201245271 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種液晶聚酯及其製造方法。 【先前技術】 液晶聚酯，係熔融流動性優異，耐熱性或強度、剛性 亦高，因此作爲以電氣、電子零件爲首之各種製品、零件 的材料被探討。當白色顏料調配於其中，而將液晶聚酯作 爲LED (發光二極體）發光裝置等之反射板的材料使用時 ’爲了使反射板之反射率提高，又爲了使反射光不易帶有 色澤’而對液晶聚酯要求高的明亮度。就該液晶聚酯而言 ’例如’於專利文獻1中’係揭示有黃色度YI爲3 2以下 ’且明亮度L·爲7 5以上之液晶聚酯，具體而言，係揭示 有：具有60莫耳％之來自p_羥苯甲酸之重複單元、2〇莫 耳％之來自對苯二甲酸之重複單元' 5莫耳。/。之來自間苯二 甲酸之重複單元、20莫耳％之來自4,4-二羥基聯苯之重複 單元’且流動起始溫度爲3 2 7°C之液晶聚酯；或具有60莫 耳°/。之來自p-羥苯甲酸之重複單元、18莫耳％之來自對苯 一甲酸之重複單元、2莫耳％之來自間苯二甲酸之重複單 兀、20莫耳％之來自4,4·二羥基聯苯之重複單元，且流動 起始溫度爲360 °C之液晶聚酯；或具有73莫耳％之來自p_ 經本甲酸之重複單元、27莫耳％之來自6_羥基_2_萘甲酸 之重複單元’且流動起始溫度爲2 9 〇 〇c之液晶聚酯。 201245271 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕曰本特開2004-256673號公 【發明內容】 〔發明所欲解決之課題〕 本發明之目的爲提供明亮度進一步更高的液 〔用以解決課題之手段〕 爲了達成前述目的，本發明係提供一種液晶 係具有來自芳香族羥基羧酸之重複單元（1)、 族二羧酸之重複單元（2)、及來自芳香族二醇 羥胺或芳香族二胺之重複單元（3):相對於全 之合計fi，前述重複單元（1)之含量爲50〜80 相對於全重複單元之合計量，前述重複單元（2 爲10〜25莫耳％;相對於全重複單元之合計量， 單元（3)之含量爲10〜25莫耳％;相對於全重 合計量，其主鏈包含1，2-伸苯基骨架或1,3-伸苯 重複單元（A)之含量爲5〜30莫耳％ :且其流 度爲270〜320 °C。 此外，本發明係提供一種液晶聚酯之製造方 適合製造前述液晶聚酯之方法，且具有：使用芳 羧酸、芳香族二羧酸、和由芳香族二醇、芳香族 香族二胺所成之群中所選出至少1種的芳香族化 聚酯。 聚酯，其 來自芳香 、芳香族 重複單元 莫耳％ ; )之含量 前述重複 複單元之 基骨架之 動起始溫 法，其係 香族羥基 羥胺及芳 合物作爲 -6- 201245271 原料單體，並藉由酸酐分別將前述芳香族羥基羧酸及前述 芳香族化合物醯化，而得到芳香族醯氧基羧酸及芳香族二 醯基化合物之步驟（1):使前述芳香族醯氧基羧酸、前 述芳香族二醯基化合物和前述芳香族二羧酸熔融聚合，而 得到熔融聚合物之步驟（2):以及使前述熔融聚合物固 態聚合，而得到固態聚合物之步驟（3 );相對於全原料 單體之合計量，前述芳香族羥基羧酸之使用量爲50〜80 莫耳％;相對於全原料單體之合計量，前述芳香族二羧酸 之使用量爲10〜25莫耳％;相對於全原料單體之合計量， 前述芳香族化合物之使用量爲10〜25莫耳％ :相對於全原 料單體之合計量，其主鏈包含1，2_伸苯基骨架或1，3-伸苯 基骨架之原料單體（A)之使用量爲5〜30莫耳％;且前 述步驟（3)中固態聚合溫度的上限爲220〜270 °C。 〔發明效果〕 本發明之液晶聚酯，係因明亮度高，因此可藉由使用 將白色顏料調配於其中所成之液晶聚酯組成物，而得到反 射率高，且反射光不易帶有色澤之反射板。 〔實施發明之最佳形態〕 本發明之液晶聚酯，係具有：來自芳香族羥基羧酸之 重複單元（1)、來自芳香族二羧酸之重複單元（2)、以 及來自芳香族二醇、芳香族羥胺或芳香族二胺之重複單元 (3 )者。 201245271 重複單元（1)，係自芳香族羥基羧酸，去除其羥基 的氫原子與其羧基的羥基所成之2價殘基；重複單元（2 )，係自香族二羧酸，去除其2個羧基的各羥基所成之2 價殘基：重複單元（3)，係自芳香族二醇，去除其2個 羥基的各氫原子所成之2價殘基、或自芳香族羥胺，去除 其羥基的氫原子與其胺基的氫原子所成之2價殘基、或自 芳香族二胺，去除其2個胺基的各氫原子所成之2價殘基 〇 重複單位（1 )之例示，係可列舉下述式（1 )所示之 重複單元：重複單位（2)之例示，係可列舉下述式（2) 所示之重複單元；重複單位（3 )之例示，係可列舉下述 式（3)所示之重複單元。 (1 ) -O-Ar'-CO-(2 ) -CO-Ar2-CO-(3 ) -X-Ar3-Y- (Afl係表示伸苯基、伸萘基或聯苯亞基（biphenylylene groups ) 。Ar2及Ar3係各自獨立表示伸苯基、伸萘基、 聯苯亞基或下述式（4)所表示之基。X及Y係各自獨立 表示氧原子或亞胺基（-NH-) 。Ar1、Ar2及Ar3所表示之 在前述基中的氫原子，亦可各自獨立被鹵素原子、烷基或 芳基所取代。） (4 ) - Ar4-Z-Ar5- (Al"4及Ar5係各自獨立表示伸苯基或伸萘基》Z係 表示氧原子、硫原子、羰基、磺醯基或烷叉基。） -8- 201245271 前述鹵素原子，係可列舉：氟原子、氯原子、溴原子 及碘原子。前述烷基之例示，係可列舉：甲基、乙基、n-丙基、異丙基、η-丁基、異丁基、s-丁基、t_ 丁基、心己 基、2-乙基己基、η-辛基及η-癸基，且其碳數一般爲 1 〇 »前述芳基之例示，係可列舉：苯基、〇-甲苯基、m-甲 苯基、P-甲苯基、1-萘基及2-萘基，且其碳數一般爲6〜 20。當前述氫原子被此等之基所取代時’其數目，係每一 Ar1、Ar2、或Ar3所表示之前述基，一般各自獨立爲2個 以下，較佳爲1個以下。 前述烷叉基之例示，係可列舉：伸甲基、亞乙基、亞 異丙基、η-亞丁基及2-乙基亞己基，且其碳數一般爲1〜 10° 重複單元（1 )，係以於前述式（1 )中，Ar1爲Ρ-伸 苯基或2,6-伸萘基者，亦即，來自p_羥苯甲酸或6-羥基-2-萘甲酸之重複單元爲佳。 重複單元（2 )，係以於前述式（2 )中，Ar2爲〇-伸 苯基、m-伸苯基、ρ-伸苯基或2,6-伸萘基者，亦即，來自 鄰苯二甲酸、間苯二甲酸、對苯二甲酸或2,6-萘二羧酸之 重複單元爲佳。 重複單元（3)，係以於前述式（3)中，X及Y各自 爲氧原子，且 Ar3爲〇 -伸苯基、m -伸苯基、ρ -伸苯基、 4,4’-聯苯亞基或2,6-伸萘基者；於前述式（3)中，X爲 氧原子，Υ爲亞胺基，且Ar3爲〇-伸苯基、m-伸苯基或ρ-伸苯基者；或於前述式（3)中，X及Y各自爲亞胺基， -9- 201245271 且Ar3爲〇-伸苯基、m-伸苯基或p-伸苯基者，亦即，來自 鄰苯二酚、間苯二酚、對苯二酚、4,4’-二羥基聯苯、2,6-萘二酚、〇-胺基苯酚、m-胺基苯酚、P-胺基苯酚、〇-伸苯 二胺、m_伸苯二胺或p-伸苯二胺之重複單元爲佳。 相對於全重複單元之合計量（以該各重複單元之式fl 來分割構成液晶聚酯之各重複單元的質量’以求得各重複 單元的物質量之相當量（莫耳），並將此等作合計所得之 値），重複單元（1)之含量，較佳爲5〜80莫耳％ ’更佳 爲50〜70莫耳％。相對於全重複單元之合計量，重複單元 (2)之含量，較佳爲10〜25莫耳％，更佳爲15〜25莫耳 %。相對於全重複單元之合計量，重複單元（3)之含量， 較佳爲〗〇〜2 5莫耳％，更佳爲1 5〜2 5莫耳％。 若重複單元（1)之含量過多，且重複單元（2)及（ 3 )之含量過少，則由於液晶聚酯脂之熔融溫度或熔融黏 度會容易變高，且於液晶聚酯之成形所需的溫度會容易變 高’因此液晶聚酯在成形時會容易著色，且成形體之明亮 度會變得容易降低。若重複單元（1)之含量過少，且重 複單元（2)及（3)之含量過多，則液晶聚酯之耐熱度或 強度、剛性會容易降低，且成形體在高溫下會變得容易變 形。 重複單元（2)之含量與重複單元（3)之含量的比率 ’係以〔重複單元（2)之含量〕/〔重複單元（3)之含 量〕（莫耳/莫耳）來表示，一般爲0.9/ 1〜1/ 0.9，較 佳爲 0.95/1〜1/0.95，更佳爲 〇98/ι 〜1/〇98。 -10- 201245271 另外，本發明之液晶聚酯，亦可各自獨立具有2種以 上之重複單元（1 )〜（3 )。此外，本發明之液晶聚酯， 雖亦可具有重複單元（1)〜（3)以外之重複單元，但相 對於全重複單元之合計量，其含量一般爲10莫耳％以下， 較佳爲5莫耳％以下。 本發明之液晶聚酯，係以具有X及Y各自爲氧原子 者’亦即，來自特定的芳香族二醇之重複單位者作爲重複 單元（3)者爲佳’並以具有僅X及γ各自爲氧原子者爲 更佳。藉此’由於液晶聚酯之熔融黏度容易變低，且可將 於液晶聚酯之成形所需的溫度降低，因此液晶聚酯在成形 時便不易著色，且成形體之明亮度會變得不易降低。 本發明之液晶聚酯，係相對於全重複單位之合計量， 其主鏈具有5〜30莫耳％，較佳爲8〜25莫耳％之包含 1，2-伸苯基骨架或1，3-伸苯基骨架之重複單元（a)者。 換言之’重複單元（A)，係含有可具有取代基或融合環 之1，2-伸苯基或1，3 -伸苯基的重複單元。 若重複單元（A)之含量過多，則如後述般爲了將液 晶聚酯之流動起始溫度設爲270。(：以上，而必須要提昇液 晶聚酯之聚合度，爲此必須將後述之固態聚合溫度提高， 因此液晶聚酯在固態聚合時會容易著色，且液晶聚酯之明 亮度會變得容易降低。若重複單位（A)之含量過少，則 如後述般爲了將液晶聚酯之流動起始溫度設爲320 〇c以下 ’而必須降低液晶聚酯之聚合度，且由於液晶聚酯中容易 殘存原料單體或寡聚物’或液晶聚酯之耐熱性或強度、剛 -11 - 201245271 性會容易降低，因此成形體在高溫下會變得容易發泡，或 成形體在高溫下會變得容易變形。 重複單位（1)之重複單元（A)的例示’係可列舉下 述式（1A)所示之重複單元；重複單位（2)之重複單元 (A )的例示，係可列舉下述式（2A )所示之重複單元； 重複單位（3)之重複單元（A)的例示，係可列舉下述式 (3A)所示之重複單元。 (1 A ) -0-Ar1A-C0-(2A ) -CO-Ar2A-CO-(3 A ) -Χ-Αγ3α-Υ- (Ar1A、Ar2A&八^4係各自獨立表示o-伸苯基、m-伸苯基、1，2-伸萘基、1，3-伸萘基或1，4-伸萘基。X及 Y 係各自獨立表示氧原子或亞胺基。Ar1A、Ar2A及Ar3A所 表示之在前述基中的氫原子，亦可各自獨立被鹵素原子、 烷基或芳基所取代。） 另外，前述鹵素原子、烷基及芳基之例示，係分別與 先前所述之 Αι·1〜Ar3中的鹵素原子、烷基及芳基之例示 相同。此外，本發明之液晶聚酯，亦可各自獨立具有2種 以上之作爲重複單元（1)之重複單元（A)、作爲重複單 元（2)之重複單元（A)、作爲重複單元（3)之重複單 元（A)。 重複單元（A)，係以於前述式（2A)中，八1*〃爲〇· 伸苯基或m-伸苯基者；於前述式（3A)中，X及Y各自 爲氧原子，且八1*〃爲〇-伸苯基或m-伸苯基者；於前述式 -12- 201245271 (3A)中，X爲氧原子，γ爲亞胺基，且^〃爲〇·伸苯 基或m -伸苯基者；此外，於前述式（3Α)中，X及Υ各 自爲亞胺基，且八一八爲〇-伸苯基或m-伸苯基者爲佳，亦 即，以來自鄰苯二甲酸、間苯二甲酸、鄰苯二酚、間苯二 酚、〇-胺基苯酚、m-胺基苯酚、〇-伸苯二胺或m-伸苯二胺 之重複單元爲佳。 此外，本發明之液晶聚酯，係如同來自羥萘甲酸、萘 二羧酸或萘二酚之重複單元般，相對於全重複單元之合計 量’含有萘環之重複單元的含量，較佳爲0〜30莫耳％， 更佳爲0〜25莫耳％，再更佳爲〇〜20莫耳％。藉此，液 晶聚酯之明亮度會變得容易提高。 本發明之液晶聚酯，其流動起始溫度爲270〜320 °C， 較佳爲290〜3 20°C。流動起始溫度亦稱爲流溫或流動溫度 ，其係使用毛細管流變儀，在9.8MPa(10 0kg/cm2)的 負荷下、以4°C/分鐘之速度一邊昇溫，一邊使液晶聚酯 熔融，並在從內徑1 ram及長度10mm的噴嘴擠出時，顯示 4800Pa · s ( 48 000泊）之黏度的溫度，且成爲液晶聚酯之 分子量的大致標準者（參照小出直之編製，「液晶聚酯-合成、成形、應用-」，CMC股份有限公司，1 9 87年6月 5日，第95頁）》 若流動起始溫度過高，則由於液晶聚酯之成形所需的 溫度會變高，因此液晶聚酯在成形時會容易著色，且成形 體之明亮度會變得容易降低。若流動起始溫度過低，則液 晶聚酯之耐熱性或強度、剛度會容易降低，且成形體在高 -13- 201245271 溫下會變得容易變形。 本發明之液晶聚酯，係可藉由使構成其之重複單元所 對應的種類及量之原料單體，在特定的條件下聚合（聚縮 合）而製造者。 原料單體，係使用芳香族羥基羧酸、芳香族二羧酸、 和由芳香族二醇、芳香族羥胺及芳香族二胺所成之群中所 選出至少1種的芳香族化合物。 芳香族羥基羧酸，係以由p-羥苯甲酸及6-羥基-2·萘 甲酸所成之群中所選出至少1種的化合物者爲佳。芳香族 二羧酸，係以由鄰苯二甲酸、間苯二甲酸、對苯二甲酸及 2,6·萘二羧酸所成之群中所選出至少1種的化合物者爲佳 。前述芳香族化合物，係以由鄰苯二酚、間苯二酚、對苯 二酚、〇 -胺基苯酚、m -胺基苯酚、p -胺基苯酚、〇_伸苯二 胺、m -伸苯二胺、p-伸苯二胺、4,4’-二羥基聯苯及2,6-萘 二酚所成之群中所選出至少1種的化合物者爲佳。 相對於全原料單體之合計量（以該各原料單體之分子 Λ來分割賦予構成液晶聚酯之各重複單元的各原料單體之 質量’以求得各原料單體之物質量（莫耳），並將此等作 合計所得之値），芳香族羥基羧酸之使用量，爲5〜80莫 耳％，較佳爲50〜70莫耳％。相對於全原料單體之合計量 ，芳香族二羧酸之使用量，爲10〜25莫耳％，較佳爲15 〜25莫耳％。相對於全原料單體之合計量，前述芳香族化 合物之使用量’爲10〜25莫耳。/。’較佳爲15〜25莫耳％ -14- 201245271 芳香族二羧酸之使用量與前述芳香族化合物之使 的比率’係以〔芳香族二羧酸之使用量〕/〔前述芳 化合物之使用量〕（莫耳/莫耳）來表示，—般爲〇. 〜1/0.9’較佳爲0.95/1〜1/0.95，更佳爲0.98/ / 0.98 。 另外’原料單體’雖亦可使用芳香族羥基羧酸、 族二羧酸及前述芳香族化合物以外的化合物，但相對 原料單體之合計量’其使用量一般爲1〇莫耳％以下， 爲5莫耳％以下。 前述芳香族化合物，係以使用芳香族二醇者爲佳 僅使用芳香族二醇者爲更佳。 相對於全原料單體之合計量，其主鏈包含ι，2 -伸 骨架或1，3 -伸苯基骨架之原料單體（A)之使用量， 〜30莫耳％’較佳爲8〜25莫耳％。換言之，原料單 A)，係含有可具有取代基或融合環之I，2-伸苯基或 伸苯基的化合物。 原料單體（A) ’係以由鄰苯二甲酸、間苯二甲 鄰苯二酚、間苯二酚、〇_胺基苯酚' m_胺基苯酚、〇_ 二胺及m-伸苯二胺所成之群中所選出至少1種的化 者爲佳。 此外’如同羥萘甲酸、萘二羧酸及萘二酚般，相 全原料單體之合計量，含有萘環之原料單體的使用量 佳爲0〜3 0莫耳％ ’更佳爲〇〜2 5莫耳。/。’再更佳爲〇 莫耳％。 用量 香族 9/1 1〜1 芳香 於全 較佳 ，以 苯基 係5 體（ 1,3- 酸、 伸苯 合物 對於 ，較 〜20 -15- 201245271 液晶聚酯之製造，係藉由下述步驟（1 )、步驟（2 ) 及步驟（3 )而進行，即：首先，步驟（1 )，以酸酐分別 將芳香族羥基羧酸及芳香族化合物醯化，而得到芳香族醯 氧基羧酸及芳香族二醯基化合物，接著，步驟（2)，使 芳香族醯氧基羧酸、芳香族二醯基化合物和芳香族二羧酸 熔融聚合，而得到熔融聚合物，然後，步驟（3)，使熔 融聚合物固態聚合，而得到固態聚合物。 步驟（1 )所使用的酸酐，係以脂肪酸酐者爲佳，其 例示係可列舉：乙酸酐 '丙酸酐、丁酸酐、異丁酸酐、戊 酸酐、三甲基乙酸酐、2-乙基己酸酐、一氯乙酸酐、二氯 乙酸酐、三氯乙酸酐、一溴乙酸酐、二溴乙酸酐、三溴乙 酸酐、一氟乙酸酐、二氟乙酸酐、三氟乙酸酐、戊二酸酐 、馬來酸酐、琥珀酸酐及A -溴丙酸酐，亦可使用此等中2 種以上。其中，以乙酸酐、丙酸酐、丁酸酐及異丁酸酐爲 佳，乙酸酐爲更佳》 相對於芳香族羥基羧酸之羥基以及前述芳香族化合物 之羥基及胺基之合計量，酸酐的使用量，較佳爲1〜1.1 莫耳倍，更佳爲1.01〜1.08莫耳倍。若酸酐的量過多，則 液晶聚酯會容易著色，且液晶聚酯之明亮度會容易降低。 若酸酐的量過少，則液晶聚酯之聚合度會容易變低，且由 於液晶聚酯中容易殘存原料單體或寡聚物，或液晶聚酯之 耐熱性或強度、剛性容易降低，因此成形體在高溫下會變 得容易發泡，或成形體在高溫下會變得容易變形。 步驟（1)，係於氮氣等之惰性氣體氛圍下，以在130 -16- 201245271 〜180 °C下進行者爲佳。另外，於步驟（1)中，亦可存在 有芳香族二羧酸。 步驟（2 )，係於氮氣等之惰性氣體氛圍下，以在1 30 〜400°C下進行者爲佳，在150〜3 5 0 °C下進行者爲更佳。 此外，步驟（2)，係以藉由在將副產羧酸或未反應之酸 酐餾除的同時，以0.1〜50°C /分鐘之速度昇溫而進行者 爲佳，以0.3〜5°C/分鐘之速度昇溫而進行者爲更佳。 此外，步驟（1)及/或（2)，係以於觸媒之存在下 進行者爲佳。藉此，醯化及/或熔融聚合會順利地進行， 且液晶聚酯之明亮度會變得容易提高。 觸媒之例示，係可列舉：乙酸鎂、乙酸亞錫、四丁基 欽酸酯（Tetra butyl titanate )、酔酸錯、乙酸鈉、乙酸 鉀、三氧化二銻等之金屬化合物、如同4-(二甲基胺基） 吡啶般之4-(二烷基胺基）吡啶等之吡啶化合物、及如同 1-甲基咪唑般之1_烷基咪唑等之咪唑化合物。其中，就液 晶聚酯之明亮度的觀點而言，以咪唑化合物爲佳。 相對於全原料單體之合計100質量份，觸媒之使用量 ，較佳爲0.005〜1質量份，更佳爲0.05〜0.5質量份。 步驟（3 )，係在將固態聚合溫度之上限設爲220〜 270 °C ’較佳爲225〜265 °C，更佳爲230〜255 °C下進行。 若固態聚合溫度之上限過高，則液晶聚酯會在固態聚合時 會容易著色，且液晶聚酯之明亮度會變得容易降低。若固 態聚合溫度之上限過低，則液晶聚酯之聚合度會容易變低 ，且由於液晶聚酯中容易殘存原料單體或寡聚物，或液晶 -17- 201245271 聚醋之耐熱性或強度、剛性會容易降低，因此成形體在高 溫下會變得容易發泡，或成形體在高溫下會變得容易變形 0 此外’步驟（3 )，係以藉由於氮氣等之惰性氣體氛 圍下’昇溫至上限溫度爲止，且在該上限溫度下保持3〜 20小時而進行者爲佳。 如此所得之本發明之液晶聚酯，係明亮度高，具體而 言，係以依據JIS Z 8729之L*a*b*表色系之明亮度L* 來表示，較佳爲86以上，更佳爲87以上。 本發明之液晶聚酯，由於明亮度高，因此將白色顏料 調配於其中所成之本發明之液晶聚酯組成物，係可適合作 爲反射板之材料使用。 白色顏料，係以使用例如：氧化鋅、硫化鋅、鉛白、 氧化鈦等之無機化合物爲佳，且可視需要使用此等中2種 以上。其中以氧化鈦爲佳。 由於白色顏料容易分散於液晶聚酯中，且容易得到具 有高反射率之反射板，故白色顏料之粒徑，係以體積平均 値表示，較佳爲0.05〜2/zm，更佳爲0.1〜l/zm，再更佳 爲0.15〜0.5// m，特別佳爲0.2〜0.4// m。 另外，在此所謂體積平均粒徑，係利用掃描式電子顯 微鏡（SEM: Scanning Electron Microscope)來拍攝白色 顔料，並利用影像解析裝置（例如，（股）NIRECO的「 RUUZEKKUSU IIIU」）將所得之SEM相片作解析，求出 —次粒徑之各粒徑區間中的粒子量（％ ) ’於以體積基準 -18- 201245271 將此等作累積所得之分布曲線中，累積度爲5 0 %時之粒徑 〇 相對於液晶聚酯1 00質量份，本發明之液晶聚酯組成 物中的白色顏料之含量，較佳爲20〜200質份，更佳爲 25〜150質量份，再更佳爲40〜100質量份。 作爲白色顏料之較佳例示的氧化鈦，其結晶形可爲金 紅石型、亦可爲銳鈦礦型，且亦可兩者混合存在，但就具 有高反射率，且容易得到耐候性優異之反射板的觀點而言 ’以含有金紅石型之氧化鈦者爲佳，實質上以僅由金紅石 型之氧化鈦所構成者爲更佳。 亦可對氧化鈦施以表面處理。例如，可藉由使用無機 金屬氧化物來施以表面處理，而使分散性或耐候性提昇。 無機金屬氧化物，係以使用氧化鋁（alumina )者爲佳。 另外，就耐熱性或強度之觀點而言，以使用未施以表面處 理之氧化鈦者爲佳。 氧化鈦之製造方法，雖可利用氯法，亦可利用硫酸法 ，但在製造金紅石型之氧化鈦時，係以氯法爲佳。在藉由 氯法而製造氧化鈦的情況，以首先，使作爲鈦源之礦石（ 由金紅石礦或鈦鐵礦所得之合成金紅石礦）與氯，在1 000 °c左右產生反應而得粗四氯化鈦，將該粗四氯化鈦利用精 餾純化之後，藉由氧進行氧化者爲佳。 本發明之液晶聚酯組成物，亦可含有1種以上塡充材 、白色顏料以外之添加劑、液晶聚酯以外之樹脂等的其他 成分。 -19- 201245271 塡充材，可爲纖維狀塡充材，亦可爲板狀塡充材，除 纖維狀及板狀以外，亦可爲球狀以外之其他的粒狀塡充材 。此外，塡充材，可爲無機塡充材，亦可爲有機塡充材。 纖維狀無機塡充材之例示，係可列舉：玻璃纖維；聚丙烯 腈（PAN )系碳纖維、瀝青（Pitch )系碳纖維等之碳纖維 ;二氧化矽纖維、氧化鋁纖維、二氧化矽-氧化鋁纖維等 之陶瓷纖維；及不鏽鋼纖維等之金屬纖維。此外，亦可列 舉：鈦酸鉀晶懸、鈦酸鋇晶鬚、矽灰石晶鬚、硼酸鋁晶鬚 、氮化矽晶_、碳化矽晶鬚等之晶m。纖維狀有機塡充材 之例示，係可列舉：聚酯纖維及醯胺纖維。板狀無機塡充 材之例示，係可列舉：滑石、雲母、石墨、矽灰石、玻璃 碎片、硫酸鋇及碳酸鈣》雲母，係可爲白雲母，亦可爲金 雲母、氟金雲母、或四矽（Tetrasilisic )雲母。粒狀無機 塡充材之例示，係可列舉：二氧化矽、氧化鋁、氧化鈦、 玻璃珠、玻璃氣球、氮化硼、碳化矽及碳酸鈣。相對於液 晶聚酯1 00質量份，液晶聚酯組成物中塡充材之含量，一 般爲0〜100質量份。 白色顏料以外的添加劑之例示，係可列舉：抗氧化劑 、熱安定劑、光安定劑、防靜電劑、界面活性劑、難燃劑 。此外，白色顏料以外之著色劑，亦可使用白色顔料以外 之顔料或染料。相對於液晶聚酯1〇〇質量份，白色顏料以 外的添加劑之含量，一般爲〇〜5質量份。 液晶聚酯以外的樹脂之例示，係可列舉：聚丙烯、聚 醯胺、液晶聚酯以外之聚酯、聚颯、聚苯硫醚、聚醚酮、 -20- 201245271 聚碳酸酯、聚苯醚、聚醚醯亞胺等之液晶 塑性樹脂；及酚樹脂、環氧樹脂、聚亞醯 樹脂等之熱硬化性樹脂。相對於液晶聚酯 晶聚酯以外的樹脂之含量，一般爲0〜20 本發明之液晶聚酯組成物，係以藉由 融混練，擠出成條狀，並進行造粒化者， 、白色顏料及視需要所使用之其他成分者 係以使用具有汽缸、設置於汽缸之1根以 於汽缸之1處以上的供給口者爲佳，以進 於汽缸之1處以上的通氣孔部者爲更佳。 可藉由將如此所得之本發明之液晶聚 而得到反射率高，且反射光不易帶有色澤 聚酯之組成物的成形法，係以熔融成形法 係可列舉：射出成形法，T模法或充氣法 、壓縮成形法、吹製成形法、真空成形法 中以射出成形法爲佳。依據射出成形法， 薄部的反射板、或複雜形狀的反射板，特 之厚度爲〇.〇lmm〜3.0mm，較佳爲〇.〇2〜 0.05〜1.0mm的小型反射板中，適合射出月 如此所得之本發明之反射板，係適合 汽車、機械等之領域中作爲反射板使用， 光反射之反射板使用。例如，適合作爲鹵 光源裝置的光反射面、或使用有LED或有 元件的發光裝置或顯示裝置的反射板使用 聚酯以外的熱可 胺樹脂、氰酸酯 1 0 0質量份’液 質量份。 使用擠出機來熔 而調製液晶聚酯 爲佳。擠出機， 上的螺桿、和設 一步使用具有設 酯組成物成形， 的反射板。液晶 爲佳，其例示， 等之擠出成形法 及壓製成形。其 可容易得到具有 別是於得到薄部 z 2.0mm，更佳爲 K形法。 在電氣、電子、 特別是用於可視 素燈、HID等之 機EL等之發光 。特別是適合作 -21 - 201245271 爲使用有LED之發光裝置的反射板使用。 【實施方式】 〔實施例〕 〔液晶聚酯之流動起始溫度的測量〕 使用流量測試儀（（股）島津製作所之「CFT-5 00型 j )，將約2g之液晶聚酯，塡充到安裝有具有內徑1mm 及長度10mm的噴嘴之模具的汽缸中，在9.8MPa(100kg /cm2)之負荷下、以41/分鐘之速度一邊昇溫，一邊 使液晶聚酯熔融，並從噴嘴擠出，測量出顯示48 OOPa · s (48000泊）的黏度之溫度。 〔液晶聚酯之明亮度的測量〕 使用測色色差計（日本電色工業（股）之「ZE-2000 」）來測量。 實施例1 將994.5g(7.2莫耳）之p-羥苯甲酸、299.0g(1.8莫 耳）之對苯二甲酸、99.7g ( 0.6莫耳）之間苯二甲酸、 446.9g(2.4 莫耳）之 4,4’-二羥基聯苯、1298.6g(12.7 莫 耳）之乙酸酐及〇.2g之1-甲基咪唑，加入具備有攪拌裝 置、轉矩測定儀、氮氣導入管、溫度計及迴流冷卻器之反 應器中，將反應器內之氣體以氮氣置換之後，在氮氣氣流 下一邊搅拌，一邊耗費3〇分鐘從室溫昇溫至15〇 〇c，並在 -22- 201245271 150 °C下迴流1小時。接著，加入0,9g之1-甲基咪唑，並 一邊將副產乙酸及未反應之乙酸酐餾除，一邊耗費2小時 50分鐘從150°C昇溫至320°C，在確認了轉矩上昇的時點 ，將內容物從反應器取出，並冷卻至室溫。利用粉碎機將 所得之固形物粉碎，在氮氣氛圍下，耗費1小時從室溫昇 溫至23 0°C，再耗費2小時從230°C昇溫至26〇t ,在260 °C下保持1 〇小時，藉此在固態聚合之後冷卻，而得到粉 末狀之液晶聚酯。 將相對於全原料單體之P-羥苯甲酸、對苯二甲酸、間 苯二甲酸、4,4’-二羥基聯苯之各使用比例（莫耳％)顯示 於表1。此外，將相對於P-羥苯甲酸之羥基及4,4’-二羥基 聯苯之羥基的合計量之乙酸酐的使用比例（莫耳倍）顯示 於表1。此外，將所得之液晶聚酯之流動起始溫度顯示於 表1。並且，將所得之液晶聚酯之明亮度L *與固態聚合前 之明亮度L * 一倂顯示於表1。 實施例2〜6、比較例1〜4 除使相對於全原料單體之P-羥苯甲酸、對苯二甲酸、 間苯二甲酸、4,4’-二羥基聯苯之各使用比例（莫耳％ )、 相對於P-羥苯甲酸之羥基及4,4’-二羥基聯苯之羥基的合 計量之乙酸酐之使用比例（莫耳倍）、以及固態聚合溫度 之上限成爲表1中所顯示的値之外，藉由與實施例1相同 的操作，而得到液晶聚酯。將所得之液晶聚酯之流動起始 溫度顯示於表1。此外，將所得之液晶聚酯之明亮度L *與 -23- 201245271 固態聚合前之明亮度L # —倂顯示於表1。 【表1】 例 nmm 比較例 1 2 3 4 5 6 1 2 3 4 P-羥苯甲酸 (莫耳％) 60 60 60 60 50 70 60 60 60 60 對苯二甲酸 (莫耳％) 15 12 12 12 0 0 17 15 15 12 間苯二甲酸 (莫耳％) 5 8 8 8 25 15 3 5 5 8 4, 4’ -二經基聯苯 (莫耳％) 20 20 20 20 25 15 20 20 20 20 乙酸酐 (莫耳倍） 1.06 1.06 1.06 1.07 1.05 1.10 1.15 1. 15 1.10 1.06 固態聚合溫度上限 0C) 260 240 260 260 240 240 305 285 285 280 流動起始溫度 (X) 299 279 300 300 314 305 360 327 327 324 明亮度L» (固態聚合前） 90.3 90.4 90.4 90.0 90.6 88.7 85.1 86.4 86.8 90.4 (固態聚合後） 86.3 86.9 86.6 86.1 88.1 86.5 83.0 83,2 83.7 85.0 -24-201245271 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal polyester and a method of manufacturing the same. [Prior Art] The liquid crystal polyester is excellent in melt fluidity, and has high heat resistance, strength, and rigidity. Therefore, it is considered as a material for various products and parts including electrical and electronic parts. When a white pigment is blended therein, and the liquid crystal polyester is used as a material of a reflector such as an LED (Light Emitting Diode) light-emitting device, 'in order to improve the reflectance of the reflector, and to make the reflected light difficult to have color' High brightness is required for liquid crystal polyester. In the liquid crystal polyester, for example, in the patent document 1, a liquid crystal polyester having a yellowness YI of 3 2 or less and a brightness L· of 75 or more is disclosed, and specifically, it is disclosed that 60 mol% of the repeating unit derived from p-hydroxybenzoic acid, 2 mol% of the repeating unit derived from terephthalic acid '5 mol. /. a repeating unit derived from isophthalic acid, 20 mol% of a repeating unit derived from 4,4-dihydroxybiphenyl, and a liquid crystal polyester having a flow initiation temperature of 3 27 ° C; or having 60 mols /. Repetitive unit derived from p-hydroxybenzoic acid, 18 mol% of repeating units derived from p-benzoic acid, 2 mol% of repeating monoterpene derived from isophthalic acid, 20 mol% from 4,4· a repeating unit of dihydroxybiphenyl, and a liquid crystal polyester having a flow initiation temperature of 360 ° C; or 73 mol% of a repeating unit derived from p_ via this formic acid, 27 mol% of 6-hydroxy-2_naphthalene A liquid crystal polyester having a repeating unit of formic acid and having a flow initiation temperature of 2 9 〇〇c. [PTL 1] [Patent Document 1] [Patent Document 1] JP-A-2004-256673, SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide a liquid having a higher brightness [ Means for Solving the Problems] In order to achieve the above object, the present invention provides a liquid crystal system having a repeating unit (1) derived from an aromatic hydroxycarboxylic acid, a repeating unit (2) of a dicarboxylic acid, and an aromatic diol. Repeating unit (3) of hydroxylamine or aromatic diamine: the content of the above repeating unit (1) is 50 to 80 with respect to the total of fi, and the above repeating unit (2 is 10 to 25) Mol%; the content of the unit (3) is 10 to 25 mol% relative to the total amount of the total repeating unit; the main chain comprises a 1,2-phenylene skeleton or 1,3-molecular relative to the total coincidence measurement. The content of the benzene-repeating unit (A) is 5 to 30 mol%: and the fluidity thereof is 270 to 320 ° C. Further, the present invention provides a method for producing a liquid crystal polyester suitable for producing the liquid crystal polyester. And has: using aromatic carboxylic acid, aromatic a dicarboxylic acid, and at least one aromatic polyester selected from the group consisting of an aromatic diol and an aromatic fragrant diamine. A polyester derived from an aromatic, aromatic repeating unit mole % ; The starting temperature method of the base skeleton of the above repeating complex unit, which is a hydroxyhydroxylamine and an aromatic compound as a raw material monomer of -6-201245271, and the aromatic hydroxycarboxylic acid and the aforementioned aromatic compound are respectively obtained by an acid anhydride Step (1) of obtaining an aromatic decyloxycarboxylic acid and an aromatic diindenyl compound by subjecting the compound to a halogenation: the aromatic methoxycarboxylic acid, the aromatic dimercapto compound, and the aforementioned aromatic dicarboxylic acid The step (2) of obtaining a molten polymer by acid melt polymerization: and the step (3) of solid-polymerizing the molten polymer to obtain a solid polymer; the aromatic hydroxycarboxyl group relative to the total amount of all raw material monomers The amount of the acid used is 50 to 80% by mole; the amount of the aromatic dicarboxylic acid used is 10 to 25 mol%, based on the total amount of the whole raw material monomers; Use of aromatic compounds The amount is 10 to 25 mol%: the amount of the raw material monomer (A) whose main chain contains 1,2_phenylene skeleton or 1,3-phenylene skeleton relative to the total amount of all raw materials monomers It is 5 to 30 mol%; and the upper limit of the solid state polymerization temperature in the above step (3) is 220 to 270 °C. [Effect of the Invention] Since the liquid crystal polyester of the present invention has high brightness, it is possible to obtain a high reflectance by using a liquid crystal polyester composition in which a white pigment is blended, and the reflected light is less likely to have a color. Reflective plate. [Best Mode for Carrying Out the Invention] The liquid crystal polyester of the present invention has a repeating unit (1) derived from an aromatic hydroxycarboxylic acid, a repeating unit (2) derived from an aromatic dicarboxylic acid, and an aromatic diol derived from an aromatic diol. A repeating unit (3) of an aromatic hydroxylamine or an aromatic diamine. 201245271 The repeating unit (1) is a divalent residue derived from an aromatic hydroxycarboxylic acid, a hydrogen atom from which a hydroxyl group is removed, and a hydroxyl group of a carboxyl group; and the repeating unit (2) is removed from the aromatic dicarboxylic acid. A valence residue formed by each hydroxyl group of a carboxyl group: a repeating unit (3) derived from an aromatic diol, a divalent residue obtained by removing each hydrogen atom of two hydroxyl groups, or removed from an aromatic hydroxylamine a divalent residue formed by a hydrogen atom of a hydroxyl group and a hydrogen atom of the amine group thereof, or a divalent residue formed by removing each hydrogen atom of the two amine groups from the aromatic diamine, repeating unit (1) For example, a repeating unit represented by the following formula (1): an example of the repeating unit (2), a repeating unit represented by the following formula (2), and an example of the repeating unit (3) may be mentioned. The repeating unit represented by the following formula (3) is listed. (1) -O-Ar'-CO-(2)-CO-Ar2-CO-(3)-X-Ar3-Y- (Afl stands for phenyl, naphthyl or biphenylylene groups Ar2 and Ar3 each independently represent a phenylene group, a naphthyl group, a biphenyl subunit or a group represented by the following formula (4). The X and Y groups each independently represent an oxygen atom or an imine group (-NH-). The hydrogen atoms in the above-mentioned groups represented by Ar1, Ar2 and Ar3 may be independently substituted by a halogen atom, an alkyl group or an aryl group.) (4) - Ar4-Z-Ar5- (Al" Each of the Ar5 groups independently represents a phenyl or a naphthyl group. The Z system represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylidene group.) -8- 201245271 The halogen atom is exemplified by a fluorine atom or a chlorine atom. , bromine atom and iodine atom. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, η-butyl group, isobutyl group, s-butyl group, t-butyl group, hexyl group, and 2-ethyl group. The hexyl group, the η-octyl group and the η-fluorenyl group, and the carbon number thereof is generally 1 〇» the aryl group is exemplified by a phenyl group, a fluorenyl-tolyl group, an m-tolyl group, a P-tolyl group, and 1 a naphthyl group and a 2-naphthyl group, and the carbon number thereof is generally from 6 to 20. When the hydrogen atom is substituted by such a group, the number of each of the groups represented by each of Ar1, Ar2, or Ar3 is generally 2 or less, preferably 1 or less. Examples of the alkylidene group include methyl group, ethylene group, isopropylidene group, η-butylene group and 2-ethylhexylene group, and the carbon number thereof is generally 1 to 10°. In the above formula (1), Ar1 is a fluorene-phenylene group or a 2,6-anthranyl group, that is, a repeating unit derived from p-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid. It is better. The repeating unit (2) is in the above formula (2), and Ar2 is a fluorene-phenylene group, an m-phenylene group, a ρ-phenylene group or a 2,6-anthranyl group, that is, from the adjacent The repeating unit of phthalic acid, isophthalic acid, terephthalic acid or 2,6-naphthalene dicarboxylic acid is preferred. The repeating unit (3) is in the above formula (3), each of X and Y is an oxygen atom, and Ar3 is a fluorene-phenylene group, an m-phenylene group, a ρ-phenylene group, 4,4'- a biphenyl subunit or a 2,6-anthranyl group; in the above formula (3), X is an oxygen atom, hydrazine is an imine group, and Ar3 is a fluorene-phenylene group, an m-phenylene group or ρ- a phenylene group; or in the above formula (3), X and Y are each an imido group, -9-201245271 and Ar3 is a fluorene-phenylene group, an m-phenylene group or a p-phenylene group. That is, from catechol, resorcinol, hydroquinone, 4,4'-dihydroxybiphenyl, 2,6-naphthalenediol, guanidine-aminophenol, m-aminophenol, P- The repeating unit of aminophenol, hydrazine-phenylenediamine, m-phenylenediamine or p-phenylenediamine is preferred. The amount of the respective repeating units constituting the liquid crystal polyester is determined by the total amount of the repeating units (the mass of each repeating unit constituting the liquid crystal polyester is determined by the formula f of each repeating unit), and the equivalent amount (mole) of each repeating unit is obtained. The content of the repeating unit (1) is preferably from 5 to 80 mol%, more preferably from 50 to 70 mol%. The content of the repeating unit (2) is preferably 10 to 25 mol%, more preferably 15 to 25 mol%, based on the total amount of the total repeating units. The content of the repeating unit (3) is preferably from 〇 to 2 5 mol%, more preferably from 1 5 to 2 5 mol%, based on the total amount of the total repeat units. If the content of the repeating unit (1) is too large, and the content of the repeating units (2) and (3) is too small, the melting temperature or melt viscosity of the liquid crystal polyester may be easily increased, and it is required for the formation of the liquid crystal polyester. The temperature tends to become high. Therefore, the liquid crystal polyester is easily colored during molding, and the brightness of the molded body is easily lowered. If the content of the repeating unit (1) is too small, and the content of the repeating units (2) and (3) is too large, the heat resistance, strength, and rigidity of the liquid crystal polyester may be easily lowered, and the formed body may be easily deformed at a high temperature. . The ratio of the content of the repeating unit (2) to the content of the repeating unit (3) is expressed by [the content of the repeating unit (2)] / [the content of the repeating unit (3)] (mol/mole), generally It is 0.9/1 to 1/0.9, preferably 0.95/1 to 1/0.95, more preferably 〇98/ι~1/〇98. Further, the liquid crystal polyester of the present invention may independently have two or more kinds of repeating units (1) to (3). Further, the liquid crystal polyester of the present invention may have a repeating unit other than the repeating units (1) to (3), but the content thereof is generally 10 mol% or less based on the total amount of the total repeating unit, preferably 5 moles below. The liquid crystal polyester of the present invention is preferably one having X and Y as oxygen atoms, that is, a repeating unit derived from a specific aromatic diol as a repeating unit (3) and having only X and γ. Those who are each an oxygen atom are preferred. Therefore, since the melt viscosity of the liquid crystal polyester is liable to be low, and the temperature required for the formation of the liquid crystal polyester can be lowered, the liquid crystal polyester is less likely to be colored during molding, and the brightness of the molded body becomes difficult. reduce. The liquid crystal polyester of the present invention has a main chain of 5 to 30 mol%, preferably 8 to 25 mol%, and a 1,2-phenylene skeleton or 1, relative to the total repeating unit. 3- Repeated unit of the phenyl skeleton (a). In other words, the 'repeating unit (A) is a repeating unit containing a 1,2-phenylene group or a 1,3-phenylene group which may have a substituent or a fusion ring. When the content of the repeating unit (A) is too large, the flow initiation temperature of the liquid crystal polyester is set to 270 as will be described later. (: Above, it is necessary to increase the degree of polymerization of the liquid crystal polyester, and it is necessary to increase the solid state polymerization temperature to be described later, so that the liquid crystal polyester is easily colored during solid state polymerization, and the brightness of the liquid crystal polyester becomes easy to be lowered. When the content of the repeating unit (A) is too small, the degree of polymerization of the liquid crystal polyester must be lowered in order to set the flow initiation temperature of the liquid crystal polyester to be lower than 320 〇c as described later, and it is liable to remain in the liquid crystal polyester. The heat resistance or strength of the raw material monomer or oligomer 'or liquid crystal polyester, and the properties of the liquid crystal polyester are easily lowered, so that the molded body becomes easy to foam at a high temperature, or the molded body becomes high at a high temperature. The example of the repeating unit (A) of the repeating unit (1) is a repeating unit represented by the following formula (1A); and the repeating unit (A) of the repeating unit (2) is exemplified. The repeating unit represented by the formula (2A); the repeating unit (A) of the repeating unit (3) is an repeating unit represented by the following formula (3A): (1 A ) -0-Ar1A-C0 -(2A ) -CO-Ar2A-CO-(3 A ) -Χ-Αγ3α-Υ- (Ar1A, Ar2A&a Mp; 八^4 each independently represents o-phenylene, m-phenylene, 1,2-anthylene, 1,3-naphthyl or 1,4-naphthyl. X and Y are each The oxygen atom or the imine group is independently represented. The hydrogen atom represented by Ar1A, Ar2A and Ar3A in the above-mentioned group may be independently substituted by a halogen atom, an alkyl group or an aryl group.) Further, the above halogen atom, alkyl group Examples of the aryl group are the same as those of the halogen atom, the alkyl group, and the aryl group in the above-mentioned oxime 1 to Ar3. Further, the liquid crystal polyester of the present invention may have two or more types independently of each other. The repeating unit (A) as the repeating unit (1), the repeating unit (A) as the repeating unit (2), and the repeating unit (A) as the repeating unit (3). The repeating unit (A) is based on the above formula In (2A), 八1*〃 is 〇·phenyl or m-phenylene; in the above formula (3A), X and Y are each an oxygen atom, and VIII 1*〃 is a fluorene-phenylene group. Or m-phenylene; in the above formula -12-201245271 (3A), X is an oxygen atom, γ is an imine group, and 〃 is a phenyl group or a m-phenylene group; In the above formula (3Α) Wherein, X and oxime are each an imido group, and it is preferred that the eighty-eight is a phenyl-phenylene group or an m-phenylene group, that is, from phthalic acid, isophthalic acid, catechol Preferably, the repeating unit of resorcinol, hydrazine-aminophenol, m-aminophenol, hydrazine-phenylenediamine or m-phenylenediamine is preferred. Further, the liquid crystalline polyester of the present invention is derived from hydroxy group. The content of the repeating unit containing a naphthalene ring relative to the total repeating unit of naphthoic acid, naphthalene dicarboxylic acid or naphthalenediol is preferably 0 to 30 mol%, more preferably 0 to 25 Mole%, and even better for 〇~20 mol%. Thereby, the brightness of the liquid crystal polyester can be easily improved. The liquid crystal polyester of the present invention has a flow initiation temperature of 270 to 320 ° C, preferably 290 to 3 20 ° C. The flow initiation temperature is also referred to as a flow temperature or a flow temperature, and a liquid crystal polyester is used while heating at a rate of 4 ° C/min under a load of 9.8 MPa (10 0 kg/cm 2 ) using a capillary rheometer. When it is extruded from a nozzle having an inner diameter of 1 ram and a length of 10 mm, it exhibits a viscosity of 4800 Pa·s (48 000 poise), and becomes a rough standard of the molecular weight of the liquid crystal polyester (refer to the preparation of the small-outlet, "Liquid Crystal Polyester - Synthesis, Forming, Application -", CMC Corporation, June 5, 1978, p. 95) If the flow initiation temperature is too high, it is required for the formation of liquid crystal polyester. Since the temperature becomes high, the liquid crystal polyester is easily colored at the time of molding, and the brightness of the molded body is liable to be lowered. If the flow initiation temperature is too low, the heat resistance, strength, and rigidity of the liquid crystal polyester are liable to lower, and the molded body becomes easily deformed at a high temperature of -13 to 201245271. The liquid crystal polyester of the present invention can be produced by polymerizing (polycondensing) a raw material monomer of a type and amount corresponding to the repeating unit constituting the same under specific conditions. The raw material monomer is an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and at least one aromatic compound selected from the group consisting of an aromatic diol, an aromatic hydroxylamine, and an aromatic diamine. The aromatic hydroxycarboxylic acid is preferably one selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2.naphthoic acid. The aromatic dicarboxylic acid is preferably one selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid. The aromatic compound is derived from catechol, resorcinol, hydroquinone, hydrazine-aminophenol, m-aminophenol, p-aminophenol, hydrazine-phenylenediamine, m- Preferably, at least one compound selected from the group consisting of phenylenediamine, p-phenylenediamine, 4,4'-dihydroxybiphenyl and 2,6-naphthalenediol is preferred. The mass of each raw material monomer is determined by dividing the total mass of the raw material monomers by the molecular weight of each raw material monomer to divide the mass of each raw material monomer constituting each repeating unit constituting the liquid crystal polyester. The amount of the aromatic hydroxycarboxylic acid used is from 5 to 80 mol%, preferably from 50 to 70 mol%, based on the total amount of the urethane. The aromatic dicarboxylic acid is used in an amount of 10 to 25 mol%, preferably 15 to 25 mol%, based on the total amount of all raw material monomers. The amount of the aromatic compound used is 10 to 25 moles based on the total amount of all raw material monomers. /. 'preferably 15 to 25 mol % -14- 201245271 The ratio of the amount of the aromatic dicarboxylic acid to the aromatic compound is 'the amount of the aromatic dicarboxylic acid used' / [the aforementioned aromatic compound The amount of use (mole/mole) is expressed as 〇. 〜1/0.9' is preferably 0.95/1 to 1/0.95, more preferably 0.98/ /0.98. Further, the 'raw material monomer' may be a compound other than the aromatic hydroxycarboxylic acid, the dicarboxylic acid, and the aromatic compound, but the total amount of the raw material monomers is generally 1% by mole or less. It is 5 mol% or less. The aromatic compound is preferably an aromatic diol, and more preferably an aromatic diol is used. The amount of the raw material monomer (A) in which the main chain contains the ι, 2 -extension skeleton or the 1,3-phenylene skeleton relative to the total amount of the whole raw material monomers, preferably 〜30 mol%' is preferably 8 ~25 mol%. In other words, the starting material unit A) is a compound containing an I, 2-phenylene group or a phenyl group which may have a substituent or a fusion ring. The raw material monomer (A) ' is based on phthalic acid, m-xylylene catechol, resorcinol, hydrazine-aminophenol 'm-aminophenol, hydrazine-diamine and m-phenylene It is preferred that at least one of the selected groups of diamines is selected. In addition, as in the case of hydroxynaphthoic acid, naphthalene dicarboxylic acid and naphthalene diphenol, the total amount of the raw material monomers is the total amount of the raw material monomers containing the naphthalene ring, preferably 0 to 30 mol%, more preferably 〇 ~ 2 5 moules. /. ‘More preferably 〇 莫 %. The amount of the aromatic 9/1 1~1 aroma is all preferred, and the phenyl type 5 body (1,3-acid, benzene derivative, compared to ~20 -15-201245271 liquid crystal polyester is manufactured by The following steps (1), (2) and (3) are carried out, that is, first, in step (1), the aromatic hydroxycarboxylic acid and the aromatic compound are respectively deuterated with an acid anhydride to obtain an aromatic oxime a carboxylic acid and an aromatic diindenyl compound, followed by step (2), melt-polymerizing an aromatic decyloxycarboxylic acid, an aromatic dimercapto compound, and an aromatic dicarboxylic acid to obtain a molten polymer, and then, In the step (3), the molten polymer is solid-state polymerized to obtain a solid polymer. The acid anhydride used in the step (1) is preferably a fatty acid anhydride, and examples thereof include acetic anhydride 'propionic anhydride, butyric anhydride, Isobutyric anhydride, valeric anhydride, trimethyl acetic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, Monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, horse As the acid anhydride, succinic anhydride, and A-bromopropionic acid anhydride, two or more of these may be used. Among them, acetic anhydride, propionic anhydride, butyric anhydride, and isobutyric anhydride are preferred, and acetic anhydride is more preferred than the aromatic hydroxyl group. The hydroxyl group of the carboxylic acid and the total amount of the hydroxyl group and the amine group of the aromatic compound, and the amount of the acid anhydride used is preferably 1 to 1.1 moles, more preferably 1.01 to 1.08 moles. If the amount of the acid anhydride is too large, The liquid crystal polyester is easily colored, and the brightness of the liquid crystal polyester is easily lowered. If the amount of the acid anhydride is too small, the degree of polymerization of the liquid crystal polyester tends to be low, and the raw material monomer or oligomer tends to remain in the liquid crystal polyester. The heat resistance, strength, and rigidity of the liquid crystal polyester are liable to lower, so that the molded body becomes easily foamed at a high temperature, or the molded body is easily deformed at a high temperature. Step (1) is performed by nitrogen gas or the like. In an inert gas atmosphere, it is preferably carried out at 130 -16 to 201245271 to 180 ° C. Further, in the step (1), an aromatic dicarboxylic acid may be present. Step (2) is carried out under nitrogen. Wait for an inert gas atmosphere at 1 30 It is preferably carried out at -400 ° C, preferably at 150 to 350 ° C. Further, step (2) is carried out by distilling off by-produced carboxylic acid or unreacted anhydride. At the same time, it is preferred to carry out the temperature increase at a rate of 0.1 to 50 ° C /min, and it is more preferable to carry out the temperature increase at a rate of 0.3 to 5 ° C /min. Further, the steps (1) and/or (2), It is preferable to carry out in the presence of a catalyst, whereby the deuteration and/or melt polymerization proceeds smoothly, and the brightness of the liquid crystal polyester is easily improved. Examples of the catalyst include: a metal compound such as magnesium acetate, stannous acetate, Tetra butyl titanate, decanoic acid, sodium acetate, potassium acetate or antimony trioxide, like 4-(dimethylamino)pyridine A pyridine compound such as 4-(dialkylamino)pyridine or the like, and an imidazole compound such as 1-methylimidazole such as 1-methylimidazole. Among them, an imidazole compound is preferred from the viewpoint of the brightness of the liquid crystal polyester. The amount of the catalyst used is preferably 0.005 to 1 part by mass, more preferably 0.05 to 0.5 part by mass, based on 100 parts by mass of the total of the raw material monomers. The step (3) is carried out by setting the upper limit of the solid state polymerization temperature to 220 to 270 ° C., preferably 225 to 265 ° C, more preferably 230 to 255 ° C. If the upper limit of the solid state polymerization temperature is too high, the liquid crystal polyester will be easily colored during solid state polymerization, and the brightness of the liquid crystal polyester will be easily lowered. If the upper limit of the solid state polymerization temperature is too low, the degree of polymerization of the liquid crystal polyester tends to be low, and the raw material monomer or oligomer is liable to remain in the liquid crystal polyester, or the heat resistance or strength of the liquid crystal -17-201245271 The rigidity is easily lowered, so that the molded body becomes easy to foam at a high temperature, or the formed body becomes easily deformed at a high temperature. Further, the 'step (3) is carried out under an inert gas atmosphere such as nitrogen. It is preferred to carry out the temperature rise to the upper limit temperature and to maintain the temperature at the upper limit temperature for 3 to 20 hours. The liquid crystal polyester of the present invention thus obtained has a high brightness, and is specifically represented by a brightness L* according to the L*a*b* color system of JIS Z 8729, preferably 86 or more. Good for 87 or above. Since the liquid crystal polyester of the present invention has a high brightness, the liquid crystal polyester composition of the present invention obtained by blending a white pigment therein can be suitably used as a material of a reflecting plate. The white pigment is preferably an inorganic compound such as zinc oxide, zinc sulfide, lead white or titanium oxide, and two or more of these may be used as needed. Among them, titanium oxide is preferred. Since the white pigment is easily dispersed in the liquid crystal polyester, and the reflecting plate having high reflectance is easily obtained, the particle diameter of the white pigment is expressed by volume average 値, preferably 0.05 to 2/zm, more preferably 0.1 to 1. l/zm, more preferably 0.15 to 0.5//m, particularly preferably 0.2 to 0.4//m. In addition, the volume average particle diameter is a white pigment by a scanning electron microscope (SEM: Scanning Electron Microscope), and the obtained SEM is obtained by a image analysis device (for example, "Russian NIRECO" "RUUZEKKUSU IIIU"). The photograph is analyzed, and the amount of particles (%) in the respective particle diameter sections of the secondary particle diameter is obtained in a distribution curve obtained by accumulating the volume-based -18-201245271, and the cumulative degree is 50%. The content of the white pigment in the liquid crystal polyester composition of the present invention is preferably 20 to 200 parts by mass, more preferably 25 to 150 parts by mass, even more preferably 100 parts by mass of the liquid crystal polyester. 40 to 100 parts by mass. The titanium oxide which is preferably exemplified as the white pigment may have a crystal form of rutile or anatase or a mixture of both, but has high reflectance and is excellent in weather resistance. From the viewpoint of the reflecting plate, it is preferable that it is a rutile-containing titanium oxide, and it is preferable that it is composed mainly of rutile-type titanium oxide. The titanium oxide can also be surface treated. For example, the surface treatment can be carried out by using an inorganic metal oxide to improve the dispersibility or weather resistance. The inorganic metal oxide is preferably one in which alumina is used. Further, from the viewpoint of heat resistance or strength, it is preferred to use titanium oxide which is not subjected to surface treatment. In the method for producing titanium oxide, the chlorine method may be used, and the sulfuric acid method may be used. However, in the case of producing rutile-type titanium oxide, the chlorine method is preferred. In the case of producing titanium oxide by the chlorine method, first, the ore which is a source of titanium (synthetic rutile ore obtained from rutile or ilmenite) and chlorine are reacted at about 1 000 °c. It is preferred that the crude titanium tetrachloride is oxidized by oxygen after the crude titanium tetrachloride is purified by rectification. The liquid crystal polyester composition of the present invention may contain one or more other components such as an enamel filler, an additive other than a white pigment, and a resin other than the liquid crystal polyester. -19- 201245271 The enamel filling material can be a fibrous enamel filling material or a platy enamel filling material. In addition to the fibrous shape and the plate shape, it can also be a granular enamel filling material other than a spherical shape. In addition, the ruthenium filler material may be an inorganic ruthenium filler or an organic ruthenium filler. Examples of the fibrous inorganic cerium filling material include glass fibers; carbon fibers such as polyacrylonitrile (PAN)-based carbon fibers and pitch (Pitch)-based carbon fibers; cerium oxide fibers, alumina fibers, and cerium oxide-alumina. Ceramic fibers such as fibers; and metal fibers such as stainless steel fibers. In addition, crystals such as potassium titanate suspension, barium titanate whisker, ash stone whisker, aluminum borate whisker, tantalum nitride crystal, and strontium carbide whisker may also be listed. Examples of the fibrous organic enamel filler include polyester fibers and guanamine fibers. Examples of the plate-shaped inorganic cerium filling material include talc, mica, graphite, ash stone, glass cullet, barium sulfate, and calcium carbonate. The mica may be muscovite, phlogopite, or fluorophlogopite. Or Tetrasilisic mica. Examples of the particulate inorganic cerium filler include cerium oxide, aluminum oxide, titanium oxide, glass beads, glass balloons, boron nitride, cerium carbide, and calcium carbonate. The content of the cerium filler in the liquid crystal polyester composition is usually from 0 to 100 parts by mass based on 100 parts by mass of the liquid crystal polyester. Examples of the additives other than the white pigment include an antioxidant, a heat stabilizer, a photostabilizer, an antistatic agent, a surfactant, and a flame retardant. Further, as the coloring agent other than the white pigment, a pigment or a dye other than the white pigment may be used. The content of the additive other than the white pigment is generally 〇 5 parts by mass based on 1 part by mass of the liquid crystal polyester. Examples of the resin other than the liquid crystal polyester include polypropylene, polyamine, polyester other than liquid crystal polyester, polyfluorene, polyphenylene sulfide, polyether ketone, -20-201245271 polycarbonate, polyphenylene A liquid crystal plastic resin such as an ether or a polyether quinone; and a thermosetting resin such as a phenol resin, an epoxy resin or a polyarylene resin. The liquid crystal polyester composition of the present invention is generally 0 to 20 in terms of the content of the resin other than the liquid crystal polyester crystal polyester, and is obtained by melt-kneading, extruding into a strip, and granulating, white The pigment and other components used as needed are preferably those having a cylinder and one of the cylinders for one or more cylinders, and one or more vent holes for the cylinder. Better. The liquid crystal of the present invention obtained as described above can be obtained by a method of forming a composition having a high reflectance and having a reflected light which is less likely to be accompanied by a color polyester. The melt molding method can be exemplified by an injection molding method and a T-die method. In the inflation method, the compression molding method, the blow molding method, and the vacuum forming method, an injection molding method is preferred. According to the injection molding method, the reflection plate of the thin portion or the reflection plate of a complicated shape is particularly suitable for injection in a small reflection plate having a thickness of 〇.〇1 mm to 3.0 mm, preferably 〇.〇2 to 0.05 to 1.0 mm. The reflector of the present invention thus obtained is suitable for use as a reflector in the field of automobiles, machinery, and the like, and is used as a reflector for light reflection. For example, a light-reflecting surface suitable as a halogen light source device or a reflecting plate using an LED or a component light-emitting device or a display device uses a thermotropic amine resin other than polyester, and a cyanate ester of 100 parts by mass liquid mass. . It is preferred to use an extruder to melt and modulate the liquid crystal polyester. The extruder, the screw on it, and the reflector which is formed by forming an ester composition are used in an alternative manner. The liquid crystal is preferred, and examples thereof include extrusion molding and press molding. It is easily obtained by having a thin portion z 2.0 mm, more preferably a K-shaped method. Illumination in electrical, electronic, and especially EL for use in visual lamps, HID, etc. Especially suitable for use as -21 - 201245271 for reflectors using LED light-emitting devices. [Embodiment] [Examples] [Measurement of flow initiation temperature of liquid crystal polyester] About 2 g of liquid crystal polyester was charged using a flow rate tester ("CFT-5 00 type j" of Shimadzu Corporation) In a cylinder to which a mold having a nozzle having an inner diameter of 1 mm and a length of 10 mm is attached, the liquid crystal polyester is melted while being heated at a speed of 41/min under a load of 9.8 MPa (100 kg / cm 2 ), and is squeezed from the nozzle. The temperature at which the viscosity of 48 OOPa · s (48,000 poise) is measured is measured. [Measurement of the brightness of the liquid crystal polyester] Measured using a colorimeter ("ZE-2000" of Nippon Denshoku Industries Co., Ltd.) . Example 1 994.5 g (7.2 mol) of p-hydroxybenzoic acid, 299.0 g (1.8 mol) of terephthalic acid, 99.7 g (0.6 mol) of phthalic acid, 446.9 g (2.4 mol) 4,4'-dihydroxybiphenyl, 1298.6 g (12.7 mol) of acetic anhydride and g.2 g of 1-methylimidazole, which are equipped with a stirring device, a torque meter, a nitrogen introduction tube, a thermometer, and In the reactor of the reflux condenser, the gas in the reactor was replaced with nitrogen, and then stirred under a nitrogen gas stream, and it was heated from room temperature to 15 ° C for 3 minutes, and at -22-201245271 150 °C. Under reflux for 1 hour. Next, 0,9 g of 1-methylimidazole was added, and while the by-produced acetic acid and unreacted acetic anhydride were distilled off, the temperature was raised from 150 ° C to 320 ° C in 2 hours and 50 minutes, and the torque was confirmed to rise. At the time, the contents were taken out of the reactor and cooled to room temperature. The obtained solid matter was pulverized by a pulverizer, and heated in a nitrogen atmosphere for 1 hour from room temperature to 23 0 ° C, and further heated for 2 hours from 230 ° C to 26 〇t, and maintained at 260 ° C for 1 〇. After that, it was cooled by solid state polymerization to obtain a powdery liquid crystal polyester. The respective use ratios (% by mole) of P-hydroxybenzoic acid, terephthalic acid, isophthalic acid, and 4,4'-dihydroxybiphenyl relative to the whole raw material monomers are shown in Table 1. Further, the use ratio (mole ratio) of acetic anhydride to the total amount of the hydroxyl group of P-hydroxybenzoic acid and the hydroxyl group of 4,4'-dihydroxybiphenyl is shown in Table 1. Further, the flow initiation temperature of the obtained liquid crystal polyester is shown in Table 1. Further, the brightness L* of the obtained liquid crystal polyester and the brightness L* before solid state polymerization are shown in Table 1. Examples 2 to 6 and Comparative Examples 1 to 4 except for the respective ratios of P-hydroxybenzoic acid, terephthalic acid, isophthalic acid, and 4,4'-dihydroxybiphenyl relative to the whole raw material monomer ( The molar ratio of the acetic anhydride to the total amount of the hydroxyl group of P-hydroxybenzoic acid and the hydroxyl group of 4,4'-dihydroxybiphenyl (mole), and the upper limit of the solid state polymerization temperature are shown in Table 1. A liquid crystal polyester was obtained by the same operation as in Example 1 except for the ruthenium shown in the above. The flow initiation temperature of the obtained liquid crystal polyester is shown in Table 1. Further, the brightness L* of the obtained liquid crystal polyester and the brightness L # - 倂 before the solid state polymerization of -23-201245271 are shown in Table 1. [Table 1] Example nmm Comparative Example 1 2 3 4 5 6 1 2 3 4 P-hydroxybenzoic acid (mol%) 60 60 60 60 50 70 60 60 60 60 Terephthalic acid (% by mole) 15 12 12 12 0 0 17 15 15 12 Isophthalic acid (% by mole) 5 8 8 8 25 15 3 5 5 8 4, 4' - Di-based biphenyl (mol%) 20 20 20 20 25 15 20 20 20 20 Acetic anhydride (mole) 1.06 1.06 1.06 1.07 1.05 1.10 1.15 1. 15 1.10 1.06 Solid state polymerization temperature limit 0C) 260 240 260 260 240 240 305 285 285 280 Flow starting temperature (X) 299 279 300 300 314 305 360 327 327 324 Brightness L» (before solid state polymerization) 90.3 90.4 90.4 90.0 90.6 88.7 85.1 86.4 86.8 90.4 (after solid state polymerization) 86.3 86.9 86.6 86.1 88.1 86.5 83.0 83,2 83.7 85.0 -24-