JPH08218216A - Production of biodegradable monofilament - Google Patents
Production of biodegradable monofilamentInfo
- Publication number
- JPH08218216A JPH08218216A JP2787095A JP2787095A JPH08218216A JP H08218216 A JPH08218216 A JP H08218216A JP 2787095 A JP2787095 A JP 2787095A JP 2787095 A JP2787095 A JP 2787095A JP H08218216 A JPH08218216 A JP H08218216A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- temperature
- monofilament
- spinneret pack
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリヒドロキシアルカ
ノエート類重合体から、漁網、海苔網、ロープ等の産業
資材用として好適な微生物分解性モノフィラメントを製
造する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a biodegradable monofilament suitable for industrial materials such as fishing nets, seaweed nets and ropes from polyhydroxyalkanoate polymers.
【０００２】[0002]
【従来の技術】従来、漁業や農業、土木用として用いら
れる産業資材用繊維としては、強度及び耐候性の優れた
ものが要求されており、主としてポリアミド、芳香族ポ
リエステル、ビニロン、ポリオレフィン等からなるもの
が使用されている。しかし、これらの繊維は自己分解性
がなく、使用後、野山や海に放置されると、景観を損な
うばかりでなく、鳥や海洋生物、ダイバー等に絡み付い
て殺傷したり、船のスクリューに絡み付いて船舶事故を
起こしたりするという問題があった。この問題は、使用
後、焼却、埋め立てあるいは回収再生により処理すれば
解決されるが、これらの処理には多大な費用を要するた
め、現実には野山や海に放置されているのが実情であ
る。2. Description of the Related Art Conventionally, fibers having excellent strength and weather resistance have been required as fibers for industrial materials used for fishing, agriculture and civil engineering, and mainly consist of polyamide, aromatic polyester, vinylon, polyolefin and the like. Things are being used. However, these fibers are not self-degrading, and if left unused in the mountains or the sea after use, they not only damage the landscape, but also entangle and kill birds and marine life, divers, etc., or entangle with the ship's screw. There was a problem of causing a ship accident. This problem can be solved by incineration, landfilling, or recovery and recycling after use, but since such processing requires a great deal of money, it is actually left in the mountains or the sea. .
【０００３】そこで、このような問題を解決する方法と
しては、微生物分解性の素材を用いることが考えられ、
種々の微生物分解性繊維が提案されている。例えば、ポ
リヒドロキシアルカノエート類重合体は、優れた微生物
分解性を有し、これを繊維化することが試みられている
（特開平５− 76354号、同５− 76355号、同５−321025
号等）。しかし、ポリヒドロキシアルカノエート類重合
体は、硬くて脆い性質を有していたり、結晶化速度が小
さかったりして、繊維を安定して製造することが困難で
あった。Therefore, as a method for solving such a problem, it is considered to use a material which is biodegradable,
Various biodegradable fibers have been proposed. For example, polyhydroxyalkanoate polymers have excellent microbial degradability, and it has been attempted to make them into fibers (JP-A-5-76354, JP-A-5-76355, and JP-A-5-321025).
No.). However, the polyhydroxyalkanoate polymer has a property of being hard and brittle, and has a low crystallization rate, so that it is difficult to stably produce a fiber.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、ポリヒドロ
キシアルカノエート類重合体から、漁網、海苔網、ロー
プ等の産業資材用として好適なモノフィラメントを安定
して製造することができる方法を提供しようとするもの
である。DISCLOSURE OF THE INVENTION The present invention provides a method for stably producing a monofilament suitable for industrial materials such as fishing nets, seaweed nets and ropes from polyhydroxyalkanoate polymers. It is what
【０００５】[0005]
【課題を解決するための手段】本発明者らは、この課題
を解決するため鋭意検討の結果、溶融紡糸時の溶融温
度、溶融時間、紡糸口金パック内での剪断速度、紡出糸
条の冷却固化及び結晶化温度、冷却固化及び結晶化時間
を厳密に制御することによって円滑な溶融紡糸、延伸が
可能で、良好なモノフィラメントを安定して製造するこ
とが可能となることを見出し、本発明に到達した。Means for Solving the Problems As a result of intensive studies to solve this problem, the present inventors have found that the melt temperature during melt spinning, the melting time, the shear rate in the spinneret pack, the spinning yarn It has been found that smooth melt spinning and stretching are possible by strictly controlling the cooling and solidification and crystallization temperature, and the cooling and solidification and crystallization time, and it becomes possible to stably produce a good monofilament, and the present invention Reached
【０００６】すなわち、本発明の要旨は、次のとおりで
ある。That is, the gist of the present invention is as follows.
【０００７】重量平均分子量が40万以上のポリヒドロキ
シアルカノエート類重合体をエクストルーダーに供給し
て溶融紡糸し、延伸して微生物分解性モノフィラメント
を製造するに際し、重合体を温度（Ｔｍ＋15）〜（Ｔｍ
＋50）℃〔Ｔｍは重合体の融点（℃）〕で６分間以内で
溶融し、溶融した重合体を温度Ｔｍ〜（Ｔｍ＋20) ℃の
紡糸口金パックに導入し、紡糸口金パック内濾過層直上
での剪断速度が２×10-2／秒以上、紡糸口金パック内滞
留時間が２分間以内となる条件で紡出し、温度（Ｔｃ−
10）〜（Ｔｃ＋10）℃〔Ｔｃは重合体の結晶化温度
（℃）〕の液体浴中で５〜10秒間冷却固化及び結晶化を
行った後、巻き取ることなしに延伸することを特徴とす
る微生物分解性モノフィラメントの製造法。なお、重合
体の重量平均分子量は、 Waters 社製 Waters-600E、41
0 示差屈折検出器システムのG.P.C.装置で、0.25重量％
クロロホルム溶液、流出速度0.8m／分の条件下で、標準
ポリスチレンに換算して、算出した値である。また、重
合体の融点Ｔｍ及び結晶化温度Ｔｃは、Perkin-Elmer社
製 DSC-7型示差走査型熱量計で、窒素雰囲気下、昇降温
速度10℃／分の条件で測定した値である。When a polyhydroxyalkanoate polymer having a weight average molecular weight of 400,000 or more is supplied to an extruder, melt-spun and stretched to produce a biodegradable monofilament, the polymer is heated at a temperature (Tm + 15) to ( Tm
+50) ° C. [Tm is the melting point (° C.) of the polymer] within 6 minutes, and the molten polymer is introduced into a spinneret pack at a temperature of Tm to (Tm + 20) ° C. and immediately above the filtration layer in the spinneret pack. Spinning at a shear rate of 2 × 10 -2 / sec or more and a residence time in the spinneret pack of 2 minutes or less at a temperature (Tc-
10) to (Tc + 10) ° C. [Tc is the crystallization temperature (° C.) of the polymer] In a liquid bath, the mixture is cooled and solidified for 5 to 10 seconds, and then crystallized, and then stretched without winding. Method for producing biodegradable monofilament. The weight average molecular weight of the polymer is Waters-600E, 41
0 0.25 wt% in GPC device of differential refraction detector system
It is a value calculated by converting to a standard polystyrene under the conditions of a chloroform solution and an outflow rate of 0.8 m / min. Further, the melting point Tm and the crystallization temperature Tc of the polymer are values measured by a Perkin-Elmer DSC-7 type differential scanning calorimeter under a nitrogen atmosphere at a temperature rising / falling rate of 10 ° C./min.
【０００８】以下、本発明について詳細に説明する。The present invention will be described in detail below.
【０００９】本発明におけるポリヒドロキシアルカノエ
ート類重合体としては、ポリ−３−ヒドロキシプロピオ
ネート、ポリ−３−ヒドロキシブチレート、ポリ−３−
ヒドロキシカプロレート、ポリ−３−ヒドロキシヘプタ
ノエート、ポリ−３−ヒドロキシオクタノエート及びこ
れらとポリ−３−ヒドロキシバリレートやポリ−４−ヒ
ドロキシブチレートとの共重合体が挙げられ、これらは
通常微生物が産生する微生物ポリエステルとして得られ
る。この中で製糸性の面から最も好ましいものはポリ−
３−ヒドロキシブチレートとポリ−３−ヒドロキシバリ
レートとの共重合体（３−ヒドロキシブチレート単位と
３−ヒドロキシバリレート単位とからなる共重合体）で
ある。The polyhydroxyalkanoate polymers in the present invention include poly-3-hydroxypropionate, poly-3-hydroxybutyrate and poly-3-.
Examples thereof include hydroxycaprolate, poly-3-hydroxyheptanoate, poly-3-hydroxyoctanoate and copolymers of these with poly-3-hydroxyvalerate and poly-4-hydroxybutyrate. Is usually obtained as a microbial polyester produced by microorganisms. Of these, the most preferable from the viewpoint of spinnability is poly-
It is a copolymer of 3-hydroxybutyrate and poly-3-hydroxyvalerate (copolymer composed of 3-hydroxybutyrate unit and 3-hydroxyvalerate unit).
【００１０】また、上記重合体には、結晶化の促進の目
的で、窒化硼素、二酸化チタン、シリカ、タルクのよう
な結晶核剤を 0.1〜５重量％、好ましくは 0.5〜２重量
％含有させることが望ましい。さらに、流動性向上の目
的で、トリアセチンのような可塑剤を１〜20重量％含有
させることも好ましい。Further, the above polymer contains 0.1 to 5% by weight, preferably 0.5 to 2% by weight, of a crystal nucleating agent such as boron nitride, titanium dioxide, silica or talc for the purpose of promoting crystallization. Is desirable. Further, for the purpose of improving fluidity, it is also preferable to contain a plasticizer such as triacetin in an amount of 1 to 20% by weight.
【００１１】ポリヒドロキシアルカノエート類重合体
は、重量平均分子量が40万以上のものであることが必要
で、特に重量平均分子量が42万以上で、多分散度（重量
平均分子量／数平均分子量) が３以下のものが好まし
い。重量平均分子量が40万未満あるいは分子量分布の広
いものは、溶融重合体の流動性が悪かったり、溶融時の
粘度が低くなるため、ドラフト切れを起こしたりして製
糸性が悪く、また、高延伸倍率での延伸が不可能であ
る。The polyhydroxyalkanoate polymer is required to have a weight average molecular weight of 400,000 or more, particularly a weight average molecular weight of 420,000 or more, and a polydispersity (weight average molecular weight / number average molecular weight). Is preferably 3 or less. A polymer having a weight average molecular weight of less than 400,000 or a wide molecular weight distribution has poor fluidity of the melt polymer or has a low viscosity at the time of melting, resulting in draft breakage and poor spinnability, and high stretching. Stretching at a magnification is impossible.
【００１２】本発明においては、まず、ポリヒドロキシ
アルカノエート類重合体をエクストルーダーに供給し、
温度（Ｔｍ＋15）〜（Ｔｍ＋50）℃で６分間以内で溶融
し、計量ポンプを経て紡糸口金パックに導入する。この
溶融温度が低すぎると重合体を完全に溶融させることが
困難であるとともに、溶融粘度が高く、定量供給が困難
となる。一方、この温度が高すぎると重合体が熱分解を
起こし、好ましくない。また、溶融時間（重合体をエク
ストルーダーに供給してから溶融重合体を計量ポンプに
送り込むまでの時間）は６分以内とすることが必要であ
る。溶融時間が長すぎると重合体が熱分解を起こし、好
ましくない。In the present invention, first, a polyhydroxyalkanoate polymer is supplied to an extruder,
It melts at a temperature (Tm + 15) to (Tm + 50) ° C. within 6 minutes, and is introduced into a spinneret pack through a metering pump. If the melting temperature is too low, it is difficult to completely melt the polymer, and the melt viscosity is high, which makes it difficult to supply a fixed amount. On the other hand, if this temperature is too high, the polymer undergoes thermal decomposition, which is not preferable. Further, the melting time (the time from the feeding of the polymer to the extruder to the feeding of the molten polymer to the metering pump) must be within 6 minutes. If the melting time is too long, the polymer is thermally decomposed, which is not preferable.
【００１３】紡糸口金パックの温度は、Ｔｍ〜（Ｔｍ＋
15) ℃とすることが必要である。この温度がＴｍより低
ければ、重合体が固化するため紡糸が不可能であり、こ
の温度が高すぎると、溶融粘度が低くなりすぎ、ノズル
から吐出される溶融重合体の線速度が速くなり、冷却固
化及び結晶化が困難になるとともに、紡出糸条が自重に
より糸切れして紡糸が不可能となる。The temperature of the spinneret pack is from Tm to (Tm +
15) It is necessary to set the temperature to ℃. If this temperature is lower than Tm, spinning is not possible because the polymer solidifies. If this temperature is too high, the melt viscosity becomes too low and the linear velocity of the molten polymer discharged from the nozzle becomes high, It becomes difficult to solidify by cooling and crystallize, and the spun yarn breaks due to its own weight, making spinning impossible.
【００１４】さらに、紡糸口金パック内濾過層直上での
溶融重合体の剪断速度が２×10-2／秒以上、紡糸口金パ
ック内滞留時間が２分間以内となる条件で紡出すること
が必要である。Further, it is necessary to carry out spinning under the conditions that the shear rate of the molten polymer immediately above the filtration layer in the spinneret pack is 2 × 10 -2 / sec or more and the residence time in the spinneret pack is 2 minutes or less. Is.
【００１５】ここで、剪断速度γは次式で規定される。 γ＝ (32ｑ／ρ) ／πＤ3 ｑは紡糸口金パック内濾過層を単位時間当たり通過する
溶融重合体の量（ｇ／秒）、ρは溶融重合体の密度 (ｇ
／cm3)、Ｄは紡糸口金パック内濾過層の直径（cm) を表
す。The shear rate γ is defined by the following equation. γ = (32q / ρ) / πD 3 q is the amount (g / sec) of the molten polymer passing through the filtration layer in the spinneret pack per unit time, and ρ is the density (g) of the molten polymer
/ Cm 3 ), D represents the diameter (cm) of the filtration layer in the spinneret pack.
【００１６】この剪断速度が小さすぎると、溶融重合体
の一部が紡糸口金パック内に長時間滞留、残存する結
果、紡糸口金パック内での溶融重合体の流動性が低下
し、最終的に紡糸口金パック内で溶融重合体が塊状にな
ってしまう。そのため、滞留ポリマーの熱分解も起こ
り、紡糸過程において熱分解物あるいは塊状物が突発的
に溶融重合体中に混入し、製糸性の悪化をもたらす。If the shear rate is too low, a part of the molten polymer remains and remains in the spinneret pack for a long time, resulting in a decrease in the fluidity of the molten polymer in the spinneret pack, and finally The molten polymer becomes agglomerated in the spinneret pack. Therefore, the retained polymer is also thermally decomposed, and the thermally decomposed product or the agglomerate is abruptly mixed in the molten polymer in the spinning process, resulting in deterioration of the spinnability.
【００１７】また、紡糸口金パック内滞留時間が長すぎ
ると、重合体が熱分解を起こし、製糸性が悪化する。If the residence time in the spinneret pack is too long, the polymer is thermally decomposed and the spinnability deteriorates.
【００１８】次に、紡出されたモノフィラメントは、温
度（Ｔｃ−10）〜（Ｔｃ＋10）℃の液体浴中で５〜10秒
間冷却固化及び結晶化が行われる。液体浴としては、
水、エチレングリコール、ポリエチレングリコール、グ
リセリン、シリコーン等が使用できる。しかし、液体浴
は高温にする必要がないので、作業性が良く、モノフィ
ラメントに付着した液体の除去の問題がなく、液体の粘
性によるモノフィラメントへの引張抵抗が小さい水を使
用するのが最も好ましい。Next, the spun monofilament is cooled and solidified and crystallized in a liquid bath at a temperature (Tc-10) to (Tc + 10) ° C. for 5 to 10 seconds. As a liquid bath,
Water, ethylene glycol, polyethylene glycol, glycerin, silicone, etc. can be used. However, since the liquid bath does not need to be heated to a high temperature, it is most preferable to use water which has good workability, has no problem of removing the liquid adhering to the monofilament, and has a small tensile resistance to the monofilament due to the viscosity of the liquid.
【００１９】冷却固化及び結晶化の温度が低すぎると、
ポリヒドロキシアルカノエート類重合体は結晶化速度が
小さいため、結晶化が十分進行せず、得られる未延伸モ
ノフィラメントは粘着性を示すものとなり、また、小さ
な外力で未延伸モノフィラメントの切断が起こり、延伸
が不可能となる。一方、この温度が高すぎると、冷却不
足で、かつ結晶化が進行しないため、モノフィラメント
とローラとの密着等の問題で未延伸モノフィラメントを
得ることが困難となる。If the temperature of cooling and solidification and crystallization is too low,
Since the polyhydroxyalkanoate polymer has a low crystallization rate, the crystallization does not proceed sufficiently, the resulting unstretched monofilament exhibits tackiness, and the unstretched monofilament is cut by a small external force to stretch it. Is impossible. On the other hand, if the temperature is too high, cooling is insufficient and crystallization does not proceed, so that it becomes difficult to obtain an unstretched monofilament due to problems such as adhesion between the monofilament and the roller.
【００２０】また、冷却固化及び結晶化の時間が短すぎ
ると、冷却不足となり、未延伸フィラメントを得ること
が困難となり、長すぎると、モノフィラメントの引き取
り速度にも関係するが、冷却固化及び結晶化浴の長さ又
は浸漬長を大きくする必要性が出てくるため、工業的な
面から考えてデメリットになる。また、ポリヒドロキシ
アルカノエート類重合体は、半結晶状態の時が延伸性良
好であり、結晶化が進行しすぎると硬くて脆くなって、
延伸性が悪化し、延伸が困難となる。If the time for solidification by cooling and crystallization is too short, cooling becomes insufficient and it becomes difficult to obtain an unstretched filament. If it is too long, it depends on the take-up speed of the monofilament. Since it becomes necessary to increase the length of the bath or the length of dipping, it is a disadvantage from an industrial viewpoint. Further, the polyhydroxyalkanoate polymer has good stretchability when in a semi-crystalline state, and becomes too hard and brittle when crystallization proceeds too much,
Stretchability deteriorates, and stretching becomes difficult.
【００２１】冷却固化及び結晶化した未延伸モノフィラ
メントは、必要に応じて、温度20〜40℃の雰囲気中で70
〜150 秒間処理して結晶化度の調整を行った後、巻き取
ることなしに延伸される。未延伸糸を一旦巻き取り、室
温で放置すると結晶化が進行して結晶化度が高くなりす
ぎ、延伸不能となる。The unstretched monofilament which has been solidified by cooling and crystallized is, if necessary, 70% in an atmosphere at a temperature of 20 to 40 ° C.
After being processed for about 150 seconds to adjust the crystallinity, it is stretched without being wound. If the undrawn yarn is wound up once and left at room temperature, crystallization proceeds and the degree of crystallinity becomes too high, making it impossible to draw.
【００２２】延伸は、一段又は二段以上の多段で行うこ
とができるが、高強度のモノフィラメントを得るために
は、二段以上の多段で行うことが好ましい。多段で延伸
する場合、温度60〜95℃の液体中で倍率６〜8.5 倍の第
一段延伸を行った後、第二段目以降の延伸を温度 100〜
140 ℃の液体中又は気体中で行い、全延伸倍率が 6.5〜
10倍となるようするのが好ましい。The drawing can be carried out in one step or in multiple steps of two or more steps, but in order to obtain a high-strength monofilament, it is preferable to carry out in two or more steps. In the case of stretching in multiple stages, after stretching the first stage at a draw ratio of 6 to 8.5 times in a liquid at a temperature of 60 to 95 ° C, the second and subsequent stages are stretched at a temperature of 100 to 100 ° C.
Performed in liquid or gas at 140 ℃, total draw ratio 6.5 ~
It is preferably 10 times.
【００２３】第一段目の延伸は加熱効率の高い液体浴中
で行ことが好ましい。液体としては水、エチレングリコ
ール、ポリエチレングリコール、グリセリン、シリコー
ン等が使用できるが、冷却固化及び結晶化の液体浴と同
様な理由で水を使用するのが最も好ましい。The first stage stretching is preferably carried out in a liquid bath with high heating efficiency. As the liquid, water, ethylene glycol, polyethylene glycol, glycerin, silicone or the like can be used, but it is most preferable to use water for the same reason as in the liquid bath for cooling and solidification.
【００２４】第一段目の延伸温度が60℃未満であると、
未延伸モノフィラメントの加熱が不足となり、延伸過程
で糸切れ等を起こし、一方、95℃を超えると、モノフィ
ラメントに対して過加熱となり、スーパードロー現象等
が起こり、分子配向したモノフィラメントが得られな
い。また、第一段目の延伸倍率が６倍未満であると、延
伸点の固定が困難となって延伸斑が起こり、一方、 8.5
倍を超えると、過延伸となり、糸切れ等の問題が起こ
り、操業性が悪化する。すなわち、上記条件範囲内で、
延伸点の移動を起こさない最適条件で延伸を行ことが必
要である。When the stretching temperature of the first stage is lower than 60 ° C,
When the undrawn monofilament is insufficiently heated, yarn breakage or the like occurs in the drawing process. On the other hand, when the temperature exceeds 95 ° C, the monofilament is overheated and a superdraw phenomenon or the like occurs, so that a molecularly oriented monofilament cannot be obtained. Further, if the draw ratio of the first stage is less than 6 times, it becomes difficult to fix the draw point to cause draw unevenness.
If it exceeds twice, overdrawing will occur, problems such as yarn breakage will occur, and operability will deteriorate. That is, within the above condition range,
It is necessary to carry out stretching under optimum conditions that do not cause movement of the stretching point.
【００２５】第二段目以降の延伸は、液体中又は気体中
で行うことが可能である。液体としては、エチレングリ
コール、ポリエチレングリコール、グリセリン、シリコ
ーン等が使用できる。気体中で延伸する場合は、通常、
空気中で行われるが、窒素ガス等の不活性気体中で行う
ことも可能である。The stretching from the second stage onward can be performed in a liquid or a gas. As the liquid, ethylene glycol, polyethylene glycol, glycerin, silicone or the like can be used. When stretching in gas, usually
Although it is carried out in air, it may be carried out in an inert gas such as nitrogen gas.
【００２６】第二段目以降の延伸温度が 100℃未満であ
ると、モノフィラメントへの加熱が不足となり、延伸性
が悪く、 140℃を超えると、モノフィラメントが融解し
たり、熱分解を起こし、良好な糸質性能のモノフィラメ
ントが得られず、また、操業性も悪化する。なお、第二
段目以降の延伸の延伸倍率は、最高 1.2倍程度であり、
これを超えると、糸切れ等の問題が起こる。If the drawing temperature after the second step is less than 100 ° C., heating to the monofilament is insufficient and the drawability is poor, and if it exceeds 140 ° C., the monofilament melts or thermally decomposes, which is good. A monofilament with excellent yarn quality cannot be obtained, and the operability also deteriorates. The stretching ratio of the second and subsequent stretching is about 1.2 times at maximum,
If it exceeds this, problems such as yarn breakage occur.
【００２７】さらに、全延伸倍率が６倍未満であると、
優れた糸質性能を有するモノフィラメントを得ることが
困難となり、10倍以上にすると操業性が悪い。Furthermore, if the total draw ratio is less than 6 times,
It becomes difficult to obtain a monofilament having excellent yarn quality performance, and if it is 10 times or more, operability is poor.
【００２８】また、必要に応じて、延伸後オーブンヒー
ター等を使用して、弛緩熱処理を行ってもよい。If necessary, relaxation heat treatment may be carried out by using an oven heater or the like after stretching.
【００２９】[0029]
【作用】本発明においては、ポリヒドロキシアルカノエ
ート類重合体を比較的高温で完全に溶融した後、紡糸口
金パックに導入し、紡糸口金パックにおいて、適度な溶
融粘度となり、かつ熱分解や塊状化の起こらない温度に
調整し、高剪断速度で濾過して紡出するので、円滑な溶
融紡糸が可能となる。また、紡出されたモノフィラメン
トは、冷却固化及び結晶化により適度の結晶化度の未延
伸モノフィラメントとなり、その状態で延伸されるた
め、延伸が円滑に行われ、糸質性能の良好なモノフィラ
メントとなる。In the present invention, the polyhydroxyalkanoate polymer is completely melted at a relatively high temperature and then introduced into the spinneret pack, and the spinneret pack has an appropriate melt viscosity and undergoes thermal decomposition or agglomeration. Since the temperature is adjusted so that the temperature does not occur and the mixture is filtered at a high shear rate and spun out, smooth melt spinning is possible. Further, the spun monofilament becomes an unstretched monofilament having an appropriate crystallinity by cooling and solidification and crystallization, and since it is stretched in that state, it is smoothly stretched and becomes a monofilament having good yarn quality performance. .
【００３０】[0030]
【実施例】次に、実施例によって本発明を具体的に説明
する。なお、引張強度特性はJIS L 1013に準じて測定し
た。また、試料を海水中に２カ月間放置して取り出し、
モノフィラメントがその形状を失っているか、引張強力
保持率が50％以下になっている場合を微生物分解性が良
好であると判断した。EXAMPLES Next, the present invention will be specifically described with reference to examples. The tensile strength characteristics were measured according to JIS L 1013. Also, leave the sample in seawater for 2 months and remove it.
The microbial degradability was judged to be good when the monofilament lost its shape or when the tensile strength retention rate was 50% or less.
【００３１】実施例１ 重量平均分子量40万、多分散度 2.2の３−ヒドロキシブ
チレート単位88モル％と３−ヒドロキシバリレート単位
12モル％とからなる共重合体のチップ（ゼネカ社製、商
品名Biopol、Ｔｍ＝ 139℃、Ｔｃ＝55℃) に窒化硼素
1.0重量％、トリアセチン７重量％を含有させてエクス
トルーダーに供給し、温度 160℃、溶融時間 4.0分間の
条件で溶融し、温度 155℃の紡糸口金パックに導入し
た。紡糸口金パック内濾過層直上での剪断速度 3.5×10
-2／秒、紡糸口金パック内滞留時間50秒、吐出量9.4g／
分の条件で、直径 2.0mmノズルを２個有する紡糸口金を
用いて紡出した。紡出糸条を50℃の水浴中で７秒間冷却
固化及び結晶化を行った後、さらに、35℃の空気中で90
秒間結晶化行い、引き続いて、71℃の水浴中で 9.0倍に
延伸し、次いで、 120℃のオーブンヒーター中で1.03倍
に延伸し、引き続いて、 100℃のオーブンヒーター中で
５％の弛緩熱処理を行い、モノフィラメントを得た。得
られたモノフィラメントの糸質性能を表１に示す。Example 1 88 mol% of 3-hydroxybutyrate units having a weight average molecular weight of 400,000 and a polydispersity of 2.2 and 3-hydroxyvalerate units
Copolymer chips consisting of 12 mol% (made by Zeneca Co., trade name Biopol, Tm = 139 ° C., Tc = 55 ° C.) and boron nitride
1.0 wt% and 7 wt% of triacetin were supplied to an extruder, melted under the conditions of a temperature of 160 ° C and a melting time of 4.0 minutes, and introduced into a spinneret pack at a temperature of 155 ° C. Shear rate immediately above the filtration layer in the spinneret pack 3.5 × 10
-2 / sec, residence time in spinneret pack 50sec, discharge rate 9.4g /
Spinning was performed using a spinneret having two nozzles with a diameter of 2.0 mm under the condition of minutes. The spun yarn was cooled and solidified in a water bath at 50 ° C for 7 seconds and then crystallized, and then 90 ° C in air at 35 ° C.
Crystallize for seconds, then draw 9.0 times in a 71 ° C water bath, then draw 1.03 times in a 120 ° C oven heater, followed by 5% relaxation heat treatment in a 100 ° C oven heater. Then, a monofilament was obtained. The yarn quality performance of the obtained monofilament is shown in Table 1.
【００３２】実施例２〜７ 表１に示した重合体のチップを用い、製糸条件を表１の
ように変更した以外は実施例１と同様にしてモノフィラ
メントを得た。得られたモノフィラメントの糸質性能を
表１に示す。Examples 2 to 7 Monofilaments were obtained in the same manner as in Example 1 except that the polymer chips shown in Table 1 were used and the spinning conditions were changed as shown in Table 1. The yarn quality performance of the obtained monofilament is shown in Table 1.
【００３３】[0033]
【表１】 [Table 1]
【００３４】比較例１〜６ 製糸条件を表２に示したように変更した以外は実施例１
と同様にしてモノフィラメントを製造することを試み
た。いずれも製糸性が不良で、円滑にモノフィラメント
を製造することができなかった。Comparative Examples 1 to 6 Example 1 except that the spinning conditions were changed as shown in Table 2.
An attempt was made to produce a monofilament in the same manner as in. In all cases, the yarn-forming property was poor, and a monofilament could not be smoothly produced.
【００３５】[0035]
【表２】 [Table 2]
【００３６】[0036]
【発明の効果】本発明によれば、ポリヒドロキシアルカ
ノエート類重合体から、漁網、海苔網、ロープ等の産業
資材用として好適なモノフィラメントを安定して製造す
ることができる。そして、本発明の方法で得られるモノ
フィラメントは、微生物分解性を有しているので、使用
後、海中や土中等の微生物により分解するため、廃棄物
による環境悪化を防止することができる。INDUSTRIAL APPLICABILITY According to the present invention, monofilaments suitable for industrial materials such as fishing nets, laver nets and ropes can be stably produced from polyhydroxyalkanoate polymers. Since the monofilament obtained by the method of the present invention has microbial degradability, it is decomposed by microorganisms in the sea, soil, etc. after use, so that environmental deterioration due to waste can be prevented.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｄ０１Ｆ 6/84 ３０３ Ｄ０１Ｆ 6/84 ３０３Ｚ (72)発明者 高橋 修治 京都府宇治市宇治小桜23番地 ユニチカ株 式会社中央研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical indication location D01F 6/84 303 D01F 6/84 303Z (72) Inventor Shuji Takahashi 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Ltd. Central Research Laboratory
Claims (3)
キシアルカノエート類重合体をエクストルーダーに供給
して溶融紡糸し、延伸して微生物分解性モノフィラメン
トを製造するに際し、重合体を温度（Ｔｍ＋15）〜（Ｔ
ｍ＋50）℃〔Ｔｍは重合体の融点（℃）〕で６分間以内
で溶融し、溶融した重合体を温度Ｔｍ〜（Ｔｍ＋20) ℃
の紡糸口金パックに導入し、紡糸口金パック内濾過層直
上での剪断速度が２×10-2／秒以上、紡糸口金パック内
滞留時間が２分間以内となる条件で紡出し、温度（Ｔｃ
−10）〜（Ｔｃ＋10）℃〔Ｔｃは重合体の結晶化温度
（℃）〕の液体浴中で５〜10秒間冷却固化及び結晶化を
行った後、巻き取ることなしに延伸することを特徴とす
る微生物分解性モノフィラメントの製造法。1. A polyhydroxyalkanoate polymer having a weight average molecular weight of 400,000 or more is supplied to an extruder, melt-spun, and stretched to produce a biodegradable monofilament, and the polymer is heated to a temperature (Tm + 15). ~ (T
m + 50) ° C. [Tm is the melting point (° C.) of the polymer] within 6 minutes, and the melted polymer is heated at a temperature Tm to (Tm + 20) ° C.
The spinneret pack was spun under conditions such that the shear rate immediately above the filtration layer in the spinneret pack was 2 × 10 -2 / sec or more and the residence time in the spinneret pack was within 2 minutes.
-10) to (Tc + 10) ° C. [Tc is the crystallization temperature (° C.) of the polymer] In a liquid bath, after cooling and solidification for 5 to 10 seconds, crystallization is performed, and then stretching is performed without winding. The method for producing a biodegradable monofilament.
が３−ヒドロキシブチレート単位と３−ヒドロキシバリ
レート単位とからなる共重合体である請求項１記載の微
生物分解性モノフィラメントの製造法。2. The method for producing a biodegradable monofilament according to claim 1, wherein the polyhydroxyalkanoate polymer is a copolymer composed of a 3-hydroxybutyrate unit and a 3-hydroxyvalerate unit.
せる請求項１又は２記載の微生物分解性モノフィラメン
トの製造法。3. The method for producing a microbial-degradable monofilament according to claim 1, wherein the polymer to be melt-spun contains a crystal nucleating agent.
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|---|---|---|---|
| JP02787095A JP3519480B2 (en) | 1995-02-16 | 1995-02-16 | Manufacturing method of biodegradable monofilament |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02787095A JP3519480B2 (en) | 1995-02-16 | 1995-02-16 | Manufacturing method of biodegradable monofilament |
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| Publication Number | Publication Date |
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| JPH08218216A true JPH08218216A (en) | 1996-08-27 |
| JP3519480B2 JP3519480B2 (en) | 2004-04-12 |
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