JPH06166908A - Ultrafine fiber and its production - Google Patents

Ultrafine fiber and its production

Info

Publication number
JPH06166908A
JPH06166908A JP4317181A JP31718192A JPH06166908A JP H06166908 A JPH06166908 A JP H06166908A JP 4317181 A JP4317181 A JP 4317181A JP 31718192 A JP31718192 A JP 31718192A JP H06166908 A JPH06166908 A JP H06166908A
Authority
JP
Japan
Prior art keywords
yarn
intrinsic viscosity
ultrafine fiber
tan
melt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP4317181A
Other languages
Japanese (ja)
Other versions
JP3224879B2 (en
Inventor
Keiji Yamashita
啓二 山下
Fumio Matsuda
文男 松田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Chemical Industry Co Ltd filed Critical Asahi Chemical Industry Co Ltd
Priority to JP31718192A priority Critical patent/JP3224879B2/en
Publication of JPH06166908A publication Critical patent/JPH06166908A/en
Application granted granted Critical
Publication of JP3224879B2 publication Critical patent/JP3224879B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

PURPOSE:To obtain ultrafine fiber, good in level dyeing properties and capable of remarkably improving the dyeing speck on the surface which has conventionally been considered as a disadvantage in a knitted or a woven fabric with hardly any yarn unevenness and to provide a method for producing the ultrafine fiber with hardly any fluff at a low cost. CONSTITUTION:This method for producing ultrafine fiber, having $ 0.3 denier single filament size and composed of a polyester prepared by reacting a bifunctional carboxylic acid consisting essentially of terephthalic acid with ethylene glycol is to melt the polymer having an intrinsic viscosity [eta] regulated to 0.3-0.6 and then melt spin the fiber at >=1500 to <=3500m/min take-off speed. The ultrafine fiber is characterized in that the intrinsic viscosity [eta] is 0.3-0.6; the dynamic loss tangent (tandelta) is tandelta40=0.05-0.045, tandelta60=0.044--0.036 and tandelta80=0.035-0.03; the apparent crystal size in (110) face in a wide angle X-ray diffractometry is >=55Angstrom ; the crystal growth degree is >=0.25 and the crystallinity is >=55%.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は極細繊維及びその製造方
法に関するものである。
FIELD OF THE INVENTION The present invention relates to an ultrafine fiber and a method for producing the same.

【0002】[0002]

【従来の技術】ポリエステル特にポリエチレンテレフタ
レートは多くの優れた性質を有しており種々の用途、特
に繊維、フィルムに広く利用されている。極細繊維を使
用した編織物は風合いが柔らかく、しなやかで利用価値
が高い。従来よく知られている極細繊維の製造方法とし
ては、ポリエステルとポリスチレンの海島型複合繊維
を形成した後、ポリスチレンを溶解法で除去する方法
(特公昭48−25362号公報)、ポリアミドとポ
リエステルの多層貼り合わせ型複合繊維を形成した後、
剥離する方法(特公昭63−8207号公報)、通常
の紡糸延伸法で極細繊維を製造する方法(特公昭62−
35481号公報、特公昭63−8206号公報)、等
が知られている。
BACKGROUND OF THE INVENTION Polyester, especially polyethylene terephthalate, has many excellent properties and is widely used in various applications, especially in fibers and films. The knitted fabric using ultrafine fibers has a soft texture, is supple and has high utility value. Conventionally well-known methods for producing ultrafine fibers include a method of forming sea-island type composite fibers of polyester and polystyrene and then removing polystyrene by a dissolution method (Japanese Patent Publication No. Sho 48-25362), a multilayer of polyamide and polyester. After forming the laminated composite fiber,
A method of peeling (Japanese Patent Publication No. 63-8207) and a method of producing ultrafine fibers by a normal spinning and drawing method (Japanese Patent Publication No. 62-62-62).
No. 3,5481, Japanese Patent Publication No. 63-8206) and the like are known.

【0003】しかしながら、これらの製造方法のうち、
海島型複合繊維の溶解法、多層貼り合わせ型複合繊維の
剥離法では、極めて複雑な工程を経るため製品コストが
高いという問題を有し、又、通常の紡糸延伸法では一旦
未延伸工程を経るため、均染性の良いものを安定的に生
産する事が出来ないという問題を有している。一般に、
紡糸延伸法の場合、一旦巻取られた未延伸糸パッケージ
は雰囲気の温湿度条件によって経時的に繊維内部の構造
が変化する事が知られている。特に極細繊維ではこの傾
向が顕著であり、パッケージの端面部が経時的に応力緩
和を起こすため、延伸後、繊維の染色性を評価すると糸
長方向に未延伸糸の端面周期に一致する濃染斑が発生す
る。
However, among these manufacturing methods,
The sea-island type composite fiber melting method and the multi-layer bonding type composite fiber peeling method have a problem that the product cost is high due to an extremely complicated process, and the ordinary spin-drawing method requires a non-drawing step. Therefore, there is a problem that it is not possible to stably produce a product having good levelness. In general,
In the case of the spinning and drawing method, it is known that the structure of the inside of the fiber of the undrawn yarn package once wound changes with time depending on the temperature and humidity conditions of the atmosphere. This tendency is particularly noticeable with ultrafine fibers, and stress relaxation occurs at the end face of the package over time.Therefore, when the dyeability of the fiber is evaluated after drawing, the deep dyeing that matches the end face cycle of the undrawn yarn in the yarn length direction Spots occur.

【0004】また、未延伸糸を経ない技術として直接紡
糸延伸法が知られており一般的な単糸デニールの繊維の
製造には広く実施されているが、本発明者らが極細繊維
でこの直接紡糸延伸法を試みた結果、ポリマーの吐出時
の斑が直ちに糸切れにつながる事、フィラメント数が多
いので走行糸の空気抵抗が大きくなり、張力が増大し、
各種糸道カイドでの摩擦抵抗による毛羽、糸切れ等の問
題がある等直接紡糸延伸法により極細繊維を製造するこ
とは極めて難度が高いという事が判った。
The direct spinning and drawing method is known as a technique which does not pass through undrawn yarn and is widely practiced in the production of general single yarn denier fibers. As a result of trying the direct spinning and drawing method, unevenness at the time of discharging the polymer immediately leads to yarn breakage, and since the number of filaments is large, the air resistance of the running yarn increases and the tension increases,
It has been found that it is extremely difficult to produce ultrafine fibers by the direct spinning drawing method due to problems such as fluff and yarn breakage due to frictional resistance in various yarn guides.

【0005】[0005]

【発明が解決しようとする課題】本発明の目的は、均染
性の良い極細繊維、及び効率的、低コストでの製造方法
を提供することにある。
SUMMARY OF THE INVENTION An object of the present invention is to provide an ultrafine fiber having a good leveling property and an efficient and low cost production method.

【0006】[0006]

【課題を解決するための手段】本発明者らは上記の点を
鋭意検討した結果、ポリマーの固有粘度の調整が直接紡
糸延伸法では極めて重要である事、また、引取速度につ
いても毛羽、糸切れを発生させない範囲があり、これら
の関係を究明する事により本発明に到達した。即ち、本
発明は、次のとおりである。その一つは、単糸デニール
が0.3デニール以下であり、テレフタル酸を主とする
二官能性カルボン酸とエチレングリコールを反応させた
ポリエステルからなり、下記(a)〜(d)項を満たす
ことを特徴とする極細繊維。 (a)固有粘度〔η〕が0.3〜0.6 (b)力学的損失正接(tanδ)のtanδ40が0.
05〜0.045、tanδ60が0.044〜0.03
6、tanδ80が0.035〜0.03 (c)(110)面の見掛けの結晶サイズが55Å以上 (d)結晶成長度が0.25以上 (e)結晶化度が55%以上、 であり、もう一つは、ポリエステルを直接紡糸延伸法に
より、極細繊維を製造する方法であって、引取速度が1
500m/分以上3000m/分以上で溶融紡糸するこ
とを特徴とする請求項1記載の極細繊維の製造方法、で
ある。
Means for Solving the Problems As a result of intensive studies on the above points, the present inventors have found that the adjustment of the intrinsic viscosity of the polymer is extremely important in the direct spinning / drawing method, and the fluff and the yarn are also related to the take-up speed. There is a range in which breakage does not occur, and the present invention was reached by investigating these relationships. That is, the present invention is as follows. One of them is a polyester having a single yarn denier of 0.3 denier or less, a polyester obtained by reacting ethylene glycol with a bifunctional carboxylic acid mainly containing terephthalic acid, and satisfying the following items (a) to (d). Ultrafine fibers characterized by that. (A) Intrinsic viscosity [η] is 0.3 to 0.6 (b) Tan δ 40 of mechanical loss tangent (tan δ) is 0.
05-0.045, tan δ 60 is 0.044-0.03
6, tan δ 80 is 0.035 to 0.03 (c) The apparent crystal size of (110) plane is 55Å or more (d) Crystal growth is 0.25 or more (e) Crystallinity is 55% or more. The other is a method for producing ultrafine fibers by direct spinning and drawing of polyester, which has a take-up speed of 1
2. The method for producing an ultrafine fiber according to claim 1, wherein melt spinning is performed at 500 m / min or more and 3000 m / min or more.

【0007】本発明に用いる二官能性カルボン酸とエチ
レングリコールを反応させたポリエステル重合体は固有
粘度(η〕が0.3〜0.6で極細繊維の吐出を安定に
するため、溶融粘度を250ポイズ程度にする事が望ま
しく、ポリマーを285〜320℃で紡糸する事が望ま
しい。これより低い固有粘度の場合、相対的に溶融粘度
も低下し紡口のノズル部での流動が悪化し曳糸性を低下
させる。また、これより高い固有粘度の場合、曳糸性は
向上するが極細繊維としては風合いが硬くなる等商品価
値を低下させるので採用する事が出来ない。
The polyester polymer obtained by reacting a difunctional carboxylic acid and ethylene glycol used in the present invention has an intrinsic viscosity (η) of 0.3 to 0.6 and stabilizes the discharge of ultrafine fibers. The porosity is preferably about 250 poise, and the polymer is preferably spun at 285 to 320 ° C. When the intrinsic viscosity is lower than this, the melt viscosity is relatively reduced and the flow at the nozzle portion of the spinneret is deteriorated. In addition, if the intrinsic viscosity is higher than this value, the spinnability is improved, but as ultrafine fibers, the texture is hard and the commercial value is reduced, so it cannot be used.

【0008】引取し巻取る速度は、通常のマルチフィラ
メントの場合の高速紡糸では3500〜6000m/分
がよく用いられる範囲であるが、極細繊維では紡出糸条
群の空気抵抗で張力が上がるため3500m/分を越え
ると糸切れ、毛羽が増大するだけでなく、強度、伸度を
中心とした糸物性も低下してくる。一方1500m/分
以下では経済的に得策でない。
[0008] The take-up and take-up speed is 3500 to 6000 m / min, which is often used in high-speed spinning in the case of ordinary multifilaments, but in ultrafine fibers, tension increases due to air resistance of spun yarn groups. If it exceeds 3500 m / min, not only the yarn breakage and fluffing increase, but also the physical properties of the yarn centering on strength and elongation decrease. On the other hand, if it is less than 1500 m / min, it is not economically advantageous.

【0009】以上説明したように、本発明の製造方法
は、糸切れ、毛羽の少ない、糸長方向に均染なかつ糸斑
の少ない糸が得られ、従来、編織物で欠点とされていた
表面の染色斑を著しく改善する事が出来る。これは一旦
未延伸糸を経ると経時的に非晶構造部が緊張するため、
その後の延伸がかかりにくくなるが、パッケージの外層
程早く変化するため特に側面部で糸長方向に周期的に延
伸斑が発生し、染色斑となるためと思われる。高速紡糸
では一旦未延伸糸を経ないまま延伸を行うため均一なも
のが得られる。
As explained above, according to the production method of the present invention, a yarn having few yarn breakages, fluffs, level dyeing in the yarn length direction and less yarn unevenness is obtained, and the surface of the knitted fabric which has hitherto been a defect has Dyeing spots can be remarkably improved. This is because the amorphous structure part becomes tense over time once it passes through the undrawn yarn.
Although it is difficult for the subsequent drawing to take place, it is considered that unevenness in drawing occurs periodically in the yarn length direction, especially in the side surface portion, because it changes faster in the outer layer of the package, resulting in dyeing unevenness. In high-speed spinning, a uniform product is obtained because the drawing is performed without passing through the undrawn yarn.

【0010】[0010]

【実施例】以下,本発明の実施例を挙げ、詳細に説明す
る。なお、評価項目の測定条件を下記に示す。 (1)固有粘度(η) O−クロルフェノール溶媒下3
5℃で求めた極限粘度。 (2)tanδ40、tanδ60、tanδ80 東洋ボー
ルドウィン社製商品名VIBRON DDV−IIc型
測定器で10℃/分の昇温速度、周波数110Hzでt
anδ−温度特性を測定した時40℃、60℃、80℃
におけるtanδ値。 (3)見掛けの結晶サイズ (110)面の見掛けの結
晶サイズは、広角X線回折図における赤道回折曲線の回
折強度の半値幅より、次の式(1)で求める。
EXAMPLES Hereinafter, examples of the present invention will be described in detail. The measurement conditions of the evaluation items are shown below. (1) Intrinsic viscosity (η) under O-chlorophenol solvent 3
Intrinsic viscosity determined at 5 ° C. (2) tan δ 40 , tan δ 60 , tan δ 80 Toyo Baldwin Co., Ltd. trade name VIBRON DDV-IIc type measuring instrument at a temperature rising rate of 10 ° C./min and a frequency of 110 Hz.
an δ-temperature characteristics are measured 40 ℃, 60 ℃, 80 ℃
Tan δ value at. (3) Apparent crystal size The apparent crystal size of the (110) plane is calculated by the following formula (1) from the half width of the diffraction intensity of the equatorial diffraction curve in the wide-angle X-ray diffraction diagram.

【0011】[0011]

【数1】 [Equation 1]

【0012】(4)結晶成長度 結晶成長度は、広角X
線回折図における赤道回折曲線の回折強度より、次の式
で求める。 結晶成長度=1−(2H2 /H1 +H3 ) (ただし上記式中、H1 は(100)と(010)の反
射間の強度の最小値、H2 は(100)反射の最大強
度、H3 は(010)反射の最大強度を示す。) (5)結晶化度 結晶化度は次の方法で求める。広角X
線回折図における赤道回折曲線より、2θが7°と2θ
が35°の間にある回折強度曲線間を、直線で結びベー
スラインとする。次に、2θが20°付近の谷を頂点と
し、低角側及び高角側のすそに沿って直線で結び、結晶
部と非晶部に分離し、次式に従って面積法で求める。
(4) Crystal growth degree The crystal growth degree is wide angle X.
It is determined by the following formula from the diffraction intensity of the equatorial diffraction curve in the line diffraction diagram. Crystal growth degree = 1- (2H 2 / H 1 + H 3) ( provided that in the above formula, H 1 is the minimum value, maximum intensity of H 2 are (100) reflection intensity between reflections (100) and (010) , H 3 represents the maximum intensity of (010) reflection.) (5) Crystallinity Crystallinity is determined by the following method. Wide angle X
From the equatorial diffraction curve in the line diffraction diagram, 2θ is 7 ° and 2θ
A straight line connects the diffraction intensity curves lying between 35 ° and 35 ° to form a baseline. Next, a valley near 2θ of 20 ° is used as a vertex, and a straight line is connected along the skirts of the low-angle side and the high-angle side to separate into a crystalline portion and an amorphous portion, and the area method is calculated according to the following equation.

【0013】結晶化度(%)=結晶部の散乱強度/全般
乱強度×100 (6)紡糸安定性 5kg巻きパッケージを採取した
時、連続して5回以上糸切れ無しで製糸出来たものを
〇、それ以下を×とした。 (7)毛羽 5kg巻きパッケージの外観を肉眼で判別
し表面の毛羽が5個以下を〇、6〜20個を△、20個
以上を×とした。 (8)風合 採取した試料を筒編地とし、これについて
触感判定を実施した。一旦未延伸糸として巻取ってから
延伸工程で延伸する通常の紡糸延伸法で得られた従来品
の風合いを〇、それ以外を×とした。 (9)均染性 採取した試料を筒編地とし、次いで分散
染料を使用し、owf3%、浴比1:100で、20分
で常温から100℃に昇温し、その後100℃で1時間
保ち染色編地を得る。得られた編地の染斑を肉眼で判定
し均一なものを〇、濃淡差の軽度なものを△、濃淡差の
大きいものを×とした。 (10)糸斑 Keisokki製の測定機で、電気的
な測定手段を用い測定速度100m/minで繊維試料
の断面を容量的に測定し、試料の単位長さ当たり重量の
各瞬間値をXi 、平均値をX、積分の行われる長さをL
として、下記式(2)を用い糸斑を算出した。
Crystallinity (%) = scattering intensity of crystal part / general turbulence intensity × 100 (6) Spinning stability When a 5 kg wound package was sampled, it was possible to make yarn continuously 5 times or more without yarn breakage. ◯, and less than that were marked as x. (7) Fluff The appearance of the 5 kg wound package was visually judged, and the surface fluff was 5 or less, ◯, 6 to 20 fl, and 20 or more were x. (8) Feel The sampled sample was made into a tubular knitted fabric, and the tactile sensation was determined. The texture of the conventional product obtained by the ordinary spin-drawing method in which the undrawn yarn is once wound and then stretched in the stretching step is indicated by ◯, and the other products are indicated by x. (9) Level dyeing property The sampled sample was used as a tubular knitted fabric, and then a disperse dye was used. The temperature was raised from room temperature to 100 ° C in 20 minutes at owf 3% and a bath ratio of 1: 100, and then at 100 ° C for 1 hour. Keep dyed fabric. The unevenness of the obtained knitted fabric was judged with the naked eye, and the uniform one was marked with ◯, the one with a slight difference in shade was marked with Δ, and the one with a large shade difference was marked with x. (10) Yarn spots A cross section of a fiber sample is capacitively measured at a measuring speed of 100 m / min using an electric measuring means with a measuring machine manufactured by Keisokki, and each instantaneous value of the weight per unit length of the sample is X i , X is the average value and L is the length of integration.
As a result, the yarn unevenness was calculated using the following formula (2).

【0014】[0014]

【数2】 [Equation 2]

【0015】[0015]

【実施例1】ポリエチレンテレフタレートの固有粘度
〔η〕が0.45のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、70℃に加熱した第1
ゴデットローラーで引取り、次いで150℃に加熱した
第2ゴデットローラーとの間で1.7倍に延伸した後、
2800m/分で引取り巻取って、110d/1100
fの糸を得た。得られた糸の固有粘度〔η〕が0.41
であった。又、この糸の物性、均染性を測定して表1に
示したが濃染斑の少ない良好なものが得られた。
Example 1 Polyethylene terephthalate having an intrinsic viscosity [η] of 0.45 was melt-extruded, discharged from a spinneret nozzle, cooled, applied with an oil agent, and then heated to 70 ° C.
After being drawn by a godet roller and then stretched 1.7 times with a second godet roller heated to 150 ° C.,
Winding at 2800 m / min and winding, 110d / 1100
The thread of f was obtained. The intrinsic viscosity [η] of the obtained yarn is 0.41.
Met. Further, the physical properties and level dyeing property of this yarn were measured and shown in Table 1. As a result, a good product with few deep dyeing spots was obtained.

【0016】[0016]

【実施例2】ポリエチレンテレフタレートの固有粘度
〔η〕が0.56のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、70℃に加熱した第1
ゴデットローラーで引取り、次いで150℃に加熱した
第2ゴデットローラーとの間で1.8倍に延伸した後、
2600m/分で引取り巻取って、105d/700f
の糸を得た。得られた糸は固有粘度〔η〕が0.50で
あった。又、この糸の物性、均染性を測定して表1に示
したがこここでも濃染斑の少ない良好なものが得られ
た。
Example 2 Polyethylene terephthalate having an intrinsic viscosity [η] of 0.56 was melt-extruded, discharged from a spinneret nozzle, cooled, applied with an oil agent, and then heated to 70 ° C.
After being drawn by a godet roller and then stretched 1.8 times with a second godet roller heated to 150 ° C.,
Winding and winding at 2600m / min, 105d / 700f
Got the thread. The obtained yarn had an intrinsic viscosity [η] of 0.50. In addition, the physical properties and level dyeing property of this yarn were measured and shown in Table 1. In this case, a good product with few deep dyeing spots was obtained.

【0017】[0017]

【実施例3】ポリエチレンテレフタレートの固有粘度
〔η〕が0.56のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、70℃に加熱した第1
ゴデットローラーで引取り、次いで150℃に加熱した
第2ゴデットローラーとの間で2.5倍に延伸した後、
1500m/分で引取り巻取って、105d/700f
の糸を得た。得られた糸は固有粘度〔η〕が0.50で
あった。又、この糸の物性、均染性を測定して表1に示
したがここでも濃染斑の少ない良好なものが得られた。
Example 3 Polyethylene terephthalate having an intrinsic viscosity [η] of 0.56 was melt-extruded, discharged from a spinneret nozzle, cooled, applied with an oil agent, and then heated to 70 ° C.
After being drawn by a godet roller and then stretched 2.5 times with a second godet roller heated to 150 ° C.,
Take-up and winding at 1500m / min, 105d / 700f
Got the thread. The obtained yarn had an intrinsic viscosity [η] of 0.50. Further, the physical properties and level dyeing property of this yarn were measured and shown in Table 1, and a good product with few deep dyeing spots was obtained here as well.

【0018】[0018]

【比較例1】ポリエチレンテレフタレートの固有粘度
〔η〕が0.45のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、1500m/分で一旦
未延伸糸を巻取った。このパッケージを改めて延撚機に
て90℃に加熱した第1ローラーと150℃に加熱した
ホットプレートを経由して第2ローラーとの間で1.7
倍に延伸し500m/分で巻取り、110d/1100
fの糸を得た。この糸の物性、均染性を測定して表1に
示したが濃染斑の大きいものが得られた。
Comparative Example 1 Polyethylene terephthalate having an intrinsic viscosity [η] of 0.45 was melt-extruded, discharged from a spinneret nozzle, cooled, applied with an oil agent, and then unwound at 1500 m / min. . This package is newly used by a twisting machine between the first roller heated to 90 ° C. and the second roller via the hot plate heated to 150 ° C. to 1.7.
Double stretching and winding at 500m / min, 110d / 1100
The thread of f was obtained. The physical properties and level dyeing property of this yarn were measured and shown in Table 1. As a result, those with large dark spots were obtained.

【0019】[0019]

【比較例2】ポリエチレンテレフタレートの固有粘度
〔η〕が0.56のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、1500m/分で一旦
未延伸糸を巻取った。このパッケージを改めて延撚機に
て90℃に加熱した第1ローラーと150℃に加熱した
ホットプレートを経由して第2ローラーとの間で1.8
倍に延伸し500m/分で巻取り、105d/700f
の糸を得た。この糸の物性、均染性を測定して表1に示
したがここでも濃染斑の大きいものが得られた。
[Comparative Example 2] Polyethylene terephthalate having an intrinsic viscosity [η] of 0.56 was melt extruded, discharged from a spinneret nozzle, cooled, and after applying an oil agent, an undrawn yarn was once wound at 1500 m / min. . This package was newly re-stretched by a twisting machine between the first roller heated to 90 ° C. and the second roller via a hot plate heated to 150 ° C. to be 1.8.
Double stretching and winding at 500m / min, 105d / 700f
Got the thread. The physical properties and level dyeing property of this yarn were measured and are shown in Table 1. In this case, too, a dye with large dark spots was obtained.

【0020】[0020]

【比較例3】ポリエチレンテレフタレートの固有粘度
(η〕が0.65のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、70℃に加熱した第1
ローラーで引取り、次いで150℃に加熱した第2ロー
ラーとの間で1.8倍に延伸した後、2600m/分で
巻取り、105d/700fの糸を得た。この糸の物
性、均染性を測定して表1に示したがここでも濃染斑の
少ない良好なものが得られた。
Comparative Example 3 A polyethylene terephthalate having an intrinsic viscosity (η) of 0.65 was melt-extruded, discharged from a spinneret nozzle, cooled, and after applying an oil agent, heated to 70 ° C.
The yarn was taken up by a roller, then drawn 1.8 times with a second roller heated to 150 ° C., and wound at 2600 m / min to obtain a yarn of 105d / 700f. The physical properties and level dyeing property of this yarn were measured and are shown in Table 1. In this case as well, a good product with few deep dyeing spots was obtained.

【0021】この糸を筒編地として風合いを触感判定し
たが従来品に比べて硬く、極細繊維としての商品性に劣
るが事が判った。
When this yarn was used as a tubular knitted fabric, the texture was judged to be tactile, but it was found that the yarn was harder than the conventional product and was inferior in commercial property as an ultrafine fiber.

【0022】[0022]

【比較例4】ポリエチレンテレフタレートの固有粘度
〔η〕が0.28のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、70℃に加熱した第1
ローラーで引取り、次いで、150℃に加熱した第2ロ
ーラーとの間で1.8倍に延伸した後、2600m/分
で巻取り、105d/700fの糸を得ようとしたが紡
口での糸切れが多くパッケージを採取する事が難しかっ
た。
[Comparative Example 4] Polyethylene terephthalate having an intrinsic viscosity [η] of 0.28 was melt extruded, discharged from a spinneret nozzle, cooled, applied with an oil agent, and then heated to 70 ° C.
It was taken up by a roller, then drawn 1.8 times with a second roller heated to 150 ° C., and then wound at 2600 m / min to obtain a yarn of 105d / 700f. It was difficult to collect the package due to many thread breaks.

【0023】[0023]

【比較例5】ポリエチレンテレフタレートの固有粘度
〔η〕が0.56のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、70℃に加熱した第1
ローラーで引取り、次いで、150℃に加熱した第2ロ
ーラーとの間で1.4倍に延伸した後、3600m/分
で巻取り、105d/700fの糸を得た。この糸の物
性、均染性を測定して表1に示したが濃染斑の少ない良
好なものが得られた。一方パッケージの外観をチェック
したところ毛羽多発で商品としては使えない事が判っ
た。
[Comparative Example 5] Polyethylene terephthalate having an intrinsic viscosity [η] of 0.56 was melt extruded, discharged from a spinneret nozzle, cooled, applied with an oil agent, and then heated to 70 ° C.
It was taken up by a roller, then drawn 1.4 times with a second roller heated to 150 ° C., and wound up at 3600 m / min to obtain a yarn of 105d / 700f. The physical properties and level dyeing property of this yarn were measured and shown in Table 1. As a result, a good product with few deep dyeing spots was obtained. On the other hand, when the appearance of the package was checked, it was found that there was a lot of fuzz and it could not be used as a product.

【0024】[0024]

【表1】 [Table 1]

【0025】[0025]

【発明の効果】本発明の極細繊維は、従来のものに比較
して均染性が良く、糸斑が少ないものである。また、本
発明の製造方法は、毛羽、糸切れ等の問題がなく効率
的、低コストで極細繊維を得ることができる。
EFFECTS OF THE INVENTION The ultrafine fibers of the present invention have good leveling properties and less yarn unevenness than conventional ones. In addition, the production method of the present invention can obtain ultrafine fibers efficiently and at low cost without problems such as fluff and yarn breakage.

【図面の簡単な説明】[Brief description of drawings]

【図1】本発明の製造方法を説明する概略の説明図。FIG. 1 is a schematic explanatory view illustrating a manufacturing method of the present invention.

【符号の説明】[Explanation of symbols]

1 口金 2 冷却装置 3 集束ガイド 4 第1油剤付与ガイド 5 第1交絡付与装置 6 第1セパレーターロール 7 第1コデットロール 8 第2ゴデットロール 9 第2セパレーターロール 10 第2交絡付与装置 11 第2油剤付与ガイド 12 綾振りガイド 13 ワインダー DESCRIPTION OF SYMBOLS 1 Base 2 Cooling device 3 Focusing guide 4 1st oiling agent application guide 5 1st confounding application device 6 1st separator roll 7 1st codet roll 8 2nd godet roll 9 2nd separator roll 10 2nd entangling application device 11 2nd oiling agent application Guide 12 Traverse guide 13 Winder

─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成5年1月27日[Submission date] January 27, 1993

【手続補正1】[Procedure Amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】特許請求の範囲[Name of item to be amended] Claims

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【特許請求の範囲】[Claims]

【手続補正2】[Procedure Amendment 2]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0003[Name of item to be corrected] 0003

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0003】しかしながら、これらの製造方法のうち、
海島型複合繊維の溶解法、多層貼り合わせ型複合繊維の
剥離法では、極めて複雑な工程を経るため製品コストが
高いという問題を有し、又、通常の紡糸延伸法では一旦
未延伸工程を経るため、均染性が良く且つ、糸斑の小さ
ものを安定的に生産する事が出来ないという問題を有
している。一般に、紡糸延伸法の場合、一旦巻取られた
未延伸糸パッケージは雰囲気の温湿度条件によって経時
的に繊維内部の構造が変化する事が知られている。特に
極細繊維ではこの傾向が顕著であり、パッケージの端面
部が経時的に応力緩和を起こすため、延伸後、繊維の染
色性を評価すると糸長方向に未延伸糸の端面周期に一致
する濃染斑が発生する。
However, among these manufacturing methods,
The sea-island type composite fiber melting method and the multi-layer bonding type composite fiber peeling method have a problem that the product cost is high due to an extremely complicated process, and the ordinary spin-drawing method requires a non-drawing step. Therefore, the level dyeing property is good and the yarn unevenness is small.
There is a problem that can not be produced in a stable manner things brewing. It is generally known that in the case of the spinning and drawing method, the structure of the inside of the fiber of the undrawn yarn package once wound changes with time depending on the temperature and humidity conditions of the atmosphere. This tendency is particularly noticeable with ultrafine fibers, and stress relaxation occurs at the end face of the package over time.Therefore, when the dyeability of the fiber is evaluated after drawing, the deep dyeing that matches the end face cycle of the undrawn yarn in the yarn length direction Spots occur.

【手続補正3】[Procedure 3]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0006[Correction target item name] 0006

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0006】[0006]

【課題を解決するための手段】本発明者らは上記の点を
鋭意検討した結果、ポリマーの固有粘度の調整が直接紡
糸延伸法では極めて重要である事、また、引取速度につ
いても毛羽、糸切れを発生させない範囲があり、これら
の関係を究明する事により本発明に到達した。即ち、本
発明は、次のとおりである。その一つは、単糸デニール
が0.3デニール以下であり、テレフタル酸を主とする
二官能性カルボン酸とエチレングリコールを反応させた
ポリエステルからなり、下記(a)〜(d)項を満たす
ことを特徴とする極細繊維。 (a)固有粘度〔η〕が0.3〜0.6 (b)力学的損失正接(tanδ)のtanδ40が0.
05〜0.045、tanδ50が0.044〜0.03
6、tanδ60が0.035〜0.03 (c)(110)面の見掛けの結晶サイズが55Å以上 (d)結晶成長度が0.25以上 (e)結晶化度が55%以上 であり、もう一つは、ポリエステルを直接紡糸延伸法に
より、極細繊維を製造する方法であって、引取速度が1
500m/分以上3000m/分以で溶融紡糸するこ
とを特徴とする請求項1記載の極細繊維の製造方法、で
ある。
Means for Solving the Problems As a result of intensive studies on the above points, the present inventors have found that the adjustment of the intrinsic viscosity of the polymer is extremely important in the direct spinning / drawing method, and the fluff and yarn There is a range in which breakage does not occur, and the present invention was reached by investigating these relationships. That is, the present invention is as follows. One of them has a monofilament denier of 0.3 denier or less and is composed of a polyester obtained by reacting ethylene glycol with a bifunctional carboxylic acid mainly containing terephthalic acid and satisfies the following items (a) to (d). Ultrafine fibers characterized by that. (A) Intrinsic viscosity [η] is 0.3 to 0.6 (b) Tan δ 40 of mechanical loss tangent (tan δ) is 0.
05-0.045, tan δ 50 is 0.044-0.03
6, tan δ 60 is 0.035 to 0.03 (c) The apparent crystal size of (110) plane is 55Å or more (d) Crystal growth is 0.25 or more (e) Crystallinity is 55% or more Another is a method for producing ultrafine fibers by direct spinning and drawing of polyester, which has a take-up speed of 1
The method of producing ultrafine fibers of claim 1, wherein the melt spun at 500 meters / min or more 3000 m / min or less under a.

【手続補正4】[Procedure amendment 4]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0007[Correction target item name] 0007

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0007】本発明に用いる二官能性カルボン酸とエチ
レングリコールを反応させたポリエステル重合体は固有
粘度η〕が0.3〜0.6で極細繊維の吐出を安定に
するため、溶融粘度を250ポイズ程度にする事が望ま
しく、ポリマーを285〜320℃で紡糸する事が望ま
しい。これより低い固有粘度の場合、相対的に溶融粘度
も低下し紡口のノズル部での流動が悪化し曳糸性を低下
させる。また、これより高い固有粘度の場合、曳糸性は
向上するが極細繊維としては風合いが硬くなる等商品価
値を低下させるので採用する事が出来ない。
The polyester polymer obtained by reacting ethylene glycol with a bifunctional carboxylic acid used in the present invention has an intrinsic viscosity [ η] of 0.3 to 0.6 and stabilizes the discharge of ultrafine fibers. It is desirable to set it to about 250 poise, and it is desirable to spin the polymer at 285 to 320 ° C. When the intrinsic viscosity is lower than the above range, the melt viscosity is relatively lowered, the flow in the nozzle portion of the spinneret is deteriorated, and the spinnability is lowered. In addition, if the intrinsic viscosity is higher than this, the spinnability is improved, but as ultrafine fibers, the texture is hard and the commercial value is lowered, so it cannot be used.

【手続補正5】[Procedure Amendment 5]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0008[Correction target item name] 0008

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0008】引取巻取る速度は、通常のマルチフィラ
メントの場合の高速紡糸では3500〜6000m/分
がよく用いられる範囲であるが、極細繊維では紡出糸条
群の空気抵抗で張力が上がるため3500m/分を越え
ると糸切れ、毛羽が増大するだけでなく、強度、伸度を
中心とした糸物性も低下してくる。一方1500m/分
以下では経済的に得策でない。
[0008] The take-up winding take rate is in the high-speed spinning is usually the case of multi-filament is in the range of 3500~6000m / minute is often used, because the tension rises in the air resistance of the spun yarn group in the ultra-fine fibers If it exceeds 3500 m / min, not only the yarn breakage and fluffing increase, but also the physical properties of the yarn centering on strength and elongation decrease. On the other hand, if it is less than 1500 m / min, it is not economically advantageous.

【手続補正6】[Procedure correction 6]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0010[Correction target item name] 0010

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0010】[0010]

【実施例】以下、本発明の実施例を挙げ、詳細に説明す
る。なお、評価項目の測定条件を下記に示す。 (1)固有粘度η〕 O−クロルフェノール溶媒下3
5℃で求めた極限粘度。 (2)tanδ40、tanδ50、tanδ60 東洋ボー
ルドウィン社製商品名VIBRON DDV−IIc型
測定器で10℃/分の昇温速度、周波数110Hzでt
anδ−温度特性を測定した時40℃、60℃、80℃
におけるtanδ値。 (3)見掛けの結晶サイズ (110)面の見掛けの結
晶サイズは、広角X線回析図における赤道回析曲線の回
析強度の半値幅より、次の式(1)で求める。
EXAMPLES Hereinafter, examples of the present invention will be described in detail. The measurement conditions of the evaluation items are shown below. (1) Intrinsic viscosity [ η] Under O-chlorophenol solvent 3
Intrinsic viscosity determined at 5 ° C. (2) tan δ 40 , tan δ 50 , tan δ 60 manufactured by Toyo Baldwin Co., Ltd. under the trade name VIBRON DDV-IIc type measuring instrument at a temperature rising rate of 10 ° C./min and a frequency of 110 Hz.
an δ-temperature characteristics are measured 40 ℃, 60 ℃, 80 ℃
Tan δ value at. (3) Apparent crystal size The apparent crystal size of the (110) plane is determined by the following formula (1) from the half-value width of the diffraction intensity of the equatorial diffraction curve in the wide-angle X-ray diffraction diagram.

【手続補正7】[Procedure Amendment 7]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0015[Name of item to be corrected] 0015

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0015】[0015]

【実施例1】ポリエチレンテレフタレートの固有粘度
〔η〕が0.45のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、70℃に加熱した第1
ゴデットローラーで引取り、次いで150℃に加熱した
第2ゴデットローラーとの間で1.7倍に延伸した後、
2800m/分で引取り巻取って、110d/1100
fの糸を得た。得られた糸の固有粘度〔η〕が0.4
1、糸斑(%)が1.3であった。又、この糸の物性、
均染性を測定して表1に示したが濃染斑の少ない良好な
ものが得られた。
Example 1 Polyethylene terephthalate having an intrinsic viscosity [η] of 0.45 was melt-extruded, discharged from a spinneret nozzle, cooled, applied with an oil agent, and then heated to 70 ° C.
After being drawn by a godet roller and then stretched 1.7 times with a second godet roller heated to 150 ° C.,
Winding at 2800 m / min and winding, 110d / 1100
The thread of f was obtained. The intrinsic viscosity [η] of the obtained yarn is 0.4
1, the yarn unevenness (%) was 1.3 . Also, the physical properties of this thread,
The level dyeing property was measured and is shown in Table 1. As a result, a good dyeing product with few dark spots was obtained.

【手続補正8】[Procedure Amendment 8]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0016[Correction target item name] 0016

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0016】[0016]

【実施例2】ポリエチレンテレフタレートの固有粘度
〔η〕が0.56のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、70℃に加熱した第1
ゴデットローラーで引取り、次いで150℃に加熱した
第2ゴデットローラーとの間で1.8倍に延伸した後、
2600m/分で引取り巻取って、105d/700f
の糸を得た。得られた糸の固有粘度〔η〕が0.50、
糸斑(%)が1.3であった。又、この糸の物性、均染
性を測定して表1に示したがここでも濃染斑の少ない良
好なものが得られた。
Example 2 Polyethylene terephthalate having an intrinsic viscosity [η] of 0.56 was melt-extruded, discharged from a spinneret nozzle, cooled, applied with an oil agent, and then heated to 70 ° C.
After being drawn by a godet roller and then stretched 1.8 times with a second godet roller heated to 150 ° C.,
Winding and winding at 2600m / min, 105d / 700f
Got the thread. The obtained yarn has an intrinsic viscosity [η] of 0.50,
The yarn unevenness (%) was 1.3 . Further, the physical properties and level dyeing property of this yarn were measured and shown in Table 1, and a good product with few deep dyeing spots was obtained here as well.

【手続補正9】[Procedure Amendment 9]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0017[Correction target item name] 0017

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0017】[0017]

【実施例3】ポリエチレンテレフタレートの固有粘度
〔η〕が0.56のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、70℃に加熱した第1
ゴデットローラーで引取り、次いで150℃に加熱した
第2ゴデットローラーとの間で2.5倍に延伸した後、
1500m/分で引取り巻取って、105d/700f
の糸を得た。得られた糸の固有粘度〔η〕が0.50、
糸斑(%)が1.2であった。又、この糸の物性、均染
性を測定して表1に示したがここでも濃染斑の少ない良
好なものが得られた。
Example 3 Polyethylene terephthalate having an intrinsic viscosity [η] of 0.56 was melt-extruded, discharged from a spinneret nozzle, cooled, applied with an oil agent, and then heated to 70 ° C.
After being drawn by a godet roller and then stretched 2.5 times with a second godet roller heated to 150 ° C.,
Take-up and winding at 1500m / min, 105d / 700f
Got the thread. The obtained yarn has an intrinsic viscosity [η] of 0.50,
The yarn unevenness (%) was 1.2 . Further, the physical properties and level dyeing property of this yarn were measured and shown in Table 1, and a good product with few deep dyeing spots was obtained here as well.

【手続補正10】[Procedure Amendment 10]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0018[Correction target item name] 0018

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0018】[0018]

【比較例1】ポリエチレンテレフタレートの固有粘度
〔η〕が0.45のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、1500m/分で一旦
未延伸糸を巻取った。このパッケージを改めて延撚機に
て90℃に加熱した第1ローラーと150℃に加熱した
ホットプレートを経由して第2ローラーとの間で1.7
倍に延伸し500m/分で巻取り、110d/1100
fの糸を得た。この糸の物性、均染性を測定して表1に
示したが濃染斑が大きく、糸斑の大きいものが得られ
た。
Comparative Example 1 Polyethylene terephthalate having an intrinsic viscosity [η] of 0.45 was melt-extruded, discharged from a spinneret nozzle, cooled, applied with an oil agent, and then unwound at 1500 m / min. . This package is newly used by a twisting machine between the first roller heated to 90 ° C. and the second roller via the hot plate heated to 150 ° C. to 1.7.
Double stretching and winding at 500m / min, 110d / 1100
The thread of f was obtained. The physical properties and level dyeing property of this yarn were measured and shown in Table 1. As a result, there were large deep dye spots and large yarn spots .

【手続補正11】[Procedure Amendment 11]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0019[Correction target item name] 0019

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0019】[0019]

【比較例2】ポリエチレンテレフタレートの固有粘度
〔η〕が0.56のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、1500m/分で一旦
未延伸糸を巻取った。このパッケージを改めて延撚機に
て90℃に加熱した第1ローラーと150℃に加熱した
ホットプレートを経由して第2ローラーとの間で1.8
倍に延伸し500m/分で巻取り、105d/700f
の糸を得た。この糸の物性、均染性を測定して表1に示
したがここでも濃染斑が大きく、糸斑の大きいものが得
られた。
[Comparative Example 2] Polyethylene terephthalate having an intrinsic viscosity [η] of 0.56 was melt extruded, discharged from a spinneret nozzle, cooled, and after applying an oil agent, an undrawn yarn was once wound at 1500 m / min. . This package was newly re-stretched by a twisting machine between the first roller heated to 90 ° C. and the second roller via a hot plate heated to 150 ° C. to be 1.8.
Double stretching and winding at 500m / min, 105d / 700f
Got the thread. The physical properties and level dyeing property of this yarn were measured and are shown in Table 1. Again, there were large dark spots and large yarn spots were obtained.

【手続補正12】[Procedure Amendment 12]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0020[Correction target item name] 0020

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0020】[0020]

【比較例3】ポリエチレンテレフタレートの固有粘度
η〕が0.65のものを溶融押出後、紡口ノズルより
吐出、冷却後油剤を付与した後、70℃に加熱した第1
ローラーで引取り、次いで150℃に加熱した第2ロー
ラーとの間で1.8倍に延伸した後、2600m/分で
巻取り、105d/700fの糸を得た。この糸の物
性、均染性を測定して表1に示したがここでも濃染斑の
少ない良好なものが得られたが、糸斑が大きかった。
Comparative Example 3 Intrinsic viscosity of polyethylene terephthalate
After melt extrusion of [ η] of 0.65, the mixture was discharged from the spinneret nozzle, cooled, applied with an oil agent, and then heated to 70 ° C.
The yarn was taken up by a roller, then drawn 1.8 times with a second roller heated to 150 ° C., and wound at 2600 m / min to obtain a yarn of 105d / 700f. The physical properties and level dyeing property of this yarn were measured and shown in Table 1. Good yarns with few deep dye spots were obtained, but the yarn spots were large.

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 単糸デニールが0.3デニール以下であ
り、テレフタル酸を主とする二官能性カルボン酸とエチ
レングリコールを反応させたポリエステルからなり、下
記(a)〜(d)項を満たすことを特徴とする極細繊
維。 (a)固有粘度(η〕が0.3〜0.6 (b)力学的損失正接(tanδ)のtanδ40が0.
05〜0.045、tanδ60が0.044〜0.03
6、tanδ80が0.035〜0.03 (c)(110)面の見掛けの結晶サイズが55Å以上 (d)結晶成長度が0.25以上 (e)結晶化度が55%以上
1. A single yarn denier of 0.3 denier or less, comprising a polyester obtained by reacting a difunctional carboxylic acid mainly containing terephthalic acid with ethylene glycol, and satisfying the following items (a) to (d): Ultrafine fibers characterized by that. (A) Intrinsic viscosity (η) is 0.3 to 0.6 (b) Tan δ 40 of mechanical loss tangent (tan δ) is 0.
05-0.045, tan δ 60 is 0.044-0.03
6, tan δ 80 is 0.035 to 0.03 (c) The apparent crystal size of (110) plane is 55Å or more (d) Crystal growth is 0.25 or more (e) Crystallinity is 55% or more
【請求項2】 ポリエステルを直接紡糸延伸法により極
細繊維を製造する方法であって引取速度が1500m/
分以上3500m/分以下で溶融紡糸することを特徴と
する請求項1記載の極細繊維の製造方法。
2. A method for producing ultrafine fibers by direct spinning and drawing a polyester, wherein the take-up speed is 1500 m /
The method for producing ultrafine fibers according to claim 1, wherein melt spinning is performed at a speed of at least 3500 m / min.
JP31718192A 1992-11-26 1992-11-26 Ultrafine fiber and method for producing the same Expired - Fee Related JP3224879B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP31718192A JP3224879B2 (en) 1992-11-26 1992-11-26 Ultrafine fiber and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP31718192A JP3224879B2 (en) 1992-11-26 1992-11-26 Ultrafine fiber and method for producing the same

Publications (2)

Publication Number Publication Date
JPH06166908A true JPH06166908A (en) 1994-06-14
JP3224879B2 JP3224879B2 (en) 2001-11-05

Family

ID=18085361

Family Applications (1)

Application Number Title Priority Date Filing Date
JP31718192A Expired - Fee Related JP3224879B2 (en) 1992-11-26 1992-11-26 Ultrafine fiber and method for producing the same

Country Status (1)

Country Link
JP (1) JP3224879B2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003041432A (en) * 2001-07-27 2003-02-13 Asahi Kasei Corp Polyester ultrafine fiber
CN107761407A (en) * 2017-10-18 2018-03-06 马多浩 A kind of level dyeing technique of superfine fiber synthetic leather

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003041432A (en) * 2001-07-27 2003-02-13 Asahi Kasei Corp Polyester ultrafine fiber
CN107761407A (en) * 2017-10-18 2018-03-06 马多浩 A kind of level dyeing technique of superfine fiber synthetic leather

Also Published As

Publication number Publication date
JP3224879B2 (en) 2001-11-05

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