JPS61143439A - Continuous preparation of high molecular weight polymer stock solution - Google Patents

Abstract

PURPOSE:To continuously obtain at low cost the titled homogeneous stock solution capable of giving low-cost high-quality fiber with both high-sterngth and modulus, by feeding a polymer and solvent either separately or after mixing at specific temperature to twin-screw kneading extruder followed by dissolving and kneading at specified condition. CONSTITUTION:When a high molecular weight polymer of a weight-average molecular weight >=200,000 is homogeneously dissolved in a solvent to form a 3-50wt% solution, said polymer and the solvent are continuously fed, either separately or after mixing at a temperature <=(Ts-10) deg.C (Ts: the temperature at which said polymer begins to dissolve), to a twin-screw kneading extruder followed by dissolving and kneading the both components at a temperature >=(Ts+10) deg.C but below the boiling point of the solvent, pref. between (Ts+20) deg.C and (Ts+70) deg.C and also lower than the boiling point minus 10 deg.C, for 1-10min. to obtain the objective homogeneously dissolved stock solution. The molecular weight of said polymer and the kneading temperature are selected so as to be 1,000-50,000 poises in the viscosity of the stock solution. Said polymer should be either of polyolefin with a weight-average molecular weight >=800,000 or of polyvinyl alcohol with a weight-average molecular weight >=400,000.

Description

【発明の詳細な説明】 〈産業上の利用分野〉 本発明は引張強度ならびにモジュラスのきわめて大きな
繊維並びにフィルム等の成型物を製造するｔめの紡糸原
液調製法に関するものであり、特に安価で連続的に均一
な高濃度原液を得ようとするものである。[Detailed Description of the Invention] <Industrial Field of Application> The present invention relates to a method for preparing a spinning stock solution for producing molded products such as fibers and films with extremely high tensile strength and modulus, and particularly relates to a method for preparing a spinning dope that is inexpensive and continuous. The aim is to obtain a highly uniform stock solution with high concentration.

〈従来の技術〉 一般にポリマーの分子鎖末端は繊維微細構造上の欠陥部
となるため、分子量の大きいポリマーはど単位体積当り
の分子鎖末端が少なく大きな強度が出ると期待されてい
る。<Prior Art> Generally, the molecular chain ends of a polymer become defects in the fiber microstructure, so it is expected that a polymer with a large molecular weight will have fewer molecular chain ends per unit volume and will have greater strength.

しかし、高分子量ポリマーを紡糸する場合、亮い溶融弾
性と高い溶融粘性のために、単独で押出機により溶融紡
糸することは困難でちった。However, when spinning high molecular weight polymers, it is difficult to melt-spun them using an extruder alone due to their bright melt elasticity and high melt viscosity.

制分子量ポリマーを繊維化する方法として、ポリマーを
溶剤に溶解した原液音用い紡糸時に冷却固化する方法が
特公昭４４−２６４０９号公報に示され、その後超高分
子量ポリエチレンを同様に溶剤に溶解し、紡糸時に冷却
固化するいわゆるゲル紡糸法が特開昭５５−１０７５０
６号公報や特開８８５８−５２２８号公報などに示され
た。As a method for making fibers from controlled molecular weight polymers, Japanese Patent Publication No. 44-26409 discloses a method in which the polymer is dissolved in a solvent and then cooled and solidified during spinning. The so-called gel spinning method, which solidifies by cooling during spinning, was published in Japanese Patent Application Laid-Open No. 55-10750.
This was disclosed in Publication No. 6 and Japanese Patent Application Laid-open No. 8858-5228.

これらの方法は希薄なポリマー溶液から安定した紡糸を
行なって繊維化する方法としてきわめて優ｎたものであ
るが、ポリマー濃度が低いため、工業生産の場合、溶剤
回収費や生産量低下による設備費などの増大があり好ま
しくなかった。These methods are extremely superior as methods for stably spinning a dilute polymer solution into fibers, but because the polymer concentration is low, in the case of industrial production, solvent recovery costs and equipment costs due to reduced production volume are required. This was not desirable.

一方、高分子量ポリマーの濃度が高いと、粘度増大によ
って均一の原液調製が非常に難しくなることは知られて
いる。On the other hand, it is known that when the concentration of high molecular weight polymers is high, it becomes extremely difficult to prepare a uniform stock solution due to increased viscosity.

この点に関し、本発明者の実験によると、バッチ式でポ
リマーと溶剤の分散液を加熱してポリマー溶液溶解せし
める際に、ポリマーが溶解の始まつた部分に凝集して粘
度のきわめて大きな塊りを作る比め不均一原液となり易
く、かつ均一化するのに長時間かかることが判明し九〇
また原液粘度を低下させるために溶解混会時の温度を高
くするとポリマーの分解を起こし易いことも判明した０
さらにバッチ式では原液排出後に溶解機内に一部原液が
残り、その処置と溶解機の洗浄が時々必要である欠点も
みられ次。操業におけるスケールアップを考えた場合、
原液調製はバッチ方式より連続方式の方が設備費や電気
蒸気などの原動費が安く有利でめるが、原液状態はポリ
マーの溶解開始温度で急変し低粘度の分散液から高粘度
の不均一溶液に変化するため、通常連続方式で均一原液
を作るのは難しいと思われていた。特に溶剤が液体の場
合、ポリマーとの分散液を通常の単軸押出機に供給する
と、両者の粘度が大きく異なるため混合が出来ず、溶剤
がポリマーとスクリューの間で滑剤として働きほとんど
押出しが出来なかつｔ。In this regard, according to experiments conducted by the present inventor, when a dispersion of polymer and solvent is heated in a batch process to dissolve the polymer solution, the polymer aggregates at the beginning of dissolution and forms extremely viscous lumps. It has been found that it tends to result in a non-uniform stock solution and takes a long time to homogenize compared to making a stock solution.In addition, increasing the temperature during melting and mixing to reduce the viscosity of the stock solution may easily cause decomposition of the polymer. Turned out 0
Furthermore, the batch type has the disadvantage that some of the stock solution remains in the dissolver after the stock solution is discharged, and it is necessary to dispose of it and clean the dissolver from time to time. When considering scale-up in operations,
For stock solution preparation, a continuous method is more advantageous than a batch method because it requires lower equipment costs and driving costs such as electricity and steam, but the state of the stock solution changes rapidly at the temperature at which the polymer begins to dissolve, and can vary from a low-viscosity dispersion to a high-viscosity nonuniform solution. Because it changes into a solution, it was thought to be difficult to create a uniform stock solution using a continuous method. In particular, when the solvent is liquid, when a dispersion with the polymer is fed to a normal single-screw extruder, the viscosity of the two is greatly different, so they cannot be mixed, and the solvent acts as a lubricant between the polymer and the screw, making extrusion almost impossible. Nakatsut.

従って特開昭５９−１６８１１６号公報などにみられる
如く浴剤として室温で固体のパラフィンフックスを用い
、ポリマーとの粘度４を少なくして単軸押出機で連続調
製する方法が一つの打開策として考えられてき念。しか
し、単軸押出機ではスクリューとバレル（本体）壁面と
の間隙による剪断力が二軸混練押出機より不十分であす
、短時間でポリマーを溶解し混練する効果は低く、均一
溶解原液を得ることは難１−い。ざらに溶剤が室温で固
体で那点が高い場合は、乾燥により溶剤を飛散すること
は難しく、押出法により溶剤を除去しなければならない
制約を受け、溶剤の回収などに煩雑さを伴う。Therefore, one solution is to use paraffin fuchs, which is solid at room temperature as a bath agent, to reduce the viscosity 4 with the polymer, and to continuously prepare it using a single-screw extruder, as shown in JP-A-59-168116. I hope you can think about it. However, in a single-screw extruder, the shear force created by the gap between the screw and the barrel (main body) wall is insufficient compared to a twin-screw kneading extruder, and the effect of dissolving and kneading the polymer in a short time is low, resulting in a uniformly dissolved stock solution. That is difficult. If the solvent is solid at room temperature and has a high temperature point, it is difficult to scatter the solvent by drying, and there is a restriction that the solvent must be removed by extrusion, making recovery of the solvent complicated.

〈発明が解決しようとする問題点〉 以上の背景をふまえて本発明は、高分子量ポリマーｔ−
浴剤、特に室温で液体である浴剤に菌濃度で均一に溶解
せしめるための尚分子量ポリマー原液の連続調製法を提
供せんとするものである。<Problems to be Solved by the Invention> Based on the above background, the present invention provides a high molecular weight polymer t-
It is an object of the present invention to provide a method for continuously preparing a stock solution of a molecular weight polymer for uniformly dissolving bacteria at a concentration in a bath agent, particularly a bath agent that is liquid at room temperature.

く問題点を解灰するための手段〉 すなわち本発明は高分子量ポリマーの勾−な溶解原液を
連続的に安価に得るｋめの方法として、該ポリマーと溶
剤を二軸混練押出機に供給し、温度と滞留時間を選定す
ることにより均一溶解原液を連続的に製造し９るように
したものでめる０更に詳しく述べれば本発明は ［１，重量平均分子量が２０万以上の尚分子量ポリマー
を溶剤に３〜５０重ｉｔチ均−浴屏させる方法において
、該ポリマーと溶剤を別々に、またはあらかじめ少なく
ともポリマーの溶解開始温度（ｒ８）よ０１０℃低い温
度で両者を混会して二軸混練押出機に連続供給し、少な
くともＴｓより１０℃尚い温度で、かつ溶剤の沸点未満
の温度で１〜１０分゛間溶解混練し、均一溶解原液にす
ることを特徴とする高分子量ポリマー原液の連続調製法
。In other words, the present invention provides a method for continuously and inexpensively obtaining a gradient solution of a high molecular weight polymer by supplying the polymer and a solvent to a twin-screw kneading extruder. In more detail, the present invention is made by continuously producing a uniform solution stock solution by selecting the temperature and residence time. In the method of uniformly bathing 3 to 50 parts of the polymer in a solvent, the polymer and the solvent are mixed separately or in advance at a temperature at least 010°C lower than the dissolution start temperature (r8) of the polymer. A high molecular weight polymer stock solution that is continuously fed to a kneading extruder and melted and kneaded for 1 to 10 minutes at a temperature at least 10°C higher than Ts and below the boiling point of the solvent to obtain a uniformly dissolved stock solution. continuous preparation method.

２、特許請求の範囲第１項において、該均一溶解原液の
粘度が１０００〜５００００ポイズになるようにポリマ
ーの分子量、濃度および二軸混練押出機の温度を設定す
ることを特徴とする高分子量ポリマー原液の連続調製法
。2. A high molecular weight polymer according to claim 1, characterized in that the molecular weight and concentration of the polymer, and the temperature of the twin-screw kneading extruder are set so that the viscosity of the uniformly dissolved stock solution is 1,000 to 50,000 poise. Continuous preparation method of stock solution.

３、　９許請求の範囲第１ないし２項において、二軸混
練押出機の供給口の温度をＴｓ−１０℃以下にし、ポリ
マーのブロッキングを防止することを特徴とする高分子
量ポリマー原液の連続調製法。3 and 9 Claims 1 and 2, the continuous preparation of a high molecular weight polymer stock solution is characterized in that the temperature at the feed port of the twin-screw kneading extruder is set to Ts-10°C or lower to prevent blocking of the polymer. Law.

４、特許請求の範囲第１ないし３項において、該ポリマ
ーが重量平均分子量が８０万以上のポリオレフィン系ポ
リマーであることを特徴とする高分子量ポリマー原液の
連ｆｆｒ、ｖＩ４Ｍ法。4. The continuous ffr, vI4M method for a high molecular weight polymer stock solution according to claims 1 to 3, wherein the polymer is a polyolefin polymer having a weight average molecular weight of 800,000 or more.

５、特許請求の範囲第１ないし３項において、該ポリマ
ーが重量平均分子量が４０万以上のポリビニルアルコー
ル系ポリマーであることを特徴とする高分子量ポリマー
原液の連続調製法０６、特許請求の範囲第１ないし３項
において、該ポリマーが重量平均分子量が４０万以上の
ポリアクリロニトリル系ポリマーであることｔ　ｑ＋徴
とする高分子量ポリマー原液の連続調製法。5. A continuous preparation method for a high molecular weight polymer stock solution 06, characterized in that the polymer is a polyvinyl alcohol polymer having a weight average molecular weight of 400,000 or more, as set forth in Claims 1 to 3. The method for continuously preparing a high molecular weight polymer stock solution according to Items 1 to 3, characterized in that the polymer is a polyacrylonitrile polymer having a weight average molecular weight of 400,000 or more.

７゜特許請求の範囲第１ないし６項において、該溶剤は
１２０〜２２０℃の沸点を有する室温で液体のものであ
り、二軸混練押出機内の温度がＴｓ＋２０℃ないしＴｓ
＋７０℃でかつ該浴剤の沸点より少なくとも１０℃低い
温度であることを％徴とする高分子量ポリマー原液の連
続調製法。7. In claims 1 to 6, the solvent has a boiling point of 120 to 220°C and is liquid at room temperature, and the temperature in the twin-screw extruder is between Ts+20°C and Ts.
A process for the continuous preparation of a high molecular weight polymer stock solution at a temperature of +70°C and at least 10°C below the boiling point of the bath agent.

８、特許請求の範囲第１ないし７項において、二軸混練
押出機は少なくとも押出部と混線部を１セク／ヨンずつ
有し、かつ最初の１又は２七クシヨンの温度がｉ＆後の
１又は２セクションの温度より１０℃以上高いことを特
徴とする縄分子量ポリマー原液の連続調製法。」である
。8. In claims 1 to 7, the twin-screw kneading extruder has at least one extrusion section and one cross section per section, and the temperature of the first one or twenty-seven sections is i & the second section or section. A method for continuously preparing a stock solution of a rope molecular weight polymer, characterized in that the temperature is 10°C or more higher than the temperature of two sections. ”.

以下本発明について詳述する。The present invention will be explained in detail below.

本発明に言うポリマーとはポリオレフィン系、ポリビニ
ルアルコール系、ポリオキシメチレン系、ポリエチレン
グリコール系、ポリアクリロニトリル系、ポリエステル
系、ポリアミド系などｓＭＭ、平均分子−が２０万以上
で紡糸ｕＪ能なポリマーを意味し、改質のために他のモ
ノマまたはポリマーを共Ｎ曾したものであっても、るる
いは第３成分を添加混什したものでろってもイσｊんら
支障はない０ポリマーのｌｉｔ平均分子量が２０万未満
ではｌｖＪ頻力および高モジュラスな繊維並びにフィル
ム等の成形物を得ることは難しく、ポリオレフィン系で
ハ好ましくは８０万以上、ポリビニルアルコール系では
好ましくは４０万以上、ポリアクリロニトリル系では好
ましくは４０万以上である。The term "polymer" used in the present invention refers to a polymer with an average molecular weight of 200,000 or more and spinnability, such as polyolefin, polyvinyl alcohol, polyoxymethylene, polyethylene glycol, polyacrylonitrile, polyester, or polyamide. However, there is no problem even if other monomers or polymers are added for modification, or if a third component is added and mixed. If the average molecular weight is less than 200,000, it is difficult to obtain molded products such as fibers and films with high lvJ frequency and high modulus. Polyolefins are preferably 800,000 or more, polyvinyl alcohols are preferably 400,000 or more, and polyacrylonitrile-based materials are preferably used. It is preferably 400,000 or more.

ボｌ？−！−溶解する浴剤は呈温で献体または固体のど
ちらでめっても良いが乾燥による溶剤の除去や回収なと
全考慮すると沸点の低い献体が好ましい。籍に核＃剤の
沸点は、ポリマーの俗解温腿（Ｔｓ）より２０℃以上高
い温度、例えば１２０〜２２０℃がより好ましい。なお
溶剤の節点温度に範囲がある場合、本発明ではｉ低温＆
をその溶剤の沸点とする。溶剤の沸点が低い場合は二軸
混練押出内で沸騰し易く、気泡の生成や原液の講度斑金
起こして好ましくない。溶剤の沸点が縞い場合は簡単な
乾燥による溶剤除去が難しく他の業剤による抽出などで
回収の費用が多くかかる。かかる溶剤はポリマーにより
異なるが、ポリオレフィン糸の場合は例えばノナン、デ
カン、ウンデカン、ドデカン、パラフィンなどの脂肪族
炭化水素、あるいはキシレン、デカリン、テトラリン、
ナフタリンなどの脂環族炭化水素、るるいは石油系ソル
ベントやジクロルベンゼンなどのノ・ロゲン化炭化水素
などがある。ポリ、ビニルアルコール系の場合は、ジ）
ｌ　ｆ　ル、（ルホキシド、水あるいはエチレンクリコ
ールやグリセリンなどの多価アルコール系があり、ポリ
アクリロニトリル系の場合はジメチルホルムアミド・、
ジメチルスルホキシドなどが考えられるが、本発明はこ
れらに限定されるものではない。Bol? -! - The bath agent that dissolves can be either a donated body or a solid body at different temperatures, but taking into account the removal and recovery of the solvent by drying, a donated body with a low boiling point is preferable. In particular, the boiling point of the core agent is preferably 20°C or more higher than the Ts of the polymer, for example 120 to 220°C. In addition, if the nodal temperature of the solvent has a range, in the present invention, i low temperature &
Let be the boiling point of the solvent. If the boiling point of the solvent is low, it will easily boil in the twin-screw kneading extruder, which is undesirable as it will cause the formation of air bubbles and the formation of rough spots in the stock solution. If the boiling point of the solvent is uneven, it is difficult to remove the solvent by simple drying, and recovery costs are high due to extraction with other chemicals. Such solvents vary depending on the polymer, but in the case of polyolefin threads, for example, aliphatic hydrocarbons such as nonane, decane, undecane, dodecane, and paraffin, or xylene, decalin, tetralin,
These include alicyclic hydrocarbons such as naphthalene, petroleum solvents, and chlorogenated hydrocarbons such as dichlorobenzene. In the case of poly or vinyl alcohol, di)
l f le, (sulfoxide, water, or polyhydric alcohols such as ethylene glycol and glycerin; in the case of polyacrylonitrile, dimethylformamide,
Dimethyl sulfoxide and the like may be considered, but the present invention is not limited thereto.

また他のポリマーに対しても本発明の要件を満たす溶剤
であれば有機溶剤でも無機溶剤でも何んら支障はない〇 本発明において採用できるポリマーの濃度は３〜５０重
量％で６る。３重量−未満では溶剤回収や生産量の低下
で不利であり、５０ＴＬｔ％を超えると不均一な溶解が
起こり易く、かつ本発明の目的である高強力で高モジュ
ラスな繊維′！几は成型物を得ることは難しい。原液粘
度は脱泡、均一溶解、安定吐出などの点で１０００〜５
００００ボイズが好ましく、該粘度範囲になるようにポ
リマーの分子量、濃度および二軸混練押出機の温度を設
定するのが良い。九だし、温度については高すぎるとポ
リマーの分解、架橋、着色などが起り易いので、溶解速
度の大きい範囲内で出来る限り低温に設定するのが望ま
しい。There is no problem with using other polymers, either organic or inorganic, as long as the solvent satisfies the requirements of the present invention. The concentration of the polymer that can be used in the present invention is 3 to 50% by weight6. If it is less than 3% by weight, it is disadvantageous due to solvent recovery and a decrease in production, and if it exceeds 50TLt%, non-uniform dissolution tends to occur, and the high strength and high modulus fiber' which is the object of the present invention! It is difficult to obtain molded products. The viscosity of the stock solution is 1000-5 in terms of defoaming, uniform dissolution, stable discharge, etc.
0,000 voids is preferred, and the molecular weight and concentration of the polymer and the temperature of the twin-screw kneading extruder are preferably set so as to fall within this viscosity range. However, if the temperature is too high, polymer decomposition, crosslinking, coloring, etc. are likely to occur, so it is desirable to set the temperature as low as possible within a range that allows a high dissolution rate.

ポリマーの分子量により最適濃度は異なり、ポリオレフ
ィン系の場合は生産性、均一溶解性および繊維または成
型物の性能の点から重量平均分子蓋１３０万ないし５０
０万で濃度５〜２０重量≠が好ましい。The optimum concentration varies depending on the molecular weight of the polymer, and in the case of polyolefins, the weight average molecular weight is 1.3 million to 50 million from the viewpoint of productivity, uniform solubility, and performance of fibers or molded products.
00,000 and a concentration of 5 to 20 weight≠ is preferable.

本発明において、該ポリマーと溶剤を二軸混練押出機に
供給する場合、各々別個に供給してもよいし、あらかじ
め両者を混合し次状態で供給してもよいが、いずれの場
合もＴａ−１０℃以下の温度にて供給する必要がある。In the present invention, when the polymer and the solvent are supplied to a twin-screw kneading extruder, they may be supplied separately, or they may be mixed in advance and supplied in the following state, but in either case, Ta- It is necessary to supply at a temperature of 10°C or less.

供給時のポリマーおよび／または溶剤の温度がＴｓ−１
０℃を超えるとポリマーの潤膨が起こり粘度の高い不均
一な塊りが生成し易く供給量の不安定化や原液の酸度斑
を紡発して好ましぐない。また上記の点から二軸混練押
出機の供給口の温度もポリマーの７０ツキング（膨＋１
４＠着による塊りの生成）を防ぐためにＴｓ−１０℃以
下の温度が望ましく、かつ溶解を促進する点でＴｓ−６
０℃以上の温度が好ましい。The temperature of the polymer and/or solvent at the time of supply is Ts-1
If the temperature exceeds 0°C, the polymer will swell, resulting in the formation of highly viscous and non-uniform lumps, making the supply amount unstable and producing acidity spots in the stock solution, which is undesirable. In addition, from the above point, the temperature at the feed port of the twin-screw kneading extruder should also be adjusted to 70 kg (swelling + 1
4@Ts-10℃ or lower is desirable to prevent formation of lumps due to adhesion, and Ts-6 in terms of promoting dissolution.
Temperatures above 0°C are preferred.

なお本発明にｄ９浴溶解始温度とは調製原液のポリマー
濃度と同じ濃度になるようにポリマーと溶剤を攪拌下で
混合し、３０分以内でポリマーが膨潤し粘性のめる状態
になる時の温度を意味する。In the present invention, the d9 bath melting temperature refers to the temperature at which the polymer swells and becomes viscous within 30 minutes when the polymer and solvent are mixed under stirring so that the concentration is the same as the polymer concentration in the prepared stock solution. means.

二軸混練押出機は少なくとも押出部と混線部を１セクシ
ョンずつイするもので、ポリマーの溶解速度を大きくシ
、かつポリマーの分解を抑える友めに最初の１又は２セ
クションの温度ｌｒ：最後の１父は２セクションの温度
より１０℃以上高くすることが望ましい。また供給口付
近はチッ素でポリマーの酸化分解を抑えると同時に、加
圧により溶剤の逆流ｆスクリュー受けからの漏れを防ぐ
のがよい。なお、二軸混練押出機を２基以上連続して用
いても二軸混練機と二軸押出機を別々に連続して用いて
も例んら支障ないが採算性の点では二軸混練押出機１基
で原液調製出来るのが望ましい。A twin-screw kneading extruder has at least one extrusion section and one cross-section section, and the temperature of the first or two sections is set to 1 to increase the dissolution rate of the polymer and to suppress the decomposition of the polymer. It is desirable that the temperature of the first section be at least 10°C higher than the temperature of the second section. Further, it is preferable to use nitrogen near the supply port to suppress oxidative decomposition of the polymer, and at the same time to prevent the solvent from leaking from the backflow f screw receiver by applying pressure. It should be noted that there is no problem in using two or more twin-screw kneading extruders in series or in consecutively using a twin-screw kneading machine and a twin-screw extruder separately, but from the point of view of profitability, twin-screw kneading extrusion is preferable. It is desirable to be able to prepare the stock solution with one machine.

スクリューは混線効果を十分維持させるために同方向浅
溝タイプで１００　ｒｐｍ以上の回転を有するものが好
ましい。バレル（本体）温度は’ｒｓ＋ｔｏ℃以上で、
かつ溶剤の沸点未満であることが好ましく、より好まし
くは、ＴＳｌ＋２０℃ないしＴｓ　＋７０℃でかつ溶剤
の沸点より少なくとも１０℃低い温度である。バレル温
度がＴｓ　＋１０℃未満ではポリマーの溶解が出来ない
かめるいは溶解に非常に時間かかかり採算性が悪くなり
、溶剤の沸点以上ではポリマーの分解や気泡の生成が激
しくなり好ましくない。The screws are preferably of the same direction shallow groove type and rotate at 100 rpm or more in order to sufficiently maintain the crosstalk effect. Barrel (body) temperature is above 'rs+to℃,
and is preferably below the boiling point of the solvent, more preferably at a temperature between TSl + 20°C and Ts + 70°C and at least 10°C lower than the boiling point of the solvent. If the barrel temperature is less than Ts + 10°C, the polymer cannot be dissolved or it takes a very long time to dissolve, making it unprofitable. If the barrel temperature is above the boiling point of the solvent, the polymer will decompose and bubbles will be violently generated, which is undesirable.

バレル内での原液の滞留時間は１〜ｌＯ分、好ましくは
３〜６分である。滞留時間を１分未満にすることは溶解
混練が不十分となり均一な静液を得ることは難しく１０
分を超えると、ポリマーの分解や吐出量低下による採算
性の悪化などの欠点が現われる。滞留時間を左右する要
因としては混練部の数やスクリューエレメントの形状、
供給量スクリュー径と長さの比ＣＬ／Ｄ）などが考えら
れるＯ また二軸混練押出機の先端にはダイを設置し原液をスト
ランド状またはスリット状に押出して、紡糸ノズルへ送
液して繊維化したりフィルム状に成型することが可能で
あるが、安定吐出および脱泡の点で押出機の先端圧は５
１ｗ／ｄ　以上であることが望ましい０ ま之、バレル本体に設置したベントロより弱い吸引など
で原液を脱泡することは得られる製品の品質同上の点で
より好ましい０ 以上説明したように本願発明は連続方式で高分子量ポリ
マーの均一溶解原液をつくるのに直接ポリマーと溶剤金
二細混練押出機に供給し、バレル温度や原液の滞留時間
を規制し、さらに原液粘度でポリマーの分子量と濃度を
規制することで可能とし、それによって安価で品質の良
い高強力および高モジュラス繊維またはフィルム等の成
型物を得ることを可能にしｔものでめる。The residence time of the stock solution in the barrel is 1 to 10 minutes, preferably 3 to 6 minutes. If the residence time is less than 1 minute, dissolution and kneading will be insufficient and it will be difficult to obtain a uniform static liquid10
If it exceeds 10 minutes, disadvantages such as deterioration of profitability due to decomposition of the polymer and decrease in discharge amount will appear. Factors that affect residence time include the number of kneading sections, the shape of the screw element,
Supply amount (screw diameter to length ratio CL/D), etc. can be considered.O In addition, a die is installed at the tip of the twin-screw kneading extruder to extrude the stock solution in a strand shape or slit shape, and send it to the spinning nozzle. It is possible to make it into fibers or form it into a film, but the tip pressure of the extruder must be 5 to ensure stable discharge and defoaming.
1 w/d or more is preferable. However, defoaming the stock solution with weaker suction than the vent installed in the barrel body is more preferable in terms of the quality of the obtained product. As explained above, the present invention In order to create a uniformly dissolved stock solution of a high molecular weight polymer using a continuous method, the polymer and solvent are directly fed to a two-fine kneading extruder, the barrel temperature and residence time of the stock solution are regulated, and the molecular weight and concentration of the polymer are controlled by the viscosity of the stock solution. This makes it possible to obtain molded products such as high-strength and high-modulus fibers or films at low cost and of good quality.

く実施例〉 以下に本発明上実施例により具体的に説明する。Example The present invention will be specifically explained below using Examples.

実施例１ 重量平均分子量が１５０万のポリエチレン粉末と酸化防
止剤（ポリエチレンに対し１ｍ１ｔ＝Ａ）と全沸点が１
８５〜２１０℃の石油系ノルベントにポリエチレン濃度
が１５重量慢になるようにスラリ一槽へ投入し１１０℃
にて混合して分散液を作成した。該分散液中のポリエチ
レンは膨潤せず攪拌全停止すると溶剤と要分４を起こす
状態でめり、ポリマーの溶解開始温度は１２３℃であつ
几。Example 1 Polyethylene powder with a weight average molecular weight of 1.5 million, an antioxidant (1 m1t = A for polyethylene) and a total boiling point of 1
Pour petroleum-based norbent at 85 to 210°C into a slurry tank so that the polyethylene concentration is 15% by weight, and then add it to a slurry tank at 110°C.
A dispersion liquid was prepared by mixing. The polyethylene in the dispersion did not swell and when the stirring was completely stopped, it was mixed with the solvent in a state where the polymer melted at a temperature of 123°C.

該分散赦ｔ−撹拌しながら４，２ｋｐＡｌｒの供給量で
二軸混練押出機の供給口に添加し、以下の条件で原液の
連続調製を行なった。While stirring the dispersion, a supply amount of 4.2 kp Alr was added to the supply port of a twin-screw kneading extruder, and a stock solution was continuously prepared under the following conditions.

Ｏスクリュー径：３６φ（Ｌ／Ｄ＝　３６　）○スクリ
ューデザイン：同方同浅碑タイプで押出部が３カ所、混
線部が２ カ所あり５つのセクショ ン金有する。O Screw diameter: 36φ (L/D = 36) ○ Screw design: Same-sided and shallow type with 3 extrusion parts, 2 cross-connection parts, and 5 sections.

Ｏスクリュー回転数：２００ｒｐｍ Ｏ供給ロ二Ｎ２シールをしながら１１０℃に加熱ｏバレ
ル（本体）温度：第１および第２セクションは１７５℃
、第３ないし ｇ５セクションは１６０℃ Ｏ原液加留時間＝４．２分 ０先端圧：　２０〜５０　ｋｐ／ｃｄ Ｏ脱泡：先端近くのベントロより０１１１１）ＣＩｌ〜
−５０ｍ陽の吸引で脱泡 孔径４ｍで３ホールのダイより吐出された原液は均一透
明なもので着色や気泡もなく、粘度は約５０００ボイズ
で紡糸可能なものであった。該原液をギヤポンプで酎貴
し、６５ｒ／分の・吐出電で２４ホールの紡糸ノズルよ
り押出し、冷却風によりゲル化して繊維化し友。O screw rotation speed: 200 rpm O supply Roni Heat to 110°C while sealing N2 O barrel (main body) temperature: 175°C for 1st and 2nd sections
, 3rd to g5 sections are 160°C O stock solution retention time = 4.2 minutes 0 Tip pressure: 20 to 50 kp/cd O defoaming: from the vent near the tip 01111) CIl~
The stock solution discharged from a 3-hole die with a defoaming hole diameter of 4 m under suction of -50 m positive was uniformly transparent, had no coloration or air bubbles, and had a viscosity of approximately 5000 voids, allowing spinning. The stock solution is distilled with a gear pump, extruded through a 24-hole spinning nozzle with a discharge current of 65 r/min, and gelled with cooling air to form fibers.

捲取速度１５ｍ／分にて連続４日間紡糸を行なったが断
糸は１度もなく、フィルター詰りによる紡糸ヘッド圧の
上昇ｕｌｔとんど見られなかつｆＣ。Spinning was carried out for 4 consecutive days at a winding speed of 15 m/min, but there was no yarn breakage, and no increase in spinning head pressure due to filter clogging was observed.

紡糸ノズルより吐出されｔ原ｇ、を採取し、溶剤飛散前
俊の重量測定により４日間のポリエチレン濃度全算出し
たが１０±０．１５％とほぼ一尼値を示した。また得ら
れた紡糸原糸のデニール変ＩＩＪＪ率を測定したところ
２％以内で低く均一な原液が得られていることが判明し
た。The raw material g discharged from the spinning nozzle was collected, and the total polyethylene concentration over 4 days was calculated by measuring the weight before the solvent was blown away, and it showed a value of approximately 10% ± 0.15%. Furthermore, when the denier variable IIJJ ratio of the obtained spun yarn was measured, it was found that a uniform stock solution was obtained with a low denier ratio of 2% or less.

さらに紡糸原糸を１３５℃のデカリンに０．０５ｒ／１
００−溶解し粘度を測定して、３点法により極限粘度〔
マ〕を求めてみたが４日間で大きな変動はなくポリマー
の分解などによる重合度低下は見られなかった。Furthermore, the spun yarn was soaked in decalin at 135°C at 0.05 r/1.
00-Dissolve and measure the viscosity, and use the three-point method to determine the intrinsic viscosity [
There was no significant change over 4 days, and no decrease in the degree of polymerization due to decomposition of the polymer was observed.

さらに分子鎖の切断やからみ度合の差からくる延伸性お
よび繊維性能の変動をみたが１５日間の連続延伸でも羽
捲付きは３回めったが断糸はなく強度２（１／ｄ以上、
モジュラス７００　ｆ／ｄ以上の延伸糸が安定して得ら
れることが判明した。Furthermore, we looked at the variations in drawability and fiber performance caused by molecular chain scission and differences in the degree of entanglement, and even after 15 days of continuous drawing, there were only 3 cases of winding, but there was no yarn breakage, and the strength was 2 (1/d or more,
It was found that a drawn yarn with a modulus of 700 f/d or more could be stably obtained.

実施例２ 重量平均分子量が８４万のポリビニルアルコール５ｍ１
ｔ部と沸点が１９８℃のエチレングリコール９２重量部
を別々に室温にてスクリュー径６０φの二軸混練押出機
に供給した。供給口温度は１２０℃でありバレル内は押
出部−７工も練酩−押出部の３つのセクンヨ／に分かｎ
ｌすべてのセクションを１６０℃に加熱し連続的に醪解
混＃！を行なつ之０赤色の低分子菫ポリビニルアルコー
ルチップを用いて７ｆｔｔ　１１時間を測定したところ
２．７分であった。Example 2 5 ml of polyvinyl alcohol with a weight average molecular weight of 840,000
Part t and 92 parts by weight of ethylene glycol having a boiling point of 198°C were separately supplied at room temperature to a twin-screw kneading extruder with a screw diameter of 60φ. The supply port temperature is 120°C, and the inside of the barrel is divided into three sections: extrusion section, kneading section, and extrusion section.
lHeat all sections to 160℃ and mix continuously! Using a red low-molecular violet polyvinyl alcohol chip, 7ftt 11 hours was measured and the time was 2.7 minutes.

なおポリビニルアルコールの溶解開始温度は１３８℃で
あった。Note that the melting start temperature of polyvinyl alcohol was 138°C.

吐出される原液は均一透明で禾溶解物や分解物は見られ
ず粘度は約３０００ボイズでめつｆｃＯ’！九最初は気
泡を多く含んでいたが押出機の先端圧が約４０時／ｃｄ
であり、ベントロを開けることにより脱泡さ−ｎｆｃ原
液が得られた。The discharged stock solution is uniform and transparent, with no visible dissolved or decomposed substances, and a viscosity of approximately 3000 voids, which is extremely low. 9. Initially, it contained a lot of air bubbles, but the pressure at the tip of the extruder was about 40 hours/cd.
By opening the vent, a defoamed NFC stock solution was obtained.

該原液を２００ホールの紡糸ノズルより押出し、冷却固
化して繊維化した。吐出量２８０１１分、捲取速度３０
ｍ／分にて１ｉ！！間紡糸しｔが単糸切れが１度あつ九
だけで紡糸性は非常に良好でおつ九。ま之４時間毎にポ
リビニルアルコールの濃度を測定したが８十０．０９％
とほとんど変動していない事が判明した。′ 紡糸時に原糸をメタノール浴に入れて溶剤のエチレング
リコール金はとんど抽出し、約４０℃の熱風によりメタ
ノールを飛散させて捲取った。得られ次紡糸原糸を、ヒ
ーターを用いローラー間で２５倍の延伸ｔ−２０日間行
なつ九が毛羽捲付３回および断糸１回がめったが、延伸
の張力変動も少なく＃よぼ均一な紡糸原糸であることが
裏付けられ友。ま次延伸糸のデニール変動率も３分以内
と低く強度は１７〜２０　ｆ／ｄ　１モジユラスは３５
・０〜４５０ｔ／ｄであり、高強力で高モジュラスなポ
リビニルアルコール繊維が得られ次。The stock solution was extruded through a 200-hole spinning nozzle, cooled and solidified to form fibers. Discharge amount 28011 minutes, winding speed 30
1i at m/min! ! During inter-spinning, there was only one single yarn breakage, and the spinnability was very good. The concentration of polyvinyl alcohol was measured every 4 hours and it was 80.09%.
It turned out that there was almost no change. ' At the time of spinning, the raw yarn was placed in a methanol bath to extract most of the ethylene glycol gold solvent, and the methanol was blown away with hot air at about 40°C before winding. The obtained next spun raw yarn was stretched 25 times between rollers using a heater for 20 days. Although it was rarely fluffed 3 times and yarn was broken once, the tension fluctuation during stretching was small and the yarn was almost uniform. It is confirmed that it is a spinning yarn. The denier fluctuation rate of the multi-drawn yarn is as low as within 3 minutes, and the strength is 17 to 20 f/d, and the 1 modulus is 35.
・0 to 450 t/d, high strength and high modulus polyvinyl alcohol fibers are obtained.

実施例３ 重量平均分子ｆｉ５００万のポリプロピレンｔ−ａ度２
５重量％になるように沸点が１８７〜１９６℃のデカリ
／に添加し、両者を１２０℃で混合攪拌して分散液を作
成した。Example 3 Polypropylene with weight average molecular fi 5 million t-a degree 2
The mixture was added to Decali having a boiling point of 187 to 196° C. in an amount of 5% by weight, and both were mixed and stirred at 120° C. to prepare a dispersion.

該分散液を攪拌しながらスクリュー径６０φの二軸混練
押出機に連続画に供給した。なおポリマａピレンの溶解
開始温度は１３３℃であった。The dispersion was continuously fed to a twin-screw kneading extruder with a screw diameter of 60φ while stirring. Note that the melting start temperature of the polymer a-pyrene was 133°C.

供給口温度は１２０℃でバレル内は押出部３カ所と、混
線部２カ所の５つのセクションに分か扛最初の押出部と
混線部の２つのセクションの温度を１８０℃、他の３つ
のセクションの温度・と１６５℃にし友。なお原液の滞
留時間は７．４分であり、粘度が約３００００ポイズと
高く気泡を多くよんでい友ので、ベントロより脱泡し次
。得られた原液をスリットノズルより押出し水中で冷却
固化した後、溶剤金倉んだシート状のもの金、熱風炉中
で二方向に延伸しながら溶剤を蒸発させた。The supply port temperature is 120℃, and the inside of the barrel is divided into 5 sections: 3 extrusion sections and 2 cross-conducting sections.The temperature of the first extrusion section and the cross-conducting section is 180℃, and the temperature of the other 3 sections is 180℃. The temperature is set to 165℃. The residence time of the stock solution was 7.4 minutes, and the viscosity was high at about 30,000 poise, which caused a lot of bubbles, so it was degassed from the vent. The obtained stock solution was extruded through a slit nozzle, cooled and solidified in water, and then a sheet-like material filled with solvent was stretched in two directions in a hot air oven to evaporate the solvent.

得られたフィルムは気泡や異物（未溶解粒ンなどがなく
、厚さもほぼ均一で、引裂強力も従来にない大きな値を
示し次。The resulting film was free of air bubbles and foreign matter (undissolved particles, etc.), had a nearly uniform thickness, and exhibited unprecedented tear strength.

比較例１ｊ？よび２ 比較例１として実施例１でスクリューデザインを押出部
が２カ所、混線部を１カ所の３つのセクションを有する
ものにし原液の滞留時間を５０秒して、吐出量増大を試
みたが吐出され次原液にはポリマーの透明な塊状物が点
在し、濃度斑を起こしていることが判明しｆｌ＝６ 比較例２として、実施例２でバレル温度ヲ２０５℃にし
たところ吐出された原液は黄褐色に着色し紡糸原糸のポ
リマー分子量は溶解前のポリマー分子量に対し約１／２
に低下し次。Comparative example 1j? 2 As Comparative Example 1, an attempt was made to increase the discharge amount by changing the screw design of Example 1 to have three sections, two extrusion sections and one cross-conducting section, and increasing the residence time of the stock solution to 50 seconds, but the discharge amount was It was found that the stock solution was dotted with transparent lumps of polymer, causing concentration unevenness. is colored yellowish brown, and the polymer molecular weight of the spun yarn is approximately 1/2 of the polymer molecular weight before dissolution.
The next drop.

延伸倍率も１５倍と低く延伸糸の強度はｌ　Ｑ　ｆ／ｄ
であった。The drawing ratio is as low as 15 times, and the strength of the drawn yarn is l Q f/d.
Met.

Claims (1)

【特許請求の範囲】 １、重量平均分子量が２０万以上の高分子量ポリマーを
溶剤に３〜５０重量％均一溶解させる方法において、該
ポリマーと溶剤を別々にまたはあらかじめ少なくともポ
リマーの溶解開始温度（Ｔｓ）より１０℃低い温度で両
者を混合して、二軸混練押出機に連続供給し、少なくと
もＴｓより１０℃高い温度でかつ溶剤の沸点未満の温度
で１〜１０分間溶解混練し、均一溶解原液にすることを
特徴とする高分子量ポリマー原液の連続調製法。 ２、特許請求の範囲第１項において、該均一溶解原液の
粘度が１０００〜５００００ポイズになるようにポリマ
ーの分子量、濃度および二軸混練押出機の温度を設定す
ることを特徴とする高分子量ポリマー原液の連続調製法
。 ３、特許請求の範囲第１ないし２項において、二軸混練
押出機の供給口の温度をＴｓ−１０℃以下にしてポリマ
ーのブロッキングを防止することを特徴とする高分子量
ポリマー原液の連続調製法。 ４、特許請求の範囲第１ないし３項において、該ポリマ
ーが重量平均分子量が８０万以上のポリオレフィン系ポ
リマーであることを特徴とする高分子量ポリマー原液の
連続調製法。 ５、特許請求の範囲第１ないし３項において、該ポリマ
ーが重量平均分子量が４０万以上のポリビニルアルコー
ル系ポリマーであることを特徴とする高分子量ポリマー
原液の連続調製法。 ６、特許請求の範囲第１ないし３項において、該ポリマ
ーが重量平均分子量が４０万以上のポリアクリロニトリ
ル系ポリマーであることを特徴とする高分子量ポリマー
原液の連続調製法。 ７、特許請求の範囲第１ないし６項において、該溶剤は
１２０〜２２０℃の沸点を有する室温で液体のものであ
り二軸混練押出機のバレル温度がＴｓ＋２０℃ないしＴ
ｓ＋７０℃でかつ該溶剤の沸点より少なくとも１０℃低
い温度であることを特徴とする高分子量ポリマー原液の
連続調製法。 ８、特許請求の範囲第１ないし７項において、二軸混練
押出機は少なくとも押出部と混練部を１セクションずつ
有しかつ最初の１又は２セクションの温度が最後の１又
は２セクションの温度より１０℃以上高いことを特徴と
する高分子量ポリマー原液の連続調製法。[Scope of Claims] 1. In a method of uniformly dissolving 3 to 50% by weight of a high molecular weight polymer having a weight average molecular weight of 200,000 or more in a solvent, the polymer and the solvent may be dissolved separately or in advance at least at the dissolution start temperature (Ts) of the polymer. ) are mixed at a temperature 10°C lower than Ts, continuously fed to a twin-screw kneading extruder, and melted and kneaded for 1 to 10 minutes at a temperature at least 10°C higher than Ts and below the boiling point of the solvent to form a uniformly dissolved stock solution. A method for continuously preparing a high molecular weight polymer stock solution. 2. A high molecular weight polymer according to claim 1, characterized in that the molecular weight and concentration of the polymer, and the temperature of the twin-screw kneading extruder are set so that the viscosity of the uniformly dissolved stock solution is 1,000 to 50,000 poise. Continuous preparation method of stock solution. 3. A continuous preparation method for a high molecular weight polymer stock solution according to claims 1 or 2, characterized in that the temperature at the feed port of the twin-screw kneading extruder is set to Ts-10°C or lower to prevent blocking of the polymer. . 4. A method for continuously preparing a high molecular weight polymer stock solution according to claims 1 to 3, wherein the polymer is a polyolefin polymer having a weight average molecular weight of 800,000 or more. 5. A method for continuously preparing a high molecular weight polymer stock solution according to claims 1 to 3, wherein the polymer is a polyvinyl alcohol polymer having a weight average molecular weight of 400,000 or more. 6. A method for continuously preparing a high molecular weight polymer stock solution according to claims 1 to 3, wherein the polymer is a polyacrylonitrile polymer having a weight average molecular weight of 400,000 or more. 7. In claims 1 to 6, the solvent has a boiling point of 120 to 220°C and is liquid at room temperature, and the barrel temperature of the twin screw extruder is between Ts+20°C and Ts.
A process for the continuous preparation of a high molecular weight polymer stock solution, characterized in that the temperature is at +70°C and at least 10°C lower than the boiling point of the solvent. 8. In claims 1 to 7, the twin-screw kneading extruder has at least one extrusion section and one kneading section, and the temperature of the first one or two sections is higher than the temperature of the last one or two sections. A continuous preparation method for a high molecular weight polymer stock solution characterized by a temperature higher than 10°C.