TW201124469A - Polycarbonate resin composition - Google Patents

Abstract

Provided are: a polycarbonate resin composition which comprises (A) 100 parts by mass of an aromatic polycarbonate resin that contains a polycarbonate-polyorganosiloxane copolymer, (B) 30 to 100 parts by mass of graphite, (C) 1 to 10 parts by mass of polytetrafluoroethylene, and (D) 0.05 to 1 part by mass of an organoalkali metal salt and/or an organoalkaline earth metal salt and which exhibits excellent flame retardance (even in a thin-wall state), thermal conductivity, and impact characteristics, even without using a chlorinated flame retardant, a brominated flame retardant, or a phosphorus-based flame retardant; and molded products of the composition.

Description

201124469 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種聚碳酸酯樹脂組合物及包含該樹脂組 合物之成形體，又，本發明係關於一種即便不使用氣系阻 燃劑、溴系阻燃劑及磷系阻燃劑，阻燃性（尤其是薄壁之 阻燃性）、導熱性、衝擊特性亦優異之聚碳酸酯樹脂組合 物及包含其之成形體。 【先前技術】 於電氣電子領域之製品開發中，隨著數位相機、數位攝 影機之高像素化、高速處理化，投影儀之小型化，電腦、 移動機器之高速處理化，各種光源之LED(Light Emitting Diode，發光二極體）化等，已將重點放在散熱對策上。 亦採取由金屬零件構成散熱電路之對策，但於小型化之 機器中，會使散熱電路變得複雜，故要求一種可將樹脂殼 體與散熱電路—體化，導熱性優異，且作為殼體之機械強 度亦優異之樹脂材料。 又，於小型電子機器中，亦對殼體、底板要求薄壁化， 伴隨此，亦要求薄壁之成形體之阻燃性。 •已头上述電子機器之殼體等中通用聚碳酸酯樹脂，但 為使包含聚碳_樹脂組合物之成形體阻燃化，而添加氯 :糸：燃劑、溴系阻燃劑等齒素系阻燃劑 '然而，近年來， 就:全性、廢棄、焚燒時對環境之影響之觀點*言，市場 上需求利用不含函素之阻燃劑之阻燃化方法。為將作為上 述之非函素系阻燃劑的有機罐系阻燃劑、尤其是有機構酸 I51933.doc 201124469 醋化合物調配於聚碳酸酯樹脂組合物中而進行阻燃化，必 需調配相對較多量之破酸醋化合物。聚碳酸酯樹脂成形溫 度較高’溶融黏度亦較高，故存在成形溫度變高之傾向。 因此，磷酸酯化合物雖通常有助於阻燃性，但存在成形加 工時之模具腐蝕、氣體之產生等、成形環境或成形品外觀 上未必充分之情形。 因此，要求發現一種不使用氣系阻燃劑、溴系阻燃劑等 鹵素系阻燃劑或磷系阻燃劑便可達成所要求之成形體之阻 燃性（尤其是薄壁之阻燃性），且導熱性優異之聚碳酸酯樹 脂組合物。 作為對熱塑性樹脂賦予上述散熱性之方法，已知有調配 石墨之方法（參照專利文獻丨、專利文獻2)。於專利文獻工 中，揭示有藉由在熱塑性樹脂中調配特定之石墨，可獲得 金屬腐姓性較少’且導熱性優異之熱塑性樹脂組合物，但 。己載有為改良阻燃性，較佳為使用函化碳酸酯寡聚物、鹵 化環氧化合物等有機鹵素系阻燃劑或磷酸酯系阻燃劑，並 未揭不不使用氣系阻燃劑、溴系阻燃劑及磷系阻燃劑之技 術。 又於專利文獻2中’對收納發熱體之散熱殼體進行了 闡述，但未對電子機器等之殼體所要求之阻燃性進行闡 述作為視需要而調配之添加劑，揭示了有機溴系阻燃劑 或磷系阻燃劑等阻燃劑，但並未揭示積極地不使用氣系阻 ' /臭系阻燃劑及碌系阻燃劑之技術，又，可認為，於 實靶例中，由於未添加阻燃劑、抗滴落劑，故不具有充 151933.doc 201124469 分之阻燃性。 進而，已知有為對聚碳酸酯樹脂賦予抗靜電性或導電性 而調配石墨且調配有阻燃劑之聚碳酸酯樹脂組合物（參照 專利文獻3、專利文獻4)。於專利文獻3中，揭示有於包含 芳香族聚碳酸酯樹脂與石墨之調配物中含有特定之聚矽氧 化〇物而成之芳香族聚碳酸酯樹脂組合物，並且與抗靜電 哇同β平價了阻燃性，但並未記載以電子機器等之殼體所 要求之1.5 mm左右之薄壁可獲得充分之阻燃性之技術内 谷。又，於專利文獻4中，作為積極地不使用氯系阻燃 Μ 士溴系阻燃劑及磷系阻燃劑之技術，揭示有包含聚碳酸 酉曰樹月曰石墨、及有機磺酸鹼（土）金屬鹽之阻燃性樹脂組 合物’於阻燃性評價中，僅對厚度2 5 _之成形體進行了 °平價’與專利文獻3同I ’以電子機器等之殼體所要求之 1.5 mm左右之薄壁無法獲得充分之阻燃性。 先前技術文獻 專利文獻 專利文獻1:曰本專利特開2007-31611號公報 專利文獻2 :日本專利特開2008-31358號公報 專利文獻3 :曰本專利特開2007-126499號公報 專利文獻4 .日本專利特開2006-273931號公報 【發明内容】 發明所欲解決之問題 本毛明之目的在於提供一種不使用氣系阻燃劑、溴系阻 燃劑及磷系阻燃劑而薄壁成形體之阻燃性(厚度為:二.〇 15I933.doc 201124469 mm，以下稱作「薄壁阻燃性」）優異，具有高導熱性，且 衝擊特性優異之聚碳酸酯樹脂組合物及成形體。 解決問題之技術手段 本發明者專人反覆銳,¾、研究’結果發現，藉由以特定比 率調配含有聚碳酸酯-聚有機矽氧烷共聚物之芳香族聚碳 酸酯樹脂、石墨、聚四氟乙烯、及有機鹼金屬鹽及/或有 機驗土金屬鹽，而可獲得薄壁阻燃性優異，進而導熱性、 衝擊特性亦優異之聚碳酸酯樹脂組合物，從而完成本發 明。 即，本發明係提供下述者： (1) 一種聚碳酸酯樹脂組合物，其係相對於（A)含有聚碳酸 醋-聚有機矽氧烷共聚物之芳香族聚碳酸酯樹脂1〇〇質量 份，包含（B)石墨30〜100質量份、（C)聚四氟乙烯卜1〇質量 份、及（D)有機鹼金屬鹽及/或有機鹼土金屬鹽0 05η質量 份； (2) 如上述（1)之聚碳酸酯樹脂組合物，其中（A)中之聚有機 矽氧烷之含量為1〜6質量％ ; (3) 如上述（1)或之聚碳酸酯樹脂組合物，其中芳香族聚 碳酸6旨-聚有機矽氧烷共聚物之聚有機矽氧烷為聚二 一^〒基 矽氧烷； (4) 如上述（1)至（3)中任一項之聚碳酸酯樹脂組合物，其中 石墨為天然石墨； (5) 如上述（1)至（3)中任一項之聚碳酸酯樹脂組合物，其中 石墨為人造石墨； 151933.doc 201124469 ⑼有機驗金眉Γ中任一項之聚碳酸醋樹脂组合物，其中 金屬踏右她帛及/或有機鹼土金屬鹽為選自有機磺酸驗 =二驗土金屬鹽、聚苯乙稀續酸驗金屬鹽及 聚本乙烯〜g文鹼土金屬鹽之至少一種； (7)—種成形體 酯樹脂組合物； 其包含如上述（1)至（6)中任— 項之聚碳酸 ⑻如上述⑺之成形體’其係電氣、電子機器用零件； ⑼如上述⑺之成形體，其係電氣、電子機器用殻體； (10)如上述（7)之成形體，其係電氣、電子機器用底板。 發明之效果 根據本發明，可獲得一種不損及聚碳酸酯所具有之原本 之機械物性，薄壁阻燃性、衝擊特性及導熱性優異，並且 造粒時之分子量降低得到抑制，可更高地維持製品之強度 的樹脂組合物。 【實施方式】 以下’對本發明進行詳細說明。 本發明之聚碳酸酯樹脂（以下有時簡稱為r PC樹脂」）組 合物係以（A)芳香族聚碳酸酯樹脂、（b)石墨、（〇聚四氟乙 烯、及（D)有機鹼金屬鹽及/或有機鹼土金屬鹽作為必須成 分者。 作為本發明中之（A)芳香族聚碳酸酯樹脂，可使用含有 (A-1)聚碳酸酯-聚有機矽氧烷共聚物（以下有時簡稱為 「PC-POS共聚物」）者。 具體而言，可單獨為上述（A-l) PC-POS共聚物，或者可 151933.doc 201124469 於其令含有藉由二元酚與碳酸酯前驅物之反應而製造之 (A-2)芳香族聚碳酸酯樹脂（以下有時簡稱為「一般pc樹 月日」）。可較佳地使用上述PC_p〇s共聚物之含量為10〜1〇〇 質量％之芳香族聚碳酸酯樹脂。 關於（A)成分中之（A-2)成分即一般pC樹脂，其製造方法 並無特別限制，可使用藉由先前之各種方法而製造者。例 如可使用藉由溶液法（界面縮聚合法）或熔融法（酯交換法） 使二元酚與碳酸酯前驅物反應而製造者，即藉由以下方法 進行反應而製造者：於末端終止劑之存在下，使二元酚與 光氣反應之界面縮聚合法；或者於末端終止劑之存在下， 使二元齡與碳酸二苯酯等反應之酯交換法等。 作為二70酚，可列舉各種者，尤其可列舉：2,2-雙（4_羥 基苯基）丙烷[雙酚A]、雙（4-羥基苯基）甲烷、丨，卜雙（4羥 基苯基）乙烷、2,2-雙（4-羥基_3,5_二曱基笨基）丙烷、4,4·_ 二羥基二苯、雙（4_羥基苯基）環烷烴、雙（4_羥基苯基）醚、 雙（4-羥基苯基）硫醚、雙（4_羥基苯基）砜、雙（4_羥基苯基） 亞颯及雙（4-羥基苯基）酮等。此外，亦可列舉對苯二酚、 間苯二酚及鄰苯二酚等。該等可分別單獨使用，亦可組合 使用二種以上，該等之中，較佳為雙（羥基苯基）烷烴系 者，尤佳為雙酚Α。 另一方面，作為碳酸酯前驅物，為醯鹵、羰基酯、或鹵 甲酸酯等，具體為光氣、二元酚之二_甲酸酯、碳酸二苯 酷、破酸二甲酯及碳酸二乙酯等。 再者，該一般PC樹脂可具有分支結構，作為分支劑，有 151933.doc 201124469 1，1，1-三（4-羥基苯基）乙烷、α，α’，αΜ-三（4-羥基苯基）-1,3,5- 二異丙基苯、間苯三酚、偏苯三曱酸及靛紅雙（鄰曱酚） 等。 於本發明中，用作（Α-2)成分之一般pc樹脂之黏度平均 分子量（Mv)通常為1〇,〇〇〇〜50,〇〇〇，較佳為13 〇〇〇〜 35,〇〇〇’ 更佳為 15 〇〇〇〜2〇,〇〇〇。 該黏度平均分子量（Μν)係使用烏氏黏度計，測定2〇°c下 之二氣甲烷溶液之黏度，由此求出極限黏度，利用下 式而算出者。 [η] = 1·23><10_5 Μν0.83 於該（Α)成分之芳香族聚碳酸酯樹脂中，（A]) pC_p〇s 共聚物係包含聚碳酸酯部與聚有機矽氧烷部者，例如可藉 由以下方式而製造：使預先製造之構成聚碳酸酯部之聚碳 酸酯寡聚物（以下簡稱為PC募聚物）、與構成聚有機矽氧烷 。戸（鏈段）之於末端具有鄰烯丙基苯酚殘基、對羥基苯乙烯 殘基、丁香油酚殘基等反應性基之聚有機矽氧烷，溶解於 二氯曱烷、氯苯、氯仿等溶劑中，添加二元酚之苛性鹼水 冷液，使用二級胺（二乙基胺等）或四級銨鹽（三甲基苄基氯 化録等）作為觸媒，於末端終止劑之存在下，進行界面縮 聚合反應。 用於該PC-POS共聚物之製造iPC寡聚物例如可藉由在 二氯甲炫等溶劑中’使上述二⑽與光氣等碳酸_前驅物 反應，或者使二元酚、與碳酸醋化合物例如碳酸二笨酯之 類之碳酸酯前驅物反應而容易地製造。 151933.doc 201124469 又’作為碳酸酯化合物，可列舉：碳酸二笨酯等碳酸二 芳醋、或碳酸二甲酯、碳酸二乙酯等碳酸二烷酯。 供於PC-POS共聚物之製造之PC寡聚物可為使用一種上 述二元盼之均寡聚物’又，亦可為使用二種以上之上述二 π酚之共寡聚物。進而，還可為將多官能性芳香族化合物 與上述二元紛併用所得之熱塑性無規分支寡聚物。 於該情形時，作為分支劑（多官能性芳香族化合物），可 使用 1 ’ 1 1 -二（4-經基苯基）乙烧、α，α'，α'·_三（4_經基笨 基）-1，3,5-三異丙基苯、甲基·α(4,羥基苯基）乙基]_4_ [α ’α -雙（4''-羥基苯基）乙基]苯、間苯三酚、偏苯三甲酸、 靛紅雙（鄰甲酚）等》 該pc-p〇s共聚物例如揭示於曰本專利特開平3_292359號 △報日本專利特開平4_2〇2465號公報、日本專利特開平 _62()號公報、日本專利制平8·3()2ΐ78號公報及日本專 利特開平10-7897號公報等中。 入乍為》亥PC POS共聚物’可較佳地使用聚碳酸酯部之聚 口度為3〜1〇〇左右’聚有機矽氧烷部之聚合度為2〜左右 者。 入 牙.^PC樹脂組合物之阻燃性賦予效果、耐衝擊 性賦予效果、及經濟性之平衡等觀點而言，該PC-POS共 =中之聚有財氧燒部於⑷成分整體中之含量較佳為 s又為1〜6質量〇/〇。 進而，該PC-POS共聚铷+叙— $ 之黏度平均分子量（Μν)通常為 5’000〜1〇〇,〇0〇，較佳為 υ’〇〇〇〜30,〇〇〇，尤佳為 12,〇〇〇〜 151933.doc 201124469 30,000。此處， 樹脂同樣地求出 該等黏度平均分子量（Mv)可與上述一般pc 作為该PC-P0S共聚物令之聚有機石夕氧炫部，較佳為包 3聚甲基夕氧烷、聚二乙基矽氧烷、聚甲基苯基矽氧烷 等之鏈段’尤佳為聚二甲㈣氧院鏈段。 至於⑷成分中之⑹）pc_p〇s共聚物與作為（η)成分 之4又PC树知之使用比率，較佳為以該共聚物中 之聚有機石夕氧院部於⑷成分整財之含量成為Η質量％ 之方式進行調整，χ，以作為⑷成分整體之原料分子量 (黏度平均分子量)成為17，_〜3〇，_之範s、較佳為 18,000〜26,000之方式進行調整。 例如關於聚有切氧院部之含量，於使用具有超出” 量％之高含有率之聚有機石夕氧院部的PC-POS共聚物時，可 藉由使用大量一般p f1嫩日t 又L树月曰，又，於使用低含有率之PC_ POS共聚物時’可藉由不使用一般pc樹脂或使用少量一般 PC樹脂，而將於⑷成分整體中之含量調整為卜6質量％。 通常，⑷成分中之（Α_υ Pc_p〇s共聚物係於ι〇〜⑽質 量％之範圍内使用°PC彻共聚物之比率較多時，容易獲 得成形體之衝擊強度，又，可抑製造粒時之分子量降低。 作為用作該（A)成分之芳香族pc樹脂中之分子末端基的 分子量調節劑，通常為用於聚碳酸醋之聚合者即可可使 用各種-兀酚。具體而言’例如可列$ :苯酚、對曱酚、 對第三丁基苯紛、對第三辛基笨齡、對異丙苯基苯驗、溴 笨盼、三溴苯酚、壬基苯紛等。 151933.doc 201124469 於本發明之PC樹脂組合物中，除了上述芳香族pc樹脂 及PC-POS共聚物以外，可於不損及本發明之目的之範圍 内適當含有：#由在對苯二甲酸等二官能性㈣或其醋形 成衍生物等酯前驅物之存在下進行聚碳酸酯之聚合而獲得 的聚酯-聚碳酸酯樹脂等共聚樹脂、或其他聚碳.酸酯樹 脂。 於本發明之聚;ε反酸g旨樹脂組合物中，主要為賦予導熱性 而調配（Β)石墨。 作為本發明中使用之石墨，可利用天然石墨、或各種人 造石墨之任一者》作為天然石墨，可利用土狀石墨、鱗狀 石墨（亦稱作塊狀石墨之Vein Graphite)、及鱗片狀石墨 (Flake Graphite)之任一者。於上述例示之天然石墨中可 較佳地使用鱗片狀石墨。藉由應用天然石墨，可獲得更高 之導熱性與更高之彈性模數。 人造石墨係對非定形碳進行熱處理，人工進行不規則排 列之微小石墨結晶之定向而成者，除了通常用於碳材料之 人造石墨以外，亦包括凝析石墨、分解石墨、及熱分解石 墨等。通常用於碳材料之人造石墨通常可以石油焦或煤系 瀝青焦作為主原料，藉由石墨化處理而製造。 相比上述天然石墨，上述人造石墨彈性、導熱性變低， 但具有可改良較高之焊接強度之優點。 (B)成分之調配量相對於上述（A)成分1〇〇質量份，必需 设為30〜1 〇〇質量份之範圍，較佳為3〇〜7〇質量份之範圍。 若調配量未達30質量份，則難以獲得充分之導熱性，若超 151933.doc •12· 201124469 出100質量份，則存在衝擊強度容易降低之問題。 於本發明中，關於石墨之粒徑，可較佳地使用50%累積 粒徑為30〜180 4!^者。石墨之固定碳量較佳為8〇重量％以 上，更佳為90重量❶/。以上，尤佳為98重量％以上。又 墨之揮發成分較佳為3重量％以下，*伟 又住马1.5重量％以 下’尤佳為1重量％以下。 關於石墨之表面，只要不損及本發明之組合物之特性， 則為了增加與熱塑性樹脂之親和性，亦可實施表面處理， 例如環氧處理、胺基甲酸酯處理、矽烷偶合處理及氧化處 理等。 於本發明之聚碳酸酯樹脂組合物中，為提高薄壁阻燃性 而調配（C)聚四氟乙烯（PTFE)。該（c)成分對本發明之樹脂 &物賦予抗溶融滴落效果，表現優異之薄壁阻燃性。 (C)成分較佳為具有纖維形成能力者。此處，所謂「纖 隹形成Sb力」，係指藉由剪切力等外力作用而表現出樹脂 彼此結合而形成纖維狀之傾向。作為本發明之（C)成分， 例如可列$ :聚四氟乙烯、四氟乙烯系共聚物(例如四氟 乙稀/六氣丙稀共聚物等）等。該等之中，較佳為聚四氟乙 烯。 具有纖維形成能力之PTFE具有極高之分子量，以根據 心準比重求出之數量平均分子量計，通常為50萬以上，較 佳為50萬〜ι5〇〇萬，更佳為ι〇〇萬〜1〇〇〇萬。具體而言可 藉由在水性溶劑中，於過二硫酸鈉、過二硫酸鉀或過二硫 酸錄之；fe jfe π 廿仕下，於7〜700 kPa左右之壓力下，於溫度 151933.doc 13 201124469BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition and a molded body comprising the resin composition, and the present invention relates to a method, even if no gas-based flame retardant is used, A bromine-based flame retardant and a phosphorus-based flame retardant, a polycarbonate resin composition excellent in flame retardancy (especially, thin-wall flame retardancy), thermal conductivity, and impact properties, and a molded article including the same. [Prior Art] In the development of products in the field of electrical and electronic products, with the high pixelation and high-speed processing of digital cameras and digital cameras, the miniaturization of projectors, the high-speed processing of computers and mobile devices, and the LEDs of various light sources (Light Emitting Diode, light-emitting diodes, etc., have focused on heat dissipation measures. In the case of a miniaturized machine, the heat dissipating circuit is complicated, so that the resin case and the heat dissipating circuit are required to be formed, and the thermal conductivity is excellent, and the housing is excellent. A resin material that is also excellent in mechanical strength. Further, in a small electronic device, the casing and the bottom plate are required to be thinned, and the flame retardancy of the thin molded body is also required. • A polycarbonate resin is used in the case of the above-mentioned electronic device, and the like, in order to flame-retard the molded body containing the polycarbo-resin composition, a chlorine, a cerium, a bromine-based flame retardant, or the like is added. Prime-based flame retardants' However, in recent years, the concept of environmental impact on the whole, waste, and incineration is considered to be a flame-retardant method using a flame retardant containing no element. In order to flame-retard the organic tank-based flame retardant as the above-mentioned non-fossil-based flame retardant, in particular, the organic acid I51933.doc 201124469 vinegar compound is blended in the polycarbonate resin composition, it is necessary to mix relatively A large amount of broken vinegar compounds. The polycarbonate resin has a high molding temperature. The melt viscosity is also high, so that the molding temperature tends to be high. Therefore, the phosphate compound generally contributes to the flame retardancy, but there is a case where the mold is corroded during molding, gas is generated, and the molding environment or the appearance of the molded article is not necessarily sufficient. Therefore, it has been found that a flame retardant (especially a thin-walled flame retardant) can be obtained without using a halogen-based flame retardant such as a gas-based flame retardant or a bromine-based flame retardant or a phosphorus-based flame retardant. A polycarbonate resin composition excellent in thermal conductivity. A method of blending graphite is known as a method of imparting the above-described heat dissipation property to a thermoplastic resin (see Patent Document 2, Patent Document 2). In the work of the patent document, it is disclosed that a thermoplastic resin composition having a small metal corrosion resistance and having excellent thermal conductivity can be obtained by blending a specific graphite with a thermoplastic resin. The organic halogen-based flame retardant or the phosphate-based flame retardant such as a functionalized carbonate oligomer or a halogenated epoxy compound is preferably used for improving the flame retardancy, and the gas-based flame retardant is not disclosed. Technology of bromine-based flame retardants and phosphorus-based flame retardants. Further, in Patent Document 2, the heat-dissipating casing that houses the heating element has been described. However, the flame retardancy required for the casing of an electronic device or the like is not described as an additive to be added as needed, and an organic bromine-based resistance is disclosed. A flame retardant such as a flammable agent or a phosphorus-based flame retardant, but does not disclose a technique of actively not using a gas-based resistance/smoke-type flame retardant and a flame retardant, and it can be considered that in a real target case Since no flame retardant or anti-drip agent is added, it does not have the flame retardancy of 151933.doc 201124469. Further, a polycarbonate resin composition in which graphite is blended with a flame retardant to impart antistatic properties or conductivity to a polycarbonate resin is known (see Patent Document 3 and Patent Document 4). Patent Document 3 discloses an aromatic polycarbonate resin composition comprising a specific polyfluorene oxide containing a mixture of an aromatic polycarbonate resin and graphite, and is equivalent to antistatic wow and β. Although the flame retardancy is not described, a technical inner valley in which sufficient flame retardancy is obtained by a thin wall of about 1.5 mm required for a casing such as an electronic device is not described. Further, in Patent Document 4, as a technique for actively not using a chlorine-based flame retardant bromine-based flame retardant and a phosphorus-based flame retardant, it is disclosed that it contains a polycarbonate barium sulphate graphite and an organic sulfonate base. In the evaluation of the flame retardancy of the (cemental) metal salt-based flame retardant resin composition, the molded article having a thickness of 25 _ is only subjected to the "valence of the product" and the patent document 3 is the same as the case of the electronic device. A thin wall of about 1.5 mm does not provide sufficient flame retardancy. CITATION LIST Patent Literature Patent Literature 1: Patent Publication No. 2007-31611 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei. No. 2008-31358. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a thin-walled molded body which does not use a gas-based flame retardant, a bromine-based flame retardant, and a phosphorus-based flame retardant. The polycarbonate resin composition and the molded article which are excellent in flame retardancy (thickness: 〇15I933.doc 201124469 mm, hereinafter referred to as "thin-wall flame retardancy") and have high thermal conductivity and excellent impact properties. Technical Solution to Problem The inventors of the present invention have repeatedly responded to the problem, and found that by blending an aromatic polycarbonate resin containing polycarbonate-polyorganosiloxane copolymer, graphite, and polytetrafluoroethylene at a specific ratio The ethylene resin, the organic alkali metal salt, and/or the organic soil metal salt can be obtained by obtaining a polycarbonate resin composition which is excellent in thin-wall flame retardancy and further excellent in thermal conductivity and impact properties. That is, the present invention provides the following: (1) A polycarbonate resin composition which is based on (A) an aromatic polycarbonate resin containing a polycarbonate-polyorganosiloxane copolymer. The parts by mass include (B) 30 to 100 parts by mass of graphite, (C) polytetrafluoroethylene, 1 part by mass, and (D) an organic alkali metal salt and/or an organic alkaline earth metal salt of 0.057 mass parts; The polycarbonate resin composition of the above (1), wherein the content of the polyorganosiloxane in (A) is from 1 to 6 mass%; (3) the polycarbonate resin composition according to (1) above, Wherein the polyorganosiloxane of the aromatic polycarbonate 6-polyorganosiloxane is a poly(dialkyl) oxime; (4) a polycondensation according to any one of the above (1) to (3) The polycarbonate resin composition, wherein the graphite is a natural graphite; (5) The polycarbonate resin composition according to any one of the above (1) to (3), wherein the graphite is artificial graphite; 151933.doc 201124469 (9) Organic gold test A polycarbonate resin composition according to any one of the eyebrows, wherein the metal is placed on the ground and/or the organic alkaline earth metal salt is selected from the group consisting of organic sulfonic acid. At least one of a soil metal salt, a polystyrene acid test metal salt, and a polyethene metal salt; (7) a shaped body ester resin composition; comprising the above (1) to (6) (10) The molded article of the above (7) is a component for electrical and electronic equipment, and the molded article of the above (7) is a casing for an electric or electronic device; (10) as described above (7) The molded body is a base plate for electric and electronic equipment. Advantageous Effects of Invention According to the present invention, it is possible to obtain a mechanical property which does not impair the original mechanical properties of polycarbonate, and is excellent in thin-wall flame retardancy, impact properties and thermal conductivity, and the molecular weight reduction during granulation is suppressed, and the product can be maintained higher. The strength of the resin composition. [Embodiment] Hereinafter, the present invention will be described in detail. The polycarbonate resin (hereinafter sometimes abbreviated as r PC resin) composition of the present invention is (A) an aromatic polycarbonate resin, (b) graphite, (yttrium polytetrafluoroethylene, and (D) an organic base. A metal salt and/or an organic alkaline earth metal salt is an essential component. As the (A) aromatic polycarbonate resin in the present invention, (A-1) polycarbonate-polyorganosiloxane copolymer (hereinafter, Sometimes referred to as "PC-POS copolymer". Specifically, it can be the above (Al) PC-POS copolymer alone, or it can be 151933.doc 201124469, which contains a precursor of dihydric phenol and carbonate. The (A-2) aromatic polycarbonate resin (hereinafter sometimes referred to simply as "general pc tree moon day") produced by the reaction of the object. The content of the above PC_p〇s copolymer is preferably 10 to 1 〇. The aromatic polycarbonate resin of the (%) component (A-2) is not particularly limited as long as it is a general pC resin, and can be produced by various methods. Can be used by solution method (interface polycondensation method) or melting method (transesterification method) Producing a dihydric phenol with a carbonate precursor, that is, by reacting by reacting a dihydric phenol with phosgene in the presence of a terminal terminator; or terminating at the end In the presence of the agent, a transesterification method in which a binary age is reacted with diphenyl carbonate or the like is used. Examples of the di-70 phenol include various examples, and in particular, 2,2-bis(4-hydroxyphenyl)propane [ Bisphenol A], bis(4-hydroxyphenyl)methane, anthracene, bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-didecyl)propane, 4,4·_ Dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) Sulfone, bis(4-hydroxyphenyl) anthracene, bis(4-hydroxyphenyl) ketone, etc. Further, hydroquinone, resorcinol, catechol, etc. may be mentioned. Two or more types may be used in combination, and among them, those of bis(hydroxyphenyl)alkane are preferred, and bisphenolphthalein is preferred. On the other hand, as a carbonate precursor, it is a halogen halide. a carbonyl ester, or a haloformate, etc., specifically a phosgene, a di-formate of a dihydric phenol, a diphenyl carbonate, a dimethyl ester, and a diethyl carbonate. Further, the general PC resin can be used. Has a branched structure, as a branching agent, there are 151933.doc 201124469 1,1,1-tris(4-hydroxyphenyl)ethane, α,α',αΜ-tris(4-hydroxyphenyl)-1,3, 5-diisopropylbenzene, phloroglucinol, trimellitic acid, and eosin double (o-nonylphenol), etc. In the present invention, the viscosity average molecular weight of a general pc resin used as the component (Α-2) (Mv) is usually 1 〇, 〇〇〇 ~ 50, 〇〇〇, preferably 13 〇〇〇 ~ 35, 〇〇〇 'better than 15 〇〇〇 ~ 2 〇, 〇〇〇. The viscosity average molecular weight (??) was calculated by using a Ubbelohde viscometer and measuring the viscosity of a two-gas methane solution at 2 〇 °c to determine the ultimate viscosity, which was calculated by the following formula. [η] = 1·23><10_5 Μν0.83 In the aromatic polycarbonate resin of the (Α) component, (A]) the pC_p〇s copolymer contains a polycarbonate portion and a polyorganosiloxane. For example, it can be produced by forming a polycarbonate oligomer constituting a polycarbonate portion (hereinafter abbreviated as PC condensed polymer) and a polyorganosiloxane. a polyorganosiloxane having a reactive group such as an o-allylphenol residue, a p-hydroxystyrene residue or a eugenol residue at the end of the oxime (segment), dissolved in dichloromethane, chlorobenzene, In a solvent such as chloroform, a caustic alkali water-cooling solution of a dihydric phenol is added, and a secondary amine (diethylamine or the like) or a quaternary ammonium salt (trimethylbenzyl chloride chloride, etc.) is used as a catalyst, and a terminal terminator is used. In the presence of the interface, the interfacial polycondensation reaction is carried out. The iPC oligomer used for the production of the PC-POS copolymer can be, for example, by reacting the above two (10) with a carbonic acid precursor such as phosgene in a solvent such as dichloromethane or a dihydric phenol or a carbonated vinegar. A carbonate precursor such as a compound such as diphenyl ester is easily produced by reacting with a carbonate precursor. 151933.doc 201124469 Further, examples of the carbonate compound include diaryl carbonate such as diphenyl carbonate or dialkyl carbonate such as dimethyl carbonate or diethyl carbonate. The PC oligomer to be used for the production of the PC-POS copolymer may be one using the above-mentioned binary desired oligomer or 'co-oligomer using two or more of the above two π phenols. Further, it may be a thermoplastic random branched oligomer obtained by using a polyfunctional aromatic compound in combination with the above binary. In this case, as a branching agent (polyfunctional aromatic compound), 1 '1 1 -di(4-pyridylphenyl)ethene, α,α',α'·_3 (4_ -1,3,5-triisopropylbenzene, methyl·α(4,hydroxyphenyl)ethyl]_4_[α 'α-bis(4''-hydroxyphenyl)ethyl] Benzene, phloroglucinol, trimellitic acid, ruthenium bis (o-cresol), etc. The pc-p〇s copolymer is disclosed, for example, in Japanese Patent Laid-Open No. Hei 3_292359, Japanese Patent Application No. 4-2〇2465 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In the case of the "Hei PC POS copolymer", the degree of polymerization of the polycarbonate portion is preferably about 3 to 1 Å, and the degree of polymerization of the polyorganosiloxane is about 2 to about. From the point of view of the flame retardancy imparting effect, the impact resistance imparting effect, and the economic balance of the PC resin composition, the PC-POS total is included in the (4) component as a whole. The content is preferably s and is 1 to 6 mass 〇/〇. Further, the viscosity average molecular weight (Μν) of the PC-POS copolymer 铷+ —-$ is usually 5'000~1〇〇, 〇0〇, preferably υ'〇〇〇~30, 〇〇〇, especially good For 12, 〇〇〇 ~ 151933.doc 201124469 30,000. Here, the resin is similarly determined to have the same viscosity average molecular weight (Mv) as the above-mentioned general PC as the PC-POS copolymer, and the polyorganooxime portion, preferably 3-polymethyloxane, A segment of polydiethyl decane, polymethylphenyl siloxane or the like is particularly preferably a polydimethyl (tetra) oxygen chain segment. As for the (6) component (6)), the ratio of the pc_p〇s copolymer to the (n) component of 4 and the PC tree is preferably the content of the (4) component of the polyorganisms in the copolymer. The method of adjusting the mass % of the component is adjusted so that the molecular weight (viscosity average molecular weight) of the whole component (4) is adjusted to be 17, _ to 3 〇, _ s, preferably 18,000 to 26,000. For example, when the PC-POS copolymer of the polyorganisms having a high content rate exceeding the amount of "%" is used, it is possible to use a large amount of general pf1. In the case of using a PC_POS copolymer having a low content ratio, the content of the component (4) can be adjusted to 6% by mass by using no PC resin or a small amount of a general PC resin. In general, when the ratio of the Α_υ Pc_p〇s copolymer in the range of ι〇 to (10)% by mass is large, the impact strength of the molded body is easily obtained, and granulation can be suppressed. When the molecular weight of the molecular terminal group in the aromatic pc resin used as the component (A) is generally used for the polymerization of polycarbonate, various indophenols can be used. For example, it can be listed as: phenol, p-nonylphenol, p-tert-butylbenzene, p-third octyl idyl, p-cumyl benzene, bromine, tribromophenol, nonylbenzene, etc. 151933 .doc 201124469 In the PC resin composition of the present invention, in addition to the above In addition to the aromatic PC resin and the PC-POS copolymer, it may be appropriately contained within a range not detracting from the object of the present invention: #from an ester precursor such as a difunctional (tetra) such as terephthalic acid or a vinegar-forming derivative thereof There is a copolymer resin such as a polyester-polycarbonate resin obtained by polymerizing polycarbonate, or another polycarbonate resin. In the present invention, the ε-reverse acid-g resin composition is mainly imparted. As the graphite used in the present invention, any of natural graphite or various artificial graphites can be used as natural graphite, and earthy graphite or scaly graphite (also referred to as a block shape) can be used. Any of Fein Graphite) and flake graphite (Flake Graphite). It is preferable to use flaky graphite in the above-exemplified natural graphite. By using natural graphite, higher thermal conductivity and higher can be obtained. High elastic modulus. Artificial graphite is a heat treatment of amorphous carbon, artificially performing the orientation of irregularly arranged tiny graphite crystals, in addition to the artificial graphite commonly used for carbon materials, including condensate Graphite, decomposed graphite, and thermally decomposed graphite, etc. The artificial graphite generally used for carbon materials can be produced by graphitization using petroleum coke or coal-based pitch coke as a main raw material. Compared with the above natural graphite, the above-mentioned artificial graphite is elastic. The thermal conductivity is low, but it has the advantage of improving the welding strength. (B) The amount of the component is required to be in the range of 30 to 1 〇〇 by mass based on 1 part by mass of the above component (A). It is preferably in the range of 3 〇 to 7 〇 parts by mass. If the amount is less than 30 parts by mass, it is difficult to obtain sufficient thermal conductivity, and if it exceeds 151,933.doc •12·201124469, 100 parts by mass, the impact strength is easy. Reduce the problem. In the present invention, as for the particle diameter of graphite, a 50% cumulative particle diameter of 30 to 180 4 is preferably used. The amount of fixed carbon of graphite is preferably 8% by weight or more, more preferably 90% by weight. The above is particularly preferably 98% by weight or more. Further, the volatile component of the ink is preferably 3% by weight or less, and more preferably 1.5% by weight or less, particularly preferably 1% by weight or less. Regarding the surface of the graphite, surface treatment such as epoxy treatment, urethane treatment, decane coupling treatment, and oxidation may be performed in order to increase the affinity with the thermoplastic resin as long as the characteristics of the composition of the present invention are not impaired. Processing and so on. In the polycarbonate resin composition of the present invention, (C) polytetrafluoroethylene (PTFE) is formulated for the purpose of improving the thin-wall flame retardancy. The component (c) imparts an anti-smelting dripping effect to the resin & matter of the present invention, and exhibits excellent thin-wall flame retardancy. The component (C) is preferably one having fiber forming ability. Here, "the formation of the Sb force by the fiber" means that the resin is bonded to each other to form a fibrous shape by an external force such as a shearing force. The component (C) of the present invention may, for example, be a polytetrafluoroethylene or a tetrafluoroethylene copolymer (e.g., a tetrafluoroethylene/hexapropylene copolymer). Among these, polytetrafluoroethylene is preferred. The PTFE having the fiber forming ability has an extremely high molecular weight, and the number average molecular weight determined based on the core specific gravity is usually 500,000 or more, preferably 500,000 to 1,500,000, more preferably 10,000 million. 1 million. Specifically, it can be recorded in an aqueous solvent in sodium peroxodisulfate, potassium peroxydisulfate or peroxodisulfate; under the pressure of 7 to 700 kPa at a temperature of 151,933 kPa. 13 201124469

0〜200 C左右、較佳為20〜100°C下，使四氟乙烯進行聚八 而獲得。 Q 又，除了固體形狀以外，亦可使用水性分散液形態者， 可使用根據ASTM標準而分類為類型3者。作為分類為該類 型3之市售品，例如可列舉：「Tefl〇n 6_j」[商品名， PONT-MITSUI FLUOROCHEMICALS(股）製造]、「P〇lyfl D-i」及「Polyflon F_103」[商品名，大金工業（股）製造°; 等。又，除了類型3以外，可列舉r Aig〇fl〇n F5」[商品 名，Solvay Solexis公司製造]、及「p〇lyfl〇n ΜρΑρΑ· 100」[商品名，大金工業（股）製造]等。 上述PTFE可單獨使用，或者可組合使用2種以上。 (C)聚四氟乙烯（PTFE)之調配量相對於上述芳香族聚 碳酸醋樹脂1〇〇質量份，為卜1〇質量份之範圍，較佳為 1.5〜9質i份。若該調g己量未達}質量份，則抗滴落效果消 失，若超出10質量份，則衝擊特性降低。 具有作為抗滴落劑之效 ’則不但具有作為抗滴落 度、脫模性之提高效果， 於調配量為1〜1.5質量份時，J 果’若超出1.5質量份進行調配， 劑之效果’而且亦可發揮衝擊強度 成形時之脫模作用亦變好。 為進一步提高本發明之聚碳酸醋樹脂組合物之薄壁阻燃 性，而調配（D)有機驗金屬鹽及/或有機驗土金屬鹽。…It is obtained by polytetrafluoroethylene at about 0 to 200 C, preferably at 20 to 100 °C. Q Further, in addition to the solid shape, an aqueous dispersion may be used, and those classified as Type 3 according to the ASTM standard may be used. For example, "Tefl〇n 6_j" (product name, PONT-MITSUI FLUOROCHEMICALS), "P〇lyfl Di", and "Polyflon F_103" [product name," Daikin Industrial Co., Ltd. manufactures °; In addition to the type 3, r Aig〇fl〇n F5" [trade name, manufactured by Solvay Solexis], and "p〇lyfl〇n ΜρΑρΑ·100" (product name, Daikin Industries Co., Ltd.) Wait. The above PTFE may be used singly or in combination of two or more. (C) The amount of the polytetrafluoroethylene (PTFE) to be added is 1 part by mass based on 1 part by mass of the aromatic polycarbonate resin, preferably 1.5 to 9 parts by mass. If the amount is less than 5% by mass, the anti-dripping effect is lost, and if it exceeds 10 parts by mass, the impact characteristics are lowered. The effect of having an anti-drip agent is not only an effect of improving dripping resistance and mold release property, but also when the amount is 1 to 1.5 parts by mass, if the amount exceeds 1.5 parts by mass, the effect of the agent is adjusted. 'And it is also possible to exert a release effect when the impact strength is formed. In order to further improve the thin-wall flame retardancy of the polycarbonate resin composition of the present invention, (D) an organic metal salt and/or an organic soil metal salt is formulated. ...

151933.doc 乂负微蛻土金屬鹽，可列舉各 個碳原子之有機酸或有機酸酯之 14 201124469 此•處·’有機酸或有機酸酯為有機磺酸、有機綾酸等。另 方面驗金屬為鐘、鈉、鉀、铯等，驗土金屬為錄、 的、錄、鋇等，其中，可較佳地使用鈉、鉀之鹽。又，該 有機酸之鹽可經如氟、氣、溴之鹵素所取代。鹼金屬鹽及 有機驗土金屬鹽可單獨使用一種或者組合使用二種以上。 上述各種有機鹼金屬鹽及有機鹼土金屬鹽中，例如於有 機巧酸之情形時，可較佳地使用下述通式（1)所表示之全氟 烷磺酸之鹼金屬鹽及鹼土金屬鹽。151933.doc 乂 蜕 蜕 蜕 蜕 蜕 蜕 蜕 蜕 蜕 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 On the other hand, the metals are bell, sodium, potassium, barium, etc., and the soils for soil examination are recorded, recorded, sputum, etc., among which sodium and potassium salts can be preferably used. Further, the salt of the organic acid may be substituted with a halogen such as fluorine, gas or bromine. The alkali metal salt and the organic soil test metal salt may be used alone or in combination of two or more. In the case of the above-mentioned various organic alkali metal salts and organic alkaline earth metal salts, for example, in the case of an organic acid, an alkali metal salt and an alkaline earth metal salt of perfluoroalkanesulfonic acid represented by the following general formula (1) can be preferably used. .

(CeF 2e + 1 S〇3)fM ⑴ 式中，e表示卜1〇之整數，Μ表示鋰、鈉、鉀、绝等鹼 金屬’鎮、H錄、鎖等驗土金屬，f表示Μ之原子價。 作為該等化合物’例如日本專利特公昭Ο#⑽C號公報 中所記載者相當於此。 上述通式（1)中，#為全氣院績酸，例如可列舉：全氣 甲〜酸、全氣乙確酸、全氣丙確酸、全氣丁石黃酸、全氣甲 基丁續I H己績酸、全氟庚韻、全1辛績酸等。尤 4為使用4等之鉀鹽。此外可列舉：冑甲苯項酸、2,5_二 氣苯’ 2’4,5·三氯苯續酸；二苯基硬_3_項酸；二苯基 砜-3,3 磺酸；萘三磺酸等有機磺酸之鹼金屬鹽等。 又，作為有機緩酸，例如可列舉：全氣甲酸、全氣甲 全氣乙烧甲酉夂、全氟丙院曱酸、全氟丁炫甲酸、 氣甲基丁炫^甲酸、令》蠢p h 齓己烷甲酸、全氟庚烷甲酸、全氟 烧甲酸等，可使用該等有機繞酸之驗.金屬臨。 繼而，作為可用於⑼成分之聚苯乙稀續酸之驗金屬 151933.doc ' 15 · 201124469 及/或鹼土金屬鹽，可使用下述通式（2)所 基之芳香族乙烯系樹脂。 不之含磺酸鹽 [化1](CeF 2e + 1 S〇3)fM (1) where e represents an integer of Bu, and Μ represents lithium, sodium, potassium, and an alkali metal such as 'town, H record, lock, etc., and f represents Μ之之Atomic price. As described in the above-mentioned compound, for example, the Japanese Patent Publication No. (10) No. C corresponds to this. In the above formula (1), # is a full-gas acid, for example, all gas methyl-acid, total gas, acid, total gas, acid, total gas, and total gas methyl Continued IH has acid, perfluorinated rhyme, all 1 acid and so on. In particular, 4 is a potassium salt. Further, exemplified by: fluorene toluic acid, 2,5-di-benzene Benzene 2'4,5·trichlorobenzene acid; diphenyl hard_3_-acid; diphenyl sulfone-3,3 sulfonic acid; An alkali metal salt of an organic sulfonic acid such as naphthalene trisulfonic acid. Further, examples of the organic acid retardation include: total gas formic acid, total gas, full gas, ethylene, formazan, perfluoropropene, decanoic acid, perfluorobutyric acid, gas methylbutylate, formic acid, and stupidity. Ph 齓 hexanecarboxylic acid, perfluoroheptanecarboxylic acid, perfluorocarboxylic acid, etc., can be used to test the organic acid. Metal. Then, as the metal 151933.doc '15 · 201124469 and/or the alkaline earth metal salt which can be used for the poly(styrene) acid of the component (9), an aromatic vinyl resin based on the following formula (2) can be used. Not containing sulfonate [Chemical 1]

’ Z表示氫原子或碳數 h表示莫耳分率，且 上述式（2)中，Ζι表示磺酸鹽基 1〜10之烴基。g為1〜5之整數。 0<hg 1 〇 此處， 作為金屬 鳃、鋇等 磺酸鹽基為磺酸之鹼金屬鹽及/或鹼土 ，可列舉鈉、鉀、鋰、铷、鉋、鈹、 金屬鹽， 鎂、鈣、 …Z為氫原子或碳數】〜】〇之烴基，較佳為 甲基。I又，…〜5之整數’，為咖之關係。即:' : ^基的相對於芳香環’可為全取代者，亦可為部分心 為進-步提高本發明之聚碳酸醋樹脂組合物之阻 果，考慮含續酸鹽基之芳香族乙稀系樹脂之含量等而决1 續酸鹽基之取代㈣，通常使用取代H)〜、疋 再者，於聚苯乙烯磺酸之鹼金屬鹽及/或鹼土金屬略 中’含績酸鹽基之芳香族乙婦系樹脂並不限定於上述通式 (2)之聚苯乙烯樹脂，亦可為苯乙烯系單體與可共聚合之二 他單體之共聚物。 Μ 151933.doc 201124469 此處’作為含石黃酸鹽基之芳香族乙稀系樹脂之製造方 法，有⑴使上述具有績酸基等之芳香族乙稀系單體聚合， 或者使該等芳香族乙烯系單體與可共聚合之其他單體進行 共聚合之方法；（戦芳香族乙稀系聚合物、或芳香族乙 烯系單體與其他可共聚合之單體之共聚物、或該等之混入 聚合物進行魏，讀金屬化合物及/或驗土金屬化合物 加以中和之方法等。 例如，作為上述（η)之方法，藉由在聚苯乙稀樹脂之仏 二氯乙烧溶液中添加濃硫酸與乙酸針之混合液，進行加 熱’反應數小時’而製造聚苯乙烯績酸化物。繼而，以與 賴基等莫耳量之氫氧切或氫氧錢進行巾#，藉此^ 獲付^^本乙稀績酸卸鹽或納鹽。 作為本發明中所使用之含續酸鹽基之芳香族乙稀系樹脂 之重量平均分子量，宜為1 000~3〇〇〇〇〇左右較佳為 2，刪〜扇，_左右。再者，重量平均分子量可利用 GPC(Ge丨 Permeation Chr〇mat〇graphy ’凝膠滲透層析译而 測定。 上述（D)有機鹼金屬鹽及/或有機鹼土金屬鹽可使用一 種，亦可組合使用二種以上。又，其含量㈣於（a)芳香 族聚碳酸醋樹脂⑽質量份’宜為…質量份較佳為 0.1〜0.9質量份。若上述含量未達〇〇5質量份，則難以達成 目標之薄壁阻燃性，若超出lff份，則存在熱穩定性降 低之問題。 於本發明之聚碳酸酯樹脂組合財，為改善成形性、耐 15l933.doc •17· 201124469 衝擊性 '外觀、耐候性及剛性等，可於包含上述（A)〜(D) 之成分中含有酚系、磷系、硫系之（£)抗氧化劑、及（F)脫 模劑。 關於（E)抗氧化劑之調配量，磷系抗氧化劑較佳為 0.001〜0.5質量份。若為0.001質量份以上，則可維持造粒 步驟、成形步驟中之熱穩定性，若未達〇 5質量份，則難 以引起分子量降低。又，酚系抗氧化劑較佳為添加 0.001〜0.5質量份，容易提高衝擊強度。 作為（F)脫模劑’只要為調配於聚碳酸酯樹脂中可改善 成形時之脫模性者，則並無特別限定。尤其是蜂蠟、甘油 單硬脂酸酯、甘油三硬脂酸酯、季戊四醇單硬脂酸酯、季 戊四醇三硬脂酸酯、季戊四醇四硬脂酸酯、褐煤酸酯蠟、 羧酸酯等有機化合物表現優異之脫模性，可較佳地使用。 該等有機化合物例如可列舉：三木化學工業公司製造之 「Beeswax Go丨den Brand」，趾印 Vitamin(股）製造之 「Rikemal S-100A」、「Rikemal SL_9〇〇」、及「尺如咖 EW-440A」’ Cognis japan公司製造之「L〇xi〇1 νρ(}86ι」， aadant Japan公司製造之「Uc_x E」，〜邮㈣抓公 司製造之「LoxiM EP_32」。關於其調配量，較佳為 0.001〜2質量份。 進而，視需要亦可含有其他合成樹脂、彈性體、熱塑性 樹脂中常用之添加劑成分。作為上述添加劑，可列舉：抗 靜電劑、聚醯胺聚驗嵌段共聚物（賦予永久抗靜電性能）、 苯并三Μ或二苯甲_系紫外線吸㈣、受阻㈣光穩定 151933.doc 201124469 劑（耐候劑）、塑化劑、抗菌劑、相溶劑及著色劑（染料、顏 料）等。 匕關於任意成分之調配量’只要為可維持本發明之聚碳酸 酯樹脂組合物之特性之範圍，則並無特別限制。 繼而，對本發明之聚碳酸酯樹脂組合物之製造方法進行 說明。 本發明之聚碳酸酯樹脂組合物可藉由以上述比例調配上 述各成分（A)〜(D)，進而以適當比例調配視需要所使用之 各種任意成分’並進行混練而獲得。 調配及混練可利用通常使用之機器例如帶型攪拌機、鼓 式滾筒等進行預備混合，並使用亨舍爾混合機、班伯裏混 合機、單螺桿擠出機、雙螺桿擠出機、多螺桿擠出機及雙 向捏合機（Ko-kneader)等之方法而進行。混練時之加熱溫 度通常於240〜32(TC之範圍内適當選擇。作為該熔融混練 成形，較佳為使用擠出成形機，尤其是排氣式擠出成形 機。 再者，聚碳酸酯樹脂以外之含有成分亦可預先與聚碳酸 商旨樹脂或其他熱塑性樹脂熔融混練，即以母料之形式而添 加。 本發明之聚碳酸酯樹脂組合物可藉由上述熔融混練成形 機，或者以所得顆粒物作為原料，藉由射出成形法、射出 壓縮成形法、擠出成形法、吹塑成形法、擠壓成形法、真 空成形法及發泡成形法等’而製造各種成形體。尤其是， 可較佳地利用射出成形及射出壓縮成形，以所得之顆粒物 151933.doc •19· 201124469 製造射出成形體。 包含本發明之聚碳酸酯樹脂組合物之成形體例如可較佳 地用作： (1) 電視、卡式收錄音機（radio cassette)、攝影機、錄景《 機、音頻播放器、DVD(digital video disc，數位多功能盤 片）播放器、空氣調節器、行動電話、顯示器、計算機、 記錄器（register)、計算器、影印機、印表機、傳真機等電 氣、電子機器用零件； (2) 上述1之電氣、電子機器用之殼體； (3) 上述1之電氣、電子機器用之底板等。 實施例 以下，表示實施例及比較例對本發明進行更加具體之說 明’但本發明並不受該等例之任何限制。 將性能評價方法及使用原料表示如下。 [性能評價方法] (1) 黏度平均分子量 利用烏式黏度管，測定抓下之二氣甲烧溶液之極限黏 度[η]，根據以下關係式（SchneU之式）進行計算。 [η] = 1.23χ10'5χΜν° 83 再者，顆粒物分子量係將評價用顆粒物樣品溶解於二氣 曱烧中’分離出不溶解成分，測定經萃取之聚碳酸酿樹脂 之分子量。 (2) 阻燃性 使用依據UL標準94而製作之試驗片（長127 _、寬ι2·7 151933.doc -20- 201124469 mm、厚丨.2 mm)來進行垂直燃燒試驗。 或V-2之等級 評價為UL94 V-0、v 為V- 2外。 根據試驗之結果， 將未達到V-2者設 再者，所謂UL標準94，係根據使保持垂直之特定大小 W驗片與燃燒器之火焰接觸1〇秒後之餘焰 燃性之方法。 °”貝阻 (3) 導熱率 使用導熱率測定裝置「TPA_501」[京都電子工業(股)製 造]，利用Hot Disk法進行測定。 (4) 密度 依據JIS K7112 : 〇進行測定。 (5) 彎曲特性 彈性模數：依據ASTMD：790進行測定。 彎曲強度：依據ASTM D790進行測定。 (6) 衝擊特性 帶缺口之艾氏衝擊強度（IZ0D) 使用以射出成形機而製作之試驗片（县〗）7 、仅 z·7 mm、寬 63 mm、高3.2 mm)，依據ASTM標準d_256，於韦,卜、w十'Z' represents a hydrogen atom or a carbon number h represents a molar fraction, and in the above formula (2), Ζι denotes a hydrocarbon group of a sulfonate group of 1 to 10. g is an integer from 1 to 5. 0<hg 1 〇 Here, as the alkali metal salt and/or alkaline earth of the sulfonate group such as ruthenium or osmium, sodium, potassium, lithium, cesium, planer, bismuth, metal salt, magnesium and calcium are mentioned. , Z is a hydrogen atom or a carbon number of hydrazine, preferably a methyl group. I, the integer of ...~5, is the relationship of coffee. Namely: ': ^ base relative to the aromatic ring' may be a full substitute, or may be part of the heart to further improve the resistance of the polycarbonate resin composition of the present invention, considering the aromatic salt containing a salt group The content of the ethylene resin, etc., and the replacement of the acid salt group (IV), usually using the substitution H)~, 疋, and the alkali metal salt and/or alkaline earth metal of the polystyrene sulfonic acid The salt-based aromatic berry resin is not limited to the polystyrene resin of the above formula (2), and may be a copolymer of a styrene monomer and a copolymerizable di-monomer. 151 151933.doc 201124469 Here, as a method for producing a rhodamine-based aromatic vinyl resin, (1) polymerizing the aromatic vinyl monomer having the acid group or the like, or making the aromatic a method of copolymerizing a group of vinyl monomers with another monomer copolymerizable; (a copolymer of an aromatic vinyl monomer or an aromatic vinyl monomer and another copolymerizable monomer, or Such as mixing the polymer into the Wei, reading the metal compound and/or the method of neutralizing the metal compound, etc. For example, as the method of the above (η), by using a solution of the styrene dichloride in the polystyrene resin Adding a mixture of concentrated sulfuric acid and acetic acid needle, heating to 'react for several hours' to produce a polystyrene acid salt. Then, with a molar amount of hydrogen peroxide or a hydroxyl oxygen to the substrate, borrow The weight average molecular weight of the aromatic vinyl-containing resin containing the acid salt group used in the present invention is preferably 1 000 to 3 〇〇〇. 〇〇 is preferably 2, deleted ~ fan, _ or so. Again, The weight average molecular weight can be measured by GPC (Ge丨Permeation Chr〇mat〇graphy 'gel permeation chromatography. The above (D) organic alkali metal salt and/or organic alkaline earth metal salt may be used alone or in combination. Further, the content (4) of (a) the aromatic polycarbonate resin (10) parts by mass is preferably 0.1 parts by mass to 0.9 parts by mass. If the above content is less than 5 parts by mass, it is difficult to achieve the target. The thin-wall flame retardancy is a problem that the thermal stability is lowered if it exceeds 1 ff. The polycarbonate resin composition of the present invention is improved in formability and resistance to abrasion, appearance and weather resistance. And the rigidity, etc., may contain a phenol-based, phosphorus-based, sulfur-based (£) antioxidant, and (F) release agent in the components including the above (A) to (D). The amount of the phosphorus-based antioxidant is preferably 0.001 to 0.5 parts by mass. When the amount is 0.001 part by mass or more, the thermal stability in the granulation step and the molding step can be maintained, and if it is less than 5 parts by mass, the molecular weight is less likely to be lowered. In addition, phenolic antioxidants It is preferable to add 0.001 to 0.5 parts by mass, and it is easy to improve the impact strength. The (F) release agent is not particularly limited as long as it is blended in a polycarbonate resin to improve the mold release property at the time of molding. Excellent performance of organic compounds such as beeswax, glyceryl monostearate, glyceryl tristearate, pentaerythritol monostearate, pentaerythritol tristearate, pentaerythritol tetrastearate, montan acid ester wax, and carboxylate The release property is preferably used. For example, "Beeswax Go丨den Brand" manufactured by Miki Chemical Industry Co., Ltd., "Rikemal S-100A" manufactured by Tokai Vitamin Co., Ltd., and "Rikemal" are mentioned. "L_xi〇1 νρ(}86ι" manufactured by Cognis japan, "Uc_x E" manufactured by aadant Japan, "postal (4)" LoxiM EP_32". The amount of the compound is preferably 0.001 to 2 parts by mass. Further, other synthetic resins, elastomers, and additives commonly used in thermoplastic resins may be contained as needed. Examples of the above additives include an antistatic agent, a polyamidamide polyblock copolymer (providing permanent antistatic properties), a benzotrifluorene or a benzophenone ultraviolet absorber (four), and a hindered (four) light stability 151933.doc 201124469 Agent (weathering agent), plasticizer, antibacterial agent, phase solvent and coloring agent (dye, pigment), etc. The amount of the optional component is not particularly limited as long as it is a range in which the properties of the polycarbonate resin composition of the present invention can be maintained. Next, a method for producing the polycarbonate resin composition of the present invention will be described. The polycarbonate resin composition of the present invention can be obtained by blending the above components (A) to (D) in the above ratio, and further blending various optional components as needed in an appropriate ratio and kneading them. The mixing and kneading can be carried out by using a commonly used machine such as a belt mixer, a drum drum, etc., and using a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi-screw It is carried out by a method such as an extruder and a two-way kneader (Ko-kneader). The heating temperature at the time of kneading is usually suitably selected within the range of 240 to 32 (TC). As the melt kneading, it is preferred to use an extrusion molding machine, particularly a venting extrusion molding machine. Further, a polycarbonate resin The component other than the component may be melt-kneaded with a polycarbonate resin or another thermoplastic resin in advance, that is, in the form of a masterbatch. The polycarbonate resin composition of the present invention may be obtained by the above melt-kneading molding machine, or may be obtained. The particulate matter is used as a raw material, and various molded articles are produced by injection molding, injection compression molding, extrusion molding, blow molding, extrusion molding, vacuum molding, foam molding, etc., in particular, The injection molded body is preferably produced by the injection molding and the injection compression molding, and the obtained pellet 151933.doc • 19·201124469. The molded body comprising the polycarbonate resin composition of the present invention can be preferably used, for example, as: ) TV, radio cassette, camera, video recorder, audio player, DVD (digital video disc) Electrical and electronic equipment parts such as radios, air conditioners, mobile phones, monitors, computers, recorders, calculators, photocopiers, printers, and fax machines; (2) Electrical and electronic equipment of the above 1 (3) The base plate for electrical and electronic equipment of the above 1 and the like. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited by the examples. The performance evaluation method and the raw materials used are expressed as follows. [Performance evaluation method] (1) Viscosity average molecular weight The U-type viscosity tube was used to measure the ultimate viscosity [η] of the captured gas-burning solution, according to the following relationship (SchneU) [η] = 1.23χ10'5χΜν° 83 Further, the molecular weight of the particulate matter is obtained by dissolving the sample for evaluation of the particulate matter in the gas, and separating the insoluble component, and measuring the extracted polycarbonate resin. Molecular weight (2) Flame retardancy A vertical burning test was carried out using a test piece (length 127 _, width ι 2·7 151933.doc -20-201124469 mm, thickness 丨. 2 mm) prepared in accordance with UL standard 94. Or the rating of V-2 is evaluated as UL94 V-0, and v is outside V-2. According to the result of the test, the one that does not reach V-2 is set, and the so-called UL standard 94 is based on the specific size to keep vertical. The method of the flame-flammability after the test piece is in contact with the flame of the burner for one second. °"Bei resistance (3) The thermal conductivity is measured by the thermal conductivity measuring device "TPA_501" [Made in Kyoto Electronics Manufacturing Co., Ltd.], using Hot Disk The method was measured. (4) The density was measured in accordance with JIS K7112: 〇. (5) Bending characteristics Elastic modulus: Measured in accordance with ASTM D:790. Flexural strength: measured according to ASTM D790. (6) Izod impact strength with notched impact characteristics (IZ0D) A test piece (county) made with an injection molding machine 7 (only z·7 mm, width 63 mm, height 3.2 mm), according to ASTM standard d_256 , Yu Wei, Bu, w ten

义刮疋溫度23 C 下測衝擊強度。 [使用原料] (A)芳香族聚碳酸酯樹脂 ，，π啊L出光興 (股）製造，「FC1700」；黏度平均分子量=17,8〇〇，聚_ 基石夕氧烧（PDMS)部之聚合度=40，PDMS令*〜， u 3里〜3.；5質量％] 151933.doc •21 · 201124469 A-l(2):藉由下述製造例1而獲得之聚碳酸酯-聚二曱基 石夕氧院共聚物[黏度平均分子量=17,300，聚二曱基矽氧燒 (PDMS)部之聚合度=9〇，PdmS含量=6.6質量％] 製造例1 (聚碳酸酯寡聚物合成步驟） 於5.6質量％氫氧化鈉水溶液中，相對於其後溶解之雙酚 A(BPA) ’添力口 2,〇〇〇 ppm之連二亞硫酸納，並於其中以 BPA濃度成為13.5質量％之方式溶解BPA，而製備BPA之氣 氧化鈉水溶液。 將該BPA之氫氧化納水溶液以40 Ι/hr之流量、二氣甲院 以15 Ι/hr之流量、光氣以4.0 kg/hr之流量連續通入内徑6 mm、管長30 m之管型反應器中。管型反應器具有夹套部 分’使冷卻水通過夾套，而使反應液之溫度保持於4〇。〇以 下。 將自管型反應器導出之反應液連續導入至具備後掠翼 (sweptback wing)之内容積40 L之附擋板之槽型反應器中， 於其中進而以2.8 Ι/hr添加BPA之氫氧化鈉水溶液、以〇.〇7 Ι/hr添加25質量％氫氧化納水溶液、以17 Ι/hr添加水、以 0.64 Ι/hr添加1質量％三乙基胺水溶液，進行反應。連續抽 出自槽型反應器溢出之反應液，並進行靜置，藉此分離去 除水相，採集二氯曱烷相。 以上述方式所得之聚碳酸酯寡聚物濃度為3 1 8 g/Ι，氣甲 酸酯基濃度為0.75 mol/1。 (聚碳酸酯-聚二甲基矽氧烷共聚物之製造例1) 151933.doc -22· 201124469 於具備隔板、槳型攪拌翼及冷卻用夾套之5〇 [槽型反應 器中，投入上述所製造之聚碳酸酯寡聚物溶液15 L、二氣 甲烷9.0 L、一甲基矽氧烷單元之重複數為9〇之烯丙基苯酚 末端改性聚二甲基矽氧烷（pDMS)396 g及三乙基胺8 8 mL，於攪拌下向其中添加6 4質量％氫氧化鈉水溶液1389 g，使聚碳酸酯寡聚物與烯丙基苯酚末端改性pDMS反應1 〇 分鐘。 於该聚合液中添加對第三丁基苯酚（pTBp)之二氯甲烷溶 液（使PTBP 140 g溶解於二氣甲烷2 〇 [中而成者）、BpA之 氫氧化鈉水溶液（於使Na〇H 577 g與連二亞硫酸鈉2 〇 g溶 解於水8.4 L而成之水溶液中溶解有BpA 1〇12 §者），進行 50分鐘之聚合反應。 為進行稀釋而添加二氯甲烷1〇 L並攪拌1〇分鐘後，將其 分離成含有聚碳酸醋-聚^曱基石夕氧烧共聚物之有機相與 含有過量BPA及NaOH之水相，單離有機相。 將以上述方式所得之聚碳酸酯-聚二甲基矽氧烷共聚物 之二氯f烧溶液相對於該溶液，依序以15體積％之〇〇3 mol/L NaOH水溶液、〇 2 mGl/L鹽酸進行清洗，繼而以純 水反覆'月洗直至清洗後之水相中之導電度成為G.01 pS/m以 下。 對藉由β洗所得之聚碳酸酯_聚二甲基矽氧烷共聚物之 、甲貌’谷液進行濃縮並粉碎’於減壓下，於12 0 °C下乾 燥所得之鱗片。 所侍聚碳酸酯-聚二甲基矽氧烷共聚物之藉由核磁共振 151933.doc •23· 201124469 ^厘11)而求出之？〇]\18殘基量（？〇]^共聚合量）為6.6質量 % ’依據IS01628-4(1999)而測定之黏度數為46.7，黏度平 均分子量Mv=17,300。 A-1 (3):藉由下述製造例2而獲得之聚碳酸酯-聚二甲基 矽氧烷共聚物[黏度平均分子量=17,300，聚二甲基矽氧烷 (PDMS)部之聚合度=4〇，PDMS含量=10質量〇/〇] 製造例2 (聚碳酸酯-聚二甲基矽氧烷共聚物之製造例2) 於具備隔板、槳型攪拌翼及冷卻用夾套之5〇 L槽型反應 器中’投入上述A-1(2)之製造中所使用之聚碳酸酯寡聚物 溶液15 L、二氣曱烷8.9 L、二曱基矽氧烷單元之重複數為 40之烯丙基苯酚末端改性pDMS 670 g及三乙基胺8.8 mL， 於授拌下向其中添加6.4質量％氫氧化鈉水溶液13 89 g，使 聚碳酸酯寡聚物與烯丙基苯酚末端改性PDMS反應10分 鐘。 於該聚合液中添加對第三丁基笨酚（PTBP)之二氯甲燒溶 液（使PTBP 137.9 g溶解於二氣曱烷2.0 L中而成者）、βρα 之氫氧化鈉水溶液（於使NaOH 581 g與連二亞硫酸鈉2.3 g 溶解於水8.5 L而成之水溶液中溶解有βρα 1147 g者），實 施50分知之聚合反應。為進行稀釋而添加二氣甲院1〇 l並 攪拌10分鐘後’將其分離成含有聚碳酸酯之有機相與含有 過量BPA及NaOH之水相，單離有機相。 將以上述方式所得之聚碳酸酯之二氣曱烷溶液相對於該The impact strength was measured at a scraping temperature of 23 C. [Use raw materials] (A) Aromatic polycarbonate resin, π L L produced by Xingguang Co., Ltd., "FC1700"; viscosity average molecular weight = 17,8 〇〇, poly _ keishixi oxygen burning (PDMS) Degree of polymerization=40, PDMS order*~, u3~3.; 5 mass%] 151933.doc •21 · 201124469 Al(2): Polycarbonate-polydiod obtained by the following Production Example 1 Basestone compound copolymer [viscosity average molecular weight=17,300, degree of polymerization of polydidecyloxysilane (PDMS) section=9〇, PdmS content=6.6 mass%] Production Example 1 (Polycarbonate oligomer synthesis step In a 5.6 mass% sodium hydroxide aqueous solution, the bisphenol A (BPA) ' dissolved in the latter was added to the bismuth bismuth sulfite, and the BPA concentration thereof was 13.5% by mass. In this way, BPA is dissolved to prepare an aqueous sodium oxide solution of BPA. The BPA aqueous solution of sodium hydroxide was continuously introduced into a tube having an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 40 Torr/hr, a flow rate of 15 Ι/hr, and a phosgene flow rate of 4.0 kg/hr. In the reactor. The tubular reactor has a jacket portion to allow cooling water to pass through the jacket while maintaining the temperature of the reaction liquid at 4 Torr. Below you. The reaction liquid derived from the tubular reactor was continuously introduced into a grooved reactor equipped with a 40 L inner volume of a sweptback wing, in which TiO 2 of BPA was further added at 2.8 Torr/hr. The sodium aqueous solution was added with a 25% by mass aqueous sodium hydroxide solution at 〇.〇7 Ι/hr, water was added at 17 Torr/hr, and a 1% by mass aqueous solution of triethylamine was added at 0.64 Torr/hr to carry out a reaction. The reaction liquid overflowing from the tank type reactor was continuously withdrawn, and allowed to stand, thereby separating and removing the water phase, and collecting the dichlorodecane phase. The polycarbonate oligomer obtained in the above manner had a concentration of 3 1 8 g/Ι and a gas ester group concentration of 0.75 mol/1. (Production Example 1 of Polycarbonate-Polydimethyloxane Copolymer) 151933.doc -22· 201124469 In a tank reactor having a separator, a paddle type stirring blade and a cooling jacket, The allyl phenol end-modified polydimethyl methoxy oxane (15 L of the above-prepared polycarbonate oligomer solution, 9.0 L of di-methane, and 9-fold repeating number of monomethyl methoxy olefin units) pDMS) 396 g and 8 8 mL of triethylamine, and 1389 g of a 64% by mass aqueous sodium hydroxide solution was added thereto under stirring to react the polycarbonate oligomer with the allylphenol end-modified pDMS for 1 minute. . To the polymerization solution, a solution of p-tert-butylphenol (pTBp) in methylene chloride (140 g of PTBP dissolved in di-methane methane 2) and a sodium hydroxide solution of BpA (for Na〇) H 577 g was dissolved in an aqueous solution of sodium dithionite 2 〇g dissolved in 8.4 L of water to dissolve BpA 1〇12 §), and polymerization was carried out for 50 minutes. After adding 1 〇L of dichloromethane for the dilution and stirring for 1 〇, it is separated into an organic phase containing a polycarbonate-polyfluorene-based oxy-copolymer and an aqueous phase containing excess BPA and NaOH, From the organic phase. The dichloro-f-sintering solution of the polycarbonate-polydimethylaluminoxane copolymer obtained in the above manner is sequentially 15% by volume of 〇〇3 mol/L NaOH aqueous solution, 〇2 mGl/ relative to the solution. L hydrochloric acid is washed, and then washed with pure water for 'monthly washing until the conductivity in the aqueous phase after washing becomes G.01 pS/m or less. The polycarbonate-polydimethyloxane copolymer obtained by the ? washing was concentrated and pulverized under a reduced pressure, and the obtained scale was dried at 120 °C. What is the obtained polycarbonate-polydimethyloxane copolymer obtained by nuclear magnetic resonance 151933.doc •23· 201124469 ^ PCT 11)? 〇]\18 residue amount (?〇)^ copolymerization amount) was 6.6 mass%. The viscosity number determined according to IS01628-4 (1999) was 46.7, and the viscosity average molecular weight Mv was 17,300. A-1 (3): Polycarbonate-polydimethyloxane copolymer obtained by the following Production Example 2 [viscosity average molecular weight = 17,300, polymerization of polydimethyl siloxane (PDMS) portion Degree = 4 〇, PDMS content = 10 mass 〇 / 〇] Production Example 2 (Production Example 2 of polycarbonate-polydimethyl siloxane copolymer) A separator, a paddle type stirring blade, and a cooling jacket were provided. In the 5〇L tank reactor, 'repeated into the polycarbonate oligomer solution 15 L, dioxane 8.9 L, and dimercapto oxane unit used in the manufacture of the above A-1 (2) A total of 40 allyl phenol end-modified pDMS 670 g and triethylamine 8.8 mL, and a mixture of 6.4% by mass aqueous sodium hydroxide 13 89 g was added thereto to make polycarbonate oligomers and allylic groups. The phenolic end-modified PDMS reaction was carried out for 10 minutes. To the polymerization solution, a solution of tributyl methoxide (PTBP) in dichloromethane (a solution in which 137.9 g of PTBP is dissolved in 2.0 L of dioxane) and a sodium hydroxide solution of βρα are added. 50 minutes of NaOH 581 g and 2.3 g of sodium dithionite dissolved in 8.5 L of water were dissolved in βρα 1147 g), and 50 minutes of polymerization was carried out. To the dilution, a second gas mixture was added and stirred for 10 minutes, and then separated into an organic phase containing polycarbonate and an aqueous phase containing excess BPA and NaOH, and the organic phase was separated. The dioxane solution of the polycarbonate obtained in the above manner is relative to the

溶液，依序以15體積°/。之0.03 mol/L NaOH水溶液、0.2 N 151933.doc •24· 201124469 鹽酸進行清洗’繼而以純水反覆清洗直至清洗後之水相中 之導電度成為0.01 μ8Λη以下。對藉由清洗所得之聚碳酸酯 之二氯甲烷溶液進行濃縮並粉碎，於減壓下，於12〇它下 乾燥所得之鱗片。 藉由NMR而求出之PDMS殘基之量為1〇 〇質量％，依據 IS01628-4(1999)而測定之黏度數為46 6，黏度平均分子量 Mv=17,300。 Α·2(1广聚碳酸酯[出光興產(股)製造，由雙酚a而製造之 均聚碳酸酯「Tarfl〇n FN1900A」’黏度平均分子量 = 19,500] A-2(2):聚碳酸酯[出光興產（股）製造，由雙酚八而製造之 均聚碳酸醋「Tarflon FN2200A」，黏度平均分子量 =21,500] A-2(3):聚碳酸醋[出光興產（股）製造，由雙❹而製造之 均聚碳酸醋「Tarflcm FN2600A」，黏度平均分子量 =26,000] 再者，表中之POS含量：㈧成分中之聚有機石夕氧烧 含量（質量％)。 (B)石墨 B-1 :天然石墨[日本黑鉛工業公司製造「cb_i5〇」；鱗片 狀；粒度分佈：63_以下為77〜87%，1〇6_以上為外以 下；視密度G.2〜0.3 g/cm3; 5G%累積粒徑為31〜48 _ :固 定碳為98質量％以上；灰分為lf量％以下；揮發成分為】 質量％以下] 151933.doc •25· 201124469 B-2 :人造石墨[日本黑鉛工業公司製造「PAG-420」；不定 形；50%累積粒徑為30~40 μηι(50 μηι以上為50%以下）；視 密度為0.29〜0.37 g/cm3 ;固定碳為99.4質量％以上；灰分 為0.3質量％以下；揮發成分為0.3質量％以下] (C) 聚四氟乙烯（PTFE) C-1 : PTFE[Solvay Solexis 公司製造，「Algoflon F5」； Algoflon F5容易凝聚，故暫時以PC鱗片進行母料化（混合 比率（質量）PC : PTFE=90 : 10〜80 : 20)後再調配] (D) 有機鹼（土）金屬鹽 D-1 :全 It 丁續酸鉀鹽[Mitsubishi Materials(股）製造， 「Eftop KFBS」] D-2 ： 對曱苯磺酸鈉鹽[DAH DIING CHEMICAL INDUSTRY公司製造；純度93%品；作為雜質的硫酸鈉為3 質量％以下、水分為5質量％以下] (E) 其他添加劑抗氧化劑 E-1 :磷系抗氧化劑（亞磷酸二苯基異辛基酯）[ADEKA公司 製造，「Adekastab C」] E-2 :酚系抗氧化劑（3-(3,5-二-第三丁基-羥基苯基）丙酸十 八烷基酯）[Ciba Japan(股）製造 ’「Irganox 1076」] (F) 其他添加劑脫模劑 F-1 :硬脂酸單甘油酯[Riken Vitamin(股）製造，「Rikemal S-100A」] F-2 :季戊四醇四硬脂酸酯[Riken Vitamin(股）製造， 「RikesterEW-440A」] 151933.doc -26- 201124469 實施例1〜1 3、及比較例1〜7 以表1及表2所示之比例混合各成分’將其供給於排氣式 雙軸擠出成形機[東芝機械公司製造：TEM35]，於機筒、、ra 度為3〇0〜32〇t、螺桿轉速為_轉、嘴出量為1〇〜3〇 kg/hr之條件下進行熔融混練，獲得評價用顆粒物樣品。 使用該評價用顆粒物樣品，測定黏度平均分子旦。 ㈣ίϋ & $機制作用以進行各試驗之試 試驗。將其結果示於表i及表2中。 ，並進行各 151933.doc -27- 201124469 151933.doc ΟΟΌ00 °0Ό3 00Ό5 oo.s οο.ε ".0 91Ό 91*0 02 02 00-- οοο-ι i 一-Λ 0- 寸一 00s 06 寸‘寸 00·Η 00,98 0·0 00·ε —053 1°寸 Ό 9ΙΌ 91,0 02 02 00气61 00-- 000- 一-Λ •的 寸·Ι i^ 06 Γ寸 00.69 00, ιεThe solution was sequentially 15 volumes ° /. 0.03 mol/L NaOH aqueous solution, 0.2 N 151933.doc •24·201124469 Hydrochloric acid was washed' and then washed repeatedly with pure water until the conductivity in the aqueous phase after washing became 0.01 μ8 Λη or less. The methylene chloride solution obtained by washing the polycarbonate was concentrated and pulverized, and the obtained scale was dried under reduced pressure at 12 Torr. The amount of the PDMS residue determined by NMR was 1% by mass, the viscosity number determined according to IS01628-4 (1999) was 46, and the viscosity average molecular weight Mv was 17,300. Α·2 (1 wide polycarbonate [produced by Idemitsu Kosan Co., Ltd., a homopolycarbonate manufactured by bisphenol a "Tarfl〇n FN1900A" 'viscosity average molecular weight = 19,500] A-2 (2): poly Carbonate [manufactured by Idemitsu Kosan Co., Ltd., homopolycarbonate "Tarflon FN2200A" manufactured by bisphenol VIII, viscosity average molecular weight = 21,500] A-2 (3): Polycarbonate [Ishigaki Kogyo Co., Ltd.) Manufactured, homopolycarbonate "Tarflcm FN2600A" manufactured by bismuth, viscosity average molecular weight = 26,000] Further, the POS content in the table: (8) The content of polyorganisms in the composition (% by mass). ) Graphite B-1: Natural graphite [Cb_i5〇 manufactured by Japan Black Lead Industrial Co., Ltd.; scales; particle size distribution: 63_87.77~87%, 1〇6_ or more is outside; visual density G.2~ 0.3 g/cm3; 5G% cumulative particle size is 31~48 _: fixed carbon is 98% by mass or more; ash is divided into lf amount% or less; volatile component is 】% by mass] 151933.doc •25· 201124469 B-2 : Artificial graphite [PAG-420 manufactured by Japan Black Lead Industrial Co., Ltd.; amorphous; 50% cumulative particle size is 30~40 μηι (50 μηι or more is 50% or less); The density is 0.29 to 0.37 g/cm3; the fixed carbon is 99.4% by mass or more; the ash content is 0.3% by mass or less; the volatile component is 0.3% by mass or less; (C) Polytetrafluoroethylene (PTFE) C-1: PTFE [Solvay Solexis Made by the company, "Algoflon F5"; Algoflon F5 is easy to agglomerate, so it is temporarily doped with PC scales (mixing ratio (mass) PC: PTFE = 90: 10~80: 20) and then blended] (D) Organic base ( Earth) Metal salt D-1: All It Potassium Salt [Mitsubishi Materials, "Eftop KFBS"] D-2 : p-Toluenesulfonic acid sodium salt [DAH DIING CHEMICAL INDUSTRY company; purity 93% Product; sodium sulfate as an impurity is 3% by mass or less, and water is 5% by mass or less] (E) Other additives Antioxidant E-1: Phosphorus-based antioxidant (diphenylisooctyl phosphite) [Manufactured by ADEKA Corporation , "Adekastab C"] E-2: phenolic antioxidant (octadecyl 3-(3,5-di-t-butyl-hydroxyphenyl)propionate) [manufactured by Ciba Japan] Irganox 1076"] (F) Other additive release agent F-1: stearic acid monoglyceride [Riken Vitamin, "Rikemal S-100A" F-2: pentaerythritol tetrastearate [Riken Vitamin, "Rikester EW-440A"] 151933.doc -26- 201124469 Examples 1 to 1 3, and Comparative Examples 1 to 7 Table 1 and Table In the ratio shown in 2, the components are mixed and supplied to a vented twin-axis extrusion molding machine (manufactured by Toshiba Machine Co., Ltd.: TEM35), and the barrel is rotated at a temperature of 3〇0 to 32〇t, and the screw rotation speed is The melt-kneading was carried out under the conditions of 1 to 3 〇 kg/hr, and a sample of the particles for evaluation was obtained. Using the particle sample for evaluation, the viscosity average molecular denier was measured. (d) The role of the ίϋ & $ mechanism to conduct trials for each test. The results are shown in Tables i and 2. And proceed to each 151933.doc -27- 201124469 151933.doc ΟΟΌ00 °0Ό3 00Ό5 oo.s οο.ε ".0 91Ό 91*0 02 02 00-- οοο-ι i one-Λ 0- inch one 00s 06寸' inch 00·Η 00,98 0·0 00·ε —053 1° inch Ό 9ΙΌ 91,0 02 02 00 gas 61 00-- 000- one-Λ • inch Ι i^ 06 Γ inch 00.69 00 , ιε

OOOS -'V 0-8 8寸Ό 9Γ0 91.0 32 32 000贫 i-l 002 Ι·Λ σ卜 寸·ι 0-8 001 0·卜 ο— 00·- 00d3 GOT10 00·- 00-寸 OOOS ι001-1 00.0^ ο-'ε οσε 0-ε i -'Ό -'_0 02 02 ς寸.0-'.0 -'Όοε_ο 02 00-- 00寸*13 οοο-ι i- 1-Λ 0- 寸.1OOOS -'V 0-8 8 inch Ό 9Γ0 91.0 32 32 000 lean il 002 Ι·Λ σ Bu inch·ι 0-8 001 0·布ο— 00·- 00d3 GOT10 00·- 00-inch OOOS ι001-1 00.0^ ο-'ε οσε 0-ε i -'Ό -'_0 02 02 ς.0-'.0 -'Όοε_ο 02 00-- 00 inch*13 οοο-ι i- 1-Λ 0- inch. 1

°06K 06 寸- 003*61 §3- Ι-Λ 0.卜°06K 06 inch - 003*61 §3- Ι-Λ 0.

寸I 00卜- •9Inch I 00 Bu - • 9

OOOS 00Ό3 00.卜寸 ΖΓΙ 0-e 00_e 00.0^ οο.ε ΟΟΌ' s寸_0 -'_0 -'.0 ο叫ο— S-0 -'Ό— -'.0 02 iOOOS 00Ό3 00.卜寸 ΖΓΙ 0-e 00_e 00.0^ οο.ε ΟΟΌ' s inch_0 -'_0 -'.0 ο叫ο—— S-0 -'Ό— -'.0 02 i

SS 00 寸-3 οοε-ι i- ι.Λ •α 寸.1 0?- 06 9·寸 ooe*- 00" Λ -s 寸*1 009- 86 0- 9M>-駟 ei吾辑駟 °0·卜 8SS 00 inch-3 οοε-ι i- ι.Λ •α inch.1 0?- 06 9·inchooe*- 00" Λ -s inch*1 009- 86 0- 9M>-驷ei 吾 驷° 0·b 8

TIW §·- 00·卜寸 0'ε οο.ε§Ι.0ΓTIW §·- 00·卜寸 0'ε οο.ε§Ι.0Γ

5寸.0 -'Ό -'Ό— 02 — SO 00-- 00 寸-1 000- ι.Λ -1° 寸.1 00ε- C6 们5 inch.0 -'Ό -'Ό— 02 — SO 00-- 00 inch-1 000- ι.Λ -1° inch.1 00ε- C6

OOTS 00.卜呀 0-e οο.ε 00-' -'Ό -',0 02 0^0—OOTS 00.卜呀 0-e οο.ε 00-' -'Ό -',0 02 0^0—

00 寸二Z 00寸-1 §0- 1-Λ 0·ε ΓΙ i*寸 06 Γ9 00·- ο·- °0,3 卜 00,83 °0·ει 00♦卜寸 00.卜寸 0·ε 0·ε 寸 οο.ε 00,06 οοτ 00.0? 0-1οο,οί -Ό 0·'ι 00Ό5 s寸.0 -'.0 -1Ό 02 02 S寸ο -',0 -'Ό 0·101 0·101 •°寸.0 -'「οι -'•ο 02 02 S寸Ό -'.0 τττ 00寸*- 00寸- ooot Ι-Λ odl •一 008κ S6 ·寸 00寸*1300 inch two Z 00 inch-1 §0- 1-Λ 0·ε ΓΙ i* inch 06 Γ9 00·- ο·- °0,3 00,83 °0·ει 00♦卜寸00. · ε 0·ε inch οο.ε 00,06 οοτ 00.0? 0-1οο,οί -Ό 0·'ι 00Ό5 s inch.0 -'.0 -1Ό 02 02 S inch ο -',0 -'Ό 0 ·101 0·101 •° inch.0 -'“οι -'•ο 02 02 S inch Ό -'.0 τττ 00 inch*- 00 inch - ooot Ι-Λ odl • 008κ S6 · inch 00 inch*13

0SI 009- Ι-Λ •α 寸.1 00 卜- °6 •10 00-81 00Γ- 00- ι.Λ •ί 寸.1 009- 0°° 一- 00-810SI 009- Ι-Λ • α 寸.1 00 卜 - °6 •10 00-81 00Γ- 00- ι.Λ • inch.1 009- 0°° one - 00-81

000-I 00ε- 1-Λ •° 寸.1 i- s ·寸 sl-v s-'v sz.v £ F5 (％ί 鉍)#<Hsod (V) (α)Ί5Γ(a) -28- £ ?Ε 3.1^-ίτ)^黎'ΚΙ ^°-2】福班^酰 【Bds】^想喵鉍 (^/οίο^φ) 斯拓ΩΟΖΙ 201124469 表2 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 比較例7 調 西己 比 例 量 - — ㈧ Α-1Π) A-l(2) 53.00 53.00 53.00 53.00 53.00 53.00 A-l(3) A-2⑴ 100.00 A-2⑵ Α·2(3) 47.00 47.00 47.00 47.00 47.00 47.00 POS含量(質量％) 無 3.50 3.50 3.50 3.50 3.50 3.50 (B) Β-1 Β-2 50.00 25.00 120.00 50.00 50.00 50.00 50.00 _(c) C-1 1.50 3.00 3.00 0.50 13.00 3.00 3.00 (D) D-1 0.15 D-2 0.30 0.30 0.30 0.30 0.03 1.50 (E) Ε-1 0.15 0.30 0.30 0.30 0.30 0.30 0.30 Ε-2 0,15 0.15 0.15 0.15 0.15 0.15 0.15 (F) F-1 0.15 0.15 0.15 0.15 0.15 0.15 0.15 F-2 0.45 0.45 0.45 0.45 0.45 0.45 0.45 分子暑 原料分子量 19,500 21,400 21,400 21,400 21,400 21,400 21,400 (黏度平起 ]分子量) 顆粒物分子量 17,500 19,300 18,300 19,000 17,900 18,200 17,3〇〇 分子量降低 2,000 2,100 3,100 2,400 3,500 2,600 4,100 阻燃性(厚度1.2 mm) V_2外 V-2外 V-2外 V-2外 V-2外 V-2外 V-2外 物理特性 導熱率[W/m_K] 5.5 3.0 12.0 5.5 5.5 5.5 5.5 密度[g/cm3] 1.4 1.3 1.5 1.4 1.4 1.4 1.4 f曲特性 彈性模數[Mpa] 5,300 3,800 8,700 5,300 5,400 5,800 5,150 彎曲強度[Mpa] 90 90 95 91 86 100 92 衝擊特性 IZOD衝擊 (帶缺口 KJ/m2) 4.0 6.2 4.1 5.2 4,6 5.3 4.5 根據表1及表2，可明確下述内容。 根據表1，於全部滿足本發明之（A)成分至（1))成分之實 施例1至實施例13中，可獲得薄壁（厚度12爪叫阻燃性、 導熱性、彎曲特性、及衝擊強度優異，進而，造粒時之聚 碳酸酯樹脂之分子量降低得到抑制之聚碳酸酯樹脂組合 物0 根據表2 ,於僅包含均聚碳酸酯樹脂之比較例丨中，薄辟 阻燃性降低。於（B)成分之石墨含量較少之比較例：中;& 熱性降低，於（B)成分過多之比較例3中，衝擊強度降低。 於（C)成分之PTFE含量較少之比較例 又* 列4 f，溥壁阻燃性降 -29· 151933.doc 201124469 低，於（C)成分過多之比較例5中，衝擊強度降低。 於（D)成分之金屬鹽含量較少之比較例6中，薄壁阻燃性 降低，於（D)成分過多之比較例7中，造粒時之聚碳酸酯樹 脂之分子量降低較大。 151933.doc -30-000-I 00ε- 1-Λ •° inch.1 i- s ·inch sl-v s-'v sz.v £ F5 (%ί 铋)#<Hsod (V) (α)Ί5Γ(a) - 28- £ ?Ε 3.1^-ίτ)^黎'ΚΙ ^°-2】Fuban^Acyl [Bds]^想喵铋(^/οίο^φ) 斯拓ΩΟΖΙ 201124469 Table 2 Comparative Example 1 Comparative Example 2 Comparison Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Proportion of 调西己 - (8) Α-1Π) Al(2) 53.00 53.00 53.00 53.00 53.00 53.00 Al(3) A-2(1) 100.00 A-2(2) Α·2 (3) 47.00 47.00 47.00 47.00 47.00 47.00 POS content (% by mass) None 3.50 3.50 3.50 3.50 3.50 3.50 (B) Β-1 Β-2 50.00 25.00 120.00 50.00 50.00 50.00 50.00 _(c) C-1 1.50 3.00 3.00 0.50 13.00 3.00 3.00 (D) D-1 0.15 D-2 0.30 0.30 0.30 0.30 0.03 1.50 (E) Ε-1 0.15 0.30 0.30 0.30 0.30 0.30 0.30 Ε-2 0,15 0.15 0.15 0.15 0.15 0.15 0.15 (F) F-1 0.15 0.15 0.15 0.15 0.15 0.15 0.15 F-2 0.45 0.45 0.45 0.45 0.45 0.45 0.45 Molecular heat source molecular weight 19,500 21,400 21,400 21,400 21,400 21,400 21,400 (viscosity flat) molecular weight) Particle molecular weight 17,500 19 ,300 18,300 19,000 17,900 18,200 17,3〇〇Molecular weight reduction 2,000 2,100 3,100 2,400 3,500 2,600 4,100 Flame retardancy (thickness 1.2 mm) V_2 outside V-2 outside V-2 outside V-2 outside V-2 outside V-2 Physical properties of V-2 external thermal conductivity [W/m_K] 5.5 3.0 12.0 5.5 5.5 5.5 5.5 Density [g/cm3] 1.4 1.3 1.5 1.4 1.4 1.4 1.4 f-curvature elastic modulus [Mpa] 5,300 3,800 8,700 5,300 5,400 5,800 5,150 Bending Strength [Mpa] 90 90 95 91 86 100 92 Impact characteristics IZOD impact (with gap KJ/m2) 4.0 6.2 4.1 5.2 4,6 5.3 4.5 According to Tables 1 and 2, the following can be clarified. According to Table 1, in Examples 1 to 13 in which all of the components (A) to (1)) of the present invention are satisfied, a thin wall (thickness 12, flame retardancy, thermal conductivity, bending property, and The polycarbonate resin composition which is excellent in the impact strength and further suppresses the decrease in the molecular weight of the polycarbonate resin during granulation. According to Table 2, in the comparative example containing only the homopolycarbonate resin, the flame retardancy is improved. In the comparative example in which the graphite content of the component (B) is small, the thermal property is lowered, and in the comparative example 3 in which the component (B) is excessive, the impact strength is lowered. The PTFE content of the component (C) is small. The comparative example is further *column 4 f, the flame retardancy of the crucible wall is lowered -29. 151933.doc 201124469 is low, in the comparative example 5 in which the component (C) is excessive, the impact strength is lowered. The metal salt content of the component (D) is small. In Comparative Example 6, the thin-wall flame retardancy was lowered, and in Comparative Example 7 in which the component (D) was excessive, the molecular weight of the polycarbonate resin at the time of granulation was largely lowered. 151933.doc -30-

Claims (1)

201124469 七、申請專利範圍：201124469 VII. Patent application scope: 3(B)石墨30〜100質量份、（c)聚四氟乙烯質 及（D)有機鹼金屬鹽及/或有機鹼土金屬鹽 鹽0.05〜1 質量份。 2. 如請求項}之聚碳酸酯樹脂組合物，其中中之聚有機 矽氧烷之含量為1〜6質量％。 3. 如請求項丨或2之聚碳酸酯樹脂組合物其中芳香族聚碳 酸醋-聚有機石夕氧烧共聚物之聚有機石夕氧院為聚二甲基^ 氧烷。 4. 如請求項丨至3中任一項之聚碳酸酯樹脂組合物，其中石 墨為天然石墨。 5. 如請求項丨至3中任一項之聚碳酸酯樹脂組合物，其中石 墨為人造石墨。 6·如請求項1至5中任一項之聚碳酸酯樹脂組合物，其中（D) 有機鹼金屬鹽及/或有機鹼土金屬鹽為選自有機磺酸鹼金 屬鹽、有機磺酸鹼土金屬鹽、聚苯乙烯磺酸鹼金屬鹽及 聚笨乙烯磺酸鹼土金屬鹽之至少一種。 7. —種成形體，其包含如請求項1至6中任一項之聚碳酸酯 樹脂組合物。 8. 如請求項7之成形體，其係電氣、電子機器用零件。 9. 如請求項7之成形體’其係電氣、電子機器用殼體。 10·如請求項7之成形體’其係電氣、電子機器用底板。 151933.doc 201124469 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無） 151933.doc3 (B) 30 to 100 parts by mass of graphite, (c) polytetrafluoroethylene and (D) an organic alkali metal salt and/or an organic alkaline earth metal salt of 0.05 to 1 part by mass. 2. The polycarbonate resin composition of claim 1, wherein the polyorganosiloxane is contained in an amount of from 1 to 6 mass%. 3. The polycarbonate resin composition according to claim 2 or 2, wherein the polyorganocene oxide of the aromatic polycarbonate-polyorgano oxysulfuric copolymer is polydimethyloxane. 4. The polycarbonate resin composition according to any one of claims 3 to 3, wherein the graphite is natural graphite. 5. The polycarbonate resin composition according to any one of claims 3 to 3, wherein the graphite is artificial graphite. The polycarbonate resin composition according to any one of claims 1 to 5, wherein (D) the organic alkali metal salt and/or the organic alkaline earth metal salt is selected from the group consisting of an organic sulfonic acid alkali metal salt and an organic sulfonic acid alkaline earth. At least one of a metal salt, an alkali metal salt of polystyrene sulfonate, and an alkali metal salt of polystyrene sulfonate. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 6. 8. The molded body of claim 7, which is a component for electrical and electronic equipment. 9. The molded body of claim 7 which is a housing for electrical and electronic equipment. 10. The molded article of claim 7 which is a base plate for electrical and electronic equipment. 151933.doc 201124469 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 151933.doc