JP5173271B2 - Method for producing high toughness fiber - Google Patents
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- JP5173271B2 JP5173271B2 JP2007157178A JP2007157178A JP5173271B2 JP 5173271 B2 JP5173271 B2 JP 5173271B2 JP 2007157178 A JP2007157178 A JP 2007157178A JP 2007157178 A JP2007157178 A JP 2007157178A JP 5173271 B2 JP5173271 B2 JP 5173271B2
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- 239000000835 fiber Substances 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000007788 liquid Substances 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 24
- 230000009477 glass transition Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 230000005484 gravity Effects 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 11
- -1 polyethylene terephthalate Polymers 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002074 melt spinning Methods 0.000 claims description 4
- 238000009864 tensile test Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 description 22
- 238000009987 spinning Methods 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 16
- 230000035882 stress Effects 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 8
- 238000004804 winding Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006240 drawn fiber Polymers 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Description
本発明は、ポリエステル繊維などの高タフネス繊維の製造方法に関するものであり、詳しくは、延伸性に優れ、力学特性に優れた高タフネス繊維を製造する製造方法に関する。 The present invention relates to a method for producing high toughness fibers such as polyester fibers, and more particularly to a production method for producing high toughness fibers having excellent stretchability and excellent mechanical properties.
ポリエチレンテレフタレート繊維に代表されるポリエステル繊維は、高強力・高タフネスであり、耐候性、寸法安定性にも優れており、かつ溶融紡糸・延伸、さらには高速紡糸法などにより安価に製造できるため、衣料用途のみならず産業資材用途でも広く使用されている。それでも、近年は、更なる機械物性の向上が望まれており、従来なみの物性では満足されなくなってきている。
その中でも、紡糸した繊維を巻き取るまでにポリマーの配向や結晶性を制御する方法としては、種々の技術が提案されている。例えば、特許文献１（特開平１−１６２８２０号公報）では、ポリエステルの溶融紡糸において、巻取り前に常温の液浴中に導入してポリマーの結晶かを抑制するために急冷を行っている。これをさらに低倍率で延伸することにより、高強度繊維を得ている。しかしながら、伸度が十分あるとは言えず、ある程度の伸度を要求する用途には不向きであるという問題点がある。また、特許文献２（特表平５−５０８４４３号公報）では、液浴をガラス転移温度よりも高温にすることで断面内構造分布が発現しないように等温結晶化を促進させることにより、一工程で高強度化を達成しているが、これもまた従来の繊維を凌駕するような十分な強度とはいえない。
Among them, various techniques have been proposed as a method for controlling the orientation and crystallinity of a polymer before winding a spun fiber. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 1-162820), in polyester melt spinning, rapid cooling is performed in order to suppress polymer crystals introduced into a liquid bath at room temperature before winding. This is further stretched at a low magnification to obtain high-strength fibers. However, it cannot be said that the elongation is sufficient, and there is a problem that it is not suitable for applications requiring a certain degree of elongation. Further, in Patent Document 2 (Japanese Patent Publication No. 5-508443), one step is performed by promoting isothermal crystallization so that the structure distribution in the cross section does not appear by setting the liquid bath to a temperature higher than the glass transition temperature. However, this is also not enough strength to surpass conventional fibers.
本発明は、上記従来技術における問題点を解決し、産業用途に適した高強度・高タフネスの繊維を製造する方法を提供することにある。 An object of the present invention is to solve the above-mentioned problems in the prior art and to provide a method for producing high strength and high toughness fibers suitable for industrial use.
本発明は、繊維形成性ポリマーから形成され、比重法から求めた結晶化度が１５％未満であり、かつ下記式で表される絡み合いパラメータαが０．３以下である未延伸糸を、３倍以上の倍率にて延伸することを特徴とする高タフネス繊維の製造方法に関する。
絡み合いパラメータα＝σ／（λ２−λ-１）
λ＝１００／（１００−ｓ）
ここで、ｓ；沸水収縮率（％）、σ；収縮応力（ＭＰａ）
The present invention relates to an undrawn yarn formed from a fiber-forming polymer, having a crystallinity of less than 15% determined by a specific gravity method, and an entanglement parameter α represented by the following formula of 0.3 or less: It is related with the manufacturing method of the high toughness fiber characterized by extending | stretching by the magnification more than double.
Entanglement parameter α = σ / (λ 2 −λ −1 )
λ = 100 / (100−s)
Where, s: boiling water shrinkage (%), σ: shrinkage stress (MPa)
本発明の方法によれば、強度が１．３ｃＮ／ｄｔｅｘ以上、破断伸度が４００％以上である高タフネス未延伸、およびこれを延伸・熱処理することによって、強度が８ｃＮ／ｄｔｅｘ以上、伸度が１５％以上、強度×√伸度で表されるタフネスが３５ｃＮ／ｄｔｅｘ・√％以上で、繊維直径比が１．５以上の高タフネス延伸繊維を製造できることが可能となった。 According to the method of the present invention, high toughness unstretched with a strength of 1.3 cN / dtex or more and a breaking elongation of 400% or more, and by stretching and heat-treating the same, the strength is 8 cN / dtex or more. Is 15% or more, and the toughness expressed by strength × √elongation is 35 cN / dtex · √% or more, and a high toughness drawn fiber having a fiber diameter ratio of 1.5 or more can be produced.
本発明によれば、紡糸線上の温度履歴の制御によって延伸性を保ったままタフネスを大幅に向上できる。
すなわち、本発明では、ポリエステルなどの高タフネス繊維を形成することが可能な繊維形成性ポリマーを溶融紡糸するに際し、紡糸口金から紡出後、複数の液体槽を通過させる際に、少なくとも一つ以上の液体槽がガラス転移温度以上に設定されており、最終的にはポリマーがガラス転移温度以下に冷却される前に、ガラス転移温度未満に設定した液体槽を通過させることで、急冷を施すことによって前述した課題を解決する。すなわち、分子鎖の運動性が高い状態で大きな歪を与えた後に急冷することにより、分子鎖の絡み合いを減少したまま固定することが可能となるため、高タフネス繊維となる。
According to the present invention, toughness can be significantly improved while maintaining stretchability by controlling the temperature history on the spinning line.
That is, in the present invention, when melt-spinning a fiber-forming polymer capable of forming high toughness fibers such as polyester, at least one or more when passing through a plurality of liquid tanks after spinning from a spinneret. The liquid tank is set to the glass transition temperature or higher, and finally, the polymer is cooled to below the glass transition temperature before passing through the liquid tank set to a temperature lower than the glass transition temperature for rapid cooling. The above-mentioned problem is solved. That is, when a large strain is applied in a state where the mobility of the molecular chain is high and then rapidly cooled, it becomes possible to fix the molecular chain while reducing the entanglement of the molecular chain, resulting in a high toughness fiber.
本発明の高タフネス繊維の製造方法は、繊維形成性ポリマーから形成され、比重法から求めた結晶化度が１５％未満であり、かつ下記式で表される絡み合いパラメータαが０．３以下である未延伸糸を、３倍以上の倍率にて延伸する。
絡み合いパラメータα＝σ／（λ２−λ-１）
λ＝１００／（１００−ｓ）
ここで、ｓ；沸水収縮率（％）、σ；収縮応力（ＭＰａ）
The high toughness fiber production method of the present invention is formed from a fiber-forming polymer, the crystallinity obtained from the specific gravity method is less than 15%, and the entanglement parameter α represented by the following formula is 0.3 or less. A certain undrawn yarn is drawn at a magnification of 3 times or more.
Entanglement parameter α = σ / (λ 2 −λ −1 )
λ = 100 / (100−s)
Where, s: boiling water shrinkage (%), σ: shrinkage stress (MPa)
ここで、本発明に用いられる高タフネス繊維を形成することが可能な繊維形成性ポリマーとしては、ポリエステルが好ましい。このポリエステルは、全繰り返し単位中の少なくとも９０モル％がエチレンテレフタレート単位であるポリエチレンテレフタレートから形成される必要がある。さらに好ましくは、少なくとも９５モル％がエチレンテレフタレート単位であることである。また、本発明の目的を阻害しない範囲内、例えば全酸成分を基準として１０モル％以下の範囲内で第三成分が共重合されたものであってもよい。さらに、上記ポリエチレンナフタレート中には少量の他の重合体や酸化防止剤、制電剤、顔料、蛍光増白剤その他の添加剤が含有されていてもよい。 Here, as the fiber-forming polymer capable of forming the high toughness fiber used in the present invention, polyester is preferable. This polyester needs to be formed from polyethylene terephthalate in which at least 90 mol% of all repeating units are ethylene terephthalate units. More preferably, at least 95 mol% is ethylene terephthalate units. Further, the third component may be copolymerized within a range that does not impair the object of the present invention, for example, within a range of 10 mol% or less based on the total acid component. Further, the polyethylene naphthalate may contain a small amount of other polymers, antioxidants, antistatic agents, pigments, fluorescent brighteners and other additives.
かかるポリエチレンテレフタレートの固有粘度［フェノール／テトラクロロエタン混合溶媒（混合重量比＝６／４）にて、３５℃で測定］は、通常、０．７〜２．０ｄｌ／ｇ、好ましくは０．８〜１．３ｄｌ／ｇである。上記固有粘度が０．７ｄｌ／ｇ未満の場合には、製糸後の切断強度や切断伸度が低くなる傾向にあるので産業用途として好ましくない。一方、固有粘度が２．０ｄｌ／ｇを超えると、繊維の製造が困難となる。 The intrinsic viscosity of the polyethylene terephthalate [measured at 35 ° C. with a phenol / tetrachloroethane mixed solvent (mixing weight ratio = 6/4)] is usually 0.7 to 2.0 dl / g, preferably 0.8 to 1.3 dl / g. When the intrinsic viscosity is less than 0.7 dl / g, the cutting strength and cutting elongation after yarn forming tend to be low, which is not preferable for industrial use. On the other hand, when the intrinsic viscosity exceeds 2.0 dl / g, it becomes difficult to produce the fiber.
本発明の製造方法において、未延伸糸の結晶化度は１５％未満、好ましくは０％〜１５％未満、さらに好ましくは０〜１０％未満である。未延伸糸の比重法から求めた結晶化度が１５％以上であると、紡糸工程で配向結晶化が進んでいるため、高強度化に必要な高倍率延伸が不可能となる。 In the production method of the present invention, the degree of crystallinity of the undrawn yarn is less than 15%, preferably 0% to less than 15%, more preferably 0 to less than 10%. When the degree of crystallization obtained from the specific gravity method of undrawn yarn is 15% or more, oriented crystallization is progressing in the spinning process, and thus high-strength drawing necessary for high strength becomes impossible.
また、未延伸糸の絡み合いパラメータαは古典的なゴム弾性理論に基づいた弾性率を示しており、αが低いことは収縮応力に寄与する高分子鎖の絡み合い点の密度が低いことを意味する。すなわち、αが０．３より大きい未延伸糸の場合は、絡み合いが多くなり高強度化が困難となる。絡み合いパラメータαは、好ましくは０．００１〜０．３、さらに好ましくは０．０１〜０３である。
なお、αを求める際の沸水収縮率sは、通常、１〜９０％、好ましくは１０〜７０％、さらに好ましくは２０〜６０％である。
また、αを求める際の収縮応力は、通常、０．０１〜３ＭＰａ、好ましくは０．０５〜２ＭＰａである。
Further, the entanglement parameter α of the undrawn yarn indicates an elastic modulus based on the classical rubber elasticity theory, and a low α means that the density of the entanglement points of the polymer chain contributing to the shrinkage stress is low. . That is, in the case of an undrawn yarn having α larger than 0.3, the entanglement increases and it is difficult to increase the strength. The entanglement parameter α is preferably 0.001 to 0.3, and more preferably 0.01 to 03.
In addition, the boiling water shrinkage | contraction rate s at the time of calculating | requiring (alpha) is 1-90% normally, Preferably it is 10-70%, More preferably, it is 20-60%.
Moreover, the shrinkage stress when calculating | requiring (alpha) is 0.01-3 Mpa normally, Preferably it is 0.05-2 Mpa.
また、この際、未延伸糸の強度は、好ましくは１．３ｃＮ／ｄｔｅｘ以上、さらに好ましくは１．３〜９．０ｃＮ／ｄｔｅｘ、特に好ましくは１．３〜７ｃＮ／ｄｔｅｘ、破断伸度は好ましくは４００％以上、さらに好ましくは４００〜１，０００％、特に好ましくは、４００〜９００％である。強度が１．３ｃＮ／ｄｔｅｘ未満では、延伸熱処理後に十分な強度を発現することができない。また。破断伸度が４００％未満では、高倍率延伸ができなくなり、延伸後の強度を高めることができない。
ここで、未延伸糸の強度を１．３ｃＮ／ｄｔｅｘ以上にするには、液体槽の長さを十分に長くすることが必要である。
また、破断伸度を４００％以上にするには、液体槽の温度をガラス転移温度よりも十分に高くすることが必要である。
At this time, the strength of the undrawn yarn is preferably 1.3 cN / dtex or more, more preferably 1.3 to 9.0 cN / dtex, particularly preferably 1.3 to 7 cN / dtex, and the elongation at break is preferably Is 400% or more, more preferably 400 to 1,000%, and particularly preferably 400 to 900%. If the strength is less than 1.3 cN / dtex, sufficient strength cannot be expressed after the stretching heat treatment. Also. If the elongation at break is less than 400%, high-stretching cannot be performed, and the strength after stretching cannot be increased.
Here, in order to increase the strength of the undrawn yarn to 1.3 cN / dtex or more, it is necessary to sufficiently increase the length of the liquid tank.
Moreover, in order to make the breaking elongation 400% or more, it is necessary to make the temperature of the liquid tank sufficiently higher than the glass transition temperature.
さらに、紡出糸条における未延伸糸の引張試験破断時の繊度あたりの破断真強度は、好ましくは９．０ｃＮ／ｄｔｅｘ以上、さらに好ましくは９．０〜２０．０ｃＮ／ｄｔｅｘ、特に好ましくは９．０〜１８．０である。９．０ｃＮ／ｄｔｅｘ未満では、高いタフネスが要求される産業用途での使用十分耐えられない。
ここで、上記強度を９．０ｃＮ／ｄｔｅｘ以上にするには、例えば未延伸糸のガラス転移温度以上に保った液体恒温槽の液温をできるだけ高く保ち、またはより長く繊維が接するよう、恒温槽の長さを延長すればよい。通常、未延伸糸の破断真強度は、破断強度を向上させれば伸度が低下し、逆に伸度を向上させようとすれば破断強度が低下するため、両立は困難であったが、このような方法を用いることにより、破断強度と破断伸度の両方の値を高いレベルに保つことが可能となる。
Further, the true breaking strength per fineness at the time of breaking the undrawn yarn in the spun yarn is preferably 9.0 cN / dtex or more, more preferably 9.0 to 20.0 cN / dtex, and particularly preferably 9 0.0-18.0. If it is less than 9.0 cN / dtex, it cannot be sufficiently used in industrial applications requiring high toughness.
Here, in order to make the above strength 9.0 cN / dtex or more, for example, the liquid temperature of the liquid thermostat kept at or above the glass transition temperature of the undrawn yarn is kept as high as possible, or the thermostat is kept in contact with the fiber for a longer time. Should be extended. Usually, the true breaking strength of the undrawn yarn decreases the elongation if the breaking strength is improved, and conversely, if it is attempted to improve the elongation, the breaking strength decreases. By using such a method, it is possible to keep both the breaking strength and breaking elongation at high levels.
さらに、紡出糸条である未延伸糸の比重は、好ましくは１．３３５以上１．３５未満、である。比重がこの範囲内にあると、延伸時に結晶化を抑えて高倍率延伸することができるために強度が向上しやすい。
上記未延伸糸の比重は、引取り速度などにより調整することができる。
Furthermore, the specific gravity of the undrawn yarn that is the spun yarn is preferably 1.335 or more and less than 1.35. When the specific gravity is within this range, crystallization can be suppressed at the time of stretching and the film can be stretched at a high magnification, so that the strength is easily improved.
The specific gravity of the undrawn yarn can be adjusted by the take-up speed or the like.
述のような高タフネス繊維を製造する方法としては、紡糸口金直下に設置した複数の液体槽を通過させ引き取る製造方法であって、少なくとも一つの液体槽（１）の液体温度が未延伸のガラス転移温度（Ｔｇ）以上、好ましくは融点（Ｔｍ）未満であり、最後の液体槽（２）に進入するときのポリマー温度が好ましくはＴｇ以上であり、液体槽（２）の液体温度がＴｇ未満であることが必要である。液体槽（１）〜（２）の液体温度が全てＴｇ未満である場合、液浴中でのポリマーの運動は凍結されており、原理上分子鎖に作用を及ぼすことができないため、少なくとも一つの液体槽（１）はＴｇ以上、好ましくはＴｍ未満である必要がある。さらに好ましくは、１５０〜３２０℃、特に好ましくは２００〜３００℃である。Ｔｍ以上であると、液浴中の張力が低下しすぎるために破断してしまうので好ましくない。また、最後の液体槽（２）に進入する時のポリマー温度はＴｇ以上、好ましくはＴｍ未満である必要がある。Ｔｇに満たないと、ポリマーを急冷することにならず、絡み合いの固定ができない。なお、Ｔｍ以上では、液浴中で融着を引き起こすので好ましくない。また、最後の液体槽の温度がＴｇ以上である場合も同様に効果がなくなってしまう。 A method for producing the high toughness fiber as described above is a production method in which a plurality of liquid tanks installed just below the spinneret are passed through and pulled, and the liquid temperature of at least one liquid tank (1) is unstretched glass. Transition temperature (Tg) or more, preferably less than the melting point (Tm), the polymer temperature when entering the last liquid tank (2) is preferably Tg or more, and the liquid temperature in the liquid tank (2) is less than Tg It is necessary to be. When the liquid temperatures in the liquid baths (1) to (2) are all lower than Tg, the movement of the polymer in the liquid bath is frozen and cannot in principle affect the molecular chain, so that at least one The liquid tank (1) needs to be Tg or more, preferably less than Tm. More preferably, it is 150-320 degreeC, Most preferably, it is 200-300 degreeC. If it is Tm or more, the tension in the liquid bath is too low, so that it breaks. Moreover, the polymer temperature when entering the last liquid tank (2) needs to be Tg or more, preferably less than Tm. If it is less than Tg, the polymer is not rapidly cooled and entanglement cannot be fixed. In addition, when Tm or more, fusion is caused in the liquid bath, which is not preferable. Similarly, the effect is lost when the temperature of the last liquid tank is equal to or higher than Tg.
このようにして得られた繊維は十分な強度と伸度を有しているが、一旦巻き取った後、あるいは一旦巻き取ることなく延伸工程において、３倍以上の倍率で延伸することが必要である。すなわち、最終的に高強度の繊維を製造するには、少なくとも３倍以上、好ましくは３〜１０倍、さらに好ましくは３〜６倍の延伸倍率で延伸する必要がある。３倍未満であると、産業用途に要求される十分な強度を発現しない。 Although the fiber thus obtained has sufficient strength and elongation, it must be stretched at a magnification of 3 times or more in the stretching process after being wound once or without being wound once. is there. That is, in order to finally produce a high-strength fiber, it is necessary to draw at a draw ratio of at least 3 times, preferably 3 to 10 times, more preferably 3 to 6 times. If it is less than 3 times, sufficient strength required for industrial use is not exhibited.
以下、本発明の高タフネス繊維の製造方法について、さらに具体的に説明する。
すなわち、本発明における紡糸工程は、常法によって溶融、計量された上記ポリエステルなどの繊維形成性ポリマーを紡糸口金より吐出、巻取するに際し、紡出糸条を、雰囲気温度がＴｇ以上、好ましくはＴｍ未満である液体槽（加熱装置）を通過させた後、雰囲気温度がＴｇ未満である液体槽（冷却装置）を通過させることを特徴とする。すなわち、本発明では、紡出糸条を上記特定の雰囲気温度にある加熱装置を通過させることで、紡出糸条を糸条の走行方向に配向させ（１種の延伸処理に相当する）、次いで、特定の雰囲気温度にある冷却装置を通過させることにより、この配向を固定させ、これにより、高タフネス繊維を得るものである。
Hereinafter, the manufacturing method of the high toughness fiber of this invention is demonstrated more concretely.
That is, in the spinning process of the present invention, when the fiber-forming polymer such as polyester melted and weighed by a conventional method is discharged and wound from the spinneret, the spinning yarn has an ambient temperature of Tg or higher, preferably The liquid tank (heating device) having a temperature lower than Tm is allowed to pass, and then the liquid tank (cooling device) having an ambient temperature lower than Tg is allowed to pass. That is, in the present invention, the spun yarn is passed in the running direction of the yarn by passing the spun yarn through the heating device at the above specific ambient temperature (corresponding to one kind of drawing treatment), Next, this orientation is fixed by passing through a cooling device at a specific ambient temperature, thereby obtaining high toughness fibers.
図1に本発明の繊維の製造方法を実施するための紡糸装置の１例を示す。まず、紡糸口金１ａよりフィラメントａを溶融紡糸する。次に、フィラメントａは、加熱装置２内を通過させたのち、冷却装置3内を通過させて冷却固化させ油剤付与装置４により油剤付与する。次に、フィラメントaを引取りロール６にて引取り、巻取り装置７で巻き取る。
FIG. 1 shows an example of a spinning device for carrying out the fiber manufacturing method of the present invention. First, the filament a is melt-spun from the
本発明において、フィラメントaを通過させる加熱装置および冷却装置は、内部に加熱および冷却媒体を供給、循環させる機能を持つものである。媒体の種類は特に限定されず気体、液体どちらでもよいが、フィラメント（紡出糸条）により大きな応力を与えることが可能な点で液体がより好ましい。このような装置を用いると、紡出糸条の冷却固化が進む前に加熱装置にフィラメントを導くことで該紡出糸条に大きな応力を与えることができ、フィラメントaが高配向となり、この構造を引き続き冷却装置に導くことで固定することができると考えられる。 In the present invention, the heating device and the cooling device for allowing the filament a to pass have a function of supplying and circulating a heating and cooling medium therein. The type of the medium is not particularly limited and may be either a gas or a liquid, but a liquid is more preferable in that a large stress can be applied to the filament (spun yarn). When such a device is used, a large stress can be applied to the spun yarn by guiding the filament to the heating device before the spinning yarn is cooled and solidified, and the filament a becomes highly oriented, and this structure It is thought that it can be fixed by continuously guiding to the cooling device.
加熱装置内の媒体温度（すなわち、加熱装置の雰囲気温度）は、（未延伸糸を構成するポリマーのガラス転移温度以上、好ましくは融点未満、さらに好ましくは１５０〜３２０℃、特に好ましくは２００〜３００℃である。媒体温度がポリマーのガラス転移温度未満である場合、フィラメントに高応力を付加する前に冷却固化を促進してしまい、望む物性が得られない。なお、融点以上であると、未延伸糸が融解したり、熱分解が促進され、望む物性が得られない。 The medium temperature in the heating apparatus (that is, the atmospheric temperature of the heating apparatus) is equal to or higher than the glass transition temperature of the polymer constituting the undrawn yarn, preferably less than the melting point, more preferably 150 to 320 ° C., particularly preferably 200 to 300. When the medium temperature is lower than the glass transition temperature of the polymer, cooling solidification is promoted before high stress is applied to the filament, and desired physical properties cannot be obtained. The drawn yarn is melted or thermal decomposition is accelerated, and desired physical properties cannot be obtained.
なお、フィラメントaが加熱装置を通過する最適な長さ（加熱装置の深さ）は、紡糸温度、紡糸速度、フィラメントの繊度、ポリエステルの固有粘度などその他の紡糸パラメータによって異なるが、５〜５０ｃｍが好ましい。５ｃｍ未満ではフィラメントに十分な応力がかからずに高配向とならない。一方、５０ｃｍを超えると、高配向となるものの、結晶化が進みすぎて十分な物性差が得られない。さらに好ましくは、１０〜４０ｃｍである。
また、加熱装置の最適な位置は、紡糸温度、紡糸速度、フィラメントの繊度、ポリエステルの固有粘度などその他の紡糸パラメータによって異なるが、紡糸口金面から１００ｃｍ以下とすることが望ましい。１００ｃｍを超える場合フィラメントの冷却固化が完了し、高配向とならない。さらに好ましくは、紡糸口金面から、１０〜６０ｃｍの位置である。
The optimum length of the filament a passing through the heating device (depth of the heating device) varies depending on other spinning parameters such as spinning temperature, spinning speed, filament fineness, intrinsic viscosity of the polyester, but is 5 to 50 cm. preferable. If it is less than 5 cm, sufficient stress is not applied to the filament and high orientation is not achieved. On the other hand, if it exceeds 50 cm, the orientation becomes high, but the crystallization proceeds so much that a sufficient difference in physical properties cannot be obtained. More preferably, it is 10-40 cm.
The optimum position of the heating device varies depending on other spinning parameters such as spinning temperature, spinning speed, filament fineness, and intrinsic viscosity of the polyester, but is preferably 100 cm or less from the spinneret surface. When it exceeds 100 cm, cooling and solidification of the filament is completed, and high orientation is not achieved. More preferably, the position is 10 to 60 cm from the spinneret surface.
なお、フィラメントaが加熱装置を通過する時間は、好ましくは０．０１１秒以上、さらに好ましくは０．０１１〜１．０００秒、特に好ましくは０．０１〜０．５００秒である。０．０１１秒未満では、絡み合い構造を変化させるのに不十分であり、強度向上に寄与しない。
なお、上記通過時間は、引取り速度や液体槽の深さにより調整することができる。
The time for the filament a to pass through the heating device is preferably 0.011 seconds or more, more preferably 0.011 to 1.000 seconds, and particularly preferably 0.01 to 0.500 seconds. If it is less than 0.011 seconds, it is insufficient for changing the entangled structure and does not contribute to the improvement of strength.
The passage time can be adjusted by the take-up speed and the depth of the liquid tank.
また、冷却装置内の媒体温度（すなわち、冷却装置内の雰囲気温度）は、未延伸糸のポリマーのガラス転移温度未満、好ましくは０〜６９℃、さらに好ましくは２０〜６９℃である。媒体温度がガラス転移温度以上では、冷却能力が十分でなく、望む物性が得られない。なお、媒体温度が２０℃未満では、冷却効果はそれほど増大せずに媒体温度低下のためのコストが高くなり望ましくない。 The medium temperature in the cooling device (that is, the atmospheric temperature in the cooling device) is less than the glass transition temperature of the polymer of the undrawn yarn, preferably 0 to 69 ° C., more preferably 20 to 69 ° C. When the medium temperature is equal to or higher than the glass transition temperature, the cooling capacity is not sufficient and desired physical properties cannot be obtained. If the medium temperature is less than 20 ° C., the cooling effect does not increase so much and the cost for lowering the medium temperature increases, which is not desirable.
なお、フィラメントaが冷却装置を通過する最適な長さ（冷却装置の深さ）は、紡糸温度、紡糸速度、フィラメントの繊度、ポリマーの固有粘度などその他の紡糸パラメータによって異なるが、１〜５０ｃｍが好ましい。１ｃｍ未満では冷却能力が十分でなく、望む物性が得られない。一方、５０ｃｍを超えると、冷却効果はそれほど増大せずに装置が大型化しコストが高くなり望ましくない。さらに好ましくは、１０〜３０ｃｍである。
また、冷却装置の最適な位置は、紡糸温度、紡糸速度、フィラメントの繊度、ポリマーの固有粘度などその他の紡糸パラメータによって異なるが、加熱装置下面から５０ｃｍ以下とすることが望ましい。５０ｃｍを超える場合、冷却装置にフィラメントが入る前に外気により冷却され望む物性が得られない。さらに好ましくは、加熱装置から、０〜３０ｃｍの位置である。
The optimum length of the filament a passing through the cooling device (cooling device depth) varies depending on other spinning parameters such as spinning temperature, spinning speed, filament fineness, and intrinsic viscosity of the polymer, but 1 to 50 cm. preferable. If it is less than 1 cm, the cooling capacity is not sufficient, and desired physical properties cannot be obtained. On the other hand, if it exceeds 50 cm, the cooling effect does not increase so much and the apparatus becomes larger and the cost becomes higher. More preferably, it is 10-30 cm.
The optimum position of the cooling device varies depending on other spinning parameters such as spinning temperature, spinning speed, filament fineness, and intrinsic viscosity of the polymer, but it is desirable that the cooling device is 50 cm or less from the lower surface of the heating device. When it exceeds 50 cm, the desired physical properties cannot be obtained due to cooling by the outside air before the filament enters the cooling device. More preferably, the position is 0 to 30 cm from the heating device.
なお、引取速度（巻き取り速度）は、通常、１，０００ｍ／分以下、好ましくは５０〜１，０００ｍ／分、さらに好ましくは１００〜１,０００ｍ／分である。１，０００ｍ／分を超えると、液体槽内での応力が高くなりすぎてしまい、糸切れが発生する。 The take-up speed (winding speed) is usually 1,000 m / min or less, preferably 50 to 1,000 m / min, and more preferably 100 to 1,000 m / min. If it exceeds 1,000 m / min, the stress in the liquid tank becomes too high and thread breakage occurs.
なお、図１においては、巻取り装置７でフィラメントを巻き取ったのち、または巻き取ることなく、さらに、延伸温度７０〜１００℃、好ましくは８０〜９０℃で、延伸倍率３．０倍以上、好ましくは３．０〜１０．０、さらに好ましくは３．０〜６．０、特に好ましくは３．０〜５．０で延伸する。
In addition, in FIG. 1, after winding up a filament with the winding
このようにして得られる延伸後のフィラメントaは、強度が好ましくは８ｃＮ／ｄｔｅｘ以上、さらに好ましくは８〜１７ｃＮ／ｄｔｅｘ、伸度が好ましくは１５％以上、さらに好ましくは１５〜５０％であり、強度（ｃＮ／ｄｔｅｘ）と伸度（％）の平方根との積であるタフネスが好ましくは３５以上、さらに好ましくは３５〜５０である。
強度が８ｃＮ／ｄｔｅｘ未満では、高い強度が要求される産業用途での使用に十分耐えられない。この強度は、延伸倍率により調整することができる。
また、伸度が１５％未満では、高い伸度が要求される産業用途や衣料用途での使用に十分耐えられない。この伸度は、延伸倍率により調整することができる。
さらに、タフネスが３５未満では、高いタフネスが要求される産業用途での使用に十分耐えられない。タフネスは、複数の液体槽の種々条件により調整することができる。
The filament a after stretching thus obtained has a strength of preferably 8 cN / dtex or more, more preferably 8 to 17 cN / dtex, and an elongation of preferably 15% or more, more preferably 15 to 50%. The toughness, which is the product of the strength (cN / dtex) and the square root of elongation (%), is preferably 35 or more, more preferably 35-50.
If the strength is less than 8 cN / dtex, it cannot sufficiently withstand use in industrial applications requiring high strength. This strength can be adjusted by the draw ratio.
Moreover, if elongation is less than 15%, it cannot fully endure the use in the industrial use and clothing use which require high elongation. This elongation can be adjusted by the draw ratio.
Furthermore, if the toughness is less than 35, it cannot sufficiently withstand use in industrial applications where high toughness is required. The toughness can be adjusted according to various conditions of the plurality of liquid tanks.
さらに、延伸後のフィラメントaは、繊維直径の最大径と最小径との比が好ましくは１．５以上、さらに好ましくは１．５〜１０、特に好ましくは２〜８である。１．５未満では、衣料用途において十分な嵩高性が得られない。この比は、引取り速度や液体槽の温度により調整することができる。このような繊維の直径比が存在する本発明の繊維は、強度に優れるだけではなく、嵩だかとなり衣料・内装用途にも適するものとなる。 Further, the filament a after stretching preferably has a ratio of the maximum diameter to the minimum diameter of the fiber diameter of 1.5 or more, more preferably 1.5 to 10, particularly preferably 2 to 8. If it is less than 1.5, sufficient bulkiness cannot be obtained in clothing applications. This ratio can be adjusted by the take-up speed and the temperature of the liquid tank. The fiber of the present invention having such a fiber diameter ratio is not only excellent in strength but also bulky and suitable for clothing and interior applications.
なお、本発明の高タフネス繊維の製造方法によって得られる糸条は、総繊度が０．１〜６，０００ｄｔｅｘ、好ましくは２〜２，０００ｄｔｅｘ程度、フィラメント数が１〜５００フィラメント、好ましくは１〜３００フィラメント程度が対象となる。 The yarn obtained by the method for producing high toughness fibers of the present invention has a total fineness of 0.1 to 6,000 dtex, preferably about 2 to 2,000 dtex, and a filament count of 1 to 500 filaments, preferably 1 to The target is about 300 filaments.
次に、実施例および比較例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお以下の実施例に用いた各特性の評価方法を示す。 EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples. In addition, the evaluation method of each characteristic used for the following example is shown.
（１）固有粘度
昭和電工社製、Ｓｈｏｄｅｘ ＧＰＣ−１０１を用い、溶離液ＨＦＩＰ、カラムＨＦＩＰ−８０６Ｍ×２、検出器ＲＩ、流速１．０ｍＬ／ｍｉｎにて測定し、既知の固有粘度のポリエチレンテレフタレートを用いて換算した。
（２）比重
ＪＩＳ Ｌ １０１３（２００２）に準じ、密度勾配管を用いて測定した。
なお、結晶化度χ（％）は、この比重ρ（ｇ／ｃｍ３）から、以下の式を用いて求めた。
χ＝〔（ρ−１．３３５）／０．１２〕×１００
(1) Intrinsic Viscosity Polyethylene terephthalate with a known intrinsic viscosity measured using Shodex GPC-101, manufactured by Showa Denko KK, with eluent HFIP, column HFIP-806M × 2, detector RI, flow rate 1.0 mL / min. It converted using.
(2) Specific gravity Measured using a density gradient tube according to JIS L 1013 (2002).
The crystallinity χ (%) was determined from the specific gravity ρ (g / cm 3 ) using the following formula.
χ = [(ρ−1.335) /0.12] × 100
（３）強度、伸度
ＪＩＳ Ｌ １０１３（２００２）に準じ、島津製作所社製、オートグラフを用いて測定した。
なお、破断真強度Ｔｔは、強度Ｔ（ｃＮ／ｄｔｅｘ）と伸度Ｅ（％）から、以下の式を用いて求めた。
Ｔｔ＝Ｔ×（Ｅ＋１００）／１００
（５）収縮応力
インテック社製、熱応力測定装置を用い、初期過重０．１ｃＮ／ｄｔｅｘでセットした試料を昇温速度１００℃／ｍｉｎで測定し、ピーク値を読み取った。
（６）沸水収縮率
ＪＩＳ Ｌ １０１３（２００２）に準じて測定した。
（７）未延伸糸のガラス転移温度（Ｔｇ）
示差走査熱量測定装置を用い、ＪＩＳ Ｋ ７１２１（１９８７）に準じて測定した。
（８）
繊維径比
光学顕微鏡を用い、繊維の長手方向と垂直方向から直径を測定した。
(3) Strength and elongation Measured according to JIS L 1013 (2002) using an autograph manufactured by Shimadzu Corporation.
The true fracture strength Tt was determined from the strength T (cN / dtex) and the elongation E (%) using the following formula.
Tt = T × (E + 100) / 100
(5) Shrinkage stress Using a thermal stress measuring device manufactured by Intec Corporation, a sample set with an initial overload of 0.1 cN / dtex was measured at a temperature rising rate of 100 ° C./min, and a peak value was read.
(6) Boiling water shrinkage rate Measured according to JIS L 1013 (2002).
(7) Glass transition temperature (Tg) of undrawn yarn
Measurement was performed according to JIS K 7121 (1987) using a differential scanning calorimeter.
(8)
Fiber diameter ratio Using an optical microscope, the diameter was measured from the longitudinal direction of the fiber.
実施例１〜２、比較例１〜３
固有粘度が０．６５ｄｌ／ｇのポリエチレンテレフタレートチップを減圧下２３０℃〜２４０℃で固相重合して固有粘度１．０２ｄｌ／ｇの固相重合チップを得た。このチップを定法により溶融押し出し、孔径が０．６ｍｍφの吐出孔を１ホール配置した口金より溶融ポリマーを吐出させたのち表１に示すような種々の条件で引き取った。
なお液体槽の通過長さは５ｃｍで、媒体はシリコーンオイル。シリコーンオイルは室温で１００ｍPas・秒の粘度を有するものを用いて行った。
Examples 1-2 and Comparative Examples 1-3
A polyethylene terephthalate chip having an intrinsic viscosity of 0.65 dl / g was subjected to solid phase polymerization at 230 ° C. to 240 ° C. under reduced pressure to obtain a solid phase polymerization chip having an intrinsic viscosity of 1.02 dl / g. This chip was melt-extruded by a conventional method, and after the molten polymer was discharged from a die having one hole having a hole diameter of 0.6 mmφ, it was taken out under various conditions as shown in Table 1.
The passage length of the liquid tank is 5 cm, and the medium is silicone oil. A silicone oil having a viscosity of 100 mPas · sec at room temperature was used.
比較例４〜５
液体槽を一つ以下にした以外は、実施例１と同じで、表１に示すような種々の条件で引き取った。
Comparative Examples 4-5
The sample was taken under various conditions as shown in Table 1 except that the number of liquid tanks was one or less.
さらに、以上のようにして得られた未延伸繊維を、温度８０℃の第１ローラー、温度１４０℃の第２ローラー、および温度２２０℃の第３ローラーを用いて、それぞれ表１のような延伸倍率で延伸および熱セットを行った。この際、１段延伸倍率は総延伸倍率の６０％の割合で行った。このようにして延伸を行った際、破断に至る延伸倍率の９０％の倍率、およびその時の延伸応力および延伸後の繊維の物性を以下の表１に示す。
Further, the unstretched fibers obtained as described above were stretched as shown in Table 1 using a first roller at a temperature of 80 ° C, a second roller at a temperature of 140 ° C, and a third roller at a temperature of 220 ° C. Stretching and heat setting were performed at a magnification. At this time, the one-stage draw ratio was 60% of the total draw ratio. Table 1 below shows 90% of the draw ratio that leads to breakage, the drawing stress at that time, and the physical properties of the fiber after drawing when drawing in this way.
なお、本実施例では、液体恒温槽が２個の場合についての説明であるが、本発明の効果はこれに限定されるものではなく、３個以上用いる場合にも当てはまる。
これに対し、液体恒温槽を全く使用しないあるいは１個しか使用しない場合、十分高タフネスの繊維とならない。また、最終の液体槽に突入するポリマーの温度が低すぎる場合や最初の液体槽の温度が低すぎる場合、紡糸速度が高すぎる場合にも十分高タフネスとならない。
In addition, although a present Example demonstrates the case where there are two liquid thermostats, the effect of this invention is not limited to this, It is applicable also when using three or more.
On the other hand, when the liquid thermostat is not used at all or only one is used, the fiber does not have a sufficiently high toughness. Further, when the temperature of the polymer entering the final liquid tank is too low, when the temperature of the first liquid tank is too low, or when the spinning speed is too high, the toughness is not sufficiently high.
本発明の方法により得られる高タフネス繊維は、ゴム補強やシートベルトなどの産業用途のみならず嵩高性と強度特性を同時に要求する衣料・内装用途などにも有用である。 The high toughness fiber obtained by the method of the present invention is useful not only for industrial applications such as rubber reinforcement and seat belts, but also for clothing and interior applications that require bulkiness and strength characteristics at the same time.
１ａ：紡糸口金
２ ：加熱装置
３ ：冷却装置
４ ：油剤付与装置
６ ：引取り装置
７ ：巻取り装置
1a: Spinneret 2: Heating device 3: Cooling device 4: Oil agent applying device 6: Take-up device 7: Winding device
Claims (12)
絡み合いパラメータα＝σ／（λ２−λ-１）
λ＝１００／（１００−ｓ）
ここで、ｓ；沸水収縮率（％）、σ；収縮応力（ＭＰａ） An undrawn yarn obtained by melt spinning a fiber-forming polymer and passing through two or more liquid tanks, wherein the liquid temperature of at least one liquid tank (1) is equal to or higher than the glass transition temperature of the undrawn yarn, The liquid temperature of at least one other liquid tank (2) is lower than the glass transition temperature of the undrawn yarn, the crystallinity obtained from the specific gravity method is less than 15%, and the entanglement parameter α represented by the following formula: A method for producing a high toughness fiber, wherein an unstretched yarn having a diameter of 0.3 or less is drawn at a magnification of 3 times or more.
Entanglement parameter α = σ / (λ 2 −λ −1 )
λ = 100 / (100−s)
Where, s: boiling water shrinkage (%), σ: shrinkage stress (MPa)
絡み合いパラメータα＝σ／（λEntanglement parameter α = σ / (λ ２2 −λ−λ -１-1 ）)
λ＝１００／（１００−ｓ）λ = 100 / (100−s)
ここで、ｓ；沸水収縮率（％）、σ；収縮応力（ＭＰａ）Where, s: boiling water shrinkage (%), σ: shrinkage stress (MPa)
The high toughness fiber according to claim 11 , wherein the strength is 8 cN / dtex or more, the elongation is 15% or more, and the toughness, which is a product of the strength (cN / dtex) and the square root of the elongation (%), is 35 or more.
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