JP3873403B2 - Method of melt extrusion of thermoplastic resin - Google Patents
Method of melt extrusion of thermoplastic resin Download PDFInfo
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- JP3873403B2 JP3873403B2 JP28387997A JP28387997A JP3873403B2 JP 3873403 B2 JP3873403 B2 JP 3873403B2 JP 28387997 A JP28387997 A JP 28387997A JP 28387997 A JP28387997 A JP 28387997A JP 3873403 B2 JP3873403 B2 JP 3873403B2
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- melt
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- crystal polyester
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Description
【０００１】
【発明の属する技術分野】
本発明は、流動開始温度の高い熱可塑性樹脂の溶融押し出し加工方法に関する。本発明によれば、比較的長時間、連続的に押し出し加工を継続した場合においても、押出機内での樹脂劣化が少なく、変色劣化物の含量の少ない押出製品が得られる。
【０００２】
【従来の技術】
熱可塑性のエンジニアリングプラスチックスは、その優れた耐熱性、機械特性から、電機・電子部品、ＯＡ・ＡＶ部品、自動車部品等で広く使用されている。
これらの製品は、原料ペレットから各種成形法により製造されているが、該原料ペレット生産時ならびにペレットからの製品化時に溶融混練式押出機を用いて押し出し加工を行うことが一般的である。この際、該熱可塑性樹脂は押出機内で高温下にさらされるため、押出加工時間の経時とともに該樹脂の一部が押出機内で滞留劣化すること、また、押出機内で滞留劣化した樹脂が、押出製品中に変色劣化物として混入し、不都合を生じることがあった。
【０００３】
【発明が解決しようとする課題】
本発明は、以上の問題点の中でも液晶ポリエステルに関し、比較的長時間加工を継続した場合においても押出機内での樹脂劣化が少なく、変色劣化物の含量の少ない押出製品の得られる、液晶ポリエステルの溶融押し出し加工方法を提供することを目的とするものである。
【０００４】
【課題を解決するための手段】
本発明者らは、上記問題点を解決するために鋭意検討した結果、特定の流動開始温度の液晶ポリエステルを、溶融混練式押出機を用いて押し出し加工を行うにあたり、該溶融混練式押出機の特定部位にベント口を設け、該ベント口を特定の真空度で連続的に吸引することにより、上記問題点を解決できることを見出し本発明に至った。
【０００５】
すなわち、本発明は以下に示すとおりである。
（１）下記に定義される流動開始温度が２００℃以上の液晶ポリエステルを、溶融混練式押出機スクリュウの最上流部を基準として距離Ｌ下流側の部位にベント口が設けられ、Ｌ／Ｄが５〜１５である（ここで、Ｄはスクリュウ径を示し、ＤとＬは同一のスケール単位である）溶融混練式押出機を用いて、該ベント口を６６０ｍｍＨｇより高い真空度で連続的に吸引しながら、押し出し加工することを特徴とする熱可塑性樹脂の溶融押し出し加工方法。流動開始温度：内径１ｍｍ、長さ１０ｍｍのノズルをもつ毛細管レオメーターを用い、１００ｋｇ／ｃｍ2 の荷重下において４℃／分の昇温速度で加熱溶融体をノズルから押し出すときに、溶融粘度が４８０００ポイズを示す温度
（２）液晶ポリエステルの流動開始温度が２５０℃以上である（１）記載の熱可塑性樹脂の溶融押し出し加工方法。
（３）液晶ポリエステルが、下記の式Ａ 1 で表される繰り返し構造単位を少なくとも全体の３０モル％含む液晶ポリエステルである（１）または（２）記載の液晶ポリエステルの溶融押し出し加工方法。
【０００６】
【化２】
【０００７】
【発明の実施の形態】
本発明で使用される流動開始温度が２００℃以上の液晶ポリエステルである。液晶ポリエステルは、溶融粘度の温度依存性ならびに剪断速度依存性が高い樹脂であるため、押出機内で滞留を起こし易く、本発明の効果が得られるものである。本発明で使用される液晶ポリエステルとしては、サーモトロピック液晶ポリマーと呼ばれるポリエステルであり、（１）芳香族ジカルボン酸と芳香族ジオールと芳香族ヒドロキシカルボン酸との組み合わせからなるもの、（２）異種の芳香族ヒドロキシカルボン酸からなるもの、（３）芳香族ジカルボン酸と芳香族ジオールとの組み合わせからなるもの、（４）ポリエチレンテレフタレートなどのポリエステルに芳香族ヒドロキシカルボン酸を反応させたもの、等が挙げられ、４００℃以下の温度で異方性溶融体を形成するものである。なお、これらの芳香族ジカルボン酸、芳香族ジオールおよび芳香族ヒドロキシカルボン酸の代わりに、それらのエステル形成性誘導体が使用されることもある。該液晶ポリエステルの繰り返し構造単位としては下記のものを例示することができるが、これらに限定されるものではない。
芳香族ヒドロキシカルボン酸に由来する繰り返し構造単位：
【０００８】
【化３】
【０００９】
【化４】
【００１０】
【化５】
【化６】
耐熱性、機械的特性、加工性のバランスから特に好ましい液晶ポリエステルは、前記（Ａ1 ）で表される繰り返し構造単位を少なくとも３０モル％含むものである。
具体的には繰り返し構造単位の組み合わせが下式（ａ）〜（ｆ）のものが好ましい。
（ａ）：（Ａ1 ）、（Ｂ1 ）または（Ｂ1 ）と（Ｂ2 ）の混合物、（Ｃ1 ）。
（ｂ）：（Ａ1 ）、（Ａ2 ）。
（ｃ）：（ａ）の構造単位の組み合わせのものにおいて、Ａ1 の一部をＡ2 で置きかえたもの。
（ｄ）：（ａ）の構造単位の組み合わせのものにおいて、Ｂ1 の一部をＢ3 で置きかえたもの。
（ｅ）：（ａ）の構造単位の組み合わせのものにおいて、Ｃ1 の一部をＣ3 で置きかえたもの。
（ｆ）：（ｂ）の構造単位の組み合わせたものにＢ1 とＣ1 の構造単位を加えたもの。
基本的な構造となる（ａ）、（ｂ）の液晶ポリエステルについては、それぞれ、例えば特公昭４７−４７８７０号公報、特公昭６３−３８８８号公報等に記載されている。
【００１３】
本発明においては、液晶ポリエステルに必要に応じて充填剤を添加することができる。充填材としては、ガラス繊維、シリカアルミナ繊維、ウォラストナイト、炭素繊維、チタン酸カリウムウィスカー、ホウ酸アルミニウムウィスカー、酸化チタンウィスカー等の繊維状あるいは針状の補強材；炭酸カルシウム、ドロマイト、タルク、マイカ、クレイ、ガラスビーズなどの無機充填材等が挙げられ、その一種または二種以上を用いることができる。
【００１４】
なお、本発明で用いられる液晶ポリエステルに対して、本発明の目的を損なわない範囲で染料、顔料などの着色剤；酸化防止剤；熱安定剤；紫外線吸収剤；帯電防止剤；界面活性剤などの通常の添加剤を１種以上添加することができる。また、本発明において流動開始温度が２００℃以上の熱可塑性樹脂として液晶ポリエステルを用いた場合、少量の他の熱可塑性樹脂、例えば、ポリアミド、ポリエステル、ポリフェニレンスルフィド、ポリエーテルケトン、ポリカーボネート、ポリフェニレンエーテルおよびその変性物、ポリスルフォン、ポリエーテルスルフォン、ポリエーテルイミド等や、少量の熱硬化性樹脂、例えば、フェノール樹脂、エポキシ樹脂、ポリイミド樹脂等の、一種または二種以上を添加することもできる。
【００１５】
本発明における溶融混練式押出機を用いた押し出し加工方法は、熱可塑性樹脂の造粒工程、フィルム、パイプ等の押し出し工程、ブロー成形工程等に適用されるが、これらに限定されるものではない。
また、本発明において用いられる溶融混練式押出加工機は、スクリュウ式の溶融混練式押出機であれば特に限定されないが、スクリュウが一軸のもの、二軸でその回転が同方向のものまたは異方向のものが一般的である。
【００１６】
本発明において用いられる溶融混練式押出機は、該押出機スクリュウの最上流部を基準として距離Ｌ下流側の部位にベント口が設けられ、Ｌ／Ｄが５〜１５である。Ｌ／Ｄがこの範囲よりも大きいと、溶融押出加工時に、原料フィード口から巻き込んだエアーによる樹脂の酸化劣化が起こり易くなるため好ましくない。また、Ｌ／Ｄがこの範囲よりも小さいと、溶融押出加工時に溶融が十分に進行していない原料樹脂がベント口より吸引されてしまうため好ましくない。また、溶融押出加工時のベント口の真空度は、５６０ｍｍＨｇ以下であり、さらに好ましくは３００〜１０ｍｍＨｇである。本発明において、ベント口の真空化の方法は特に限定されないが、例えば、ロータリーポンプ、油拡散ポンプ、ターボポンプ等を使って真空にする方法を挙げることができる。本発明の加工方法によってつくられる製品は、変色劣化物が極めて少ないため、外装部品等の外観が重視される用途に好適に用いることができる。
【００１７】
【実施例】
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。なお、実施例中で示す成形体中の黒色異物の測定は、以下の手順で行った。
（１）日精樹脂工業（株）製、溶融混練式押出機、商品名ＰＳ４０Ｅ５ＡＳＥのシリンダー、スクリュウ、ノズルを分解し、十分に掃除を行う。
（２）ＰＳ４０Ｅ５ＡＳＥを用いて、６４ｍｍ×６４ｍｍ×３ｍｍ厚みの成形品を２０枚成形する。
（３）上記成形品を、蛍光灯ライトボックス上へ置き、その透過光により成形品中に含まれる平均径１５０μｍ以上の異物を全量カウントした。尚、平均径１５０μｍ以上の異物の個数は、その限度見本との比較により行った。
（４）上記（３）によりカウントした異物の個数を成形品１００ｇあたりに換算した。
【００１８】
実施例１
繰り返し構造単位が前記のＡ1 、Ｂ1 、Ｂ2 、Ｃ1 からなり、Ａ1 ：Ｂ1 ：Ｂ2 ：Ｃ1 のモル比が６０：１８：２：２０であり前記の方法で求めた流動温度が３５３℃である液晶ポリエステル６０重量％に対し、ミルドガラスファイバー（セントラル硝子（株）製、商品名ＥＦＨ７５−０１）４０重量％をヘンシェルミキサーで混合後、事前にスクリュウ、シリンダーを解体掃除した二軸押出機（アイケージー（株）製、商品名ＰＣＴ−４７型）を用いて、押出機スクリュウの最上流部を基準として前記で規定したＬ／Ｄが１０の位置にベント口を設け、該ベント口を２６０ｍｍＨｇの真空度で連続的に吸引した状態で、シリンダー温度３８０℃で造粒し、液晶ポリエステル樹脂組成物ペレットを連続的に得た。本組成物ペレットを連続して１トン製造後、二軸押出機を解体したところ、スクリュウ、シリンダーともに汚れは観測されなかった。更に、連続造粒１トンを経過した時のペレットから得た成形品について、その異物レベルを調べた。その結果、平均径１５０μｍ以上の異物数は７個／１００ｇであった。本発明の方法で製造された液晶ポリエステル樹脂組成物は、その製品中への異物混入レベルが極めて低いことが判る。
【００１９】
比較例１
押出機スクリュウの最上流部を基準として前記で規定したＬ／Ｄが２０の位置にベント口を設け、該ベント口を２６０ｍｍＨｇの真空度で連続的に吸引した状態で連続的に造粒する以外は実施例１と同様な方法で実験を行った。液晶ポリエステル樹脂組成物ペレットを連続して１トン製造後、二軸押出機を解体したところ、スクリュウの上流部（前記で規定したＬ／Ｄで５〜１５の部位）が黒く変色していた。また、連続造粒１トンを経過した時のペレットから得た成形品について、その異物レベルを調べた。その結果、平均径１５０μｍ以上の異物数は８１個／１００ｇであった。比較例１のペレットから得た成形品は、実施例１のペレットから得た成形品に比べ異物混入レベルが極めて多いことがわかる。
【００２０】
【発明の効果】
本発明の液晶ポリエステルの溶融押し出し加工方法によれば、比較的長時間押出加工を継続した場合においても、押出機内での樹脂劣化が少なく、変色劣化物の含量の少ない押出製品が得られる。その製品は変色劣化物が少ないため、薄肉の電気・電子部品に好適な材料である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for melt extrusion of a thermoplastic resin having a high flow start temperature. According to the present invention, even when extrusion processing is continued continuously for a relatively long time, an extruded product with little resin deterioration in the extruder and a low content of discoloration deterioration products can be obtained.
[0002]
[Prior art]
Thermoplastic engineering plastics are widely used in electric / electronic parts, OA / AV parts, automobile parts and the like because of their excellent heat resistance and mechanical properties.
These products are produced from raw material pellets by various molding methods. Generally, extrusion processing is performed using a melt-kneading type extruder during production of the raw material pellets and production from the pellets. At this time, since the thermoplastic resin is exposed to a high temperature in the extruder, a part of the resin stays and deteriorates in the extruder as the extrusion processing time elapses. In some cases, the product mixed in as a discolored degradation product, resulting in inconvenience.
[0003]
[Problems to be solved by the invention]
The present invention relates to a liquid crystal polyester, among the above problems, and resin degradation in the extruder in the case of continued relatively long working less, obtained with less extrusion products with content of discoloration degradation product, the liquid crystal polyester The object is to provide a melt extrusion processing method.
[0004]
[Means for Solving the Problems]
As a result of intensive investigations to solve the above problems, the inventors of the present invention have carried out the process of extruding a liquid crystal polyester having a specific flow start temperature using a melt-kneading extruder. The present inventors have found that the above problems can be solved by providing a vent port at a specific site and continuously sucking the vent port at a specific degree of vacuum.
[0005]
That is, the present invention is as follows.
(1) A liquid crystal polyester having a flow start temperature defined below is 200 ° C. or more, a vent port is provided at a site downstream of the distance L with respect to the most upstream part of the melt-kneading extruder screw, and L / D is 5 to 15 (where D is the screw diameter, and D and L are the same scale unit), using a melt-kneading type extruder, the vent port is continuously sucked at a degree of vacuum higher than 660 mmHg. A method for melt extrusion of a thermoplastic resin, characterized in that the extrusion processing is performed. Flow starting temperature: When a heated melt is extruded from the nozzle at a heating rate of 4 ° C./min under a load of 100 kg / cm 2 using a capillary rheometer having a nozzle with an inner diameter of 1 mm and a length of 10 mm, the melt viscosity is 48000. The temperature at which poise is exhibited (2) The melt extrusion processing method for a thermoplastic resin according to (1), wherein the flow start temperature of the liquid crystalline polyester is 250 ° C. or higher.
(3) a liquid crystal polyester, repeated a liquid crystal polyester containing at least the entire 30 mole% of the structural units (1) or (2) melt-extrusion method of a liquid crystal polyester according to the formula A 1 below.
[0006]
[Chemical 2]
[0007]
DETAILED DESCRIPTION OF THE INVENTION
It is a liquid crystal polyester having a flow start temperature of 200 ° C. or higher used in the present invention . Since the liquid crystal polyester is a resin having a high melt viscosity temperature dependency and shear rate dependency, the liquid crystal polyester tends to stay in the extruder, and the effects of the present invention can be obtained. The liquid crystal polyester used in the present invention is a polyester called a thermotropic liquid crystal polymer, and (1) a combination of an aromatic dicarboxylic acid, an aromatic diol, and an aromatic hydroxycarboxylic acid; Examples include those composed of aromatic hydroxycarboxylic acids, (3) those composed of combinations of aromatic dicarboxylic acids and aromatic diols, and (4) those obtained by reacting aromatic hydroxycarboxylic acids with polyesters such as polyethylene terephthalate. The anisotropic melt is formed at a temperature of 400 ° C. or lower. In addition, these ester-forming derivatives may be used in place of these aromatic dicarboxylic acids, aromatic diols and aromatic hydroxycarboxylic acids. Examples of the repeating structural unit of the liquid crystalline polyester include the following, but are not limited thereto.
Repeating structural units derived from aromatic hydroxycarboxylic acids:
[0008]
[Chemical 3]
[0009]
[Formula 4]
[0010]
[Chemical formula 5]
[Chemical 6]
A particularly preferred liquid crystalline polyester from the balance of heat resistance, mechanical properties and processability is one containing at least 30 mol% of the repeating structural unit represented by (A 1 ).
Specifically, the combination of repeating structural units is preferably those of the following formulas (a) to (f).
(A): (A 1 ), (B 1 ) or a mixture of (B 1 ) and (B 2 ), (C 1 ).
(B): (A 1 ), (A 2 ).
(C): A combination of structural units of (a), wherein A 1 is partially replaced by A 2 .
(D): A combination of the structural units of (a), wherein a part of B 1 is replaced with B 3 .
(E): A combination of structural units in (a), wherein a part of C 1 is replaced with C 3 .
(F): A combination of the structural units of (b) plus the structural units of B 1 and C 1 .
The liquid crystal polyesters (a) and (b) having basic structures are described in, for example, JP-B-47-47870 and JP-B-63-3888.
[0013]
In the present invention, a filler can be added to the liquid crystal polyester as necessary. Examples of fillers include glass fibers, silica alumina fibers, wollastonite, carbon fibers, potassium titanate whiskers, aluminum borate whiskers, titanium oxide whiskers and other fibrous or needle-shaped reinforcing materials; calcium carbonate, dolomite, talc, Examples include inorganic fillers such as mica, clay, and glass beads, and one or more of them can be used.
[0014]
In addition, with respect to the liquid crystalline polyester used in the present invention, colorants such as dyes and pigments; antioxidants; thermal stabilizers; ultraviolet absorbers; antistatic agents; One or more conventional additives can be added. In the present invention, when a liquid crystal polyester is used as a thermoplastic resin having a flow start temperature of 200 ° C. or higher, a small amount of other thermoplastic resins such as polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether, and One or two or more of such modified products, polysulfone, polyethersulfone, polyetherimide, etc., and a small amount of thermosetting resin such as phenol resin, epoxy resin, polyimide resin, etc. may be added.
[0015]
The extrusion processing method using the melt-kneading type extruder in the present invention is applied to a granulation process of a thermoplastic resin, an extrusion process of a film, a pipe, etc., a blow molding process, etc., but is not limited thereto. .
Further, the melt-kneading type extruder used in the present invention is not particularly limited as long as it is a screw-type melt-kneading type extruder, but the screw is uniaxial, the biaxial rotation is the same direction, or the different direction. The ones are common.
[0016]
In the melt-kneading type extruder used in the present invention, a vent port is provided at a site downstream of the distance L with respect to the most upstream part of the extruder screw, and L / D is 5-15. When L / D is larger than this range, it is not preferable because oxidation deterioration of the resin due to air entrained from the raw material feed port easily occurs during melt extrusion. On the other hand, when L / D is smaller than this range, it is not preferable because the raw material resin whose melting has not sufficiently progressed during melt extrusion is sucked from the vent port. Moreover, the vacuum degree of the vent port at the time of melt-extrusion processing is 560 mmHg or less, More preferably, it is 300-10 mmHg. In the present invention, the method of evacuating the vent port is not particularly limited, and examples thereof include a method of evacuating using a rotary pump, an oil diffusion pump, a turbo pump, and the like. Since the product produced by the processing method of the present invention has very few discoloration degradation products, it can be suitably used for applications in which the appearance of exterior parts and the like is important.
[0017]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, the measurement of the black foreign material in the molded object shown in an Example was performed in the following procedures.
(1) Dismantle the cylinder, screw and nozzle of Nissei Plastic Industry Co., Ltd., melt-kneading type extruder, trade name PS40E5ASE, and clean thoroughly.
(2) Using PS40E5ASE, 20 molded products having a thickness of 64 mm × 64 mm × 3 mm are formed.
(3) The molded product was placed on a fluorescent lamp light box, and the total amount of foreign matters having an average diameter of 150 μm or more contained in the molded product was counted by the transmitted light. The number of foreign matters having an average diameter of 150 μm or more was determined by comparison with the limit sample.
(4) The number of foreign matters counted in the above (3) was converted per 100 g of the molded product.
[0018]
Example 1
The repeating structural unit was composed of the aforementioned A 1 , B 1 , B 2 , C 1 , and the molar ratio of A 1 : B 1 : B 2 : C 1 was 60: 18: 2: 20, and was determined by the above method. After mixing 40% by weight of milled glass fiber (manufactured by Central Glass Co., Ltd., trade name: EFH75-01) with 60% by weight of liquid crystalline polyester with a flow temperature of 353 ° C, the screw and cylinder are dismantled and cleaned in advance. Using a biaxial extruder (trade name PCT-47 manufactured by Icage Co., Ltd.), a vent port is provided at a position where the L / D defined above is 10 with reference to the most upstream part of the extruder screw. With the vent port continuously sucked at a vacuum degree of 260 mmHg, granulation was performed at a cylinder temperature of 380 ° C. to obtain liquid crystal polyester resin composition pellets continuously. After continuously producing 1 ton of the present composition pellets, the twin screw extruder was disassembled, and no contamination was observed on the screw and the cylinder. Furthermore, the foreign matter level was investigated about the molded article obtained from the pellet when 1 ton of continuous granulation passed. As a result, the number of foreign matters having an average diameter of 150 μm or more was 7/100 g. It can be seen that the liquid crystal polyester resin composition produced by the method of the present invention has a very low level of foreign matter in the product.
[0019]
Comparative Example 1
Except that the vent port is provided at the position where the L / D defined above is 20 with respect to the most upstream part of the extruder screw as a reference, and the vent port is continuously granulated in a state of being continuously sucked at a vacuum degree of 260 mmHg. The experiment was conducted in the same manner as in Example 1. After continuously producing 1 ton of liquid crystal polyester resin composition pellets, the twin screw extruder was disassembled, and the upstream portion of the screw (the portion of L / D defined above 5 to 15) had turned black. Moreover, the foreign material level was investigated about the molded article obtained from the pellet when 1 ton of continuous granulation passed. As a result, the number of foreign matters having an average diameter of 150 μm or more was 81/100 g. It can be seen that the molded product obtained from the pellets of Comparative Example 1 has an extremely high level of contamination as compared with the molded product obtained from the pellets of Example 1.
[0020]
【The invention's effect】
According to the melt-extrusion processing method of the liquid crystalline polyester of the present invention, an extruded product with little resin deterioration in the extruder and a low content of discoloration deterioration can be obtained even when extrusion is continued for a relatively long time. The product is suitable for thin-walled electrical and electronic parts because it has little discoloration degradation.
Claims (3)
流動開始温度：内径１ｍｍ、長さ１０ｍｍのノズルをもつ毛細管レオメーターを用い、１００ｋｇ／ｃｍ2 の荷重下において４℃／分の昇温速度で加熱溶融体をノズルから押し出すときに、溶融粘度が４８０００ポイズを示す温度A liquid crystal polyester having a flow start temperature defined below is 200 ° C. or more, a vent port is provided at a site downstream of the distance L with respect to the most upstream part of the melt-kneading extruder screw, and L / D is 5 to 15 (Where D represents the screw diameter, and D and L are the same scale unit), using a melt-kneading extruder, while continuously sucking the vent port at a degree of vacuum higher than 560 mmHg, A method for melt-extrusion of liquid crystalline polyester, characterized by performing extrusion processing.
Flow start temperature: When a heated melt is extruded from the nozzle at a heating rate of 4 ° C./min under a load of 100 kg / cm 2 using a capillary rheometer having a nozzle with an inner diameter of 1 mm and a length of 10 mm, the melt viscosity is 48000. Temperature indicating poise
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28387997A JP3873403B2 (en) | 1996-10-17 | 1997-10-16 | Method of melt extrusion of thermoplastic resin |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8-274800 | 1996-10-17 | ||
| JP27480096 | 1996-10-17 | ||
| JP28387997A JP3873403B2 (en) | 1996-10-17 | 1997-10-16 | Method of melt extrusion of thermoplastic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10175250A JPH10175250A (en) | 1998-06-30 |
| JP3873403B2 true JP3873403B2 (en) | 2007-01-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28387997A Expired - Fee Related JP3873403B2 (en) | 1996-10-17 | 1997-10-16 | Method of melt extrusion of thermoplastic resin |
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| Country | Link |
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| JP (1) | JP3873403B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011157422A (en) * | 2010-01-29 | 2011-08-18 | Sumitomo Chemical Co Ltd | Liquid crystalline polyester composition, method for producing the same, and connector |
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| JPH10175250A (en) | 1998-06-30 |
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