JP7473946B2 - Composite monofilament for fishery materials and method for producing same - Google Patents
Composite monofilament for fishery materials and method for producing same Download PDFInfo
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- JP7473946B2 JP7473946B2 JP2020000450A JP2020000450A JP7473946B2 JP 7473946 B2 JP7473946 B2 JP 7473946B2 JP 2020000450 A JP2020000450 A JP 2020000450A JP 2020000450 A JP2020000450 A JP 2020000450A JP 7473946 B2 JP7473946 B2 JP 7473946B2
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- 239000002131 composite material Substances 0.000 title claims description 28
- 239000000463 material Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 230000005484 gravity Effects 0.000 claims description 32
- 229920006122 polyamide resin Polymers 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002033 PVDF binder Substances 0.000 claims description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 15
- 238000009987 spinning Methods 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002074 melt spinning Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- -1 polyethylene Polymers 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920010237 Novamid® 2030J Polymers 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001529596 Pontinus kuhlii Species 0.000 description 1
- 241001504592 Trachurus trachurus Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 238000000034 method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920013653 perfluoroalkoxyethylene Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Multicomponent Fibers (AREA)
Description
本発明は、水産資材用複合モノフィラメントに関するものである。 The present invention relates to composite monofilaments for marine materials.
釣糸等の水産資材に用いられる繊維の代表的なものとして比重１．００以下（約０．９２～０．９４）の超高強力ポリエチレン繊維、比重約０．９１～０．９６のポリオレフィン繊維、比重約１．０１～１．１５のポリアミド繊維、比重約１．２７～１．３９のポリエステル繊維等が挙げられる。 Typical fibers used in fishing lines and other marine materials include ultra-high strength polyethylene fibers with a specific gravity of 1.00 or less (approximately 0.92 to 0.94), polyolefin fibers with a specific gravity of approximately 0.91 to 0.96, polyamide fibers with a specific gravity of approximately 1.01 to 1.15, and polyester fibers with a specific gravity of approximately 1.27 to 1.39.
高強力ポリエチレン繊維は、一般的な合成繊維と比べて強力が高く様々な分野で使用されているが、欠点として比重が小さいという特性がある。軽いと風が吹くと容易に流され、且つ、水に浮いてしまう。釣糸として用いる場合、風が吹いていると竿～水面までの間が弛んでしまうと共に水に浮いてしまい弛むためアタリが分からなくなる。漁網として使おうとすると浮力の影響で網が浮こうとするのに加え、水流の影響で揺れが大きくなる。
また単フィラメントが２ｄｔｅｘ以下（１．１３～１．５１ｄｔｅｘ）と極めて細いフィラメントをマルチフィラメントに加工したものであるため耐摩耗性に乏しく毛羽立ち易いという欠点もある。
High-strength polyethylene fibers are stronger than general synthetic fibers and are used in a variety of fields, but one drawback is their low specific gravity. Because they are light, they are easily swept away by the wind and float on the water. When used as a fishing line, the line between the rod and the water surface becomes loose when the wind blows, and the line floats on the water, making it difficult to tell if there's a bite. When used as a fishing net, the net tends to float due to buoyancy, and the current causes it to sway a lot.
In addition, since the single filament is an extremely fine filament of 2 dtex or less (1.13 to 1.51 dtex) processed into a multifilament, it has the disadvantages of being poor in abrasion resistance and prone to fluffing.
ポリアミド繊維は、柔軟性に優れ、強度を有し、適度な伸びを有することから、水産資材としての基本的性能をバランスよく有するものであり、水産資材として多く用いられている。ただ、比重は、水や海水よりも若干大きいだけであることから、風や水流の影響を受けやすい。 Polyamide fibers are flexible, strong, and have moderate elongation, so they have a good balance of basic performance as a fishery material and are widely used as such. However, because their specific gravity is only slightly greater than that of water or seawater, they are easily affected by wind and water currents.
ポリエステル繊維は、比重も大きく風や水流の影響を受けにくく、定置網等の固定式漁網にはその特性を生かし使用されている。しかし、釣糸として使う場合は、糸が硬く滑り性が良いという長所はあるものの、巻き癖が付きやすく、且つ、摩擦によってカールしやすい傾向にあり、比重は大きいものの、水面～竿の間でのカールによってアタリが分かりにくいという問題が生じる。 Polyester fibers have a high specific gravity and are not easily affected by wind or water currents, making use of these characteristics and being used in fixed fishing nets such as set nets. However, when used as fishing line, although it has the advantage of being a hard and slippery line, it tends to easily become tangled and curl due to friction, and although it has a high specific gravity, there is the problem that it is difficult to detect a bite due to the curling that occurs between the water surface and the fishing rod.
フロロカーボンテグスは比重１．７８と釣糸中で最も大きく、摩耗性にも強いといわれているが、糸が硬く糸癖が付きやすいという欠点がある。 Fluorocarbon fishing line has the highest specific gravity of all fishing lines at 1.78, and is said to be highly resistant to abrasion, but it has the disadvantage that the line is stiff and prone to kinking.
また近年、超高強力ポリエチレン繊維と他素材とを組み合わせることにより、比重１．２５～１．４０とし、風に流されにくく、水中で浮き難い事を特徴にした釣糸（一般に、高比重ＰＥラインとよばれている）が販売されている。この釣糸は、超高強力ポリエチレン繊維の短所である軽さを解消しており、また、強力はナイロン以上ではあるものの、結節部が弱いという欠点を有し、耐摩耗性に弱く毛羽立ち易い点においては、超高強力ポリエチレン繊維と同様であり、素人には扱い難い。 In recent years, fishing lines have been sold that combine ultra-high strength polyethylene fibers with other materials to give them a specific gravity of 1.25 to 1.40, making them less likely to be blown away by the wind or float in water (commonly known as high-density PE lines). This fishing line overcomes the drawback of ultra-high strength polyethylene fibers, which is that it is light, and although it is stronger than nylon, it has the drawback of weak knots, and is similar to ultra-high strength polyethylene fibers in that it is less resistant to abrasion and easily becomes frayed, making it difficult for amateurs to handle.
アジングや、メバリングには比重１．２～１．３くらいで浮きにくく沈みにくいものが適しているといわれている。ポリエステル繊維に代表される比重１．３５～１．３９のポリエチレンテレフタレート繊維は比較的沈みやすく根掛かりしやすい。根掛かりした際、ポリエステル繊維の様な伸度が低い素材であると結節部で切れやすい。比重が１．２より小さいと浮きやすくなり好ましくない。また、ポリエステル繊維の中には比重１．２７の脂肪族ポリエステルであるポリ乳酸繊維もあるが、極端に硬く、巻き癖も付きやすく、結節強力も低い為、耐久性を求められる水産資材には好ましくない。 For horse mackerel fishing and rockfish fishing, it is said that materials with a specific gravity of around 1.2 to 1.3 are suitable because they are difficult to float and sink. Polyethylene terephthalate fibers with a specific gravity of 1.35 to 1.39, such as polyester fibers, are relatively prone to sinking and getting snagged. When snagged, materials with low elongation such as polyester fibers are likely to break at the knots. Specific gravity less than 1.2 is undesirable as it tends to float. Polyester fibers also include polylactic acid fibers, which are aliphatic polyesters with a specific gravity of 1.27, but these are extremely hard, tend to curl, and have low knot strength, making them undesirable for fishery materials that require durability.
特許文献１は、ポリフッ化ビニリデンと、比重が１．００以下の樹脂成分とを複合紡糸することによって得られた比重が１．１９～１．７５の芯鞘または海島構造のモノフィラメントが記されている。また、特許文献２の比較例に、海部にポリフッ化ビニリデン、島部にポリアミドを配したものが挙げられており、ポリアミドがポリフッ化ビニリデンと反応して引張強度に劣り、製糸性の評価が良くない。 Patent Document 1 describes a monofilament with a core-sheath or sea-island structure with a specific gravity of 1.19 to 1.75, obtained by composite spinning of polyvinylidene fluoride and a resin component with a specific gravity of 1.00 or less. In addition, Patent Document 2 lists a comparative example in which polyvinylidene fluoride is arranged in the sea portion and polyamide is arranged in the island portion, but the polyamide reacts with polyvinylidene fluoride, resulting in poor tensile strength and poor evaluation of spinnability.
本発明は、風によって流され難く、水中で浮き難く、取り扱いが容易な水産資材用モノフィラメントを提供することを技術的な課題とする。 The technical objective of the present invention is to provide a monofilament for fishery materials that is less likely to be blown away by the wind, does not float in water, and is easy to handle.
本発明者等は、上記課題を達成すべく検討した。その結果、ポリアミド系樹脂とフッ素系樹脂とを特定の比率で複合し、特定の条件で紡糸・冷却・延伸を行うことにより、課題を達しうることを見出し、本発明に到達した。 The inventors conducted research to achieve the above object. As a result, they discovered that the object could be achieved by compounding a polyamide resin and a fluororesin in a specific ratio, and spinning, cooling, and stretching the mixture under specific conditions, thus arriving at the present invention.
すなわち、本発明は、芯部にフッ素系樹脂、鞘部にポリアミド系樹脂を配し、ポリアミド系樹脂の比率が４０～９０体積％となるように計量して、紡糸速度１２～３０ｍ／分で溶融紡糸し、溶融紡糸した糸条を５～２５℃の浴中で冷却した後、６５～９５℃の温水浴中で第一段延伸を行い、次いで、１００～２５０℃で第二段延伸と弛緩熱処理を行い、比重が１．２～１．５である芯鞘型複合モノフィラメントを得ることを特徴とする水産資材用芯鞘型複合モノフィラメントの製造方法を要旨とするものである。
That is, the present invention relates to a method for producing a sheath-core composite monofilament for fishery materials, which comprises disposing a fluororesin in the core and a polyamide-based resin in the sheath, weighing the two so that the ratio of the polyamide-based resin is 40 to 90 volume %, melt-spinning the resulting yarn at a spinning speed of 12 to 30 m/min, cooling the melt-spun yarn in a bath at 5 to 25°C, and then subjecting it to a first-stage drawing in a warm water bath at 65 to 95°C, followed by a second-stage drawing and relaxation heat treatment at 100 to 250°C to obtain a sheath-core composite monofilament having a specific gravity of 1.2 to 1.5.
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.
本発明における水産資材用モノフィラメントは、ポリアミド系樹脂とフッ素系樹脂とが芯鞘型に複合されたものであり、芯部がフッ素系樹脂、鞘部がポリアミド系樹脂により構成されてなる。なお、芯鞘型において、芯部の数は、１つであっても、２～５個程度の多芯であってもよいが、１つであることが好ましい。 The monofilament for marine materials in the present invention is a composite of polyamide resin and fluororesin in a core-sheath structure , with the core being made of fluororesin and the sheath being made of polyamide resin. In the core-sheath structure, the number of cores may be one or may be a multi-core structure of about 2 to 5, but is preferably one.
本発明におけるポリアミド系樹脂は、分子内にアミド基を有するものであれば特に限定されるものではなく、例えばナイロン６，ナイロン６６，ナイロン６９，ナイロン４６，ナイロン６１０，ナイロン１０１０，ナイロン１１，ナイロン１２，ナイロン６Ｔ，ナイロン９Ｔ，ポリメタキシレンアジパミドやこれら各成分を共重合したものやブレンドしたもの等が挙げられる。 The polyamide resin in the present invention is not particularly limited as long as it has an amide group in the molecule, and examples thereof include nylon 6, nylon 66, nylon 69, nylon 46, nylon 610, nylon 1010, nylon 11, nylon 12, nylon 6T, nylon 9T, polymetaxylene adipamide, and copolymers or blends of these components.
また、本発明におけるフッ素系樹脂は、比重が１．７以上の熱可塑性のフッ素系樹脂であればよく、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、テトラフルオロエチレンとパーフルオロアルコキシエチレンとの共重合体などが挙げられる。なかでも、ポリフッ化ビニリデン系樹脂が最も好ましい。 The fluororesin in the present invention may be any thermoplastic fluororesin having a specific gravity of 1.7 or more, such as polyvinylidene fluoride, polytetrafluoroethylene, and copolymers of tetrafluoroethylene and perfluoroalkoxyethylene. Of these, polyvinylidene fluoride resins are most preferred.
本発明において、ポリフッ化ビニリデン系樹脂とは、ポリフッ化ビニリデンホモポリマーまたはフッ化ビニリデンを主成分とするポリフッ化ビニリデンコポリマーを意味する。ポリフッ化ビニリデンコポリマーの具体例としては、フッ化ビニリデンを主成分とし、テトラフルオロエチレン、モノクロロトリフルオロエチレン、フッ化ビニル、ヘキサフルオロプロピレン、パーフルオロイソプロポキシエチレン等を共重合としたコポリマーが挙げられる。また、複合繊維の芯部または鞘部に配するポリフッ化ビニリデン系樹脂としては、異なる２種以上のポリフッ化ビニリデン系樹脂をブレンドしたブレンド体であってもよい。さらには、ポリフッ化ビニリデン系樹脂には、製糸性あるいは糸質物性、透明性等を向上させる目的で、熱安定剤、着色剤、抗酸化剤、可塑剤等を含有させてもよい。 In the present invention, the polyvinylidene fluoride resin means a polyvinylidene fluoride homopolymer or a polyvinylidene fluoride copolymer mainly composed of vinylidene fluoride. Specific examples of polyvinylidene fluoride copolymers include copolymers mainly composed of vinylidene fluoride and copolymerized with tetrafluoroethylene, monochlorotrifluoroethylene, vinyl fluoride, hexafluoropropylene, perfluoroisopropoxyethylene, etc. In addition, the polyvinylidene fluoride resin disposed in the core or sheath of the composite fiber may be a blend of two or more different polyvinylidene fluoride resins. Furthermore, the polyvinylidene fluoride resin may contain a heat stabilizer, a colorant, an antioxidant, a plasticizer, etc., for the purpose of improving the spinnability, thread quality properties, transparency, etc.
また、本発明の目的を達成しうる範囲であれば、複合モノフィラメントを構成する樹脂に、必要に応じて、例えば結晶核剤、艶消し剤、顔料、耐光剤、耐候剤、酸化防止剤、抗菌剤、香料、熱安定剤、可塑剤、染料、界面活性剤、表面改質剤、各種無機電解質及び有機電解質、微粉体、難燃剤等の各種添加剤を添加することができる。また、得られるモノフィラメントの結節強度を向上させるために、脂肪酸アミド類、例えばメタキシリレンビスステアリルアミド、メタキシリレンビスオレイルアミド、キシレンビスステアリン酸アミド、エチレンビスステアリルアミド、エチレンビスステアリン酸アミド等を添加してもよい。 In addition, as long as the object of the present invention can be achieved, various additives such as crystal nucleating agents, matting agents, pigments, light resistance agents, weather resistance agents, antioxidants, antibacterial agents, fragrances, heat stabilizers, plasticizers, dyes, surfactants, surface modifiers, various inorganic and organic electrolytes, fine powders, and flame retardants can be added to the resin constituting the composite monofilament as necessary. In addition, in order to improve the knot strength of the resulting monofilament, fatty acid amides such as metaxylylene bisstearylamide, metaxylylene bisoleylamide, xylene bisstearic acid amide, ethylene bisstearylamide, and ethylene bisstearic acid amide may be added.
本発明における複合モノフィラメントの比重は、比重１．２～１．５である。モノフィラメン トの比重が１．２～１．５であることにより、モノフィラメントを構成するポリアミド樹脂とフッ素系樹脂とを芯鞘型形態として複合し、かつ両ポリマーが保有する能力を最大限に発揮することができる。比重が１．２より低いと、ポリアミド繊維と近似する比重であるため、本発明が目的とするものではない。比重が１．５より大きいと、本発明において、実用強度を有する水産資材用モノフィラメントが得られにくい傾向となるため好ましくない。 The specific gravity of the composite monofilament in the present invention is 1.2 to 1.5. By making the specific gravity of the monofilament 1.2 to 1.5, the polyamide resin and the fluororesin constituting the monofilament can be composited in a core-sheath form, and the capabilities of both polymers can be maximized. If the specific gravity is lower than 1.2, the specific gravity is close to that of polyamide fiber, which is not the objective of the present invention. If the specific gravity is higher than 1.5, it is undesirable because it tends to be difficult to obtain a monofilament for marine materials having practical strength in the present invention.
本発明においては、複合モノフィラメントにおいて、ポリアミド系樹脂とフッ素系樹脂とを上の比重の範囲となるように複合するものであり、複合モノフィラメントにおいてポリアミド系樹脂が占める割合は４０～９０体積％である。複合モノフィラメントにおいて、ポリアミド系樹脂が占める割合が４０体積％以上とすることにより、水産資材用モノフィラメントとして実用以上の強度を発揮し、かつ優れた結節強度を有するものとなる。一方、ポリアミド系樹脂が占める割合が９０体積％以下とすることにより、風に流されにくく、水中で浮き難い水産資材用モノフィラメントを得ることができる。 In the present invention, the polyamide resin and the fluororesin are combined in the composite monofilament so that the specific gravity falls within the above range, and the proportion of the polyamide resin in the composite monofilament is 40 to 90% by volume. By making the proportion of the polyamide resin in the composite monofilament 40% by volume or more, the monofilament exhibits strength greater than that practical for use as a fishery material and has excellent knot strength. On the other hand, by making the proportion of the polyamide resin 90% by volume or less, a monofilament for fishery materials that is less likely to be blown away by the wind and less likely to float in water can be obtained.
本発明における複合モノフィラメントは、ポリアミド系樹脂が占める割合が４０～９０体積％であることにより、下に記載する結節強力を達成しうるものとなる。すなわち、モノフィラメントの糸径が０．１９ｍｍのものは、結節強力５５０Ｎ／ｍｍ２以上である。糸径が０．２０～０．３９ｍｍのものは、結節強力５００Ｎ／ｍｍ２以上である。糸径が０．４０～０．４９ｍｍのものは、結節強力４００Ｎ／ｍｍ２以上である。糸径が０．５０～０．７９ｍｍのものは、結節強力３００Ｎ／ｍｍ２以上である。糸径が０．８０ｍｍ以上のものは、結節強力２５０Ｎ／ｍｍ２以上である。なお、結節強力の測定方法は、ＪＩＳ Ｌ １０１３ 結節強さに準じて測定したものである。また、本発明の水産資材用複合モノフィラメントの糸径は０．１ｍｍ～２．０ｍｍ程度がよい。 The composite monofilament of the present invention can achieve the knot strength described below by having a polyamide resin content of 40 to 90% by volume. That is, the monofilament has a knot strength of 550 N/mm2 or more when the thread diameter is 0.19 mm. The monofilament has a knot strength of 500 N/mm2 or more when the thread diameter is 0.20 to 0.39 mm. The monofilament has a knot strength of 400 N/mm2 or more when the thread diameter is 0.40 to 0.49 mm. The monofilament has a knot strength of 300 N/mm2 or more when the thread diameter is 0.50 to 0.79 mm. The monofilament has a knot strength of 250 N/ mm2 or more when the thread diameter is 0.80 mm or more. The knot strength is measured according to JIS L 1013 knot strength. The thread diameter of the composite monofilament for fishery materials of the present invention is preferably about 0.1 mm to 2.0 mm.
本発明における水産資材用芯鞘型複合モノフィラメントは、以下のように製造することによって得られる。まず、芯鞘型複合ノズルを用い、芯部にフッ素系樹脂、鞘部にポリアミド系樹脂を配し、ポリアミド系樹脂の比率が４０～９０体積％となるように計量して溶融紡糸する。 The sheath-core composite monofilament for marine resources in the present invention can be produced as follows: First, using a sheath-core composite nozzle , a fluororesin is arranged in the core and a polyamide resin is arranged in the sheath, and the ratio of the polyamide resin is measured to be 40 to 90% by volume and melt spun.
溶融紡糸の際の紡糸速度は、１２～３０ｍ／分とする。紡糸速度が３０ｍ／分を超えると、粘性の高いフッ素系樹脂は、紡糸速度が高過ぎて、その紡糸速度での塑性変形に追随できず均一に変形できなくなって、延伸方向に太細の斑が生じ、糸径斑および延伸切れの原因となってしまう。一方、紡糸速度が１２ｍ／分未満であると、ポリアミド系樹脂に対して紡糸速度が遅すぎることから、ポリアミド系樹脂において延伸斑（太細）が発生し、糸径斑および延伸切れの原因となる。 The spinning speed during melt spinning is 12 to 30 m/min. If the spinning speed exceeds 30 m/min, the highly viscous fluororesin will not be able to keep up with the plastic deformation at that spinning speed and will not be able to deform uniformly, resulting in uneven thickness and thinness in the stretching direction, which will cause unevenness in the thread diameter and stretching breakage. On the other hand, if the spinning speed is less than 12 m/min, the spinning speed is too slow for the polyamide resin, causing stretching unevenness (thickness and thinness) in the polyamide resin, which will cause unevenness in the thread diameter and stretching breakage.
フッ素系樹脂によってモノフィラメントを構成する場合の製造方法は、溶融紡糸時の紡糸速度は、数ｍ／分から１０ｍ／分程度に設定することが一般的である。これは、フッ素系樹脂の溶融粘性が高いことから、紡糸時に延伸斑が生じないようにするために、低い速度で紡糸することが必要とされるためである。しかしながら、本発明においては、紡糸速度を上記特定の範囲とすることにより、フッ素系樹脂とポリアミド系樹脂とを複合したモノフィラメントにおいて、水産資材用として必要な性能を具備させることができたのである。 In the manufacturing method for constructing monofilaments from fluororesin, the spinning speed during melt spinning is generally set to a few meters per minute to about 10 meters per minute. This is because fluororesin has a high melt viscosity, so it is necessary to spin at a low speed to prevent uneven stretching during spinning. However, in the present invention, by setting the spinning speed in the above specific range, it is possible to provide a monofilament composite of fluororesin and polyamide resin with the performance required for use in marine materials.
次いで、溶融紡糸した糸条は、５～２５℃の浴中で冷却した後、６５～９５℃の温水浴中で第一段延伸を行う。溶融紡糸した糸条を冷却は、上記した温度の水浴であっても、エチレングリコール浴であってよいが、取り扱い性が良好であることから水浴が好ましい。 The melt-spun yarn is then cooled in a bath at 5 to 25°C, and then the first stage of drawing is performed in a warm water bath at 65 to 95°C. The melt-spun yarn may be cooled in a water bath at the above-mentioned temperature or in an ethylene glycol bath, but a water bath is preferred because it is easier to handle.
一般に、フッ素系樹脂によってモノフィラメントが構成される場合、溶融紡糸後の冷却は、エチレングリコール浴中（約２０℃）で行い、次いで、第一段延伸を１５０～１７０℃のグリセリン浴中で行うことが通常に行われている。しかしながら、本発明の複合モノフィラメントを得るためには、溶融紡糸した糸条は、５～２５℃の水中で冷却した後、６５～９５℃の温水浴中で第一段延伸を行う。水中冷却を行った後に、特定の温度範囲の温水浴中で第一段延伸を行うことにより、本発明の複合モノフィラメントは、優れた結節強力を有するものとなる。第一段延伸の際、１５０～１７０℃のグリセリン浴中で行うと、実用的な機械的強力および優れた結節強力を有するモノフィラメントを得ることができない。これは、１５０～１７０℃のグリセリン浴中において、モノフィラメントを構成するポリアミド系樹脂がスーパードローの状態となり、良好な結晶構造を形成しないためであると考える。なお、グリセリンの温度を１００℃程度に下げると粘性が高すぎて取り扱い性が悪く製造工程の妨げとなり、後工程において糸表面に付着したグリセリンを完全に除去することが困難であることから、第二段延伸以降の熱処理において、フィラメント表面が荒れたものとなり、品質に劣ったものとなる。本発明において、第一段延伸の際の延伸倍率は、３．０～４．５倍が好ましい。 In general, when a monofilament is made of a fluororesin, cooling after melt spinning is usually performed in an ethylene glycol bath (about 20°C), and then the first stage of drawing is performed in a glycerin bath at 150 to 170°C. However, in order to obtain the composite monofilament of the present invention, the melt-spun thread is cooled in water at 5 to 25°C, and then the first stage of drawing is performed in a warm water bath at 65 to 95°C. By performing the first stage of drawing in a warm water bath of a specific temperature range after water cooling, the composite monofilament of the present invention has excellent knot strength. If the first stage of drawing is performed in a glycerin bath at 150 to 170°C, it is not possible to obtain a monofilament with practical mechanical strength and excellent knot strength. This is believed to be because the polyamide resin constituting the monofilament becomes in a super-draw state in a glycerin bath at 150 to 170°C, and does not form a good crystal structure. However, if the temperature of glycerin is lowered to about 100°C, the viscosity becomes too high, making it difficult to handle and hindering the manufacturing process, and it is difficult to completely remove the glycerin attached to the yarn surface in the subsequent process, so the filament surface becomes rough in the heat treatment after the second stage drawing, resulting in poor quality. In the present invention, the draw ratio in the first stage drawing is preferably 3.0 to 4.5 times.
第一段延伸を行った糸条は、次いで、１００～２５０℃で第二段延伸と弛緩熱処理を行うことによって、本発明の水産資材用複合モノフィラメントを得ることができる。１００～２５０℃で第二段延伸および弛緩熱処理により、前述した第一段延伸によってポリアミド系樹脂中に形成した結晶構造がさらに配向することによって、実用的な機械的強力および優れた結節強力を有するモノフィラメントを得ることができると考える。第二段延伸の延伸倍率は１．３～２．０倍が好ましく、さらに必要に応じて第三段延伸を行い、全延伸倍率は５．０～７．０倍が好ましい。なお、必要に応じて行う第三段延伸は１倍を超え、１．５倍以下がよい。 The yarn that has been subjected to the first stage drawing is then subjected to a second stage drawing and relaxation heat treatment at 100 to 250°C to obtain the composite monofilament for fishery materials of the present invention. It is believed that the second stage drawing and relaxation heat treatment at 100 to 250°C further orients the crystal structure formed in the polyamide resin by the above-mentioned first stage drawing, thereby obtaining a monofilament with practical mechanical strength and excellent knot strength. The draw ratio in the second stage drawing is preferably 1.3 to 2.0 times, and a third stage drawing is further performed as necessary, with a total draw ratio of preferably 5.0 to 7.0 times. The third stage drawing, which is performed as necessary, is preferably more than 1 time and 1.5 times or less.
第二段延伸および弛緩熱処理は、１００℃であれば温水バス中にて行うとよい。１００℃を超える温度で行う場合は、加熱ヒーターを用いた乾熱雰囲気下で熱延伸するとよい。 熱延伸および弛緩熱処理後は、巻取って、複合モノフィラメントが得られる。 The second-stage drawing and relaxation heat treatment may be carried out in a hot water bath at 100° C. If the temperature exceeds 100° C., hot drawing may be carried out in a dry heat atmosphere using a heater. After the hot drawing and relaxation heat treatment, the composite monofilament is wound up to obtain the composite monofilament.
本発明における水産資材用芯鞘型複合モノフィラメントは、フッ素系樹脂とポリアミド系樹脂とが芯鞘複合型に複合されて構成してなる糸であって、水産資材用として好適な比重と機械的強力を有し、かつ優れた結節強力を有し、また、取り扱い性に優れている。 The core-sheath type composite monofilament for marine materials of the present invention is a yarn composed of a fluororesin and a polyamide resin composited in a core-sheath type, and has a specific gravity and mechanical strength suitable for use in marine materials, as well as excellent knot strength and ease of handling.
次に、本発明を実施例に基づいて説明する。なお、本発明は、下の実施例に限定されるものではない。また、実施例における特性値等の測定方法は次のとおりである。
（１）繊度（ｄｔｅｘ）
モノフィラメントを一定長（１０ｍ）採取し、その質量を測定し１０，０００ｍ当たりの質量を算出した。
（２）引張強さおよび伸び率（Ｎ／ｍｍ２）
ＪＩＳ Ｌ－１０１３ 引張強さおよび伸び率の標準時試験に準じて、定速伸長形引張試験機（島津製作所オートグラフＤＳＳ－５００）を用い、つかみ間隔２５ｃｍ、引張速度３０ｃｍ／分で測定した。また、試料の糸径を、ミツトヨ製デジマチックマイクロメーターＭＤＨ－２５ＭＢを用いて測定し、前記で得られた引張強さの値と糸径から、断面積（ｍｍ２）当たりの強力を算出した。
（３）モノフィラメントの比重
上記（１）と（２）で求めた繊度と糸径から、下記計算式を用いて比重を算出した。
The present invention will now be described with reference to examples. Note that the present invention is not limited to the following examples. The measurement methods for the characteristics and the like in the examples are as follows.
(1) Fineness (dtex)
A fixed length (10 m) of the monofilament was taken, its mass was measured, and the mass per 10,000 m was calculated.
(2) Tensile strength and elongation (N/mm 2 )
According to JIS L-1013 standard test for tensile strength and elongation, measurements were made using a constant speed extension tensile tester (Shimadzu Corporation Autograph DSS-500) with a grip distance of 25 cm and a pulling speed of 30 cm/min. The yarn diameter of the sample was measured using a Mitutoyo Corporation Digimatic Micrometer MDH-25MB, and the strength per cross-sectional area (mm 2 ) was calculated from the tensile strength value and yarn diameter obtained above.
(3) Specific Gravity of Monofilament The specific gravity was calculated from the fineness and yarn diameter obtained in (1) and (2) above using the following formula.
比重＝繊度（ｇ／１０,０００ｍ）÷（糸半径（ｃｍ）×糸半径（ｃｍ）×π×１０，０００（ｍ）×１００） Specific gravity = fineness (g/10,000m) ÷ (yarn radius (cm) x yarn radius (cm) x π x 10,000 (m) x 100)
実施例１
鞘部に配するポリアミド系樹脂として、ナイロン６・６６共重合樹脂（ＤＳＭ社製、商 品名「ノバミッド２０３０Ｊ」）を準備した。また、芯部に配するフッ素系樹脂として、 ポリフッ化ビニリデン樹脂（Ｚｅｊｉａｎｇ Ｆｌｕｏｒｉｎｅ Ｃｈｅｍｉｃａｌ Ｎｅｗ Ｍａｔｅｒｉａｌ社製 商品名「Ｚｈｅｆｌｏｎ ＦＬ２００５」）を準備した。
Example 1
A nylon 6-66 copolymer resin (manufactured by DSM, product name "Novamid 2030J") was prepared as the polyamide resin for the sheath, and a polyvinylidene fluoride resin (manufactured by Zejiang Fluorine Chemical New Material, product name "Zheflon FL2005") was prepared as the fluorine resin for the core.
ポリアミド系樹脂（鞘部）／フッ素系樹脂（芯部）＝７４．４／２５．６（体積比）となるように計量し、ポリマー温度を２５５℃で１．８ｍｍφ×６Ｈの紡糸口金から、紡糸速度１７．４ｍ／分の条件で溶融紡糸した（芯部の数は１）。溶融紡糸した糸条は、速度１７．４ｍ／分で１０℃の水浴中で冷却した後、巻き取ることなく、８５℃の温浴中にて３．２倍で延伸し（第一段延伸）、次いで巻き取ることなく、２２５℃の乾熱雰囲気中で１．８倍で延伸し（第二段延伸）、その後、リラックスさせた後、巻き取った（総延伸倍率５．８倍）。得られた複合モノフィラメントは、糸径０．２７５ｍｍ、繊度８４５ｄｔｅｘ、引張強さ８４６Ｎ／ｍｍ２、伸度２４．０％、結節強度６１９Ｎ／ｍｍ２、比重１．４２であった。 The polyamide resin (sheath)/fluororesin (core) ratio was measured at 74.4/25.6 (volume ratio), and melt spun from a 1.8 mmφ×6H spinneret at a polymer temperature of 255° C. at a spinning speed of 17.4 m/min (the number of cores was 1). The melt spun yarn was cooled in a water bath at 10° C. at a speed of 17.4 m/min, and then stretched 3.2 times in a warm bath at 85° C. without winding (first-stage stretching), then stretched 1.8 times in a dry heat atmosphere at 225° C. without winding (second-stage stretching), and then relaxed and wound (total stretching ratio 5.8 times). The composite monofilament obtained had a yarn diameter of 0.275 mm, a fineness of 845 dtex, a tensile strength of 846 N/mm 2 , an elongation of 24.0%, a knot strength of 619 N/mm 2 , and a specific gravity of 1.42.
比較例１
ポリフッ化ビニリデン樹脂（３Ｍ社製 商品名「Ｄｙｎｅｏｎ ＰＶＤＦ６０１２／００００」）のみを用い、単成分のモノフィラメントを製造した。すなわち、ポリマー温度２５０℃で１．１ｍｍφ×６Ｈの紡糸口金から、紡糸速度５．４ｍ／分の条件で溶融紡糸した（単層のフィラメント）。溶融紡糸した糸条は、速度５．４ｍ／分で６０℃のエチレングリコール浴中で冷却した後、巻き取ることなく、１５７℃のグリセリン浴中で延伸し（延伸倍率３．３倍）、さらに巻き取ることなく、１６０℃の乾熱雰囲気中で延伸し（延伸倍率１．４倍）、さらに巻き取ることなく１７０℃の乾熱雰囲気中で延伸し（延伸倍率１．２８倍）、その後、リラックスさせた後、巻き取った（総延伸倍率５．９倍）。得られたモノフィラメントは、糸径０．３０５ｍｍ、繊度１３１４ｄｔｅｘ、引張強さ８６５Ｎ／ｍｍ２、切断伸度２７．０％、結節強度４６１Ｎ／ｍｍ２、比重１．７９であった。
Comparative Example 1
A single-component monofilament was produced using only polyvinylidene fluoride resin (manufactured by 3M under the trade name "Dyneon PVDF6012/0000"). That is, melt spinning was performed at a polymer temperature of 250°C from a 1.1 mmφ×6H spinneret at a spinning speed of 5.4 m/min (single-layer filament). The melt-spun yarn was cooled in an ethylene glycol bath at 60°C at a speed of 5.4 m/min, and then stretched in a glycerin bath at 157°C without winding (stretch ratio 3.3 times), stretched in a dry heat atmosphere at 160°C without winding (stretch ratio 1.4 times), stretched in a dry heat atmosphere at 170°C without winding (stretch ratio 1.28 times), relaxed, and then wound (total stretch ratio 5.9 times). The obtained monofilament had a yarn diameter of 0.305 mm, a fineness of 1314 dtex, a tensile strength of 865 N/mm 2 , an elongation at break of 27.0%, a knot strength of 461 N/mm 2 and a specific gravity of 1.79.
実施例１のモノフィラメントは、水産資材として良好に用いうる比重を有するものであって、実用的な引張強さを有し、また、結節強度は優れたものであった。
The monofilament of Example 1 had a specific gravity suitable for use as a fishery material, had practical tensile strength, and also had excellent knot strength.
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| JP2001123328A (en) | 1999-10-21 | 2001-05-08 | Toray Ind Inc | Noctilucent conjugate fiber and its use |
| JP2002371434A (en) | 2001-06-15 | 2002-12-26 | Toray Monofilament Co Ltd | Conjugate monofilament |
| JP2005076158A (en) | 2003-09-03 | 2005-03-24 | Toray Monofilament Co Ltd | Conjugate monofilament and fishing line |
| JP2006161219A (en) | 2004-12-08 | 2006-06-22 | Ube Ind Ltd | Conjugate monofilament |
| JP2009219360A (en) | 2008-03-13 | 2009-10-01 | Toray Monofilament Co Ltd | Fishline |
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| JP2001123328A (en) | 1999-10-21 | 2001-05-08 | Toray Ind Inc | Noctilucent conjugate fiber and its use |
| JP2002371434A (en) | 2001-06-15 | 2002-12-26 | Toray Monofilament Co Ltd | Conjugate monofilament |
| JP2005076158A (en) | 2003-09-03 | 2005-03-24 | Toray Monofilament Co Ltd | Conjugate monofilament and fishing line |
| JP2006161219A (en) | 2004-12-08 | 2006-06-22 | Ube Ind Ltd | Conjugate monofilament |
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