, di-based diaryl fund just burned, class, 4, 4,-[1,3-phenylenebis(1-methylethylhexyl)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-nonanone, and 1,5-bis (4) -Hydroxyphenylthio)-2,3-dioxypentene and the like. These dihydric phenols may be used singly or in combination of two or more. When producing an aromatic polycarbonate (Α-2), a terminal terminator or a molecular weight modifier is usually used. As the molecular weight modifier, various molecular weight modifiers can be used as long as they are generally used as a polymer of a polycarbonate resin. 149464.doc - ]4 - 201114579 Specifically, a, as a monohydric phenol, for example, phenol, o-n-butyl phenol, n-butyl benzene, n-butyl benzene, o-isobutyl phenol, different Butyl silk 'p-isobutyl silk, adjacent to the third base front, between the third butyl benzene is expected to 't-butyl benzene quinone' o-n-pentyl benzene, m-n-pentyl benzene Benzophenone, o-n-hexyl phenol, m-n-hexyl benzoquinone, p-n-hexyl phenol, p-third octyl phenol, o-cyclohexyl phenol, m-cyclohexyl phenol 'p- hexyl phenol phenol ' o-phenyl phenol , stupid base phenol, p-phenyl alum, ortho-n-phenyl, decyl benzene*, n-decyl (tetra), o-cumylphenol, m-cumylphenol, p-cumene Phenol, o-naphthyl benzoquinone, m-decyl benzene, p-naphthyl benzene, 2,5-di-t-butyl phenyl, 2'4- butyl phenol, 3,5_ Di-tert-butylphenol, 2,5-diisopropylphenylphenol, 3,5-diisopropylphenylphenol, p-nonylphenol, bromophenol, tribromobenzene, ortho, meta or para Straight bond or branched burning with an average carbon number of 12 to 35 Single; 13⁄4-based benzene, 9-(4•ylphenyl)_9_(4-decyloxyphenyl), 9-(4.-yl-3-methylphenyl)-9-(4_A Oxy-3-methylphenyl), and 4-(1-adamantyl) phenol. Among the hydrazine phenols, p-tert-butylphenol, p-cumylphenol phenol and p-phenylphenol are preferably used. Of course, it is also possible to use two or more compounds in combination. Further, with respect to the above dihydric phenol-based compound, it is possible to form a branched polycondensate as a branching agent by using a branching agent in the range of G.1 to 1 mol%, and a carbonization can be used as a branching agent. Ester burn 4,4'_[ W4-[H4-pyridylphenyl) small methyl ethyl]phenyl]ethylidene bismuth, "heart"--tris(4·p-phenylene•triisopropyl Benzene, ... 149464.doc 15- 201114579 base-α-(4'-hydroxyphenyl)ethyl]-4-[α',α·-bis(4"-p-phenylphenyl)ethyl benzene] benzene, benzene a compound having three or more functional groups, such as trisphenol, trimellitic acid, and eosin bis(o-cresol). In the poly-platinic styrene resin composition used in the present invention, the former polycarbonate may be used as needed. Various additives are known in the resin composition, and examples of the additives include reinforcing materials, fillers, stabilizers, antioxidants, ultraviolet absorbing antistatic agents, lubricants, mold release agents, dyes, pigments, and further flame retardants. And an elastomer for improving impact resistance, etc. The resin composition for polycarbonate s used in the present invention can be prepared by blending the above-mentioned respective knives (Α·1) and (A-2). It can be obtained by kneading a known additive as needed. For example, a Banbu mixer, a rotary twin-screw extruder, a two-way kneading, and a kneading can be used. Henschel mixer, (dmm tumbler), single-screw extruder, combined machine, and multi-screw extruder, etc. Steps, dishes and crucibles are often selected from 250 to 320. (: 炙范圆. In the molding of the polycarbonate resin composition, various conventionally known forming methods can be employed, for example, extrusion molding, blow molding, injection molding, foaming, cage, k/extrusion. The molding method, the vacuum forming method, and the hair/fabrication are preferably carried out at a mold temperature of 60 ° C or higher, preferably 8 Å or less. The upper portion is preferably formed at the time of injection molding and at a moderate angle. The temperature is usually 280 to 36 〇 ° C, and as an injection molding method, in order to prevent the appearance of dents or light weight, 149464.doc 201114579 can be used for gas injection molding. The present invention will contain Polycarbonate with a specific structure The thickness of the portable electronic device case formed by molding the polycarbonate resin composition of the alkane copolymer is 0.5 to 1.5 mm, preferably 〇6 to 14 mm, more preferably 0. 6 to 1.3 mm. The portable electronic device casing of the present invention can be used for a portable personal computer, a personal digital assistant (PDA), a mobile phone, a portable player, and a battery-portable portable electronic device, particularly a mobile phone. EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be further described in detail. However, the present invention is not limited to these examples. [Production Example 1 of Polycarbonate-Polydimethylfluorenyl Copolymer (PC/PDMS Copolymer)] The polycarbonate oligomer was produced in a 5.6% by mass aqueous sodium hydroxide solution, and 200 〇ppm of sodium dithionite was added to the then dissolved bisphenol A (BPA), and then BPA was dissolved therein to bring the BPA concentration to 13.5. quality. /❶, thereby preparing a sodium hydroxide aqueous solution of BPA. The BPA aqueous sodium hydroxide solution was flowed at 4 liters/hr, digas methane at a flow rate of 15 liters/hr, and the carbonyl dichloride was continuously introduced into an inner diameter of 6 mm at a flow rate of 4 〇kg/hr. In a 30 m tubular reactor. The tubular reactor has a sleeve portion' to allow cooling water to pass through the casing to maintain the temperature of the reaction liquid below 40 °C. The reaction liquid from the tubular reactor is continuously introduced into a grooved reactor with a swept wing having a capacity of 149464.doc • 17- 201114579 and added thereto, and further added thereto at 2·8 liter/hr. A sodium hydroxide aqueous solution of BPA was added to a 25 mass% aqueous sodium hydroxide solution at 0. 7 liter/hr, water was added at 17 liter/hr, and a 1 mass% aqueous solution of triethylamine was added at 0.64 liter/hr to carry out a reaction. The reaction liquid overflowing from the tank type reactor was continuously withdrawn, and the aqueous phase was separated and removed by standing, and a dichloromethane phase was collected. The concentration of the polycarbonate oligomer thus obtained was 329 g/L, and the concentration of the gas ester group was 0.74 mol/L. Polycarbonate-polydimethyloxane copolymer manufactured in a 5〇L tank reactor having a separator, a paddle type agitating blade and a cooling jacket. 'Addition of the polycarbonate oligomer produced above Solution 15 L, dichloromethane 9.0 L, dimercapto methoxy olefin unit repeat number 9 〇 allyl phenolic terminal modified polydimethyl methoxy oxane (PDMS) 343 g and triethylamine 88 1389 g of a 6.4% by mass aqueous sodium hydroxide solution was added thereto with stirring, and the poly acrylate oligomer was reacted with allyl phenol-terminated pDMs for 1 minute. To the polymerization solution, a di-methane solution of p-butylphenol (pTBp) (a solution obtained by dissolving PTBp mg in 2.0 L of dioxane) and a sodium hydroxide aqueous solution of BPA (in Na〇H 577) were added to the polymerization solution. The polymerization reaction was carried out for 50 minutes by g-dissolving ΒρΑ ι〇ΐ2 with an aqueous solution obtained by dissolving hydrazine hydrate in 8.4 L of water. 10 L was added to dilute to dilute, and after (4) 1 () minutes, the organic phase containing the polycarbonate-polydimethylxanthene 7 tarane copolymer and the water containing excess BPA and NaOH were separated. Single out of the organic phase. 149464.doc 201114579 The thus obtained two-gas methane solution of polycarbonate-polydimethyloxane copolymer, with 15% by volume of 0.03 mol/L NaOH aqueous solution, 0.2 mol relative to the solution The ear/L hydrochloric acid is washed, and then washed repeatedly with pure water until the conductivity in the aqueous phase after washing reaches 0·01 pS/m or less. The dioxane solution of the polycarbonate-polydidecyloxane copolymer obtained by washing was concentrated, pulverized, and the obtained sheet was dried at 120 ° C under reduced pressure. The amount of residue (PDMS copolymerization amount) of PDMS obtained by nuclear magnetic resonance (NMR (Nuclear Magnetic Resonance)) of the obtained polycarbonate-polydidecyl decane copolymer was 5.6% by mass, according to ISO 1628-4 The viscosity number measured in (1999) was 51.2, and the viscosity average molecular weight Mv was 193 00. [Production Examples 2 to 9 of Polycarbonate-Polydimethyloxane Copolymer (PC/PDMS Copolymer)] The terminal was modified with PDMS (allylphenol terminal modified PDMS or eugenol terminal modified PDMS) The type, the number of repetitions of the dimercapto oxane unit, the amount of the terminal modified PDMS, and the amount of PTBP used were set as described in Table 1, and a polycarbonate-polydimethylsiloxane copolymer was produced. The PDMS residue amount (PDMS copolymerization amount), viscosity number, and viscosity average molecular weight Mv of the obtained polycarbonate-polydimethylsiloxane copolymer are shown in Table 1. 149464.doc -19- 201114579 【1^】 Manufacturing example Os 〇222 [154.1 I 00 ΓΟ 44.8 16500 oo 〇222 I 154.1 I 00 cn 44.8 | 16500 〇1—Η 360 I 165.6 I ο 42.5 15500 〇300 246 I 150.6 I 45.3 16700 〇222 I 154.1 I 卜 rn 44.5 | 16400 inch 〇343 I 126.3 I 50.9 | 19200 m 〇§ 276 1 128.6 I 卜 50.9 | 19200 (N 〇1—Η 276 1 128.6 I <〇·inch· 50.3 18900 T~H 〇343 1126-3 tri 51.2 19300 00 s S S purple x eugenol end-modified PDMS dimethyl methoxy siloxane unit repeat number terminal modification PDMS (g) οΓ PQ Η Ρ PD PDMS residue amount ( WT%) Viscosity number viscosity average molecular weight terminal modification PDMS usage amount PC/PDMS copolymer 149464.doc -20- 201114579 Examples 1 to 7 and Comparative Examples 1 to 3 The polycarbonates produced in Production Examples 1 to 9 were Polydidecyl fluorinated copolymer (PC/PDMS copolymer), FN1500 (trade name, manufactured by Idemitsu Kosan Co., Ltd.), BPA polycarbonate with terminal group having a third butyl phenol, viscosity number of 39.2, Viscosity average molecular weight Mv=14500), Tarflon FN1700A (trade name, Idemitsu Kosan ( Made of BPA polycarbonate with a terminal group of p-butylphenol, viscosity number 47.1, viscosity average molecular weight Mv = 1 75 00), Tarflon FN2700A (trade name, manufactured by Idemitsu Kosan Co., Ltd., terminal base) BPA polycarbonate having a third butyl phenol having a viscosity of 69.6, a viscosity average molecular weight of Mv = 27,500, and IRGAFOS 168 (trade name, manufactured by ADEKA) was blended in the mass parts described in Table 2, The granules were obtained by granulation at a resin temperature of 280 ° C using a uniaxial extruder equipped with a vent hole of 40 η ιηηφ. Further, only the resin temperature in Comparative Example 3 was 3001. The obtained granules were dried at 120 ° C for 8 hours. Thereafter, a test piece was obtained by injection molding at a molding temperature of 280 ° C 'mold temperature of 80 ° C using an injection molding machine. The following measurement was carried out using a pellet or a test piece obtained by injection molding. The results are shown in Table 2. (1) Melt Flowability MFR (Melt Flow Rate) According to JIS K7210, the amount of molten resin flowing out from a die having a diameter of 2 mm and a length of 8 mm was measured at 280 ° C under a load of 2 - 16 kg ( §/1〇 minutes). I49464.doc -21· 201114579 (2) Q value (flow value) [Unit: 10.2 mL/sec] Using an overhead rheometer, according to JIS K7210, at 280 ° C, pressure of 15.7 rivers, measured from the diameter The amount of molten resin (mL/sec) flowing out of a nozzle of 1 mm in length and 1 mm in length. The Q value indicates the amount of outflow per unit time, and the higher the value, the better the fluidity. (3) HDT (Heat Deflection Temperature) The measurement was carried out under a pressure of 0.45 MPa in accordance with ASTM D648. HDT is a standard for heat resistance. [Formation of the mobile phone model] Using the pellets obtained above, the molded article (50 mm x 88 mm, depth 4.5 mm, thickness 1.2 mm) shown in the dimension drawing of Fig. 1 was obtained by injection molding under the following conditions. Further, in Comparative Example 3, injection molding was attempted, but the viscosity was increased at 3 to 32 (the redness of rc became high and the filling could not be performed, so that the molded article could not be obtained. Further, the temperature of the cylinder was raised to 36 (rc) In an attempt to perform molding, it is impossible to obtain a molded article. When the temperature of the cylinder is increased to 38 (Γ, the coloring caused by the deterioration of the resin composition begins to occur, and the molding is stopped. The molding condition injection molding machine: Nissei resin industrial stock Co., Ltd. manufacture, electric injection molding machine ES-1000, 80 tons
成形機料缸溫度：300〜320。〇 成形週期：30秒/cycle 模具溫度：130°C 149464.doc •22· 201114579 [抗跌落衝擊性評價] 將所得之成形品放入恆溫槽中，冷卻至預定之溫度 (〇°C、-1(TC、-20°C )。 2小時後，自恆溫槽中取出成形品，立即使128〇 g之砝 碼自1.M爪之高度跌落至成形品’藉此評價抗跌落衝擊 性。 進行5次相同之試驗，將裂紋之有無 無、裂紋之種類(延性裂紋、脆性裂紋)示於表2; 將裂紋面（破裂面）為延性之 ^ . 匱升^评價為延性裂紋，將裂 紋面為脆性之情形評價為脆性裂紋。 再者，數值表示5次試驗中裂紋 無、裂纟文種冑胃> A 有…、龜裂產生之有 又種類之次數，總計為5。 149464.doc 23. 201114579Forming machine cylinder temperature: 300~320. 〇Forming cycle: 30 seconds/cycle Mold temperature: 130°C 149464.doc •22· 201114579 [Evaluation of drop impact resistance] The obtained molded product is placed in a constant temperature bath and cooled to a predetermined temperature (〇°C, - 1 (TC, -20 ° C). After 2 hours, the molded article was taken out from the constant temperature bath, and the weight of 128 〇g was immediately dropped from the height of the 1.M claw to the molded article 'to evaluate the drop impact resistance. 5 times of the same test, the presence or absence of cracks, crack types (ductile cracks, brittle cracks) are shown in Table 2; crack surface (fracture surface) is ductile ^ 匮 ^ ^ evaluated as ductile cracks, will In the case where the crack surface is brittle, it is evaluated as a brittle crack. In addition, the numerical value indicates the number of cracks in the five tests, the cracks in the sputum, the stomach, the number of the cracks, and the number of times the cracks are generated, and the total number is 5. 149464 .doc 23. 201114579
m ο 0.05 ο 〇 26000 I (N v〇 寸 I 380 I 無法 成形 <N 製造例9 〇 0.05 00 ΓΟ 16500 00 κη 300 ο ο 寸 ο ο ο 寸 ο m 實施例 r- 製造例8 1 〇 〇 1 0.05 1 g 00 ΓΟ 16500 Ό CS 00 m 300 (Ν Ο ο <Ν (Ν ο 〇 00 m 製造例7 | CN VO 0.05 卜 16200 00 CS s v〇 300 m <N Ο ο (Ν m ο ο (Ν CN 〇 卜 製造例6 Ο 0.05 300 卜 I 16200 I 00 s 300 <N Ο ο (Ν ο ο (Ν 〇 〇 寸 @造例5 I Ο ο 0.05 卜 ΓΟ 16400 〇〇 CN as v〇 m 300 m CS ο ο CS CN ο (Ν <N 〇 比較例 v〇 製造例4 | 1 0.05 1 〇〇 Τ}* 18900 二 Os in ΓΊ | 320 | — r—< ο ο o in ο Ο O 實施例 m |製造例3 1 ο ο 1 0.05 1 g 寸 19200 CS 00 〇 ro *—H 320 cs ro ο ο ο ο ο <Ν r") 〇 〇 <N 製造例2 I ο ο 1 0.05 1 — 18900 m Os P： *— 320 ro (N ο ο 寸 ο ο m CN 〇 〇 一 製造例1 0.05 § <> — 19200 rn 〇\ | 320 | ΓΛ (N ο ο ο in ο ο CN 〇 〇 _500 | ^•ΝΠΟΟΑ 1 fN2700A 1 PC/PDMS 共聚物 IRGFOS168 二甲基矽氧烷單元之重複數(η) PDMS殘基量(質量％) 黏度平均分子量 MFR@280°C(g/l〇min) ε IN o HDT@0.45 MPafC) 成形料缸溫度(°c) 無裂紋 產生龜裂 延性裂紋 脆性裂紋 無裂紋 產生龜裂 延性裂紋 脆性裂紋 無裂紋 產生龜裂 延性裂紋 脆性裂紋 調配組成 [質量份] 抗跌落衝擊性〇°c 抗跌落衝擊性-l〇°C 抗跌落衝擊性-20°C -24- 149464.doc 201114579 產業上之可利用性 藉由本發明，可提供一種薄壁且抗跌落衝擊性、流動性 及耐熱性優異之攜帶型電子機器殼體。 ^ ’ 【圖式簡單說明】 圖1係使用實施例1〜7、比較例1及2之樹脂組合物之行動 電話模型之成形品（50 mmx88 mm、深度4.5 mm、厚度1.2 mm)之尺寸說明圖。 149464.doc -25·m ο 0.05 ο 〇 26000 I (N v 〇 I 380 I cannot be formed < N Manufacturing Example 9 〇 0.05 00 ΓΟ 16500 00 κη 300 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 1 0.05 1 g 00 ΓΟ 16500 Ό CS 00 m 300 (Ν Ο ο <Ν (Ν ο 〇00 m Manufacturing Example 7 | CN VO 0.05 卜16200 00 CS sv〇300 m <N Ο ο (Ν m ο ο (Ν CN 〇 制造 Manufacturing Example 6 Ο 0.05 300 卜 I 16200 I 00 s 300 <N Ο ο (Ν ο ο (Ν 〇〇@造例5 I Ο ο 0.05 ΓΟ ΓΟ 16400 〇〇CN as v〇m 300 m CS ο ο CS CN ο (Ν <N 〇Comparative example v〇Manufacturing example 4 | 1 0.05 1 〇〇Τ}* 18900 Two Os in ΓΊ | 320 | — r—< ο ο o in ο Ο O Example m | Manufacturing Example 3 1 ο ο 1 0.05 1 g inch 19200 CS 00 〇ro *—H 320 cs ro ο ο ο ο ο <Ν r") 〇〇<N Manufacturing Example 2 I ο ο 1 0.05 1 — 18900 m Os P: *— 320 ro (N ο ο ο ο ο m 制造 m manufacturing example 1 0.05 § <> — 19200 rn 〇\ | 320 | ΓΛ (N ο ο ο in ο ο CN 〇〇_500 | ^•ΝΠΟΟΑ 1 fN2700A 1 PC/PDMS copolymer IRGFOS168 dimethyl methoxy siloxane unit repeat number (η) PDMS residue amount (% by mass) Viscosity average molecular weight MFR@280°C(g/l〇min) ε IN o HDT@0.45 MPafC) Forming cylinder temperature (°c) No cracks, cracks, ductile cracks, brittle cracks, no cracks, cracks, ductile cracks, brittle cracks, no cracks, turtles Crack ductile crack brittle crack blending composition [parts by mass] anti-drop impact 〇°c anti-drop impact-l〇°C anti-drop impact -20°C -24- 149464.doc 201114579 Industrial availability by Ben According to the invention, it is possible to provide a portable electronic device casing which is thin and has excellent drop resistance, fluidity and heat resistance. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the dimensions of a molded article (50 mm x 88 mm, depth 4.5 mm, thickness 1.2 mm) of a mobile phone model using the resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2. Figure. 149464.doc -25·