JP4361652B2 - Liquid crystalline polyester resin for extrusion molding with excellent heat resistance, extrusion molding material and extrusion molding - Google Patents

Description

【０００５】
【発明の実施の形態】
以下本発明について詳細に説明する。
本発明に用いる押出し成形用液晶性ポリエステル樹脂(以下、「本発明の樹脂」と言うことがある)は、その耐熱性の点でハンダ耐熱温度が２５０℃以上であって、特定の溶融流動性を示す押出し成形用の樹脂である。
ここでハンダ耐熱温度とは、厚みが１．２ｍｍのＪIＳ１(１／２)号ダンベルを成形したものを試験片とし、該試験片を錫６０％、鉛４０％からなる２４０℃のハンダ浴に浸漬し、同温度に６０秒間保持した後取出し、外観を観察する。その後、該ハンダ浴を１０℃ずつ昇温させては同様の実験を行い、同試験片が発泡または変形しない最高温度を言う。ハンダ耐熱温度が２５０℃未満の場合、ハンダリフロー炉での使用などに制限が多く加わり、本発明の目的の主眼とするところから外れる。
上記特定の溶融流動性は、流動開始温度下での剪断速度１０００sec ^-1 における溶融粘度(粘度１b)と、それより２０℃高い温度の同剪断速度下で測定した溶融粘度(粘度２b)との比率((粘度２b)／(粘度１b))が０．１０〜０．７０、好ましくは０．１０〜０．７０、特に好ましくは０．１２〜０．５０である溶融流動性である。
ここで、本発明における流動開始温度とは、異方性溶融相を形成し始める温度であって、４℃／minの昇温速度で加熱された樹脂を荷重１００Kgf／cm²のもとで、内径１mm、長さ１０mmのノズルから押出したときに、溶融粘度が４８０００ポイズを示す温度を言う。
溶融粘度比が上記範囲外である場合、押出し成形加工が困難であったり、得られる成形物の異方性が強く、実用に耐えない恐れがある。
【０００６】
本発明の樹脂は、流動開始温度より３０℃高い温度で測定したときの溶融張力が１０g以上であることが好ましい。
ここで溶融張力とは、樹脂の流動開始温度より３０℃高い温度に設定された長さ８．０mm×２．１mmφのダイス中で樹脂を溶融させ、ピストン速度２mm／minでこれを押出し、テンションプーリーを通した後引き取りローラーでモノフィラメント状に引き取り、引き取り速度を上げていったときに糸が破断する時のテンションプーリーにかかる力を表したものである。溶融張力が１０g未満の場合、押出し成形による成膜時の伸びが不十分となり、特にフィルム成形、ブロー成形行う場合の加工が困難となる恐れがあるので好ましくない。また、該溶融張力は、加工性の観点から４０ｇ以下とするのが好ましい。
【０００７】
本発明の樹脂は、芳香族ヒドロキシカルボン酸単位、芳香族ジカルボン酸単位、芳香族ジヒドロキシ単位の２種以上の組み合わせを含むことが好ましい。
芳香族ヒドロキシカルボン酸単位としては、下記構造等が例示できる。
【０００８】
【化３】

【０００９】
芳香族ジヒドロキシ単位としては、下記構造等が例示できる。
【００１０】
【化４】

【００１１】
芳香族ジカルボン酸単位としては、下記構造等が例示できる。
【００１２】
【化５】

【００１３】
上記各構成単位の組み合わせとその組成比は随意であるが、本発明の目的とする高い耐熱性と、適度な流動性を有するために、下記式(１)〜(４)で示される構成単位のうちの２種以上を含み、これら組み合わせの構成単位の合計が全体の９７ｍｏｌ％以上である液晶性ポリエステル樹脂とする。
【００１４】
【化６】

【００１５】
本発明の樹脂として更に好ましくは、下記(a)〜(c)の全ての条件を満たす、特定の構成単位を特定条件において有する液晶性ポリエステル樹脂が挙げられる。なお、条件中の式(１)〜(４)は、上記式(１)〜(４)で示される構成単位である。
(a):式(１)で表される構成単位の割合が全体の４０〜７０ｍｏｌ％であること、
(b):式(２)で表される構成単位及び式(３)で表される構成単位の合計の割合が全体の１５〜３０ｍｏｌであり、かつ式(２)で表される構成単位の割合が、式(２)で表される構成単位及び式(３)で表される構成単位の合計に対して０〜９５ｍｏｌ％であり、かつ式(２)で表される構成単位のうちの８０〜１００ｍｏｌ％が主鎖結合位置がパラ位である構成単位であること、
(c):式(４)で表される構成単位の割合が、式(２)で表される構成単位及び式(３)で表される構成単位の合計の割合と実質的に同量であり、かつ式(４)で表される構成単位のうちの５０ｍｏｌ％以上が主鎖結合位置がパラ位である構成単位であること。
【００１６】
本発明の樹脂の固有粘度[η]は、５．５以上である。[η]が５．５未満の場合、上述の溶融粘度特性、溶融張力を得ることが困難となる。
【００１７】
本発明の樹脂を製造する方法は特に制限はなく、公知の方法を用いることができる。たとえば、上記芳香族ヒドロキシカルボン酸単位、芳香族ジカルボン酸単位、芳香族ジヒドロキシ単位を有するモノマー化合物の２種以上の組み合わせからなる混合物を重合槽中で重縮合反応させる方法等により得られる。芳香族ヒドロキシカルボン酸単位を有するモノマー化合物としては、ヒドロキシ安息香酸、ｐ−アセトキシ安息香酸等が挙げられ、芳香族ジカルボン酸単位を有するモノマー化合物としては、テレフタル酸、イソフタル酸等が挙げられ、芳香族ジヒドロキシ単位を有するモノマー化合物としては、４，４'−ジヒドロキシジフェニル、４，４'−ジアセトキシジフェニル、ハイドロキノン、レゾルシン等が挙げられる。これら化合物の仕込みは一括方式でも、分割方式でもよい。反応は不活性気体、たとえば窒素雰囲気下に常圧、減圧またはそれらの組み合わせで行うことができる。プロセスは回分式、連続式、またはそれらの組み合わせが採用できる。
なお、上記モノマー化合物をより重合し易い化合物に変える反応（たとえば、エステル化反応）を重縮合反応に先立って行った後、引き続き重縮合反応を行うこともできる。
上記重縮合反応の温度は、通常、２７０〜３８０℃が好ましい。温度が２７０℃未満の場合、重合反応の進行が遅く、３８０℃を超えると分解等の副反応が起こり易いので好ましくない。多段階の反応温度を採用しても構わないし、場合により昇温途中で、あるいは最高温度に達したらすぐに反応生成物であるポリマーを溶融状態で抜出し、回収することもできる。また取出したポリマーの分子量をさらに上げるため、不活性ガス雰囲気下、加温により固相重合等の後処理を施すこともできる。
【００１８】
本発明において、上述のように得られた液晶性ポリエステル樹脂を押出し成形用材料として、パウダー状のまま押出し成形機にかけることもできるが、いったん造粒機でペレット形状とし、これを、押出し成形機に投入する方が取扱いの点で好ましい。
押出し成形用材料には、目的を阻害しない範囲において少量の無機充填剤、有機充填剤、酸化防止剤、熱安定剤、光安定剤、難燃剤、滑剤、帯電防止剤、防錆剤、蛍光剤、表面平滑剤、表面改良剤、離型剤の各種添加剤を添加することができる。
【００１９】
本発明の押出し成形物は、上記押出し成形用材料を押出し成形したものである。押出し成形物の形態は特に限定されないが、フィルムが好ましい。フィルムの厚さは用途に応じて適宜選択することができるが、通常、１０〜５００μｍ程度である。
本発明の押出し成形物は、上記押出し成形用材料を、通常の押出し成形により、所望の形態に賦形して調製することができる。具体的には、フィルム成形の場合、溶融した樹脂をＴダイと呼ばれるスリット状の加工機から所定の幅、厚さに押出し、冷却してそのままフィルムとするキャスト法、また押出し後、製膜方向、およびその直角方向に逐次延伸する延伸法、環状ダイから円筒状に樹脂を押出し、ガスによって巻き取り方向とそれに直角方向に同時に延伸させるインフレ−ション法等が挙げられるが、液晶ポリマーの場合、異方性のコントロールのし易さの点でインフレーション法が好ましく用いられる。
またブロー成形の場合は、環状ダイから樹脂を押出し、パリソンと呼ばれる円筒状半溶融樹脂を金型で挟んだ後ガス圧によって膨らませ賦形することにより成形できる。この方法も異方性のコントロールのし易さという点で液晶ポリマーには好適な方法である。
これらの押出し成形において、本発明の液晶性ポリエステル樹脂を含む押出し成形用材料を供する場合、通常の押出し成形機に特段の工夫を施さずに供することができる。
【００２０】
【実施例】
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらによって限定されるものではない。尚、例中における各測定は以下の方法に従って行った。
(１)物性の測定法
(a)流動開始温度：島津製作所製の高化式フローテスターＣＦＴ−５００型で測定した。すなわち、４℃／minの昇温速度で加熱された樹脂を荷重１００Kgf／cm²のもとで、内径１mm、長さ１０mmのノズルから押出したときに、溶融粘度が４８０００ポイズを示す温度を測定しこれを流動開始温度とした。
(b)溶融粘度：東洋精機社製のキャピログラフ１Ｂで、所定温度下、ダイス径０．５mm、剪断速度１００sec^-1、１０００sec^-1で測定を行った。
(c)溶融張力：東洋精機社製のキャピログラフ１Ｂを用い、各樹脂の流動開始温度より３０℃高い所定温度に設定された長さ８．０mm×２．１mmφのダイス中で樹脂を溶融させ、ピストン速度２mm／minでこれを押出し、テンションプーリーを通した後巻き取る装置において、巻き取りスピードを上げていきながら引き取り、糸が破断する時のテンションプーリーにかかる力をグラム単位で求めた。
(d)固有粘度[η]：液晶性ポリエステル樹脂を３，５−ビストリフロロメチルフェノールに溶解させ、ウベローデ粘度計を用いて６０℃で測定した。
(e)熱変形温度(ＤＴＵＬ)：ＤＴＵＬ試験片（１２７mm長×１２．７mm幅×６．４mm厚）を成形し、ＡＳＴＭ Ｄ６４８に準じて荷重１８．６Kgで測定した。
(f)ハンダ耐熱温度：厚さが１．２mmのＪIＳ１（１／２）号ダンベルを試験片として成形し、錫６０％、鉛４０％からなる２３０℃のハンダ浴に浸漬し、同温度に６０秒間保持した後取出し、外観を観察する。その後、該ハンダ浴を１０℃ずつ昇温させ同様の実験を行い、同試験片が発泡または変形しない最高温度を求めた。
(２)フィルム加工
樹脂ペレットを、東洋精機社製の円筒ダイを備えた２０mmの２軸混練押出機を用い、シリンダー設定温度２９０〜３７０℃、回転数８０ｒｐｍで溶融混練し、直径３０ｍｍ、リップ間隔１．５ｍｍ、ダイ設定温度２９０〜３７０℃の円筒ダイから上方へ溶融樹脂を押し出し、この筒状フィルムの中空部へ乾燥空気を圧入して筒状フィルムを膨張させ、次に冷却させた後、ニップロールに通して引き取り速度８〜１５ｍ／minで引き取り、１０〜３０μｍ厚の液晶ポリマーフィルムを得た。得られたフィルムを肉眼で観察し、以下の基準で評価した。
○：フィルム製膜可能で、外観も良好である。
△：フィルム製膜可能であるが、色むらが認められる。
×：フィルム製膜できない。
(３)フィルム耐熱性
上記のようにして得られた約３０μｍ厚のフィルムを１０ｃｍ角に切断し、両端をクリップで固定して２８０℃に設定した熱風循環オーブン中へ５分間放置した後のフィルム状態を観察し、以下の基準で評価した。
○：フィルム形状に変化は見られない。
×：フィルムが変形もしくは融解する。
【００２１】
実施例１
ｐ-アセトキシ安息香酸１０．８Kg（６０モル）、テレフタル酸２．４９Kg（１５モル）、イソフタル酸０．８３Kg（５モル）、および、４，４'−ジアセトキシジフェニル５．４５Kg（２０．２モル）を櫛形攪拌翼を持つ重合槽に仕込み、窒素ガス雰囲気下で攪拌しながら昇温し、３３０℃で１時間重合させた。この間に副生する酢酸を除去しながら、強力な攪拌下で重合させた。その後、系を徐々に冷却し、２００℃で得られたポリマーを系外に取出した。この得られたポリマーを細川ミクロン(株)製のハンマーミルで粉砕し、２．５mm以下の粒子とした。
これをさらにロータリーキルン中で窒素雰囲気下に２９０℃、３時間処理することにより、流動開始温度が３４１℃であり、粒子状の下記単位からなる全芳香族液晶性ポリエステル樹脂を得た。
【００２２】
【化７】

この液晶性ポリエステル樹脂を、池貝鉄工社製ＰＣＭ−３０型造粒機を用いて３５０℃で造粒し、ペレット状とした。この時のペレットから求めた流動開始温度は３３２℃、固有粘度[η]は６．８であった。この樹脂の溶融粘度、溶融粘度比、溶融張力、ハンダ耐熱性、インフレ製膜時のフィルム形状及び耐熱性を表１並びに表２に示す。
【００２３】
比較例１
実施例１と同様に２．５ｍｍ以下の粒子を得た後、ロータリーキルン中で窒素雰囲気下２８０℃、３時間処理することにより、流動開始温度が３３１℃の全芳香族液晶性ポリエステル樹脂を得た。この液晶性ポリエステル樹脂を池貝鉄工社製ＰＣＭ−３０型造粒機を用いて３４０℃で造粒し、ペレット状とした。この時のペレットから求めた流動開始温度は３２４℃、固有粘度[η]は４．８であった。この樹脂の溶融粘度、溶融粘度比、溶融張力、ハンダ耐熱性、インフレ製膜時のフィルム形状及び耐熱性を表１並びに表２に示す。
【００２４】
比較例２
ｐ−ヒドロキシ安息香酸１６．６Kg（１２．１モル）と６−ヒドロキシ−２−ナフトエ酸８．４Kg(４．５モル)および無水酢酸１８．６Ｋｇ（１８．２モル）を櫛形攪拌翼付きの重合槽に仕込み、窒素ガス雰囲気下で攪拌しながら昇温し、常圧３２０℃で１時間、さらに２．０Torrの減圧下で３２０℃１時間重合させた。この間に副生する酢酸を系外へ留出し続けた。その後、系を徐々に冷却し、１８０℃で得られたポリマーを実施例１と同様に粉砕した後、ロータリーキルン中で窒素ガス雰囲気下に２４０℃、５時間処理することによって流動開始温度が２７０℃の粒子状の下記繰り返し単位からなる全芳香族液晶性ポリエステルを得た。
【００２５】
【化８】

この液晶性ポリエステル樹脂を池貝鉄工社製ＰＣＭ−３０型造粒機を用いて２８０℃で造粒し、ペレット状とした。この時のペレットから求めた流動開始温度は２６８℃であった。この樹脂の溶融粘度、溶融粘度比、溶融張力、ハンダ耐熱性、インフレ製膜時のフィルム形状及び耐熱性を表１並びに表２に示す。
【００２６】
【表１】

【００２７】
【表２】

【００２８】
【発明の効果】
本発明は、高い耐熱性と、適度な流動性を有する液晶性ポリエステル樹脂を、押出し成形したものなので、良好な耐熱性を有し、外観の優れた押出し成形物、特にフィルムを得ることができ、広範におよぶ分野への利用が期待できる。[0001]
BACKGROUND OF THE INVENTION
The present invention has a high excellent extrusion moldability and heat resistance, relates extrudate was extruded liquid crystalline polyester resins for extrusion.
[0002]
[Prior art]
Liquid crystalline polyester resin (hereinafter sometimes referred to simply as “liquid crystal polymer”) is widely used mainly in the field of electronic materials as an injection molding material that can be precisely molded because of its excellent heat resistance and excellent fluidity when melted. It has become. Liquid crystal polymers are generally classified into type I, type II and type III (for example, “Liquid Crystal Polymer for Molding Design” Sigma Publishing (1995)). What is called a mold is made of a specific wholly aromatic component, and has a heat distortion temperature of 250 ° C. or higher, and is a material having particularly high heat resistance among liquid crystal polymers.
In addition to the excellent heat resistance of liquid crystal polymers, the gas barrier properties, low dielectric properties, chemical resistance, and other characteristics have been extensively studied in the field of extrusion molding of films and containers.
However, in general, liquid crystal polymers are said to be unsuitable for the extrusion molding field because of their low viscosity when melted and large anisotropy.
For this reason, various studies have been made in terms of materials. For example, JP-A-2-3430 discloses film formation of an aromatic polymer comprising (1) oxybenzoic acid and (2) 2,6-naphthoic acid as repeating units. Japanese Patent Application Laid-Open No. 5-186614 discloses a semi-aromatic film in which components such as ethylene glycol are added in addition to the above oxybenzoic acid and 2,6-naphthoic acid. In addition, for the purpose of improving the extrusion moldability, compounding with other resins has been studied. For example, JP-A-61-78862 discloses film formation of a composition comprising a liquid crystal polymer and polyethylene terephthalate, and JP-A-63-270760 discloses a composition comprising a liquid crystal polyester and an aromatic polycarbonate. . However, all of these are liquid crystal polymers of type II or type III and have low heat resistance or other low heat resistance materials for liquid crystal polymers including type I liquid crystal polymers to improve processability. The actual condition is that sufficient heat resistance inherent to the liquid crystal polymer is not obtained.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide an extruded product obtained by extruding a liquid crystalline polyester resin for extrusion molding which has high heat resistance, moderate fluidity and workability and gives an extruded product having an excellent appearance. is there.
[0004]
[Means for Solving the Problems]
As a result of studying film formation and blowing using a resin composed only of a liquid crystalline polyester resin from the viewpoint of heat resistance, the present inventors have found that polymer physical properties and melt fluidity satisfy certain conditions. It has been found that even a liquid crystalline polyester resin exhibiting the same level of heat resistance as that of a mold polymer can be substantially excellently extruded by itself, leading to the present invention.
That is, according to the present invention, the solder heat resistance temperature is 250 ° C. or higher ,
Including two or more of the structural units represented by the following formulas (1) to (4), the total of the structural units of these combinations is 97 mol% or more of the total,
The ratio of the melt viscosity at a shear rate of 1,000 sec ^-1 under flow temperature (viscosity 1b), therewith than 20 ° C. higher temperature melt viscosity measured under the same shear rate (viscosity 2b) ((viscosity 2b) / ( An extruded product obtained by extrusion molding a liquid crystalline polyester resin having a viscosity 1b)) of 0.10 to 0.70 and an intrinsic viscosity [η] of 5.5 or more is provided. Is done.
[Chemical formula 2]

[0005]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The liquid crystalline polyester resin for extrusion molding used in the present invention (hereinafter sometimes referred to as “the resin of the present invention”) has a solder heat resistance of 250 ° C. or higher in terms of its heat resistance, and has a specific melt fluidity. It is resin for extrusion molding which shows.
Here, the solder heat-resistant temperature is obtained by molding a JIS1 (1/2) dumbbell having a thickness of 1.2 mm as a test piece, and placing the test piece into a 240 ° C. solder bath composed of 60% tin and 40% lead. Immerse and hold at the same temperature for 60 seconds, then take out and observe the appearance. Thereafter, the temperature of the solder bath is increased by 10 ° C., and the same experiment is performed. The maximum temperature at which the test piece does not foam or deform is stated. When the solder heat-resistant temperature is less than 250 ° C., there are many restrictions on the use in a solder reflow furnace and the like, which is not the main purpose of the present invention.
The specific melt fluidity, a melt viscosity definitive shear rate of 1,000 sec ^-1 under flow temperature (viscosity 1b), melt viscosity measured under the same shear rate of it than 20 ° C. higher temperature (viscosity 2b) The ratio ((viscosity 2b) / (viscosity 1b )) is 0.10 to 0.70, preferably 0.10 to 0.70, particularly preferably 0.12 to 0.50.
Here, the flow start temperature in the present invention is a temperature at which an anisotropic melt phase starts to be formed, and a resin heated at a temperature rising rate of 4 ° C./min is loaded under a load of 100 kgf / cm ² . The temperature at which the melt viscosity shows 48000 poise when extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm.
If the melt viscosity ratio is outside the above range, extrusion molding may be difficult, or the resulting molded product may have strong anisotropy and may not be practically usable.
[0006]
The resin of the present invention preferably has a melt tension of 10 g or more when measured at a temperature 30 ° C. higher than the flow start temperature.
Here, the melt tension means that the resin is melted in a die having a length of 8.0 mm × 2.1 mmφ set at a temperature 30 ° C. higher than the resin flow start temperature, and is extruded at a piston speed of 2 mm / min. It shows the force applied to the tension pulley when the yarn breaks when the take-up roller picks up the monofilament after passing through the pulley and the take-up speed is increased. When the melt tension is less than 10 g, the elongation at the time of film formation by extrusion molding becomes insufficient, and the processing at the time of film molding or blow molding may be difficult, which is not preferable. The melt tension is preferably 40 g or less from the viewpoint of workability.
[0007]
The resin of the present invention preferably contains a combination of two or more of an aromatic hydroxycarboxylic acid unit, an aromatic dicarboxylic acid unit, and an aromatic dihydroxy unit.
Examples of the aromatic hydroxycarboxylic acid unit include the following structures.
[0008]
[Chemical 3]

[0009]
Examples of the aromatic dihydroxy unit include the following structures.
[0010]
[Formula 4]

[0011]
Examples of the aromatic dicarboxylic acid unit include the following structures.
[0012]
[Chemical formula 5]

[0013]
The combination of the above structural units and the composition ratio thereof are optional, but the structural units represented by the following formulas (1) to (4) in order to have the high heat resistance and appropriate fluidity that are the object of the present invention. It is set as the liquid crystalline polyester resin which contains 2 or more types of these, and the sum total of the structural unit of these combinations is 97 mol% or more of the whole .
[0014]
[Chemical 6]

[0015]
More preferable examples of the resin of the present invention include liquid crystalline polyester resins having specific structural units under specific conditions that satisfy all of the following conditions (a) to (c). In addition, Formula (1)-(4) in conditions is a structural unit shown by the said Formula (1)-(4).
(a): The proportion of the structural unit represented by the formula (1) is 40 to 70 mol% of the whole,
(b): The total proportion of the structural unit represented by the formula (2) and the structural unit represented by the formula (3) is 15 to 30 mol in total, and the structural unit represented by the formula (2) The proportion is 0 to 95 mol% with respect to the total of the structural unit represented by the formula (2) and the structural unit represented by the formula (3), and among the structural units represented by the formula (2) 80 to 100 mol% is a structural unit whose main chain bond position is para-position,
(c): The proportion of the structural unit represented by formula (4) is substantially the same as the total proportion of the structural unit represented by formula (2) and the structural unit represented by formula (3). And 50% by mole or more of the structural unit represented by the formula (4) is a structural unit in which the main chain bond position is in the para position.
[0016]
The intrinsic viscosity [η] of the resin of the present invention is 5.5 or more . When [η] is less than 5.5, it is difficult to obtain the above-described melt viscosity characteristics and melt tension.
[0017]
The method for producing the resin of the present invention is not particularly limited, and a known method can be used. For example, it can be obtained by a method of subjecting a mixture comprising two or more kinds of monomer compounds having the aromatic hydroxycarboxylic acid unit, aromatic dicarboxylic acid unit and aromatic dihydroxy unit to a polycondensation reaction in a polymerization tank. Examples of the monomer compound having an aromatic hydroxycarboxylic acid unit include hydroxybenzoic acid and p-acetoxybenzoic acid. Examples of the monomer compound having an aromatic dicarboxylic acid unit include terephthalic acid and isophthalic acid. Examples of the monomer compound having a group dihydroxy unit include 4,4′-dihydroxydiphenyl, 4,4′-diacetoxydiphenyl, hydroquinone, and resorcin. The charging of these compounds may be a batch method or a division method. The reaction can be carried out under an inert gas such as nitrogen atmosphere at normal pressure, reduced pressure or a combination thereof. The process can be batch, continuous, or a combination thereof.
In addition, after performing the reaction (for example, esterification reaction) which changes the said monomer compound into the compound which is easier to superpose | polymerize prior to a polycondensation reaction, a polycondensation reaction can also be performed continuously.
The temperature of the polycondensation reaction is usually preferably 270 to 380 ° C. When the temperature is less than 270 ° C., the polymerization reaction proceeds slowly, and when it exceeds 380 ° C., side reactions such as decomposition tend to occur, such being undesirable. A multi-stage reaction temperature may be employed. In some cases, the polymer as a reaction product can be withdrawn in a molten state and recovered during the temperature increase or as soon as the maximum temperature is reached. Further, in order to further increase the molecular weight of the extracted polymer, post-treatment such as solid phase polymerization can be performed by heating in an inert gas atmosphere.
[0018]
In the present invention, as an extrusion molding material a liquid crystalline polyester resin obtained as described above, can also be subjected to powdery remains extrusion forming shape machine, the pellet once with granulator, this extrusion It is preferable in terms of handling that it is charged into a molding machine.
The extrusion shi molding material, a small amount of inorganic filler within a range not impair the object, organic fillers, antioxidants, heat stabilizers, light stabilizers, flame retardants, lubricants, antistatic agents, rust inhibitors, fluorescent Various additives such as an agent, a surface smoothing agent, a surface improver and a release agent can be added.
[0019]
The extruded product of the present invention is obtained by extruding the material for extrusion molding. The form of the extruded product is not particularly limited, but a film is preferable. Although the thickness of a film can be suitably selected according to a use, it is about 10-500 micrometers normally.
The extruded product of the present invention can be prepared by shaping the above-mentioned material for extrusion molding into a desired form by ordinary extrusion molding. Specifically, in the case of film forming, a molten resin is extruded to a predetermined width and thickness from a slit-shaped processing machine called a T-die, and cooled to form a film as it is. And a stretching method that sequentially stretches in the perpendicular direction, an inflation method in which a resin is extruded from a circular die into a cylindrical shape, and is simultaneously stretched in a winding direction and a direction perpendicular thereto by a gas. The inflation method is preferably used from the viewpoint of easy control of anisotropy.
In the case of blow molding, molding can be performed by extruding a resin from an annular die, sandwiching a cylindrical semi-molten resin called a parison between molds, and then inflating and shaping by a gas pressure. This method is also suitable for the liquid crystal polymer in terms of easy control of anisotropy.
In these extrusion moldings, when the extrusion molding material containing the liquid crystalline polyester resin of the present invention is provided, it can be provided without special measures to an ordinary extrusion molding machine.
[0020]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these. In addition, each measurement in an example was performed in accordance with the following method.
(1) Physical property measurement method
(a) Flow start temperature: Measured with Koka type flow tester CFT-500 manufactured by Shimadzu Corporation. That is, when a resin heated at a heating rate of 4 ° C./min is extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 100 kgf / cm ² , the temperature at which the melt viscosity shows 48000 poise is measured. This was taken as the flow start temperature.
(b) Melt viscosity: In Capirograph 1B manufactured by Toyo Seiki Co., was carried out under a predetermined temperature, die diameter 0.5 mm, shear rate 100 sec ^-1, measured at of 1,000 sec ^-1.
(c) Melt tension: Using a Capillograph 1B manufactured by Toyo Seiki Co., Ltd., the resin was melted in a die having a length of 8.0 mm × 2.1 mmφ set at a predetermined temperature 30 ° C. higher than the flow start temperature of each resin. This was extruded at a piston speed of 2 mm / min, and was taken up while increasing the take-up speed in a device for taking up after passing through the tension pulley, and the force applied to the tension pulley when the yarn broke was determined in grams.
(d) Intrinsic viscosity [η]: The liquid crystalline polyester resin was dissolved in 3,5-bistrifluoromethylphenol and measured at 60 ° C. using an Ubbelohde viscometer.
(e) Thermal deformation temperature (DTUL): A DTUL test piece (127 mm long × 12.7 mm wide × 6.4 mm thick) was molded and measured under a load of 18.6 kg according to ASTM D648.
(f) Solder heat resistance temperature: A JIS1 (1/2) dumbbell having a thickness of 1.2 mm was molded as a test piece and immersed in a 230 ° C. solder bath composed of 60% tin and 40% lead. Take out after holding for 60 seconds and observe the appearance. Thereafter, the temperature of the solder bath was increased by 10 ° C., and a similar experiment was performed to determine the maximum temperature at which the test piece did not foam or deform.
(2) Film processing resin pellets were melt-kneaded at a cylinder setting temperature of 290 to 370 ° C. and a rotation speed of 80 rpm using a 20 mm twin-screw kneading extruder equipped with a cylindrical die manufactured by Toyo Seiki Co., Ltd., diameter 30 mm, lip interval After extruding the molten resin upward from a cylindrical die of 1.5 mm and a die set temperature of 290 to 370 ° C., pressurizing dry air into the hollow portion of this tubular film to expand the tubular film, and then cooling it, The film was drawn through a nip roll at a take-up speed of 8 to 15 m / min to obtain a liquid crystal polymer film having a thickness of 10 to 30 μm. The obtained film was observed with the naked eye and evaluated according to the following criteria.
○: A film can be formed and the appearance is also good.
Δ: Film can be formed, but uneven color is observed.
X: Film cannot be formed.
(3) Film heat resistance Film obtained by cutting the approximately 30 μm-thick film obtained as described above into 10 cm square, fixing both ends with clips and leaving it in a hot air circulating oven set at 280 ° C. for 5 minutes. The state was observed and evaluated according to the following criteria.
○: No change is observed in the film shape.
X: The film is deformed or melted.
[0021]
Example 1
p-acetoxybenzoic acid 10.8 kg (60 mol), terephthalic acid 2.49 kg (15 mol), isophthalic acid 0.83 kg (5 mol) and 4,4'-diacetoxydiphenyl 5.45 kg (20.2 kg) Mol) was charged into a polymerization tank having a comb-shaped stirring blade, heated while stirring in a nitrogen gas atmosphere, and polymerized at 330 ° C. for 1 hour. During this time, the polymerization was carried out under vigorous stirring while removing by-product acetic acid. Thereafter, the system was gradually cooled, and the polymer obtained at 200 ° C. was taken out of the system. The obtained polymer was pulverized with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles of 2.5 mm or less.
This was further treated in a rotary kiln under a nitrogen atmosphere at 290 ° C. for 3 hours to obtain a wholly aromatic liquid crystalline polyester resin having a flow start temperature of 341 ° C. and comprising the following units in the form of particles.
[0022]
[Chemical 7]

This liquid crystalline polyester resin was granulated at 350 ° C. using a PCM-30 type granulator manufactured by Ikekai Tekko Co., Ltd. to obtain a pellet. The flow starting temperature determined from the pellets at this time was 332 ° C., and the intrinsic viscosity [η] was 6.8. Tables 1 and 2 show the melt viscosity, melt viscosity ratio, melt tension, solder heat resistance, film shape and heat resistance during inflation film formation of this resin.
[0023]
Comparative Example 1
After obtaining particles of 2.5 mm or less in the same manner as in Example 1, a fully aromatic liquid crystalline polyester resin having a flow start temperature of 331 ° C. was obtained by treating in a rotary kiln under a nitrogen atmosphere at 280 ° C. for 3 hours. . This liquid crystalline polyester resin was granulated at 340 ° C. using a PCM-30 type granulator manufactured by Ikekai Tekko Co., Ltd. to obtain a pellet. The flow starting temperature determined from the pellets at this time was 324 ° C., and the intrinsic viscosity [η] was 4.8. Tables 1 and 2 show the melt viscosity, melt viscosity ratio, melt tension, solder heat resistance, film shape and heat resistance during inflation film formation of this resin.
[0024]
Comparative Example 2
16.6 kg (12.1 mol) of p-hydroxybenzoic acid, 8.4 kg (4.5 mol) of 6-hydroxy-2-naphthoic acid and 18.6 kg (18.2 mol) of acetic anhydride were equipped with a comb-shaped stirring blade. The mixture was charged into a polymerization tank and heated with stirring in a nitrogen gas atmosphere, and polymerized at 320 ° C. for 1 hour at 320 ° C. under normal pressure and further for 1 hour at 320 ° C. under a reduced pressure of 2.0 Torr. During this time, acetic acid produced as a by-product continued to be distilled out of the system. Thereafter, the system was gradually cooled, and the polymer obtained at 180 ° C. was pulverized in the same manner as in Example 1 and then treated at 240 ° C. in a nitrogen gas atmosphere for 5 hours in a rotary kiln, whereby the flow start temperature was 270 ° C. A wholly aromatic liquid crystalline polyester comprising the following repeating units in the form of:
[0025]
[Chemical 8]

This liquid crystalline polyester resin was granulated at 280 ° C. using a PCM-30 type granulator manufactured by Ikekai Tekko Co., Ltd. to obtain a pellet. The flow starting temperature determined from the pellets at this time was 268 ° C. Tables 1 and 2 show the melt viscosity, melt viscosity ratio, melt tension, solder heat resistance, film shape and heat resistance during inflation film formation of this resin.
[0026]
[Table 1]

[0027]
[Table 2]

[0028]
【The invention's effect】
The present invention has heat resistance high, the liquid crystalline polyester resin having an appropriate fluidity, so that extruded, has good heat resistance, excellent extrudate appearance, in particular obtain a film Can be used in a wide range of fields.

Claims (3)

Solder heat resistance temperature is 250 ° C or higher ,
Including two or more of the structural units represented by the following formulas (1) to (4), the total of the structural units of these combinations is 97 mol% or more of the total,
The ratio of the melt viscosity at a shear rate of 1,000 sec ^-1 under flow temperature (viscosity 1b), therewith than 20 ° C. higher temperature melt viscosity measured under the same shear rate (viscosity 2b) ((viscosity 2b) / ( An extruded product obtained by extruding a liquid crystalline polyester resin having a viscosity 1b)) of 0.10 to 0.70 and an intrinsic viscosity [η] of 5.5 or more .

The extruded product according to claim 1 , wherein all of the following conditions (a) to (c) are satisfied.
(a): The proportion of the structural unit represented by the formula (1) is 40 to 70 mol% of the whole,
(b): The total proportion of the structural unit represented by the formula (2) and the structural unit represented by the formula (3) is 15 to 30 mol in total, and the structural unit represented by the formula (2) The proportion is 0 to 95 mol% with respect to the total of the structural unit represented by the formula (2) and the structural unit represented by the formula (3), and among the structural units represented by the formula (2) 80 to 100 mol% is a structural unit whose main chain bond position is para-position,
(c): The proportion of the structural unit represented by formula (4) is substantially the same as the total proportion of the structural unit represented by formula (2) and the structural unit represented by formula (3). And 50% by mole or more of the structural unit represented by the formula (4) is a structural unit in which the main chain bond position is in the para position. The extruded product according to claim 1 or 2, wherein the form is a film.