JPH03259029A - Degradable fishing line and its production - Google Patents

Degradable fishing line and its production

Info

Publication number
JPH03259029A
JPH03259029A JP5567390A JP5567390A JPH03259029A JP H03259029 A JPH03259029 A JP H03259029A JP 5567390 A JP5567390 A JP 5567390A JP 5567390 A JP5567390 A JP 5567390A JP H03259029 A JPH03259029 A JP H03259029A
Authority
JP
Japan
Prior art keywords
fishing line
degradable
polyglycolic acid
decomposable
constituent material
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
Application number
JP5567390A
Other languages
Japanese (ja)
Other versions
JP2779972B2 (en
Inventor
Isakiyo Saitou
齋藤 巧清
Yoshito Ikada
義人 筏
Jiyoukiyuu Gen
丞烋 玄
Masakazu Suzuki
昌和 鈴木
Hideji Kagawa
秀治 香川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gunze Ltd
Original Assignee
Gunze Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Gunze Ltd filed Critical Gunze Ltd
Priority to JP2055673A priority Critical patent/JP2779972B2/en
Publication of JPH03259029A publication Critical patent/JPH03259029A/en
Application granted granted Critical
Publication of JP2779972B2 publication Critical patent/JP2779972B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Abstract

PURPOSE:To obtain a decomposable fishing line slowly decomposing and finally disappearing in natural environment by using a polyglycolic acid, a copolymer of glycolide and other monomer for decomposable polymer or a mixture of a polyglycolic acid and other decomposable polymer as constituent raw material. CONSTITUTION:The decomposable fishing line is composed of a polyglycolic acid, a copolymer of glycolide and other monomer for decomposable polymer or a mixture of a polyglycolic acid and other decomposable polymer as constituent raw material. The decomposable fishing line is preferably added with a hydrophilic processing agent (e.g. organic or inorganic hydrophilization agent) to promote the decomposition in water. The decomposable polymer to be copolymerized or mixed with polyglycolic acid is e.g. polylactide, p-dioxanone and caprolactone chemically polymerized or synthesized by using L-lactide, D,L-lactide, D-lactide or mixture of L and D lactides as a raw material.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は、釣糸及びその製造法に関し、加水分解性を有
する特殊な素材をもって構成したことに特徴を有するも
のである。
DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a fishing line and a method for producing the same, and is characterized in that it is constructed from a special hydrolyzable material.

(従来技術) 従来、釣糸を構成する素材としては安価で強度的に優れ
るナイロン、ポリエステル、ポリプロピレン等の合成繊
維が用いられている。
(Prior Art) Conventionally, synthetic fibers such as nylon, polyester, and polypropylene, which are inexpensive and have excellent strength, have been used as materials for making fishing lines.

(発明が解決しようとする問題点) しかしながら、かかる合成繊維より成る釣糸は自然の環
境下で殆んど分解せず、捨てられたり放置されればその
まま半永久的に自然界に残存する問題がある。
(Problems to be Solved by the Invention) However, there is a problem in that fishing lines made of such synthetic fibers hardly decompose in the natural environment, and if they are thrown away or left unattended, they will remain in the natural world semi-permanently.

特に、近年では釣人口の増加とともに野鳥等への影響も
深刻化しており、環境、自然保護の両面よりその改善が
強く望まれているところである。
In particular, in recent years, as the fishing population has increased, the impact on wild birds has become more serious, and improvements are strongly desired from both the environmental and nature conservation standpoints.

本発明はかかる点、自然環境下で徐々に分解し、最終的
に消失してしまう従来にない新規な釣糸並びにその製造
法を提供したものである。
In view of this, the present invention provides a novel and unprecedented fishing line that gradually decomposes in the natural environment and eventually disappears, as well as a method for manufacturing the same.

(問題を解決するための手段) しかるに、本発明はポリグリコール酸、或はグリコリド
と他の分解性高分子モノマーとの共重合物、更にはポリ
グリコール酸と他の分解性高分子との混合物をその構成
素材とすること、及び、これに親水性の加工剤を添加し
た構成、また、釣糸を構成したときの固有粘度が0.6
以上であるポリグリコール酸をその構成素材としたこと
、その切断強度が6 g/d以上、切断伸度が30〜4
0%の範囲であること、20℃の淡水または海水中に1
4日間放置したとき、その切断強度が初期に対して25
%以上維持されていることを特徴とする分解性釣糸の構
成であり、その製法においては、固有粘度が0.7以上
であるポリグリコール酸を少なくともその構成素材とし
、これを溶融紡糸し、5〜10倍に熱延伸した後0.8
5〜0.95倍の弛緩熱処理を行なうこと、及び、かか
る溶融紡糸、熱延伸、弛緩熱処理後の糸条に対し更に真
空下において結晶化温度以上、融点以下の熱処理を2時
間以上加えることに特徴を有するものである。
(Means for Solving the Problem) However, the present invention is directed to copolymers of polyglycolic acid or glycolide with other degradable polymer monomers, and furthermore, mixtures of polyglycolic acid and other degradable polymers. is used as the constituent material, and a hydrophilic processing agent is added to this, and the inherent viscosity when the fishing line is made is 0.6.
Its constituent material is polyglycolic acid, which has a cutting strength of 6 g/d or more and a cutting elongation of 30 to 4.
0% in freshwater or seawater at 20°C.
When left for 4 days, the cutting strength was 25% higher than the initial strength.
The composition of the degradable fishing line is characterized in that the polyglycolic acid has an intrinsic viscosity of 0.7 or more, and its manufacturing method includes melt-spinning polyglycolic acid having an intrinsic viscosity of 0.7 or more, and ~0.8 after hot stretching to 10 times
5 to 0.95 times the relaxation heat treatment, and further heat treatment for 2 hours or more at temperatures above the crystallization temperature and below the melting point under vacuum to the yarn after such melt spinning, hot drawing, and relaxation heat treatment. It has characteristics.

(作用) 本発明は、その構成において、特に分解性を有するポリ
グリコール@、或はグリコリドと他の分解性高分子モノ
マーとの共重合物、更には、ポリグリコール酸と他の分
解性高分子との混合物をその構成素材としているため、
水分による分解性を有し、特に、その固有粘度、共重合
化率、混合率、熱処理条件等にもよるが自然環境下に放
置し、例えば、20℃の淡水、海水中において14日後
にはその強度が約1/4〜l/2に低下し、遅くとも約
120日以上経過後においてはモノマー化して微生物の
餌となり、消失してしまうため従来のような放置に伴う
諸問題が解消できる。
(Function) In its configuration, the present invention is particularly suitable for copolymers of degradable polyglycol@ or glycolide and other degradable polymer monomers, and furthermore, polyglycolic acid and other degradable polymer monomers. Because its constituent material is a mixture of
It is degradable by moisture, and depending on its intrinsic viscosity, copolymerization rate, mixing ratio, heat treatment conditions, etc., it can be left in a natural environment, for example, after 14 days in freshwater or seawater at 20°C. Its strength decreases to about 1/4 to 1/2, and after about 120 days or more at the latest, it becomes a monomer, becomes food for microorganisms, and disappears, so various problems associated with conventional storage can be solved.

本発明を構成する素材であるポリグリコール酸とは、以
下の構造を有するものを指し、これと共重合化し、或は
、混合する分解性高分子としては、L−ラクチド、D、
L−ラクチド、D−ラクチド、L体と0体の混合ラクチ
ドを原料として化学的に重合、合成されたポリラクチド
、或はバラジオキサノン2カプロラクトン等を例示でき
る。
Polyglycolic acid, which is a material constituting the present invention, refers to one having the following structure, and degradable polymers to be copolymerized or mixed with it include L-lactide, D,
Examples include L-lactide, D-lactide, polylactide chemically polymerized and synthesized using mixed lactide of L-form and O-form as raw materials, and varadioxanone 2-caprolactone.

一般的に、これらの分解性高分子はポリグリコール酸と
は異なった分解性を示し、分解速度が遅い。従って、こ
れとの共重合化、混合において、その比率を変えること
によって所望の機能、例えば、分解速度を調整すること
ができる。
Generally, these degradable polymers exhibit a different degradability from polyglycolic acid and have a slow decomposition rate. Therefore, in copolymerization and mixing with this, desired functions, such as decomposition rate, can be adjusted by changing the ratio.

尚、かかる構成において、親水性の加工剤、例えば、有
機、無機の親水性剤を添加させることは、水中での分解
性を促進し、即ち、不要となった釣糸は、−刻も早く分
解することが望まれるため、吸水してその分解を促進す
る目的において、有効である。
In addition, in such a configuration, adding a hydrophilic processing agent, for example, an organic or inorganic hydrophilic agent, promotes decomposition in water, that is, the unnecessary fishing line is quickly decomposed. Therefore, it is effective for the purpose of absorbing water and promoting its decomposition.

また、その物性において、切断強度を6g/d以上、切
断伸度を30〜40%(これの測定はJIS法による)
とした構成は、かかる値の範囲にあることが使用時にお
ける釣糸としての要求機能を満足させるものである。
In addition, regarding its physical properties, the cutting strength is 6 g/d or more, and the cutting elongation is 30 to 40% (measured according to JIS method).
With this configuration, the value within this range satisfies the required functions of a fishing line during use.

なお、釣糸を構成したときのポリグリコール酸の固有粘
度を0.6以上と特定したのもかかる性能を付与するた
めである。
The reason for specifying the intrinsic viscosity of polyglycolic acid to be 0.6 or more when forming the fishing line is to provide such performance.

一方、本発明はその製造法において固有粘度07以上の
ものを溶融紡糸後5〜10倍に熱延伸し、しかる後0,
85〜0.95倍の弛緩熱処理を行なうことを特徴とす
る。かかる製造条件は前記した必要機能を付与するため
に必要な条件である。
On the other hand, in the manufacturing method of the present invention, a material with an intrinsic viscosity of 07 or more is hot-stretched 5 to 10 times after melt spinning, and then 0.
It is characterized by performing a relaxation heat treatment of 85 to 0.95 times. These manufacturing conditions are necessary to provide the above-mentioned necessary functions.

即ち5ポリグリコール酸は通常230〜250℃で溶融
紡糸されるが、かかる段階において固有粘度がおよそ1
.0−15℃程度低下し、紡糸性、強度を損なう原因と
なる。従ってそのために予め分子量の高い、即ち、固有
粘度0.7以上のポリグリコール酸を用いる必要があり
、かかる要件と延伸、弛緩等の処理によって前記した性
能が付与される。従って、かかる条件によって製造され
た釣糸はポリグリコール酸の固有粘度が0゜6以上とな
り、必要機能が付与される。
That is, 5-polyglycolic acid is usually melt-spun at 230 to 250°C, and at this stage the intrinsic viscosity is approximately 1.
.. The temperature decreases by about 0-15°C, which causes loss of spinnability and strength. Therefore, it is necessary to use polyglycolic acid having a high molecular weight, that is, an intrinsic viscosity of 0.7 or more, in advance, and the above-mentioned performance is imparted by such requirements and treatments such as stretching and relaxation. Therefore, the fishing line produced under these conditions has an inherent viscosity of polyglycolic acid of 0°6 or more, and is endowed with necessary functions.

尚、ここでいう固有粘度とは、ヘキサフルオロイソプロ
パツール10に対しトリクロロフェノール7の割合で混
合したfats中にポリグリコール酸を0.5g/di
の割合で添加し、これを230℃で10分間加熱処理し
て溶融させた後、30℃の恒温槽中にて測定したときの
粘度であり、この値が高いことは5分子量が高いことを
示す。
Note that the intrinsic viscosity here refers to 0.5 g/di of polyglycolic acid in fats mixed with 10 parts of hexafluoroisopropanol to 7 parts of trichlorophenol.
This is the viscosity when measured in a constant temperature bath at 30°C after heating it at 230°C for 10 minutes to melt it. A high value indicates that the molecular weight is high. show.

また、紡糸、延伸、弛緩熱処理後において適宜の条件に
よる熱処理、例えば、真空下において結晶化温度以上、
融点以下の熱処理を2時間以上具体的には、80〜20
0℃で2〜36時間の熱処理を行なえば、強度劣化の程
度を遅延させ、或は調整することが可能になる。
In addition, after spinning, stretching, and relaxation heat treatment, heat treatment under appropriate conditions, such as heating at a temperature higher than the crystallization temperature under vacuum,
Specifically, heat treatment below the melting point for 2 hours or more, 80 to 20
Heat treatment at 0° C. for 2 to 36 hours makes it possible to delay or adjust the degree of strength deterioration.

本発明は、かかる素材構成、製造方法の適用により、少
なくとも自然界におけるごく一般的な条件、即ち、20
℃の淡水、海水中に14日間放置した場合において強度
が25%以上維持され、さらにかかる状態においておよ
そ120日以上放置後においては完全に分解してモノマ
ー化し、微生物の作用よって消失してしまう理想的な機
能を有することになる。
By applying such material composition and manufacturing method, the present invention can meet at least very common conditions in nature, that is, 20
Ideally, it would maintain more than 25% of its strength when left in freshwater or seawater at ℃ for 14 days, and if left in such conditions for about 120 days or more, it would completely decompose into monomers and disappear due to the action of microorganisms. It will have a similar function.

以下、実施例を挙げて説明する。Examples will be described below.

(実施例1) 固有粘度0.8のポリグリコール酸を原料とし、これを
ノズル温度250℃で溶融紡糸した後30℃に急冷し、
90℃の環境下で6倍に延伸し1次いで0.9倍の弛緩
熱処理を行って直径022ミリの本発明釣糸を構成した
(Example 1) Using polyglycolic acid with an intrinsic viscosity of 0.8 as a raw material, it was melt-spun at a nozzle temperature of 250°C and then rapidly cooled to 30°C.
The fishing line of the present invention having a diameter of 022 mm was prepared by stretching it 6 times in an environment of 90° C. and then subjecting it to a relaxation heat treatment of 0.9 times.

(実施例2) 上記のようにして得た釣糸に対し、更にこれをボビンに
巻き、真空下において98℃、12時間熱処理して本発
明釣糸を得た。
(Example 2) The fishing line obtained as described above was further wound around a bobbin and heat-treated at 98° C. for 12 hours under vacuum to obtain a fishing line of the present invention.

このようにして得た本発明各実施例の釣糸は以下の第1
表に示すような性能を有した6第1表 かかる性能は、通常の釣糸として必要な機能を肯えたも
のであり、また、長期的には徐々に分解して強力低下を
来し自然界に消失する。
The fishing lines of each example of the present invention thus obtained were as follows:
6 Table 1 shows the performance shown in Table 1. This performance confirms the necessary functions as a normal fishing line, and over a long period of time, the line gradually decomposes, loses its strength, and disappears in the natural world. do.

尚、かかる評価において、14日後の評価は浴比1 :
600.20℃の生理食塩水中に継続して浸漬した後の
測定データであり、その測定はJIS法によって行なっ
た。
In addition, in this evaluation, the evaluation after 14 days is based on a bath ratio of 1:
600. This is measurement data after continuous immersion in physiological saline at 20°C, and the measurement was performed according to the JIS method.

(発明の効果) 本発明は以上のように経時的に強度劣化し、最終的には
自然の中で消失してしまう特性を有するので従来のよう
な環境汚染等の問題を生じない。
(Effects of the Invention) As described above, the present invention has the property of deteriorating in strength over time and eventually disappearing in nature, so it does not cause problems such as environmental pollution as in the past.

また、かかる釣糸の特徴としてヤング率が比較的高いた
めアタリが分かりやすい特徴も有する。
In addition, such fishing line has a relatively high Young's modulus, which makes it easy to notice the hit.

尚、本発明においては、分子量を変えたりポリラクチド
、パラジオキサノン、カプロラクトン等との混合、共重
合化5親水性剤の添加、熱処理等によって分解性のコン
トロールが可能であるため目的に応じて、その性能に変
化を持たせることができる。
In addition, in the present invention, degradability can be controlled by changing the molecular weight, mixing with polylactide, paradioxanone, caprolactone, etc., adding a copolymerized 5 hydrophilic agent, heat treatment, etc. Depending on the purpose, Its performance can be varied.

また、本発明においては機能改善のため釣糸に対して通
常行われるところのコーティング等の加工、あるいは、
素材中への界面活性剤、無機物等の充填を行っても良い
In addition, in the present invention, processing such as coating that is normally performed on fishing line to improve functionality, or
A surfactant, an inorganic substance, etc. may be filled into the material.

また、かかる釣糸の構成は、モノフィラメト、マルチフ
ィラメント、合撚、組紐状等その形態は任意である。
Further, the configuration of the fishing line may be arbitrary, such as monofilament, multifilament, plied, braided, etc.

更に、かかる素材を適用して糸、紐、ローブ。Furthermore, such materials can be applied to threads, strings, and robes.

網、シート、フィルム、成型物等を構成し、漁業、農業
等の産業分野において、使い捨て、放置に伴う環境汚染
を回避するに必要があればこれを利用すれば同一効果を
得ることができる。
The same effect can be obtained by constructing nets, sheets, films, molded products, etc., and using them in industrial fields such as fishing and agriculture, if necessary to avoid environmental pollution caused by disposal or neglect.

特に、その使用後放置される可能性の高い遠洋漁業用の
網、成長にあわせて張替、入替えが行なわれるホタテ貝
、真珠貝等貝の養殖用網、高級魚養殖用の網等において
は有効である。
In particular, nets for deep-sea fishing that are likely to be left unused after use, nets for cultivating shellfish such as scallops and pearl oysters that are relined and replaced as they grow, and nets for cultivating high-grade fish. It is valid.

Claims (1)

【特許請求の範囲】 1、ポリグリコール酸をその構成素材とすることを特徴
とする分解性釣糸。 2、グリコリドと他の分解性高分子モノマーとの共重合
物をその構成素材とすることを特徴とする分解性釣糸。 3、ポリグリコール酸と他の分解性高分子との混合物を
その構成素材とすることを特徴とする分解性釣糸。 4、親水性の加工剤が添加されていることを特徴とする
請求項1、2、または3記載の分解性釣糸。 5、釣糸を構成したときの固有粘度が0.6以上である
ポリグリコール酸をその構成素材としたことを特徴とす
る請求項1、2、3または4記載の分解性釣糸。 6、その切断強度が6g/d以上、切断伸度が30〜4
0%の範囲にあることを特徴とする請求項1、2、3、
4または5記載の分解性釣糸。 7、20℃の淡水または海水中に14日間放置したとき
、その切断強度が初期に対して 25%以上維持されていることを特徴とする請求項1、
2、3、4、5または6記載の分解性釣糸。 8、固有粘度が0.7以上であるポリグリコール酸を少
なくともその構成素材とし、これを溶融紡糸し、5〜1
0倍に熱延伸した後0.85〜0.95倍の弛緩熱処理
を行なうことを特徴とする分解性釣糸の製造法。 9、溶融紡糸、熱延伸、弛緩熱処理後の糸条に対し更に
真空下において結晶化温度以上、融点以下の熱処理を2
時間以上加えることを特徴とする分解性釣糸の製造法。
[Claims] 1. A degradable fishing line characterized in that its constituent material is polyglycolic acid. 2. A degradable fishing line characterized in that its constituent material is a copolymer of glycolide and other degradable polymer monomers. 3. A degradable fishing line characterized in that its constituent material is a mixture of polyglycolic acid and other degradable polymers. 4. The degradable fishing line according to claim 1, 2 or 3, further comprising a hydrophilic finishing agent. 5. The degradable fishing line according to claim 1, 2, 3 or 4, characterized in that the constituent material of the fishing line is polyglycolic acid having an intrinsic viscosity of 0.6 or more. 6. Its cutting strength is 6 g/d or more, and its cutting elongation is 30 to 4.
Claims 1, 2, 3, characterized in that it is in the range of 0%.
5. Degradable fishing line according to 4 or 5. 7. Claim 1, characterized in that when left in freshwater or seawater at 20°C for 14 days, the cutting strength is maintained at 25% or more of the initial strength.
The degradable fishing line according to 2, 3, 4, 5 or 6. 8. Polyglycolic acid having an intrinsic viscosity of 0.7 or more is used as a constituent material at least, and this is melt-spun, and 5-1
A method for producing a decomposable fishing line, which comprises hot stretching to 0 times and then subjecting it to relaxation heat treatment to 0.85 to 0.95 times. 9. After melt spinning, hot drawing, and relaxation heat treatment, the yarn is further heat treated under vacuum at a temperature above the crystallization temperature and below the melting point.
A method for producing a degradable fishing line characterized by adding time or more.
JP2055673A 1990-03-06 1990-03-06 Degradable fishing line and its production method Expired - Lifetime JP2779972B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2055673A JP2779972B2 (en) 1990-03-06 1990-03-06 Degradable fishing line and its production method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2055673A JP2779972B2 (en) 1990-03-06 1990-03-06 Degradable fishing line and its production method

Publications (2)

Publication Number Publication Date
JPH03259029A true JPH03259029A (en) 1991-11-19
JP2779972B2 JP2779972B2 (en) 1998-07-23

Family

ID=13005397

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Country Status (1)

Country Link
JP (1) JP2779972B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006211A1 (en) * 1992-11-16 1996-02-29 E.I. Du Pont De Nemours And Company Fishing lines and related products
WO2005090657A1 (en) * 2004-03-18 2005-09-29 Kureha Corporation Filament of polyglycolic acid resin and process for producing the same
JP2007077558A (en) * 2005-09-16 2007-03-29 Kureha Corp Biodegradable resin filament with controlled biodegradability and method for producing the same

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
WO2023214963A1 (en) * 2022-05-03 2023-11-09 Enviro Cast, LLC Degradable fishing lines and nets

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JPH02203729A (en) * 1989-02-02 1990-08-13 Tatsuya Kawai Fishing line
JPH04108331A (en) * 1989-11-08 1992-04-09 Mitsui Toatsu Chem Inc Fishing line and fishing hook

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02203729A (en) * 1989-02-02 1990-08-13 Tatsuya Kawai Fishing line
JPH04108331A (en) * 1989-11-08 1992-04-09 Mitsui Toatsu Chem Inc Fishing line and fishing hook

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006211A1 (en) * 1992-11-16 1996-02-29 E.I. Du Pont De Nemours And Company Fishing lines and related products
WO2005090657A1 (en) * 2004-03-18 2005-09-29 Kureha Corporation Filament of polyglycolic acid resin and process for producing the same
JPWO2005090657A1 (en) * 2004-03-18 2007-08-09 株式会社クレハ Polyglycolic acid resin filament and method for producing the same
JP4481302B2 (en) * 2004-03-18 2010-06-16 株式会社クレハ Polyglycolic acid resin filament and method for producing the same
US8808596B2 (en) 2004-03-18 2014-08-19 Kureha Corporation Process of making polyglycolic acid resin filament
JP2007077558A (en) * 2005-09-16 2007-03-29 Kureha Corp Biodegradable resin filament with controlled biodegradability and method for producing the same

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