JP2004018558A - Polybutylene terephthalate resin and thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide polybutylene terephthalate resin compositions giving thermoplastic resin compositions with favorable mechanical properties by blending polycarbonate and others. <P>SOLUTION: The polybutylene terephthalate resins show intrinsic viscosity of 0.55 or over and satisfy the relationship of formula (1):15 x [η]<SP>0.95</SP>≤[COOH] + [CH=CH<SB>2</SB>]≤48 x [η]<SP>0.60</SP>[wherein<SP></SP>[COOH] represents concentration of a carboxy terminal group (equivalent/10<SP>6</SP>g), [CH=CH<SB>2</SB>] represents concentration of a vinyl terminal group (equivalent/10<SP>6</SP>g) and [η] represents intrinsic viscosity of polybutyleneterephthalate resin, respectively]. <P>COPYRIGHT: (C)2004,JPO

Description

【００２２】
（式中、Ｗは単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基又は、−Ｏ−，−Ｓ−，−ＣＯ−，−ＳＯ−，−ＳＯ_２−で示される２価の基からなる群から選ばれるものであり、Ｙ及びＺは、ハロゲン又は炭素数１〜６の炭化水素基であり、ｐ及びｑは０〜２の整数であり、ＹとＺ、ｐとｑは、いずれも、同一であっても異なっていてもよい。）
前記式（２）で表される芳香族ジヒドロキシ化合物としては、例えば、ビス（４−ヒドロキシジフェニル）メタン、２，２−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３−ｔ−ブチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジブロモフェニル）プロパン、４，４−ビス（４−ヒドロキシフェニル）ヘプタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、４，４’−ジヒドロキシビフェニル、３，３’，５，５’−テトラメチル−４，４’−ジヒドロキシビフェニル、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）スルフィド、ビス（４−ヒドロキシフェニル）エーテル、ビス（４−ヒドロキシフェニル）ケトン等が例示されるが、特に好ましくは、２，２−ビス（４−ヒドロキシフェニル）プロパン（以下、「ビスフェノールＡ」と略す）が挙げられる。これらの芳香族ジヒドロキシ化合物は単独でも、２種以上を混合してもよい。
【００２３】
また分岐状芳香族ホ゜リカーホ゛ネートを製造しようとする場合は、少量の３価以上の多価フェノールを共重合させることもできる。また芳香族ポリカーボネートの熱安定性や耐加水分解性を向上させたり、分子量を規定する目的で、ｐ−ｔ−ブチルフェノールやｐ−クミルフェノール等の１価のフェノール類を末端封止剤として用いることができる。
又、炭酸ジエステルとしては、下記一般式（３）で表される化合物が挙げられる。
【００２４】
【化２】
Ａ−Ｏ−Ｃ（＝Ｏ）−Ｏ−Ａ’　式（３）
【００２５】
（式中Ａ及びＡ’は炭素数１〜１８の置換されていても良い脂肪族基、又は置換されていても良い芳香族基であり、互いに同一であっても異なっていてもよい。）
前記一般式（３）で表される炭酸ジエステルは、例えば、ジメチルカーボネート、ジエチルカーボネート、ジ−ｔ−ブチルカーボネート等の炭酸ジアルキル化合物、ジフェニルカーボネート、およびジトリルカーボネート等の置換ジフェニルカーボネートなどが例示されるが、好ましくはジフェニルカーボネート、置換ジフェニルカーボネートであり、特にジフェニルカーボネートが好ましい。これらの炭酸ジエステルは単独、あるいは２種以上を混合してもよい。
本発明でエステル交換法により芳香族ポリカーボネート樹脂を製造する際には、芳香族ジヒドロキシ化合物としてビスフェノールＡ、炭酸ジエステルとしてジフェニルカーボネートを用いることが好ましく、ジフェニルカーボネートはビスフェノールＡ１モルに対して、１．０１〜１．３０モル、好ましくは１．０２〜１．２０の量で用いられることが好ましい。モル比が１．０１より小さくなると、製造された芳香族ポリカーボネート樹脂の末端ＯＨ基が増加して、ポリマーの熱安定性や耐加水分解性が悪化し、また、モル比が１．３０より大きくなると、同一条件下ではエステル交換反応の速度が低下し、所望の分子量の芳香族ポリカーボネート樹脂の製造が困難となる。
【００２６】
本発明に用いられるポリカーボネート系樹脂の末端ＯＨ濃度に特に制限はないが、１以上６０当量／１０^６ｇ以下であることが好ましく、好ましくは、５当量／１０^６ｇ以上、中でも１０当量／１０^６ｇ以上、特に２０当量／１０^６ｇ以上が好ましい。一方、５０当量／１０^６ｇ以下が好ましく、中でも４０当量／１０^６ｇ以下、特には４０当量／１０^６ｇ以下が最適である。末端ＯＨ基濃度が６０当量／１０^６ｇより大きいと、ＰＢＴとの配合に際し、溶融時の着色が増加する傾向がある。
本発明でエステル交換法により芳香族ポリカーボネート樹脂を製造する際には、エステル交換触媒が使用される。該触媒としてはアルカリ金属化合物及び／又はアルカリ土類金属化合物が使用され、補助的に、塩基性ホウ素化合物、塩基性リン化合物、塩基性アンモニウム化合物、あるいはアミン系化合物などの塩基性化合物を併用することも可能であるが、物性面や取り扱いの面で、アルカリ金属化合物及び／又はアルカリ土類金属化合物が単独で使用されることが特に好ましい。
【００２７】
この触媒量としては、芳香族ジヒドロキシ化合物１モルに対して、１×１０^−８〜６×１０^−６モルの範囲で用いられるのが好ましく、さらに好ましくは１×１０^−７〜３×１０^−６モルの範囲で、特に好ましくは２×１０^−７〜２×１０^−６モルの範囲で用いられる。この量より少なければ、所定の分子量、末端ヒドロキシ基量の芳香族ポリカーボネート樹脂を製造するのに必要な重合活性が得られない傾向があり、この量より多い場合は、ポリマー色相が悪化し、分岐が多くなりポリマーの成形性が損なわれる傾向がある。
アルカリ金属化合物としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化セシウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素リチウム、炭酸水素セシウム、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、炭酸セシウム、酢酸ナトリウム、酢酸カリウム、酢酸リチウム、酢酸セシウム、ステアリン酸ナトリウム、ステアリン酸カリウム、ステアリン酸リチウム、ステアリン酸セシウム、水素化ホウ素ナトリウム、水素化ホウ素カリウム、水素化ホウ素リチウム、水素化ホウ素セシウム、フェニル化ホウ素ナトリウム、フェニル化ホウ素カリウム、フェニル化ホウ素リチウム、フェニル化ホウ素セシウム、安息香酸ナトリウム、安息香酸カリウム、安息香酸リチウム、安息香酸セシウム、リン酸水素２ナトリウム、リン酸水素２カリウム、リン酸水素２リチウム、リン酸水素２セシウム、フェニルリン酸２ナトリウム、フェニルリン酸２カリウム、フェニルリン酸２リチウム、フェニルリン酸２セシウム、ナトリウム、カリウム、リチウム、セシウムのアルコラート、フェノラート、ビスフェノールＡの２ナトリウム塩、２カリウム塩、２リチウム塩、２セシウム塩などが挙げられる。
【００２８】
また、アルカリ土類金属化合物としては、例えば、水酸化カルシウム、水酸化バリウム、水酸化マグネシウム、水酸化ストロンチウム、炭酸水素カルシウム、炭酸水素バリウム、炭酸水素マグネシウム、炭酸水素ストロンチウム、炭酸カルシウム、炭酸バリウム、炭酸マグネシウム、炭酸ストロンチウム、酢酸カルシウム、酢酸バリウム、酢酸マグネシウム、酢酸ストロンチウム、ステアリン酸カルシウム、ステアリン酸バリウム、ステアリン酸マグネシウム、ステアリン酸ストロンチウムなどが挙げられる。
エステル交換反応は一般には二段階以上の多段工程で実施される。具体的には、第１段目の反応は、９．３×１０^４〜１．３３×１０^３Ｐａの減圧下に１２０〜２６０℃、好ましくは１８０〜２４０℃の温度で０．１〜５時間、好ましくは０．１〜３時間反応させる。ついで、反応系の減圧度を上げながら反応温度を高め、最終的には１３３Ｐａ以下の減圧下、２４０〜３２０℃の温度で重縮合反応を行う。
【００２９】
反応の形式は、バッチ式、連続式、あるいはバッチ式と連続式の組み合わせのいずれの反応でもよく、使用する装置は、槽型、管型、あるいは塔型のいずれの形式であってもよい。
芳香族ポリカーボネート系樹脂の末端ＯＨ基濃度は、重合温度、重合時の真空度、コンデンサー温度等の重合条件によっても影響を受けるが、これらがある一定の条件下では、ビスフェノールＡで代表される芳香族ジヒドロキシ化合物とジフェニルカーボネートで代表される炭酸ジエステルとの仕込み比によって制御することができる。
本発明に用いられるポリカーボネート系樹脂の分子量に特に制限はないが、好ましくは、溶媒として塩化メチレンを用い、温度２５℃で測定された溶液粘度より換算した粘度平均分子量で１２０００〜４００００、さらに好ましくは１３０００〜３００００、特に好ましくは１４０００〜２６０００である。これより大きすぎると成形時の溶融流動性が低下する傾向があり、小さすぎると組成物として十分な強度が得られない怖れがある。
【００３０】
本発明に用いられるポリカーボネート系樹脂の配合割合は特に限定されるものではないが、好ましくは、ＰＢＴ１００重量部に対して、ポリカーボネート系樹脂が５〜１００重量部、好ましくは１０〜８０重量部である。配合するＰＣの量が少なすぎると衝撃強度が低下する傾向があり、多すぎると流動性が劣るため好ましくない。
尚、本発明の熱可塑性樹脂組成物中のチタン原子濃度は１０〜２４０ｐｐｍであることが好ましく、さらには１５〜１５０ｐｐｍ、中でも１５〜１２０ｐｐｍ、特には１５〜９０ｐｐｍが好ましい。チタン原子濃度１０ｐｐｍ以下の場合、ＰＢＴとＰＣを配合する際のエステル交換反応が起こりにくく、組成物の機械物性が低下する傾向にある。また、チタン原子濃度が２４０ｐｐｍより多いと配合の際のエステル交換反応や副反応が起こりやすく、組成物の機械物性や熱安定性が悪化する傾向にある。
【００３１】
又、本発明の熱可塑性樹脂組成物中のアルカリ金属濃度は１．５ｐｐｍ以下であることが好ましく、更に、好ましくは１．２ｐｐｍ以下、より好ましくは１．０ｐｐｍ以下であるが、中でも０．０５〜１．０ｐｐｍが好適である。アルカリ金属濃度が１．５ｐｐｍより多いと、ＰＢＴとＰＣを配合する際にエステル交換反応や副反応が起こりやすくなり、組成物の機械物性が悪化したり、色調が悪くなる恐れがある。アルカリ金属濃度が０．０５ｐｐｍより少ない場合、配合の際のエステル交換反応が起こりにくく、相溶性が低下するため、機械物性が低下する傾向にある。これらの金属量は、湿式灰化等の方法で熱可塑性樹脂組成物中の金属を回収した後、原子発光、プラズマ発光等を用いて測定することができる。
【００３２】
また本発明のＰＢＴの添加剤としては、公知の酸化防止剤、帯電防止剤、臭素化ポリカーボネート、臭素化エポキシ化合物、リン酸エステル化合物、フォスファゼン化合物、メラミン、シアヌル酸等の難燃剤、三酸化アンチモン、五酸化アンチモンなどの難燃助剤、可塑剤、潤滑剤、離型剤、着色剤、結晶核剤などが例示される。また、無機充填剤としては、ガラス繊維、タルク、マイカ、ガラスフレークス、カーボン繊維、シリカ、アルミナ繊維、クレー、カーボンブラック、カオリン、酸化チタン、酸化鉄、酸化アンチモン、アルミナ等の金属化合物、カリウム、ナトリウムなどのアルカリ金属化合物等が例示される。有機充填剤としては、芳香族ポリエステル繊維、液晶性ポリエステル繊維等が例示される。
【００３３】
本発明のＰＢＴに前記の種々の熱可塑性樹脂、添加剤等を配合する方法に特に制限はないが、溶融混練により配合することが好ましく、熱可塑性樹脂について通常使用される混練方法を適用することができる。具体的には、例えば、各成分を、必要により、付加的成分である物質とともに、ヘンシェルミキサー、リボンブレンダー、Ｖ型ブレンダーなどにより均一に混合した後、一軸混練押出機、多軸混練押出機、ロール、バンバリーミキサー、ラボプラストミル、ブラベンダーなどを用いて混練する方法が挙げられるが、中でも混合性能の点からは２軸押出機を使用することが好ましい。
本発明のＰＢＴおよびＰＢＴと前記の種々の熱可塑性樹脂、添加剤等との配合物の成形加工方法に特に制限はなく、熱可塑性樹脂について一般に用いられている成形法、すなわち、射出成形、中空成形、押し出し成形、プレス成形などの成形法を適用することができる。
【００３４】
【実施例】
以下、本発明を実施例により更に詳細に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。
なお、実施例および比較例において、ＰＢＴおよびＰＢＴ／ＰＣ配合物の評価は下記の方法により行った。
（１）カルボキシル末端基濃度（ＰＢＴ１０^６ｇあたりのＣＯＯＨの当量数）
ＰＢＴをベンジルアルコールに溶解し、０．０１Ｎ　ＮａＯＨ／ベンジルアルコール溶液による滴定値から算出した。
（２）ビニル末端基濃度（ＰＢＴ１０^６ｇあたりのＣＨ＝ＣＨ_２の当量数）
ＰＢＴをヘキサフルオロイソプロパノール／重水素化クロロホルム＝３／７（ｖｏｌ比）に溶解し、４００ＭＨｚ　^１Ｈ−ＮＭＲにより測定した。
（３）末端ＯＨ基濃度（ＰＣ１０^６ｇあたりのＯＨの当量数）
四塩化チタン／酢酸法（Ｍａｋｒｏｍｏｌ．　Ｃｈｅｍ．　８８　２１５（１９６５））での比色定量により求めた。
（４）固有粘度（［η］）
ＰＢＴをフェノール／１，１，２，２−テトラクロロエタン＝１／１（重量比）の混合溶液に１．０ｇ／ｄｌの濃度で溶解させた溶液の粘度を、ウベローデ粘度計を使用して３０℃で測定することにより求めた。
（５）粘度平均分子量（Ｍｖ）
濃度（Ｃ）０．６ｇ／ｄｌのポリカーボネート系樹脂の塩化メチレン溶液を用いて、温度２５℃で測定した比粘度（η_ｓｐ）から、下記の両式
【００３５】
【数４】
η_ｓｐ／Ｃ＝［η］（１＋０．２８η_ｓｐ）
［η］＝１．２３×１０^−４Ｍｖ^０．８３
【００３６】
を用いて算出した。
（６）引張強度・伸度
ＡＳＴＭ１号ダンベル片を使用して、ＡＳＴＭ　Ｄ−６３８に準拠して測定した。
（７）ウエルド引張強度・伸度
ＡＳＴＭ１号ダンベル片を使用して、ＡＳＴＭ　Ｄ−６３８に準拠して測定した。なお、ウエルド試験片は中央にウエルドが来るように成形した。
（８）Ｉｚｏｄ衝撃強度
１／８インチ厚みのノッチ付き試験片を使用して、ＡＳＴＭ　Ｄ−２５６に準拠して測定した。
（９）オリゴマー反応率
次の式により求めた。ここで、オリゴマーとはエステル化反応終了時の反応物を意味する。
【００３７】
【数５】
反応率（％）＝（（ケン化価−酸価）／ケン化価）×１００　　　　　　　（２）
【００３８】
なお、ここで、酸価はオリゴマーをジメチルホルムアミドに溶解しアルカリ滴定により算出した値であり、ケン化価はオリゴマーをアルカリ加水分解し酸で逆滴定して算出した値である。
（１０）樹脂組成物中のチタンおよびアルカリ金属濃度
試料を湿式灰化した後、プラズマ発光分析により測定した。
以下の実施例等において、部は重量部を示す。
【００３９】
［実施例１］
テレフタル酸１００部、１，４−ブタンジオール１１０部、及びチタン酸テトラブトキサイド触媒０．０９部を反応器に供給した。反応液は１５０℃から１時間で２１５℃まで昇温し、その後２１５℃で１時間３０分保持し、エステル化反応を行った。尚、エステル化反応時の系内圧力は６６．７ｋＰａに維持した。エステル化反応終了時のオリゴマー反応率は９０％以上であった。
エステル化反応終了後、系内を６６．７ｋＰａから０．１３ｋＰａまで１時間２５分かけて徐々に減圧し、反応液を２４５℃まで３０分で昇温し、２４５℃を保持したまま０．１３ｋＰａで１時間１１分重縮合反応を行い、ＰＢＴを製造した。得られたＰＢＴの物性（［η］、［ＣＯＯＨ］、［ＣＨ＝ＣＨ_２］）を表１に示す。
このＰＢＴ８０部に対して、ビスフェノールＡとジフェニルカーボネートを原料とし、炭酸セシウム０．５μｍｏｌ／ビスフェノールＡ−１ｍｏｌを触媒として、エステル交換法により得られたＭｖ＝２１０００、末端ＯＨ基濃度＝３０当量／１０^６ｇのポリカーボネート系樹脂２０部、安定剤（旭電化工業（株）製、アデカスタブＰＥＰ−３６）０．１５部を配合し、スクリュー径３０ｍｍのベント付き二軸押出機（（株）日本製鋼所、ＴＥＸ３０Ｃ）を用いて２５０℃にて溶融混練し、ストランド状に押し出してペレット化し、ＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
【００４０】
［実施例２］
実施例１において、ＰＢＴ７０部、ＰＣ３０部使用したこと以外は同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
［実施例３］
実施例１において、末端ＯＨ基濃度が４５当量／１０^６ｇのポリカーボネート系樹脂を使用したこと以外は同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
【００４１】
［実施例４］
実施例１において、末端ＯＨ基濃度が５８当量／１０^６ｇのポリカーボネート系樹脂を使用したこと以外は同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
［実施例５］
実施例１において、チタン酸テトラブトキサイド触媒を０．２４部使用し、０．１３ｋＰａでの重縮合反応を４２分行ったこと以外は同様条件でＰＢＴを製造した。得られたＰＢＴの物性を表１に示した。
また、このＰＢＴを８０部使用したこと以外は実施例１と同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
【００４２】
［実施例６］
実施例１において、炭酸セシウム６．０μｍｏｌ／ビスフェノールＡ−１ｍｏｌを触媒としてエステル交換法により得られたＭｖ＝２１０００、末端ＯＨ基濃度＝３０当量／１０^６ｇのポリカーボネート系樹脂を２０部使用したこと以外は同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
［実施例７］
実施例１において、エステル化反応時の最終到達温度を２１０℃とし、０．１３ｋＰａでの重縮合反応を１時間行ったこと以外は同様条件でＰＢＴを製造した。エステル化反応終了時のオリゴマー反応率は９０％以上であった。得られたＰＢＴの物性を表１に示した。
また、このＰＢＴを８０部使用したこと以外は実施例１と同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
【００４３】
［実施例８］
実施例１において、エステル化反応時の最終到達温度を２２０℃とし、０．１３ｋＰａでの重縮合反応を１時間２５分行ったこと以外は同様条件でＰＢＴを製造した。エステル化反応終了時のオリゴマー反応率は９０％以上であった。得られたＰＢＴの物性を表１に示した。
また、このＰＢＴを８０部使用したこと以外は実施例１と同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
［実施例９］
実施例１において、０．１３ｋＰａでの重縮合反応を１時間４０分行ったこと以外は同様条件でＰＢＴを製造した。得られたＰＢＴの物性を表１に示した。
また、このＰＢＴを８０部使用したこと以外は実施例１と同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
【００４４】
［実施例１０］
実施例１において、０．１３ｋＰａでの重縮合反応を４５分行ったこと以外は同様条件でＰＢＴを製造した。得られたＰＢＴの物性を表１に示した。
また、このＰＢＴを８０部使用したこと以外は実施例１と同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
【００４５】
［比較例１］
実施例１において、エステル化反応時の２１５℃での保持時間を２時間３０分とし、０．１３ｋＰａでの重縮合反応を２時間１０分行ったこと以外は同様条件でＰＢＴを製造した。エステル化反応終了時のオリゴマー反応率は９０％以上であった。得られたＰＢＴの物性を表１に示した。
また、このＰＢＴを８０部使用したこと以外は実施例１と同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
［比較例２］
比較例１において、ＰＢＴ７０部、およびＰＣ３０部使用したこと以外は同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
［比較例３］
実施例５において、重縮合反応時の最終到達温度を２５５℃とし、０．１３ｋＰａでの重縮合反応を４１分行ったこと以外は同様条件でＰＢＴを製造した。得られたＰＢＴの物性を表１に示した。
また、このＰＢＴを８０部使用したこと以外は実施例１と同様条件でＰＢＴ／ＰＣ配合物を得た。得られたＰＢＴ／ＰＣ配合物の機械物性を表１に示した。
【００４６】
【表１】

【００４７】
【表２】

【００４８】
【発明の効果】
本発明のＰＢＴを使用すると、良好な引っ張り強度、衝撃強度を維持しつつ優れた引っ張り伸度を有し、機械物性に優れたＰＢＴ／ＰＣ配合物を提供できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polybutylene terephthalate-based resin (hereinafter sometimes abbreviated as PBT) and a thermoplastic resin composition containing the same, and more specifically, a carboxyl end group concentration and a vinyl end group concentration within a specific range. And a thermoplastic resin composition containing the same.
[0002]
[Prior art]
PBT has been widely used in the field of injection molding as an engineering plastic because PBT has a higher crystallization rate than polyethylene terephthalate-based resin and is excellent in moldability and processability, and is also excellent in mechanical properties and electrical properties. I have.
The method for producing PBT includes transesterification between a dicarboxylic acid ester component mainly containing an ester derivative of terephthalic acid such as dimethyl terephthalate and a diol component mainly containing 1,4-butanediol; The method is roughly divided into a method in which an esterification reaction of a dicarboxylic acid component containing an acid as a main component and a diol component containing 1,4-butanediol as a main component is performed.
It is said that PBT produced by any of these methods has a problem in hydrolysis resistance due to its molecular structure, and it is said that it is effective to lower the concentration of carboxyl end groups in order to overcome this problem. For example, JP-A-9-316183 discloses that PBT having a low carboxyl end group concentration can be obtained by a specific polymerization reaction step in a melt polymerization method.
[0003]
By the way, it is widely practiced in the art to impart other useful properties to PBT by blending PBT with other resins. PBT is blended with an aromatic polycarbonate-based resin (hereinafter abbreviated as PC) or the like for use in applications requiring high toughness and ductility in addition to high-temperature resistance to load deformation.
As a result of our study, PBT having a low carboxyl end group concentration described in the above publication is effective in improving hydrolysis resistance, but is not always satisfactory in terms of mechanical properties of a PBT / PC blend. It has been found.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a PBT having excellent mechanical properties such as tensile strength and impact strength when blended with another resin, especially PC, and to improve the mechanical properties by containing the PBT. It is to provide a thermoplastic resin composition.
[0005]
[Means for Solving the Problems]
The present inventors have studied to solve the problems of the prior art, and as a result, control the relationship between the intrinsic viscosity and the concentration of carboxyl terminal groups of PBT and the concentration of vinyl terminal groups generated by thermal decomposition of the PBT main chain within a specific range. As a result, it has been found that the mechanical properties of the blend with PC are improved.
That is, the gist of the present invention is a polybutylene terephthalate resin having an intrinsic viscosity of 0.55 or more and satisfying the relationship of the following formula (1).
[0006]
(Equation 2)
15 × [η]^0.95≦ [COOH] + [CH = CH₂] ≦ 48 × [η]^0.60(1)
[0007]
(Where [COOH] is the carboxyl end group concentration of the polybutylene terephthalate resin (equivalent / 10⁶g) with [CH = CH₂] Is the concentration of vinyl end groups of polybutylene terephthalate resin (equivalent / 10⁶g). [Η] indicates the intrinsic viscosity of the polybutylene terephthalate resin. )
Another gist resides in a thermoplastic resin composition containing the polybutylene terephthalate resin and the polycarbonate resin.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
In the PBT of the present invention, the sum of the carboxyl terminal group concentration and the vinyl terminal group concentration satisfies the following formula (1).
[0008]
(Equation 3)
15 × [η]^0.95≦ [COOH] + [CH = CH₂] ≦ 48 × [η]^0.60(1)
[0009]
(Where [COOH] is the carboxyl end group concentration of the polybutylene terephthalate resin (equivalent / 10⁶g) with [CH = CH₂] Is the concentration of vinyl end groups of polybutylene terephthalate resin (equivalent / 10⁶g). [Η] indicates the intrinsic viscosity of the polybutylene terephthalate resin. )
The sum of the carboxyl terminal group concentration and the vinyl terminal group concentration is 15 × [η] of the above formula (1).^0.95If it is smaller, compatibility with PC is poor, and mechanical properties are also poor.
The sum of the carboxyl terminal group concentration and the vinyl terminal group concentration is 48 × [η] in the above formula (1).^0.60If it is larger than the above, side reactions during compounding with PC increase, mechanical properties deteriorate, and color tone also deteriorates.
Although the concentration of the vinyl end group depends on the intrinsic viscosity, it is usually 15 equivalent / 10⁶If it is less than 10 g, it is preferable because side reaction upon blending with PC is relatively small and mechanical properties are excellent.⁶g or less, most preferably 8 equivalent / 10⁶g or less. Vinyl end group concentration is 15 equivalent / 10⁶When the amount is more than g, there is a fear that side reactions may increase when blended with PC, mechanical properties may be deteriorated, and thermal stability and color tone may be deteriorated.
[0010]
On the other hand, the carboxyl end group concentration is 10 equivalent / 10⁶g or more and 45 equivalent / 10⁶If it is less than g, the compatibility with PC is good, the mechanical properties are excellent, the thermal stability and the color tone are good. Preferably, the carboxyl end group concentration is 12 eq / 10⁶g or more, more preferably 15 equivalents / 10⁶g or more, 40 equivalent / 10⁶g or less, more preferably 35 equivalent / 10⁶g or less is preferable. Carboxyl end group concentration is 10 equivalent / 10⁶If it is less than g, the compatibility with PC tends to deteriorate and the mechanical properties tend to deteriorate. In addition, the carboxyl end group concentration is 45 equivalent / 10⁶In the case of g or more, side reactions tend to increase when blended with PC, and the mechanical properties of the blend may deteriorate or the color tone may deteriorate.
[0011]
The intrinsic viscosity of the PBT of the present invention is 0.55 or more, preferably 0.6 or more, particularly 0.65 or more, particularly from the viewpoint of the mechanical strength of a blend with another thermoplastic resin such as PC. 0.7 or more is preferable. If the intrinsic viscosity is less than 0.55, sufficient mechanical strength cannot be obtained. On the other hand, it is preferably at most 1.4, more preferably at most 1.3, particularly preferably at most 1.25. If it is larger than 1.4, the melt fluidity at the time of molding tends to decrease.
In the PBT of the present invention, 90 mol% or more, more preferably 95 mol% or more of the dicarboxylic acid unit constituting the PBT is terephthalic acid unit, and 80 mol% or more, more preferably 95 mol% or more of the glycol unit. Preferably, 1,4-butanediol units occupy.
[0012]
In the present invention, there is no particular limitation on dicarboxylic acid components other than terephthalic acid. For example, phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid Acids, aromatic dicarboxylic acids such as 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane Alicyclic dicarboxylic acids such as dicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. be able to.
[0013]
These dicarboxylic acid components can be provided to the reaction as a dicarboxylic acid or as an alkyl ester of a dicarboxylic acid, preferably a dialkyl ester, and may be a mixture of a dicarboxylic acid and a dicarboxylic acid alkyl ester. There is no particular limitation on the alkyl group of the dicarboxylic acid alkyl ester, but if the alkyl group is long, the boiling point of the alkyl alcohol generated during the transesterification reaction increases, so that it does not volatilize from the reaction solution, and as a result acts as a terminal stopper and polymerizes. In order to inhibit the above, an alkyl group having 4 or less carbon atoms is preferable, and a methyl group is particularly preferable.
[0014]
Examples of the glycol units other than the 1,4-butanediol unit include, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, polytetramethylene ether glycol, 1,5-pentanediol, Aliphatic diol units such as pentyl glycol, 1,6-hexanediol and 1,8-octanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, and 1,4-cyclohexane Alicyclic diol unit such as dimethylol, aromatic diol unit such as xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone You can optionally include one or more of.
[0015]
Further, in addition to the above-mentioned raw materials, PBT in the present invention includes, for example, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid and the like. Hydroxycarboxylic acid units or alkoxycarboxylic acid units, and monofunctional component units such as stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, and benzoylbenzoic acid, and also substantially impaired thermoplasticity. If the amount is not so small, it may be one of trifunctional or higher functional units such as tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, and pentaerythritol. Species or two or more can be included as needed
[0016]
The PBT of the present invention comprises, for example, a dicarboxylic acid component containing terephthalic acid as a main component and a diol component containing 1,4-butanediol as a main component, and the molar ratio of the diol component to the dicarboxylic acid component is from 1.6 to 1.6. 2, in the presence of an esterification reaction catalyst, usually at 150 to 280 ° C., under a pressure of 6.7 to 133.3 kPa, and subjected to an esterification reaction with stirring to obtain an oligomer as an obtained esterification reaction product. It is transferred to a polycondensation reaction tank, and in the presence of a polycondensation reaction catalyst in one or more polycondensation reaction tanks, usually at 210 to 280 ° C. under a reduced pressure of 26.7 kPa or less, for 2 to 12 hours with stirring. To produce a polycondensation reaction. These may be any of a continuous type, a semi-continuous type, or a batch type. In addition, the resin obtained by the polycondensation reaction is usually transferred from the bottom of the polycondensation reaction tank to a polymer extraction die, extracted in the form of a strand, and cooled with water or after cooling with water, and then cut with a cutter to form a pellet, It is a granular material such as a chip.
[0017]
In order to obtain a PBT satisfying the relationship of the above formula (1), it is possible to obtain a PBT by appropriately selecting the above conditions. In particular, the esterification reaction is carried out at a temperature of 200 to 240 ° C. and a pressure of 46.7 to 400 ° C. It is desirable to carry out at 86.7 kPa and within 3 hours. Further, the reaction is carried out by adjusting the temperature, pressure and time of the esterification reaction and the polycondensation reaction within the above ranges.
Examples of the esterification or transesterification catalyst used in the production method of the present invention include, for example, tetramethoxide titanate, tetraisopropoxide titanate, titanium alcoholates such as tetrabutoxide titanate, tetraphenoxide titanate and the like. Organic titanium compounds such as titanium phenolate, tin compounds, magnesium compounds, calcium compounds and the like, among which titanium alcoholates are preferred. The amount of the esterification or transesterification catalyst used depends on the type of catalyst, but is usually about 10 to 500 ppm as a titanium atom with respect to the theoretical yield of PBT. For example, in the case of tetrabutoxide titanate, usually 30 to 300 ppm, preferably Is preferably 50 to 200 ppm.
[0018]
As the polycondensation reaction catalyst, the catalyst added during the esterification or transesterification reaction may be used subsequently as the polycondensation reaction catalyst without adding a new catalyst. The same catalyst as the added catalyst may be further added, and the amount used at that time depends on the type of catalyst, but is usually about 10 to 500. For example, in the case of tetrabutoxide titanate, the theoretical yield of PBT is As a titanium atom, it is usually 300 ppm or less, preferably 150 ppm or less. Further, a catalyst different from the catalyst added during the esterification or transesterification reaction, for example, an antimony compound such as diantimony trioxide, a germanium compound such as germanium dioxide or germanium tetroxide may be newly added.
[0019]
In addition, in the esterification and transesterification reaction, and / or polycondensation reaction, in addition to the catalyst, orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, and phosphorus compounds such as esters and metal salts thereof, Reaction aids such as alkali metal or alkaline earth metal compounds such as sodium hydroxide, sodium benzoate, magnesium acetate and calcium acetate, 2,6-di-t-butyl-4-octylphenol, pentaerythrityl-tetrakis [3 -(3 ', 5'-t-butyl-4'-hydroxyphenyl) propionate], dilauryl-3,3'-thiodipropionate, pentaerythrityl-tetrakis (3-laurylthiodipropionate) ), Triphenylphosphite, tris (nonylphenyl) phospha Antioxidants, such as phosphorus compounds such as tris (2,4-di-t-butylphenyl) phosphite, paraffin wax, microcrystalline wax, polyethylene wax, and long chain fats represented by montanic acid and montanic acid esters Other additives, such as release agents such as the family and its esters, silicone oils, etc., may be present.
[0020]
In the PBT of the present invention, one or more kinds of other thermoplastic resins, additives, inorganic fillers, organic fillers and the like are kneaded with the PBT of the present invention using a kneader with or without a vent. Can be crowded. The PBT can be used after it has been cooled and formed into chips, or can be supplied to the kneader directly from the polycondensation reaction apparatus in a molten state. Examples of the polycarbonate-based resin that can be blended with the PBT of the present invention include known polycarbonate-based resins, and an interface method of reacting an aromatic dihydroxy compound with phosgene, or transesterification between an aromatic dihydroxy compound and a carbonic acid diester. In the presence of a catalyst, a thermoplastic aromatic polycarbonate polymer or copolymer obtained by a transesterification method (melting method) reacted in the presence of a catalyst may be used. Particularly, an effect is obtained when an aromatic polycarbonate resin obtained by a melting method is used. large.
The aromatic dihydroxy compound is a compound having two aromatic hydroxyl groups in the molecule, and is preferably a compound represented by the following formula (2).
[0021]
Embedded image

[0022]
(W is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, or -O -, -S-, -CO-, -SO-, -SO₂Is selected from the group consisting of divalent groups represented by-, Y and Z are halogen or a hydrocarbon group having 1 to 6 carbon atoms, p and q are integers of 0 to 2, And Z and p and q may be the same or different. )
Examples of the aromatic dihydroxy compound represented by the formula (2) include bis (4-hydroxydiphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxy- 3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxybiphenyl, 3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydrido) Examples thereof include (xyphenyl) sulfide, bis (4-hydroxyphenyl) ether, and bis (4-hydroxyphenyl) ketone, and particularly preferably, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “bisphenol A”). Abbreviated as "). These aromatic dihydroxy compounds may be used alone or in combination of two or more.
[0023]
When a branched aromatic polycarbonate is to be produced, a small amount of a trihydric or higher polyhydric phenol may be copolymerized. In addition, for the purpose of improving the thermal stability and hydrolysis resistance of the aromatic polycarbonate and defining the molecular weight, a monovalent phenol such as pt-butylphenol or p-cumylphenol is used as a terminal blocking agent. be able to.
Examples of the carbonic acid diester include compounds represented by the following general formula (3).
[0024]
Embedded image
A-OC (= O) -O-A '{Formula (3)
[0025]
(In the formula, A and A ′ are an optionally substituted aliphatic group having 1 to 18 carbon atoms or an optionally substituted aromatic group, and may be the same or different.)
Examples of the carbonic acid diester represented by the general formula (3) include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate, and substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate. However, diphenyl carbonate and substituted diphenyl carbonate are preferred, and diphenyl carbonate is particularly preferred. These carbonic acid diesters may be used alone or in combination of two or more.
In producing an aromatic polycarbonate resin by a transesterification method in the present invention, it is preferable to use bisphenol A as an aromatic dihydroxy compound and diphenyl carbonate as a carbonic acid diester, and diphenyl carbonate is added in an amount of 1.01 to 1 mol of bisphenol A. It is preferably used in an amount of from 1.30 to 1.30 mol, preferably from 1.02 to 1.20. When the molar ratio is less than 1.01, the number of terminal OH groups in the produced aromatic polycarbonate resin increases, thereby deteriorating the thermal stability and hydrolysis resistance of the polymer, and when the molar ratio is greater than 1.30. Then, under the same conditions, the rate of transesterification decreases, and it becomes difficult to produce an aromatic polycarbonate resin having a desired molecular weight.
[0026]
Although the terminal OH concentration of the polycarbonate resin used in the present invention is not particularly limited, it is 1 to 60 equivalent / 10⁶g, preferably 5 equivalents / 10⁶g or more, especially 10 equivalent / 10⁶g or more, especially 20 equivalent / 10⁶g or more is preferable. On the other hand, 50 equivalent / 10⁶g or less, preferably 40 equivalent / 10⁶g or less, especially 40 equivalent / 10⁶g or less is optimal. Terminal OH group concentration is 60 equivalent / 10⁶If it is larger than g, coloring at the time of melting tends to increase when blended with PBT.
In producing an aromatic polycarbonate resin by a transesterification method in the present invention, a transesterification catalyst is used. As the catalyst, an alkali metal compound and / or an alkaline earth metal compound is used, and a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound is used in combination. Although it is possible to use an alkali metal compound and / or an alkaline earth metal compound alone, it is particularly preferable in terms of physical properties and handling.
[0027]
The amount of the catalyst was 1 × 10 5 per mole of the aromatic dihydroxy compound.^-8~ 6 × 10^-6It is preferably used in a molar range, more preferably 1 × 10^-7~ 3 × 10^-6In the molar range, particularly preferably 2 × 10^-7~ 2 × 10^-6Used in the molar range. If the amount is less than this amount, the polymerization activity required for producing an aromatic polycarbonate resin having a predetermined molecular weight and a terminal hydroxyl group amount tends to be not obtained. And the moldability of the polymer tends to be impaired.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, and carbonate. Cesium, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, Sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, hydrogen hydrogen phosphate Lithium, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, sodium, potassium, lithium, Examples include cesium alcoholate, phenolate, bisphenol A disodium salt, 2 potassium salt, 2 lithium salt, and 2 cesium salt.
[0028]
Examples of the alkaline earth metal compound include, for example, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, Examples include magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like.
The transesterification is generally carried out in two or more stages. Specifically, the reaction of the first stage is 9.3 × 10⁴~ 1.33 × 10³The reaction is carried out under a reduced pressure of Pa at a temperature of 120 to 260 ° C, preferably 180 to 240 ° C for 0.1 to 5 hours, preferably 0.1 to 3 hours. Next, the reaction temperature is increased while increasing the degree of vacuum of the reaction system, and finally the polycondensation reaction is performed at a temperature of 240 to 320 ° C. under a reduced pressure of 133 Pa or less.
[0029]
The type of reaction may be any of a batch type, a continuous type, or a combination of a batch type and a continuous type, and the apparatus used may be any of a tank type, a tube type, and a column type.
The terminal OH group concentration of the aromatic polycarbonate resin is also affected by polymerization conditions such as polymerization temperature, degree of vacuum at the time of polymerization, and condenser temperature, but under certain conditions, aromatic phenol represented by bisphenol A is used. It can be controlled by the charging ratio of the group dihydroxy compound and the diester carbonate represented by diphenyl carbonate.
The molecular weight of the polycarbonate resin used in the present invention is not particularly limited, but preferably, methylene chloride is used as a solvent, and the viscosity average molecular weight is 12,000 to 40,000, more preferably, the viscosity average molecular weight calculated from the solution viscosity measured at a temperature of 25 ° C. It is 13000-30000, particularly preferably 14000-26000. If it is too large, the melt fluidity at the time of molding tends to decrease, and if it is too small, sufficient strength as a composition may not be obtained.
[0030]
The mixing ratio of the polycarbonate resin used in the present invention is not particularly limited, but is preferably 5 to 100 parts by weight, and preferably 10 to 80 parts by weight, based on 100 parts by weight of PBT. . If the amount of PC to be blended is too small, the impact strength tends to decrease, and if it is too large, the fluidity is poor, which is not preferable.
In addition, the titanium atom concentration in the thermoplastic resin composition of the present invention is preferably 10 to 240 ppm, more preferably 15 to 150 ppm, particularly preferably 15 to 120 ppm, and particularly preferably 15 to 90 ppm. When the titanium atom concentration is 10 ppm or less, the transesterification reaction when blending PBT and PC is unlikely to occur, and the mechanical properties of the composition tend to decrease. If the titanium atom concentration is more than 240 ppm, a transesterification reaction or a side reaction at the time of compounding is likely to occur, and the mechanical properties and thermal stability of the composition tend to deteriorate.
[0031]
Further, the alkali metal concentration in the thermoplastic resin composition of the present invention is preferably 1.5 ppm or less, more preferably 1.2 ppm or less, more preferably 1.0 ppm or less, among which 0.05 ~ 1.0 ppm is preferred. When the alkali metal concentration is more than 1.5 ppm, a transesterification reaction or a side reaction is likely to occur when PBT and PC are blended, and the mechanical properties of the composition may deteriorate or the color tone may deteriorate. If the alkali metal concentration is less than 0.05 ppm, the transesterification reaction during compounding is unlikely to occur, and the compatibility tends to decrease, so that the mechanical properties tend to decrease. The amount of these metals can be measured using atomic emission, plasma emission, or the like, after recovering the metals in the thermoplastic resin composition by a method such as wet ashing.
[0032]
Examples of the PBT additives of the present invention include known antioxidants, antistatic agents, brominated polycarbonates, brominated epoxy compounds, phosphate compounds, phosphazene compounds, flame retardants such as melamine and cyanuric acid, and antimony trioxide. And a flame retardant auxiliary such as antimony pentoxide, a plasticizer, a lubricant, a release agent, a colorant, a crystal nucleating agent, and the like. As the inorganic filler, glass fiber, talc, mica, glass flakes, carbon fiber, silica, alumina fiber, clay, carbon black, kaolin, titanium oxide, iron oxide, antimony oxide, metal compounds such as alumina, potassium, Examples thereof include alkali metal compounds such as sodium. Examples of the organic filler include an aromatic polyester fiber and a liquid crystalline polyester fiber.
[0033]
The method for blending the above-mentioned various thermoplastic resins, additives and the like into the PBT of the present invention is not particularly limited, but it is preferable to blend by melt-kneading, and a kneading method generally used for thermoplastic resins is applied. Can be. Specifically, for example, each component, if necessary, together with a substance as an additional component, after uniformly mixed with a Henschel mixer, a ribbon blender, a V-type blender, etc., a single-screw kneading extruder, a multi-screw kneading extruder, A method of kneading using a roll, a Banbury mixer, a Labo Plastomill, a Brabender, or the like can be used. Among them, a twin-screw extruder is preferably used from the viewpoint of mixing performance.
There is no particular limitation on the molding method of the PBT of the present invention and the blend of the PBT and the above-mentioned various thermoplastic resins, additives, and the like, and molding methods generally used for thermoplastic resins, that is, injection molding, hollow molding, Molding methods such as molding, extrusion molding, and press molding can be applied.
[0034]
【Example】
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
In Examples and Comparative Examples, PBT and PBT / PC blends were evaluated by the following methods.
(1) Carboxyl end group concentration (PBT10⁶(equivalent number of COOH per g)
PBT was dissolved in benzyl alcohol and calculated from the titration value with a 0.01 N NaOH / benzyl alcohol solution.
(2) Vinyl terminal group concentration (PBT10⁶CH = CH per g₂Number of equivalents)
PBT is dissolved in hexafluoroisopropanol / deuterated chloroform = 3/7 (vol ratio), and 400 MHz¹It was measured by 1 H-NMR.
(3) Terminal OH group concentration (PC10⁶(equivalent number of OH per g)
It was determined by colorimetric determination with the titanium tetrachloride / acetic acid method (Makromol. Chem. 88 215 (1965)).
(4) Intrinsic viscosity ([η])
Using a Ubbelohde viscometer, the viscosity of a solution obtained by dissolving PBT at a concentration of 1.0 g / dl in a mixed solution of phenol / 1,1,2,2-tetrachloroethane = 1/1 (weight ratio) was measured. It was determined by measuring at ° C.
(5) Viscosity average molecular weight (Mv)
Specific viscosity (η) measured at a temperature of 25 ° C. using a methylene chloride solution of a polycarbonate resin having a concentration (C) of 0.6 g / dl._sp) From the following two formulas
[0035]
(Equation 4)
η_sp/C=[η](1+0.28η)_sp)
[Η] = 1.23 × 10^-4Mv^0.83
[0036]
Was calculated.
(6) Tensile strength and elongation
The measurement was performed according to ASTM No. D-638 using an ASTM No. 1 dumbbell piece.
(7) Weld tensile strength and elongation
The measurement was performed according to ASTM No. D-638 using an ASTM No. 1 dumbbell piece. The weld test piece was formed so that the weld was at the center.
(8) Izod impact strength
The measurement was performed according to ASTM No. D-256 using a ８ inch thick notched test piece.
(9) Oligomer conversion
It was determined by the following equation. Here, the oligomer means a reaction product at the end of the esterification reaction.
[0037]
(Equation 5)
Reaction rate (%) = ((saponification value−acid value) / saponification value) × 100 (2)
[0038]
Here, the acid value is a value calculated by dissolving the oligomer in dimethylformamide and alkali titration, and the saponification value is a value calculated by subjecting the oligomer to alkali hydrolysis and back titrating with an acid.
(10) Concentration of titanium and alkali metal in resin composition
After the sample was wet-ashed, it was measured by plasma emission analysis.
In the following examples and the like, parts indicate parts by weight.
[0039]
[Example 1]
100 parts of terephthalic acid, 110 parts of 1,4-butanediol, and 0.09 part of tetrabutoxide catalyst of titanate were supplied to the reactor. The reaction solution was heated from 150 ° C. to 215 ° C. in 1 hour, and then kept at 215 ° C. for 1 hour 30 minutes to perform an esterification reaction. The pressure in the system during the esterification reaction was maintained at 66.7 kPa. The oligomer reaction rate at the end of the esterification reaction was 90% or more.
After the completion of the esterification reaction, the pressure inside the system was gradually reduced from 66.7 kPa to 0.13 kPa over 1 hour and 25 minutes, and the temperature of the reaction solution was raised to 245 ° C. in 30 minutes. For 1 hour and 11 minutes to produce PBT. Physical properties of the obtained PBT ([η], [COOH], [CH = CH₂]) Are shown in Table 1.
To 80 parts of this PBT, bisphenol A and diphenyl carbonate were used as raw materials, cesium carbonate 0.5 μmol / bisphenol A-1 mol as a catalyst, and Mv = 21000 obtained by transesterification method, terminal OH group concentration = 30 equivalent / 10⁶g of 20 parts of a polycarbonate resin and 0.15 part of a stabilizer (Adekastab PEP-36, manufactured by Asahi Denka Kogyo KK), and a vented twin-screw extruder with a screw diameter of 30 mm (Nippon Steel Works, Ltd. (TEX30C), melt-kneaded at 250 ° C., extruded into strands and pelletized to obtain a PBT / PC blend. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[0040]
[Example 2]
In Example 1, a PBT / PC blend was obtained under the same conditions except that 70 parts of PBT and 30 parts of PC were used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[Example 3]
In Example 1, the terminal OH group concentration was 45 equivalent / 10⁶A PBT / PC blend was obtained under the same conditions except that g of the polycarbonate-based resin was used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[0041]
[Example 4]
In Example 1, the terminal OH group concentration was 58 equivalent / 10⁶A PBT / PC blend was obtained under the same conditions except that g of the polycarbonate-based resin was used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[Example 5]
PBT was produced in the same manner as in Example 1, except that 0.24 parts of the tetrabutoxide titanate catalyst was used and the polycondensation reaction was performed at 0.13 kPa for 42 minutes. Table 1 shows the physical properties of the obtained PBT.
Further, a PBT / PC blend was obtained under the same conditions as in Example 1 except that 80 parts of this PBT was used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[0042]
[Example 6]
In Example 1, Mv = 21000, terminal OH group concentration = 30 equivalent / 10 obtained by transesterification using 6.0 μmol of cesium carbonate / 1 mol of bisphenol A as a catalyst.⁶A PBT / PC blend was obtained under the same conditions except that 20 parts of the polycarbonate-based resin was used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[Example 7]
PBT was produced in the same manner as in Example 1 except that the final temperature during the esterification reaction was 210 ° C. and the polycondensation reaction at 0.13 kPa was performed for 1 hour. The oligomer reaction rate at the end of the esterification reaction was 90% or more. Table 1 shows the physical properties of the obtained PBT.
Further, a PBT / PC blend was obtained under the same conditions as in Example 1 except that 80 parts of this PBT was used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[0043]
Example 8
PBT was produced in the same manner as in Example 1 except that the final temperature during the esterification reaction was 220 ° C. and the polycondensation reaction at 0.13 kPa was performed for 1 hour and 25 minutes. The oligomer reaction rate at the end of the esterification reaction was 90% or more. Table 1 shows the physical properties of the obtained PBT.
Further, a PBT / PC blend was obtained under the same conditions as in Example 1 except that 80 parts of this PBT was used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[Example 9]
PBT was produced under the same conditions as in Example 1 except that the polycondensation reaction at 0.13 kPa was performed for 1 hour and 40 minutes. Table 1 shows the physical properties of the obtained PBT.
Further, a PBT / PC blend was obtained under the same conditions as in Example 1 except that 80 parts of this PBT was used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[0044]
[Example 10]
PBT was produced in the same manner as in Example 1 except that the polycondensation reaction at 0.13 kPa was performed for 45 minutes. Table 1 shows the physical properties of the obtained PBT.
Further, a PBT / PC blend was obtained under the same conditions as in Example 1 except that 80 parts of this PBT was used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[0045]
[Comparative Example 1]
PBT was produced under the same conditions as in Example 1 except that the retention time at 215 ° C. during the esterification reaction was 2 hours and 30 minutes, and the polycondensation reaction at 0.13 kPa was performed for 2 hours and 10 minutes. The oligomer reaction rate at the end of the esterification reaction was 90% or more. Table 1 shows the physical properties of the obtained PBT.
Further, a PBT / PC blend was obtained under the same conditions as in Example 1 except that 80 parts of this PBT was used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[Comparative Example 2]
In Comparative Example 1, a PBT / PC blend was obtained under the same conditions except that 70 parts of PBT and 30 parts of PC were used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[Comparative Example 3]
PBT was produced in the same manner as in Example 5, except that the final temperature during the polycondensation reaction was set to 255 ° C., and the polycondensation reaction at 0.13 kPa was performed for 41 minutes. Table 1 shows the physical properties of the obtained PBT.
Further, a PBT / PC blend was obtained under the same conditions as in Example 1 except that 80 parts of this PBT was used. Table 1 shows the mechanical properties of the obtained PBT / PC blend.
[0046]
[Table 1]

[0047]
[Table 2]

[0048]
【The invention's effect】
The use of the PBT of the present invention can provide a PBT / PC blend having excellent tensile elongation while maintaining good tensile strength and impact strength, and having excellent mechanical properties.

Claims (7)

A polybutylene terephthalate resin having an intrinsic viscosity of 0.55 or more and satisfying the relationship of the following formula (1).

(Wherein, [COOH] is a terminal carboxyl group concentration of polybutylene terephthalate resin (eq ^{/ 10 6 g), [CH} = CH 2] The polybutylene terephthalate-based vinyl end group concentration of the resin (equivalents / ¹⁰ 6 g [Η] indicates the intrinsic viscosity of the polybutylene terephthalate resin.) The polybutylene terephthalate resin according to claim 1, wherein the vinyl end group concentration is 15 equivalents / 10 ⁶ g or less. The polybutylene terephthalate-based resin according to claim 1, wherein the carboxyl end group concentration is 10 equivalents / 10 ⁶ g or more and 45 equivalents / 10 ⁶ g or less. A thermoplastic resin composition comprising the polybutylene terephthalate resin according to claim 1 and a polycarbonate resin. The thermoplastic resin composition according to claim 4, wherein the terminal OH group concentration of the polycarbonate resin is 1 to 60 equivalents / 10 ⁶ g. The thermoplastic resin composition according to claim 5, wherein the titanium atom concentration is 10 to 240 ppm. The thermoplastic resin composition according to claim 5, wherein an alkali metal concentration is 0.05 to 1.5 ppm.