JP3129542B2 - Method for producing high-strength polyethylene naphthalate fiber - Google Patents
Method for producing high-strength polyethylene naphthalate fiberInfo
- Publication number
- JP3129542B2 JP3129542B2 JP04276011A JP27601192A JP3129542B2 JP 3129542 B2 JP3129542 B2 JP 3129542B2 JP 04276011 A JP04276011 A JP 04276011A JP 27601192 A JP27601192 A JP 27601192A JP 3129542 B2 JP3129542 B2 JP 3129542B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- yarn
- polyethylene naphthalate
- heating cylinder
- acid
- 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.)
- Expired - Fee Related
Links
Landscapes
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、特にタイヤコードとし
て有用な高強度、高弾性率および高タフネスを有するポ
リエチレンナフタレート繊維の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyethylene naphthalate fiber having high strength, high elastic modulus and high toughness, which is particularly useful as a tire cord.
【0002】[0002]
【従来の技術】高強度、高弾性率繊維の製造方法に関し
ては、特にポリエチレンテレフタレート繊維の場合に多
くの提案がなされている。(例えば特公昭41−789
2号公報など)その基本的な思想は、先ず複屈折率Δn
が小さい、低配向の未延伸糸を得ることが不可欠である
ということである。2. Description of the Related Art Many methods have been proposed for producing high-strength, high-modulus fibers, especially for polyethylene terephthalate fibers. (For example, Japanese Patent Publication No. 41-789)
No. 2, etc.) The basic idea is that the birefringence index Δn
It is essential to obtain a low-oriented, low-oriented undrawn yarn.
【0003】ポリエチレンナフタレート繊維の場合にも
同様な思想による提案がなされている。例えば特公昭5
0−16446号公報には、紡糸口金直下に温度勾配を
有する加熱筒を設け、紡出糸近傍の雰囲気温度を紡糸口
金直下から該雰囲気温度がポリマーの2次転移点になる
位置までの全区間にわたり、特定の雰囲気温度に制御す
る溶融紡糸方法が開示されている。[0003] A similar idea has been proposed for polyethylene naphthalate fiber. For example, Shoko 5
In Japanese Patent Application No. 0-16446, a heating cylinder having a temperature gradient is provided immediately below a spinneret, and the ambient temperature near the spun yarn is adjusted from just below the spinneret to a position where the ambient temperature becomes a secondary transition point of the polymer. A melt spinning method that controls a specific ambient temperature has been disclosed.
【0004】しかしながら、該方法では、確かに10g
/dの高強度は達成できるものの、伸度が低く、タフネ
スが小さいという問題がある。特に最近では、いわゆる
スーパー繊維などの開発が進み、産業資材用繊維に求め
られる品質が向上してきており、ポリエチレンナフタレ
ート繊維においてもさらなる高強度化、高弾性率化およ
び高タフネス化技術の開発が切望されている。[0004] However, in this method, 10 g
Although high strength of / d can be achieved, there is a problem that elongation is low and toughness is low. In particular, recently, the development of so-called super fibers has been progressing, and the quality required for fibers for industrial materials has been improving, and the development of technologies for increasing the strength, elastic modulus, and toughness of polyethylene naphthalate fibers has been increasing. Coveted.
【0005】[0005]
【発明が解決しようとする課題】本発明の目的は、高強
度、高弾性率でかつ高タフネスを有するポリエチレンナ
フタレート繊維の製造方法を提供すること、特にタイヤ
コード、ベルト、ホースなどのゴム資材の補強用繊維に
好適なポリエチレンナフタレート繊維の製造方法を提供
することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing polyethylene naphthalate fiber having high strength, high elastic modulus and high toughness, and in particular, rubber materials such as tire cords, belts and hoses. It is an object of the present invention to provide a method for producing a polyethylene naphthalate fiber suitable for a reinforcing fiber.
【0006】[0006]
【課題を解決するための手段】本発明者らは上記問題を
解決するために鋭意検討した結果、ポリエチレンナフタ
レートを溶融紡糸する際の冷却条件を制御し、ある特定
の複屈折率および結晶化ピーク温度を有する未延伸糸と
した後該未延伸糸を延伸することにより、高強度、高弾
性率でかつ高タフネスを有するポリエチレンナフタレー
ト繊維が得られることを究明した。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have controlled the cooling conditions for melt-spinning polyethylene naphthalate to obtain a specific birefringence and crystallization. It was clarified that a polyethylene naphthalate fiber having a high strength, a high elastic modulus and a high toughness can be obtained by drawing the undrawn yarn having a peak temperature and then drawing the undrawn yarn.
【0007】かくして本発明によれば、極限粘度が0.
65ないし1.00であるポリエチレンナフタレートを
450〜1200m/分の紡糸速度で溶融紡糸するに際
し、 (イ) 紡糸口金直下に、糸条の下流側になるにつれて低
温度となる温度勾配を有する長さ70cm以上の加熱筒
を設置し、該加熱筒の上流側少なくとも30cmは紡糸
口金温度以上400℃以下、また該加熱筒の最下部は2
00℃以上250℃以下の雰囲気温度に設定して吐出糸
条を遅延冷却し、 (ロ) 次いで糸条を25℃以下の冷風で冷却し、 (ハ) 冷却された糸条を引取りローラーで引取って、下
記 (1)〜 (2)式を同時に満足する未延伸とし、 (1) Δn=0.010 (2) Tc≧205 (ただし、Δnは未延伸糸の複屈折率、Tcは結晶化ピ
ーク温度〔℃〕) (ニ) 該未延伸糸を一旦巻取った後あるいは巻取ること
なしに延伸工程に供給し全延伸する、 ことを特徴とするポリエチレンナフタレート繊維の製造
方法が提供される。Thus, according to the present invention, the limiting viscosity is 0.1.
When melt-spinning polyethylene naphthalate of 65 to 1.00 at a spinning speed of 450 to 1200 m / min, (a) a length having a temperature gradient immediately below the spinneret that becomes lower as it goes downstream of the yarn. A heating cylinder having a length of 70 cm or more is installed, and at least 30 cm upstream of the heating cylinder has a spinneret temperature of 400 ° C. or less, and
Delayed cooling of the discharged yarn by setting the ambient temperature to 00 ° C or higher and 250 ° C or lower, (b) then cooling the yarn with cold air at 25 ° C or lower, (c) taking the cooled yarn with a take-up roller Then, it is taken as undrawn that simultaneously satisfies the following expressions (1) and (2). (1) Δn = 0.010 (2) Tc ≧ 205 (where Δn is the birefringence of the undrawn yarn, and Tc is (D) Crystallizing peak temperature [° C]) (d) A method for producing a polyethylene naphthalate fiber, wherein the undrawn yarn is supplied once to the drawing step after or once without winding, and is drawn entirely. Is done.
【0008】以下、本発明の構成を詳述する。本発明で
用いるポリエチレンナフタレート(以下PENという)
とは、エチレン−2,6−ナフタレート単位を90モル
%以上含むPENであり、10モル%以下の割合で適当
な第3成分を含む共重合体であってもよい。一般にPE
Nは、ナフタレン−2,6−ジカルボン酸またはその機
能的誘導体を触媒の存在下で適当な反応条件の下に重合
せしめることによって合成される。この際、PENの重
合完結前に適当な1種または2種以上の第3成分を添加
すれば、共重合ポリエステルが合成される。Hereinafter, the configuration of the present invention will be described in detail. Polyethylene naphthalate (hereinafter referred to as PEN) used in the present invention
Is a PEN containing 90 mol% or more of ethylene-2,6-naphthalate units, and may be a copolymer containing an appropriate third component in a proportion of 10 mol% or less. Generally PE
N is synthesized by polymerizing naphthalene-2,6-dicarboxylic acid or a functional derivative thereof under appropriate reaction conditions in the presence of a catalyst. At this time, if one or more appropriate third components are added before the completion of the polymerization of PEN, a copolymerized polyester is synthesized.
【0009】適当な第3成分としては、 (a) 2個のエステル形成性官能基を有する化合物;例え
ばシュウ酸、コハク酸、アジピン酸、セバシン酸、ダイ
マー酸などの脂肪族ジカルボン酸;シクロプロパンジカ
ルボン酸、シクロブタンジカルボン酸、シクロブタンジ
カルボン酸、ヘキサヒドロテレフタル酸などの脂環族ジ
カルボン酸;フタル酸、イソフタル酸、ナフタレン−
2,7−ジカルボン酸、ジフェニルジカルボン酸、など
の芳香族ジカルボン酸;ジフェニルエーテルジカルボン
酸、ジフェニルスルホンジカルボン酸、ジフェノキシエ
タンジカルボン酸、3,5−ジカルボキシベンゼンスル
ホン酸ナトリウムなどのカルボン酸;グリコール酸、p
−オキシ安息香酸、p−オキシエトキシ安息香酸などの
オキシカルボン酸;プロピレングリコール、トリメチレ
ングリコール、ジエチレングリコール、テトラメチレン
グリコール、ヘキサメチレングリコール、ネオペンチレ
ングリコール、p−キシリレングリコール、1,4−シ
クロヘキサンジメタノール、ビスフェノールA、p,
p’−ジフェノキシスルホン−1,4−ビス(β−ヒド
ロキシエトキシ)ベンゼン、2,2−ビス(p−β−ヒ
ドロキシエトキシフェニル)プロパン、ポリアルキレン
グリコール、p−フェニレンビス(ジメチルシクロヘキ
サン)などのオキシ化合物、あるいはその機能的誘導
体;前記カルボン酸類、オキシカルボン酸類、オキシ化
合物類またはその機能的誘導体から誘導される高重合度
化合物 (b) 1個のエステル形成性官能基を有する化合物、例え
ば安息香酸、ベンゾイル安息香酸、ベンジルオキシ安息
香酸、メトキシポリアルキレングリコールなどが挙げら
れる。Suitable third components include: (a) compounds having two ester-forming functional groups; for example, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid and dimer acid; cyclopropane Alicyclic dicarboxylic acids such as dicarboxylic acid, cyclobutanedicarboxylic acid, cyclobutanedicarboxylic acid and hexahydroterephthalic acid; phthalic acid, isophthalic acid, naphthalene-
Aromatic dicarboxylic acids such as 2,7-dicarboxylic acid and diphenyldicarboxylic acid; carboxylic acids such as diphenylether dicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3,5-dicarboxybenzenesulfonate; glycolic acid , P
Oxycarboxylic acids such as oxybenzoic acid and p-oxyethoxybenzoic acid; propylene glycol, trimethylene glycol, diethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentylene glycol, p-xylylene glycol, 1,4-cyclohexane Dimethanol, bisphenol A, p,
Examples of p'-diphenoxysulfone-1,4-bis (β-hydroxyethoxy) benzene, 2,2-bis (p-β-hydroxyethoxyphenyl) propane, polyalkylene glycol, p-phenylenebis (dimethylcyclohexane) and the like An oxy compound or a functional derivative thereof; a highly polymerizable compound derived from the carboxylic acid, oxycarboxylic acid, oxy compound or a functional derivative thereof (b) a compound having one ester-forming functional group, for example, benzoic acid Acids, benzoylbenzoic acid, benzyloxybenzoic acid, methoxypolyalkylene glycol and the like.
【0010】さらに、 (c) 3個以上のエステル形成性官能基を有する化合物、
例えばグリセリン、ペンタエリスリトール、トリメチル
プロパン なども重合体が実質的に線状である範囲内で使用可能で
ある。(C) a compound having three or more ester-forming functional groups,
For example, glycerin, pentaerythritol, trimethylpropane and the like can be used within a range where the polymer is substantially linear.
【0011】また、前記ポリエステル中に二酸化チタン
などの艶消剤やリン酸、亜リン酸およびそれらのエステ
ルなどの安定剤が含まれていてよいことはいうまでもな
い。It goes without saying that the polyester may contain a matting agent such as titanium dioxide and a stabilizer such as phosphoric acid, phosphorous acid and esters thereof.
【0012】本発明で用いるポリエチレンナフタレート
は、極限粘度が0.65好ましくは0.7以上1.0以
下である。極限粘度が0.65未満では本発明の目的と
する高強度、高弾性率は得られない。また、極限粘度が
1.0を超える場合は紡糸が不安定になりやすく実用上
好ましくない。The intrinsic viscosity of the polyethylene naphthalate used in the present invention is 0.65, preferably 0.7 or more and 1.0 or less. When the intrinsic viscosity is less than 0.65, the high strength and high elastic modulus aimed at by the present invention cannot be obtained. On the other hand, when the intrinsic viscosity exceeds 1.0, spinning tends to be unstable, which is not preferable in practical use.
【0013】前記ポリエチレンナフタレートを溶融紡糸
するに際しては、紡糸口金直下に加熱筒を設置する必要
がある。即ち、ポリエチレンナフタレートは溶融粘度が
高いので、この粘度を下げるためには紡糸口金温度を高
くする必要があり、従って吐出糸条が紡糸ドラフトによ
り急激に配向固化することを避けるために口金直下での
冷却を遅らせる必要があるからである。さらに、加熱筒
の長さはポリエチレンテレフタレートなどの場合に比べ
て長くする必要があり、少なくとも70cm以上の長さ
が必要である。When melt-spinning the polyethylene naphthalate, it is necessary to install a heating cylinder immediately below the spinneret. That is, since polyethylene naphthalate has a high melt viscosity, it is necessary to increase the spinneret temperature in order to reduce the viscosity.Therefore, in order to prevent the discharged yarn from being rapidly oriented and solidified by the spinning draft, the spinneret is located just below the spinneret. This is because it is necessary to delay the cooling. Further, the length of the heating cylinder needs to be longer than that of polyethylene terephthalate or the like, and at least 70 cm or more is required.
【0014】また、該加熱筒の上流側少なくとも30c
m以上は紡糸口金温度以上で、400℃以下の雰囲気温
度に保持する必要がある。前述の通り、高強度、高弾性
率繊維を得るためには低配向未延伸糸が必要であり、こ
のためには口金直下での遅延冷却が必須となるが、この
温度が紡糸口金温度未満では遅延冷却というよりはむし
ろ徐冷となり、複屈折率の低減効果が小さくなる。一
方、400℃を越えると糸揺れが大きくなり、単繊維間
の融着が発生するなど紡糸調子が悪化する。また、加熱
する長さが30cm未満では複屈折率低減効果が小さく
なる。Also, at least 30c upstream of the heating cylinder
It is necessary to maintain the atmosphere temperature of not less than m and not less than the spinneret temperature and not more than 400 ° C. As described above, in order to obtain a high-strength, high-modulus fiber, a low-orientation undrawn yarn is necessary.For this purpose, delayed cooling immediately below the die is essential, but if this temperature is lower than the spinneret temperature, Slow cooling is performed rather than delayed cooling, and the effect of reducing the birefringence is reduced. On the other hand, when the temperature exceeds 400 ° C., the yarn sway becomes large, and the spinning condition is deteriorated, for example, fusion between the single fibers occurs. If the heating length is less than 30 cm, the effect of reducing the birefringence will be small.
【0015】さらに、該加熱筒の雰囲気温度は糸条の下
流側になるにつれて低温度となるように設定する必要が
あり、最下部は200℃以上250℃以下であることが
必要である。このような温度勾配を設定することで遅延
冷却の区間を長くすることができる。加熱筒の最下部の
温度が200℃未満の場合は、後述の、結晶化ピーク温
度が205℃に達せず、一方、250℃を越えると糸揺
れが大きくなり、紡糸調子が低下したり単繊維間の融着
が発生する。Further, it is necessary to set the ambient temperature of the heating cylinder so that the temperature becomes lower toward the downstream side of the yarn, and it is necessary that the lowermost temperature is 200 ° C. or more and 250 ° C. or less. By setting such a temperature gradient, the section of delayed cooling can be lengthened. When the temperature at the lowermost part of the heating cylinder is lower than 200 ° C., the crystallization peak temperature described below does not reach 205 ° C. On the other hand, when the temperature exceeds 250 ° C., the yarn sway becomes large, and the spinning condition decreases or the single fiber Fusion occurs between them.
【0016】次いで、紡出糸条に25℃以下、好ましく
は10℃以下の冷風を吹きつけて冷却する。冷却風の吹
出し量や吹出し長さについては特に制限はないが、吹出
し量は2〜6Nm3 /分、吹出し長さは100〜500
mm程度が好ましい。Next, the spun yarn is cooled by blowing cold air of 25 ° C. or less, preferably 10 ° C. or less. There is no particular limitation on the blowing amount and blowing length of the cooling air, but the blowing amount is 2 to 6 Nm 3 / min, and the blowing length is 100 to 500.
mm is preferable.
【0017】次いで、冷却された糸条を、常法によって
油剤を付与した後、450〜1200m/分の紡糸速度
で巻取り、下記 (1) 〜 (2) 式を同時に満足する未延
伸として、一旦巻取るかあるいは連続的に延伸工程に供
給する。 (1) Δn≦0.010 (2) Tc≧205Next, the cooled yarn is applied with an oil agent by a conventional method, then wound at a spinning speed of 450 to 1200 m / min, and is undrawn as simultaneously satisfying the following expressions (1) and (2). Once wound or continuously fed to the stretching step. (1) Δn ≦ 0.010 (2) Tc ≧ 205
【0018】Δnが0.010を越えると高倍率延伸が
できないので、高強度、高弾性率繊維とすることができ
ない。Δnは小さい程好ましいが、実質的には0.00
3程度が限界である。一方、Tcが205℃未満の場合
も、高倍率延伸ができないので高強度、高弾性率繊維と
することができない。特に、下記 (1´)〜 (2´)式を
同時に満足する未延伸糸を延伸した場合には、引張強度
が10g/d以上、引張弾性率が270g/d以上およ
びタフネスが26g/d%1/2 以上の高強度、高弾性率
繊維を得ることができる。 (1´)Δn≦0.008 (2´)Tc≧208If Δn exceeds 0.010, high-stretching cannot be performed, so that high-strength, high-modulus fibers cannot be obtained. Δn is preferably as small as possible, but is substantially 0.00
About 3 is the limit. On the other hand, when Tc is less than 205 ° C., high-stretching cannot be performed, so that high-strength, high-modulus fibers cannot be obtained. In particular, when an undrawn yarn that simultaneously satisfies the following formulas (1 ′) and (2 ′) is drawn, the tensile strength is 10 g / d or more, the tensile modulus is 270 g / d or more, and the toughness is 26 g / d%. High strength and high modulus fibers of 1/2 or more can be obtained. (1 ′) Δn ≦ 0.008 (2 ′) Tc ≧ 208
【0019】延伸は、引取りローラーから一旦巻取っ
て、いわゆる別延伸法で延伸してもよく、あるいは引取
りローラーから連続的に延伸工程に未延伸糸を供給す
る、いわゆる直延伸法で延伸しても構わない。延伸倍率
は紡糸速度に依存するが、6.0倍以上に延伸するのが
好ましい。また、繊維の熱寸法安定性を向上させるため
にも、延伸工程で熱セットを行なうことが好ましい。The drawing may be carried out once by a take-up roller and then drawn by a so-called separate drawing method, or by a so-called straight drawing method in which undrawn yarn is continuously supplied from the take-up roller to a drawing step. It does not matter. The draw ratio depends on the spinning speed, but it is preferable that the draw ratio is 6.0 times or more. In order to improve the thermal dimensional stability of the fiber, it is preferable to perform heat setting in the drawing step.
【0020】[0020]
【発明の作用】本発明は以上の構成を採っているので以
下の作用を奏する。前述のように、高強度、高弾性率繊
維を製造するためには、低結晶、低配向の未延伸糸を
得、これを高倍率延伸することが不可欠である。従来よ
り、ポリエステル系未延伸繊維の結晶性は密度、配向性
は複屈折率Δnで表されるのが一般的であり、従って密
度およびΔnを極力小さくすることが高強度、高弾性率
化には有利であると考えられていた。Since the present invention adopts the above-described configuration, the following operations are provided. As described above, in order to produce a high-strength, high-modulus fiber, it is indispensable to obtain a low-crystal, low-orientation undrawn yarn and draw it at a high magnification. Conventionally, the crystallinity and orientation of polyester-based undrawn fibers are generally represented by the birefringence Δn. Therefore, it is necessary to reduce the density and Δn as much as possible to obtain high strength and high elastic modulus. Was considered advantageous.
【0021】ところが、本発明者らの検討によれば、紡
糸速度が450m/分以上のいわゆる中紡速域になる
と、密度よりも結晶化のピーク温度Tcの方が結晶の状
態を良く反映していることが判明した。例えば、紡速1
000m/分では密度1.329g/cm3 でTcは1
87℃であるのに対し、紡速2000m/分では密度は
1.335g/cm3 とほとんど変化していないのにT
cは158℃まで低下している。即ち、密度が同程度で
あっても、結晶化ピーク温度Tcが微細な結晶性の差異
を検出しているものと考えられる。However, according to the study of the present inventors, when the spinning speed is in a so-called medium spinning speed range of 450 m / min or more, the crystallization peak temperature Tc reflects the crystal state better than the density. Turned out to be. For example, spinning speed 1
At 000 m / min, the density is 1.329 g / cm 3 and Tc is 1
At a spinning speed of 2000 m / min, the density was 1.335 g / cm 3, which was almost unchanged at 87 ° C.
c has dropped to 158 ° C. That is, it is considered that the crystallization peak temperature Tc detects a minute difference in crystallinity even when the density is almost the same.
【0022】本発明において用いられる、糸条の下流側
になるにつれて低温度となる温度勾配を有する加熱筒
は、前述の特公昭50−16446号公報にも開示され
ている。しかしながら、該公報に記載の方法は、紡出糸
条を2次転移温度(113℃)近傍まで徐冷するのに対
し、本発明では、加熱筒の最下部の温度を200〜25
0℃、つまり結晶化ピーク温度近傍とし、遅延冷却を行
なう点において、根本的にその技術思想を異にしてい
る。The heating cylinder used in the present invention and having a temperature gradient that becomes lower as it goes downstream of the yarn is also disclosed in the above-mentioned Japanese Patent Publication No. Sho 50-16446. However, the method described in this publication gradually cools the spun yarn to near the secondary transition temperature (113 ° C.), whereas in the present invention, the temperature of the lowermost part of the heating cylinder is set to 200 to 25.
The technical idea is fundamentally different in that delayed cooling is performed at 0 ° C., that is, near the crystallization peak temperature.
【0023】即ち、加熱筒の最下部の温度を2次転移温
度近傍にまで冷却した場合、確かに複屈折率の低減効果
はあるものの、遅延冷却というよりはむしろ徐冷の効果
により結晶化が促進される傾向がある。具体的には、結
晶化ピーク温度Tcが、本発明で特定する205℃以上
といった高温域には入らず、200℃以下の低温側に存
在する。このことはとりもなおさず、密度では検出でき
ない結晶化の兆しが表れてきていることを示唆してお
り、従って高倍率延伸ができない。That is, when the temperature at the lowermost part of the heating cylinder is cooled to near the second-order transition temperature, although the effect of reducing the birefringence is certainly obtained, the crystallization is caused by the slow cooling effect rather than the delayed cooling effect. Tends to be promoted. Specifically, the crystallization peak temperature Tc does not enter the high temperature range of 205 ° C. or higher specified in the present invention, but exists on the low temperature side of 200 ° C. or lower. This suggests that crystallization, which cannot be detected by density, is appearing, and thus high-magnification stretching cannot be performed.
【0024】以下、実施例により本発明を更に具体的に
説明する。なお、実施例における測定値は、以下の方法
により求めたものである。Hereinafter, the present invention will be described more specifically with reference to examples. The measured values in the examples were obtained by the following methods.
【0025】(1) 強伸度 JIS L 1070に準拠し測定した。(1) Strong elongation Measured in accordance with JIS L 1070.
【0026】(2) 弾性率 岩本製作所製粘弾性測定器「スペクトロメーター」を用
いて、室温、周波数10Hzの条件下で測定した動的弾
性率E’の値を弾性率とした。(2) Elastic Modulus The value of the dynamic elastic modulus E 'measured under the conditions of room temperature and a frequency of 10 Hz using a viscoelasticity meter "Spectrometer" manufactured by Iwamoto Seisakusho was defined as the elastic modulus.
【0027】(3) 極限粘度 チップを、フェノールとオルトクロロベンゼンとの混合
溶媒(容量比6:4)に溶解し、35℃で測定した相対
粘度より外挿法で算出した。(3) Intrinsic Viscosity The chip was dissolved in a mixed solvent of phenol and orthochlorobenzene (volume ratio: 6: 4), and was calculated by extrapolation from the relative viscosity measured at 35 ° C.
【0028】(4) 複屈折率Δn ベレックのコンペンセーターを用いて、リターデーショ
ン法により求めた。(詳細は共立出版の「高分子実験学
講座、高分子の物性II」を参照のこと)(4) Birefringence Δn The birefringence was determined by a retardation method using a Bellek compensator. (For details, see Kyoritsu Shuppan's “Experimental Course on Polymer Experiments, Physical Properties of Polymers II”)
【0029】(5) 結晶化ピーク温度Tc 理学電機製THERMOFLEX TAS20型示差熱
量計を用い、試料量10mg、窒素雰囲気中10℃/分
の昇温速度でDSC曲線を求め、結晶化による発熱ピー
クの位置を結晶化ピーク温度Tcとした。(5) Crystallization peak temperature Tc Using a THERMOFLEX TAS20 type differential calorimeter manufactured by Rigaku Denki, a DSC curve was obtained at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere with a sample amount of 10 mg. The position was defined as the crystallization peak temperature Tc.
【0030】[0030]
【実施例1〜4、比較例1〜5】極限粘度0.85のポ
リエチレン−2,6−ナフタレートチップを孔数25
0、孔径0.4mmの円形紡糸孔(L/D=2)を有す
る紡糸口金からポリマー温度315℃、紡糸速度500
m/分で溶融紡糸し、10500de/250filの
未延伸糸を得た。この際、口金直下に30cmの長さの
円筒型加熱筒を3段連結して各々を種々の温度に設定し
た。この3段の加熱筒を上流側からHS1、HS2、H
S3と名付ける。一部の場合は、加熱筒を2段(HS1
とHS2、計60cm長)あるいは1段(HS1、30
cm長)にて紡糸した。さらに加熱筒の直下で20℃の
冷却風を長さ45cmに亘って3.5Nm3/分吹き付
けて糸条の冷却をはかった。次いでオイリングローラー
にて油剤を付与した後、引取りローラーに導き、巻取り
機で巻取った。EXAMPLES 1-4, COMPARATIVE EXAMPLES 1-5 A polyethylene-2,6-naphthalate chip having an intrinsic viscosity of 0.85 was filled with 25 holes.
0, a polymer temperature of 315 ° C. and a spinning speed of 500 from a spinneret having a circular spinning hole (L / D = 2) having a hole diameter of 0.4 mm.
Melt spinning was performed at m / min to obtain an undrawn yarn of 10500 de / 250 fill. At this time, a cylindrical heating cylinder having a length of 30 cm was connected in three stages immediately below the base, and each was set to various temperatures. HS1, HS2, H
Name it S3. In some cases, the heating cylinder is two-stage (HS1
And HS2, total length of 60 cm) or 1 step (HS1, 30
cm length). Further, a cooling air at 20 ° C. was blown over the length of 45 cm at a rate of 3.5 Nm 3 / minute directly below the heating cylinder to cool the yarn. Next, after applying an oil agent with an oiling roller, it was guided to a take-up roller and wound up by a winder.
【0031】該未延伸糸に1%のプリテンションをかけ
た後、155℃の加熱供給ローラーと第1段延伸ローラ
ーとの間で第1段延伸を行ない、次いで第1段延伸ロー
ラーと第2段延伸ローラーとの間で1.06倍第2段延
伸を行なった。さらに、熱セット工程として第2段延伸
ローラーと非加熱の巻取りローラーとの間で2%の弛緩
率で収縮熱セットを行なって200m/分で巻取った。
加熱筒の温度、延伸条件、未延伸糸および延伸糸の物性
を表1に示す。After applying 1% pretension to the undrawn yarn, the first drawing is carried out between the heating supply roller at 155 ° C. and the first drawing roller, and then the first drawing roller and the second drawing The second stage stretching was performed 1.06 times with the stage stretching roller. Further, as a heat setting step, shrinkage heat setting was performed at a relaxation rate of 2% between the second-stage stretching roller and the unheated winding roller, and winding was performed at 200 m / min.
Table 1 shows the temperature of the heating tube, the drawing conditions, and the physical properties of the undrawn yarn and the drawn yarn.
【0032】[0032]
【表1】 [Table 1]
【0033】[0033]
【実施例5、6、比較例6】実施例1において、以下の
条件を変更して紡糸を行なった以外は実施例1と同様に
実施した。まず実施例5では延伸を直延伸法で行なっ
た。また、比較例6では加熱筒下の冷却風温度を30℃
とした。さらに、実施例6では加熱筒下の冷却風温度を
10℃とした。結果を表2に示す。Examples 5 and 6 and Comparative Example 6 The same procedures as in Example 1 were carried out except that spinning was carried out with the following conditions changed. First, in Example 5, stretching was performed by the direct stretching method. In Comparative Example 6, the cooling air temperature under the heating cylinder was 30 ° C.
And Further, in Example 6, the cooling air temperature under the heating cylinder was set to 10 ° C. Table 2 shows the results.
【0034】[0034]
【表2】 [Table 2]
【0035】[0035]
【実施例7、8、比較例7】実施例1において、紡糸速
度を表3に示す如く変更した以外は実施例1と同様に実
施した。結果を表3に示す。Examples 7 and 8 and Comparative Example 7 The same procedure as in Example 1 was carried out except that the spinning speed was changed as shown in Table 3. Table 3 shows the results.
【0036】[0036]
【表3】 [Table 3]
【0037】[0037]
【発明の効果】本発明により、特にタイヤコードやベル
ト材の補強用に好適な、高強度、高弾性率で高タフネス
を有するポリエチレン−2,6−ナフタレート繊維が製
造できる。According to the present invention, polyethylene-2,6-naphthalate fiber having high strength, high elastic modulus and high toughness, particularly suitable for reinforcing tire cords and belt materials, can be produced.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平4−352811(JP,A) 特開 昭50−5619(JP,A) (58)調査した分野(Int.Cl.7,DB名) D01F 6/62 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-352811 (JP, A) JP-A-50-5819 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) D01F 6/62
Claims (2)
ポリエチレンナフタレートを450〜1200m/分の
紡糸速度で溶融紡糸するに際し、 (イ) 紡糸口金直下に、糸条の下流側になるにつれて低
温度となる温度勾配を有する長さ70cm以上の加熱筒
を設置し、該加熱筒の上流側少なくとも30cmは紡糸
口金温度以上400℃以下に、また該加熱筒の最下部は
200℃以上250℃以下の雰囲気温度に設定して吐出
糸条を遅延冷却し、 (ロ) 次いで糸条を25℃以下の冷風で冷却し、 (ハ) 冷却された糸条を引取りローラーで引取って、下
記 (1)〜 (2)式を同時に満足する未延伸糸とし、 (1) Δn≦0.010 (2) Tc≧205 (ただし、Δnは未延伸糸の複屈折率、Tcは結晶化ピ
ーク温度〔℃〕) (ニ) 該未延伸糸を一旦巻取った後あるいは巻取ること
なしに延伸工程に供給し全延伸する ことを特徴とするポリエチレンナフタレート繊維の製造
方法。(1) When melt-spinning polyethylene naphthalate having an intrinsic viscosity of 0.65 to 1.00 at a spinning speed of 450 to 1200 m / min, (a) immediately downstream of a yarn immediately below a spinneret. A heating cylinder having a temperature gradient of 70 cm or more having a temperature gradient that becomes lower as the temperature rises, at least 30 cm on the upstream side of the heating cylinder is at a spinneret temperature or more and 400 ° C or less, and the lowermost part of the heating cylinder is 200 ° C or more and 250 ° C or less. (B) Then, cool the yarn with cold air of 25 ° C or less, and (c) take up the cooled yarn with a take-up roller. (1) Δn ≦ 0.010 (2) Tc ≧ 205 (where Δn is the birefringence index of the undrawn yarn and Tc is the crystallization peak) Temperature (° C)) (d) The undrawn yarn was once wound Or method for producing polyethylene naphthalate fibers, which comprises supplying to the drawing step without winding total draw.
上、引張弾性率が270g/d以上およびタフネスが2
6g/d%1/2 以上であることを特徴とする請求項1記
載のポリエチレンナフタレート繊維の製造方法。2. A fiber having a tensile strength of 10 g / d or more, a tensile modulus of elasticity of 270 g / d or more and a toughness of 2
The method for producing polyethylene naphthalate fiber according to claim 1, wherein the amount is 6 g / d% 1/2 or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04276011A JP3129542B2 (en) | 1992-10-14 | 1992-10-14 | Method for producing high-strength polyethylene naphthalate fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04276011A JP3129542B2 (en) | 1992-10-14 | 1992-10-14 | Method for producing high-strength polyethylene naphthalate fiber |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06128810A JPH06128810A (en) | 1994-05-10 |
JP3129542B2 true JP3129542B2 (en) | 2001-01-31 |
Family
ID=17563544
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP04276011A Expired - Fee Related JP3129542B2 (en) | 1992-10-14 | 1992-10-14 | Method for producing high-strength polyethylene naphthalate fiber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3129542B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103189553A (en) * | 2010-11-15 | 2013-07-03 | 株式会社吴羽 | Polyglycolic acid resin undrawn yarn, polyglycolic acid resin drawn yarn using same, and method for producing each |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100402839B1 (en) * | 2001-05-10 | 2003-10-22 | 주식회사 효성 | Polyethylene naphtalate fiber of high strength |
KR100591208B1 (en) * | 2002-03-22 | 2006-06-19 | 주식회사 효성 | Polyethylene-2,6-naphthalate fibers having high strength and low shrinkage and the process for preparing the same |
KR100505016B1 (en) * | 2003-06-30 | 2005-07-28 | 주식회사 효성 | Polyethylene-2,6-naphthalate fibers by using high speed spinning and process for preparing the same |
AU2003272123A1 (en) * | 2003-08-22 | 2005-03-10 | Hyosung Corporation | High tenacity polyethylene-2,6-naphthalate fibers |
JP4713999B2 (en) * | 2005-10-31 | 2011-06-29 | 帝人ファイバー株式会社 | Synthetic fiber manufacturing method |
JP4928308B2 (en) | 2007-02-28 | 2012-05-09 | 帝人ファイバー株式会社 | Polyethylene naphthalate fiber for industrial materials and production method thereof |
JP5296645B2 (en) * | 2009-09-14 | 2013-09-25 | 帝人株式会社 | Industrial material string |
JP2011058145A (en) * | 2009-09-14 | 2011-03-24 | Teijin Fibers Ltd | Tension member and high tension voltage cable using the same |
KR101953763B1 (en) * | 2012-12-27 | 2019-03-04 | 코오롱인더스트리 주식회사 | Process of preparing polyester fiber for seatbelt |
WO2014003487A1 (en) * | 2012-06-28 | 2014-01-03 | 코오롱인더스트리 주식회사 | Polyester fiber for seat belts, and method for manufacturing same |
CN105696140A (en) * | 2016-01-26 | 2016-06-22 | 吴江市震宇缝制设备有限公司 | High-strength composite sewing thread and preparing method thereof |
-
1992
- 1992-10-14 JP JP04276011A patent/JP3129542B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103189553A (en) * | 2010-11-15 | 2013-07-03 | 株式会社吴羽 | Polyglycolic acid resin undrawn yarn, polyglycolic acid resin drawn yarn using same, and method for producing each |
CN103189553B (en) * | 2010-11-15 | 2014-09-24 | 株式会社吴羽 | Polyglycolic acid resin undrawn yarn, polyglycolic acid resin drawn yarn using same, and method for producing each |
Also Published As
Publication number | Publication date |
---|---|
JPH06128810A (en) | 1994-05-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR870001130B1 (en) | Polyester fiber having excellent thermal dimensional stability chemical stability and high tenacity and process for the production thereof | |
JP3129542B2 (en) | Method for producing high-strength polyethylene naphthalate fiber | |
KR101537131B1 (en) | Polyethylene naphthalate fiber and process for producing the polyethylene naphthalate fiber | |
JP3133177B2 (en) | Polyethylene naphthalate fiber excellent in heat stability and method for producing the same | |
JP2954391B2 (en) | Polyethylene naphthalate fiber and method for producing the same | |
US5397527A (en) | High modulus polyester yarn for tire cords and composites | |
KR101537132B1 (en) | Polyethylene naphthalate fiber and process for producing the polyethylene naphthalate fiber | |
JP2629075B2 (en) | High modulus polyester yarn for tire cords and composites | |
JP2011058116A (en) | Tire cord and tire produced by using the same | |
JP2945130B2 (en) | Naphthalate polyester fiber for reinforcing tire cord or belt material and method for producing the same | |
KR100235758B1 (en) | High modulous polyester yarn for tire cord and composites and the manufacture method | |
JPS62156312A (en) | Polyester fiber | |
JP2602617B2 (en) | An improved high stress spinning process for polyester industrial yarn. | |
KR0140230B1 (en) | Manufacturing method of dimensional stability polyester yarn | |
JP2861335B2 (en) | Method for producing naphthalate polyester fiber | |
JP3217900B2 (en) | Polyethylene naphthalate fiber and method for producing the same | |
JP2948006B2 (en) | Polyethylene naphthalate fiber | |
JPH0450407B2 (en) | ||
JPH04222215A (en) | Polyester fiber and production thereof | |
JP2859508B2 (en) | High shrinkage polyester fiber | |
JP5108938B2 (en) | Polyethylene naphthalate fiber and method for producing the same | |
JP2006322110A (en) | Method for producing polyethylene naphthalate fiber | |
JPH024693B2 (en) | ||
JPH04361610A (en) | Production of polyester fiber | |
JP5108937B2 (en) | Polyethylene naphthalate fiber and method for producing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081117 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081117 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091117 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101117 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111117 Year of fee payment: 11 |
|
LAPS | Cancellation because of no payment of annual fees |