JPH0350002B2 - - Google Patents
Info
- Publication number
- JPH0350002B2 JPH0350002B2 JP57110400A JP11040082A JPH0350002B2 JP H0350002 B2 JPH0350002 B2 JP H0350002B2 JP 57110400 A JP57110400 A JP 57110400A JP 11040082 A JP11040082 A JP 11040082A JP H0350002 B2 JPH0350002 B2 JP H0350002B2
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- polyester
- strength
- less
- denier
- 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 - Lifetime
Links
- 239000000835 fiber Substances 0.000 claims description 135
- 229920000728 polyester Polymers 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000005520 cutting process Methods 0.000 claims description 11
- 230000005484 gravity Effects 0.000 claims description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 6
- 230000008646 thermal stress Effects 0.000 claims description 5
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 claims description 2
- 239000002657 fibrous material Substances 0.000 claims 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- 238000000034 method Methods 0.000 description 23
- 239000000523 sample Substances 0.000 description 22
- 238000005259 measurement Methods 0.000 description 19
- 239000010410 layer Substances 0.000 description 16
- 238000009826 distribution Methods 0.000 description 13
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000009987 spinning Methods 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012770 industrial material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012120 mounting media Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- PZNPLUBHRSSFHT-RRHRGVEJSA-N 1-hexadecanoyl-2-octadecanoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[C@@H](COP([O-])(=O)OCC[N+](C)(C)C)COC(=O)CCCCCCCCCCCCCCC PZNPLUBHRSSFHT-RRHRGVEJSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- CRIXWWLOCUMSDZ-UHFFFAOYSA-N 4-(4-carboxy-4-phenylcyclohexa-1,5-dien-1-yl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CCC(C=2C=CC=CC=2)(C(O)=O)C=C1 CRIXWWLOCUMSDZ-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 238000001464 small-angle X-ray scattering data Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Artificial Filaments (AREA)
Description
[産業上の利用分野]
本発明は新規なポリエステル繊維に関し、特に
ゴム類等の補強用として優れた強度と耐疲労特性
を有し、あるいはミシン糸として優れた強度と低
伸度を有する単糸デニールの小さいポリエステル
繊維に関するものである。
[従来の技術]
本発明で意図する繊維の原料たるポリエステル
とは、構成単位の85モル%以上、好ましくは95モ
ル%以上がエチレンテレフタレートからなるもの
であり、少量混入させることのできる他の構成単
位としてはジエチレングリコール、炭素数が1〜
10の他のポリエチレングリコール、ヘキサヒドロ
−P−キシリレングリコール、イソフタル酸、ジ
安息香酸、p−ターフエニル−4,4′−ジカルボ
ン酸、ヘキサヒドロテレフタル酸等の芳香属ジカ
ルボン酸、アジピン酸等の脂肪族ジカルボン酸、
ヒドロキシ酢酸等のヒドロキシ酸等が挙げられ、
この様なポリエステル素材は通常の溶融紡糸法に
よつて繊維化される。
上記の様なポリエステル繊維にゴム製品補強用
等として優れた物性を与える為の延伸熱処理法と
しては、たとえば特公昭41−7892号、同48−1966
号、特開昭53−1367号等に開示された方法が知ら
れている。ところが本発明者らが従来のポリエス
テル繊維の物性と構造について種種研究を行なつ
たところ、次の様な事実が確認された。即ち通常
の紡糸延伸法によつて繊維化したポリエチレンテ
レフタレート繊維の繊維断面内における複屈折率
の分布は、外層の方が内層より高い傾向があり、
切断強度も高々9.5g/d程度しかない。又、繊
維断面内の複屈折率が、内層部より外層部へ行く
に従つて大きくなるという分布を有していること
が、紡糸及び延伸工程における曳糸性や延伸性を
阻害する要因となつていると考えられる。
[発明が解決しようとする課題]
そこで紡糸、延伸技術について鋭意研究を行な
つたところ、次の様な知見を得た。即ち、延伸工
程で例えば糸条表装部の局部的に加熱しながら延
伸する等によつて伸長応力を糸条中心部に集中さ
せることができれば、延伸変形パターンが非常に
マイルドになり、到達最高延伸媒率を通常の延伸
法に比べて高めることができる。しかも従来の延
伸糸で指摘される様に、「糸条表層部に延伸応力
が集中して歪欠陥が生じ繊維強度が理論強度より
も大幅に低下する」という現象が抑制され、最終
的な繊維内微細構造をClarkらの提唱する超延伸
構造[参考文献:W.N.Taylor.Jr.、E.S.Clark、
Polym.Eng.Sci.、18、518(1978).]に近づける
ことが可能になり、従来の産業資材用高強力繊維
に比べて卓越した引張強度及び破断強度を有する
ポリエチレンテレフタレート繊維を得ることが可
能となる。一方、特開昭51−15021号公報に見ら
れる様に、単糸デニールが1000d以上の太デニー
ルポリエステルモノフイラメントであれば、フイ
ラメントの表面の近くにおける重合鎖セグメント
の低い配向部を除けば、実質的に均一な内部構造
を有するものも知られているが、該公開明細書に
も明示されている様に低デニールフイラメントに
対して適した方法であるからといつて、太デニー
ルモノフイラメントに対して同等の性質を与える
ことはできない。またこの公開明細書に記されて
いるモノフイラメントの切断強力は高々8.4g/
dに過ぎず、本発明の意図する様な低デニールの
高強力フイラメントとは全く異なるものである。
本発明は上記の様な知見を基に更に研究の結果
完成されたものであり、その目的は、従来の産業
資材用高強力繊維に比べても一段と優れた引張強
度及び破断強度を有する細デニールの高強力ポリ
エステル繊維を提供しようとするものである。
[課題を解決するための手段]
上記課題を解決することのできた本発明に係る
ポリエステル繊維の構成は、前述の条件で測定し
た固有粘度が、0.50以上好ましくは、0.58〜1.0で
構成単位の85%以上(好ましくは95%以上)がエ
チレン成分及びテフタル酸成分よりなり、且つ繊
維断面内における複屈折率が下記〔1〕式(好ま
しくは〔2〕式)を満足し
−10×10-3<ΔnA−ΔnB<0……〔1〕
−10×10-3<ΔnA−ΔnB≦−1.0×10-3
……〔2〕
但し
ΔnA:r/R=0.9の位置における繊維の複屈折
率
ΔnB:r/R=0.0の位置における繊維の複屈折率
R:繊維断面の半径
r:繊維断面の中心軸からの距離
更に単糸デニールが100デニール以下(より好
ましくは35デニール以下)であり、繊維の複屈折
率Δが195×10-3以上、小角X線回折による繊維
長周期が170〓以上、比重が1.390以上、乾熱収縮
率が15%以下、切断強度が10g/d以上、繊維の
力学的特性(110c/sにおける測定値)である損
失正接(Tanδ)が最大となる温度(Tα)が160°
以上であるところに要旨が存在する。
[作用]
本発明のポリエステル繊維は、通常の熱可塑性
ポリマー繊維に比べて繊維断面内の複屈折率の分
布が逆転しており、繊維外層部分よりも内層部分
の方が複屈折率が高いという特異な複屈折率分布
を有している。また、繊維長周期が170〓以上で
あつて通常の高強力ポリエステル繊維に比べて長
く、切断伸度が10%以下でかつ繊維の複屈折率
Δnが195×10-3以上であり、しかも広角X線回折
による(100)面の配合角が8°以下であつて非常
に高い結晶配向度を有すると共に、微細構造的に
も長延伸構造に対応する傾向を持つている。加え
て比重は0.390以上、定長昇温熱応力ピーク温度
は210℃以上、乾熱収縮率SHDは15%以下であ
り、十分に延伸処理された物性値を示す。又最も
重要な実用性能というべき繊維の切断強度DTは
10g/d以上であり、従来の高強力ポリエステル
繊維の強度が高々9.5g/dであるのに比べて著
しく改善されている。
以上のことから、本発明の高強力ポリエステル
繊維は、従来より存在している高強力ポリエステ
ル繊維と比較すると、全く新規な微細構造を有し
ているものといえる。しかも特に素材自体の分子
量を高くする必要がなく、固有粘度が0.51以上、
好ましくは0.58〜1.0程度のもので十分である。
勿論、ポリマーの分子量は高い方が好ましいが微
細構造的に改良されたものである点に本発明のポ
リエステル繊維最大の特徴がある。ポリエチレン
テレフタレートを主成分とするポリエステル繊維
は、衣料用及び工業用繊維としての広範囲に使用
されているが、その大きな用途の一つにタイヤコ
ードを中心とするゴム補強材があげられる。かか
るゴム補強用ポリエステル繊維を製造する方法と
して高分子量のポリエステルを使用する方法
(USP2880057、フランス特許1261056号、特公昭
53−1367号)、太デニールモノフイラメントによ
る方法(特開昭51−15021号)、高分子量ポリエス
テルを用いて紡糸した後、多段延伸する方法
(USP3651198号)、紡糸時の冷却固化を送らせる
方法等が提案されている。しかしながら、本発明
ポリエステル繊維の様に、低デニールフイラメン
トで繊維断面内に複屈折率が繊維外層部分よりも
内層部分の方が高い、という特異な複屈折率分布
を与えることによつて高強力繊維としての要請を
満足しようとする思想自体はこれまでに提案され
たことがない。
上記の様な特異な微細構造は、P−クロロフエ
ノール/テトラクロロエタン=3/1(重量比)
の溶媒中30℃で測定した固有粘度が1.50以上、好
ましくは0.65〜1.20、より好ましくは0.58〜1.00
で、構成単位の少なくとも85%がポリエチレンテ
レフタレートからなるポリエステルを用いた場合
に有効に発現され、殊に高強力化、耐疲労性向上
等に顕著な効果が発揮される。これは、ポリエチ
レンテレフタレートを主成分とするポリエステル
繊維の場合、従来法では、低デニール高強力フイ
ラメントの繊維断面内複屈折率分布は、繊維外層
部分が内層部分よりも高くなり易く、そのために
繊維の洩糸性や延伸性が阻害され実質的に高強力
化に寄与するタイ分子鎖の数を増加させることが
困難であつたためと考えられる。
また本発明においては単繊維デニールが100d
以下、好ましくは35d以下であるところにも特異
性を有している。これは単繊維デニールが大きく
なると、糸条内層部分に均一な延伸応力集中を発
現させることが困難となり、逆に延伸性を阻害す
る要因となるためである。
従来より知られている高強力ポリエステルフイ
ラメントの結晶配向度は、(100)面の配向角
(OA)で10°以上、結晶配向度fc(下記〔3〕式)
fc=180−OA/180×100(%) ……〔3〕
は95%未満であるのに対し、本発明の高強力ポリ
エステル繊維の場合は(100)面の配向角で8°未
満、結晶配合度(fc)で表示すると95%以上であ
り著しく高い結晶配向度を有している。又、延伸
熱履歴のメジヤーである定長昇温熱応力ピーク温
度が210℃以上であることも、本発明ポリエステ
ルの大きな特徴である。特に該ピーク温度が210
℃未満であると、本発明の特徴である繊維断面内
の複屈折率の特異な分布を発現させることが困難
となる。産業資材用高強力繊維、特にタイヤコー
ドを中心とするゴム補強材として用いる場合、高
温での力学特性が実用性能上最も重要な要素の一
つとなるが、高温での力学特性評価はかなり困難
であり、実際に試験を行なつても測定間にポリマ
ーが劣化す等のトラブルが起こり易く測定精度や
再現性に問題がある。
本発明者らは、高温での繊維の力学特性を代表
するメジヤーとして動的粘弾性の温度依存性、力
学温度分散特性を110c/sの正弦歪を与えた状態
で評価した。その結果、損失正接(Tanδ)が最
大となる温度(Tα)が、通常の高強力ポリエス
テル繊維であれば高々160℃未満であるが、本発
明のポリエステル繊維は、該温度(Tα)が160℃
以上という高い値を示すことが確認された。Tα
は、非晶部分のポリマーの剛直性を示すものであ
り、Tαが高いほど非品質部分の拘束力が大きく、
熱刺激による分子運動がより高温側まで抑え込ま
れることを意味するもので、高温における力学特
性は低下度合いが小さい。従つて本発明の高強力
ポリエステル繊維の高温での力学特性は、従来公
知の高強力ポリエステル繊維よりも優れていると
いえる。殊に本発明のポリエステル繊維は高温に
曝らしたときの強度低下が少ないところから、た
とえばタイヤコードの如きゴム補強材等として使
用するとき、繊維を埋め込んだ状態でゴムの加熱
加硫を行なつた場合でも該繊維の強度劣化が少な
く、高い補強効果を持続するという特長も有して
いる。
次に本発明にいう繊維断面内での複屈折率分布
を更に具体的に説明すると、
−10×10-3<ΔnA−ΔnB<0 ……〔1〕
好ましくは
−10×10-3<ΔnA−ΔnB≦−1.0×10-3
……〔2〕
[但し、ΔnA、ΔnBは前述の通り]
のものが選択される。〔1〕、〔2〕式において
ΔnAは糸条外層部のΔn、ΔnBは糸条内層部のΔn
を代表するものであり、本発明のポリエステル繊
維は、糸条外層部の方が内層部よりもΔnが小さ
いという非常に特異な微細構造を有するものであ
る。尚本発明では上記の様にΔnA−ΔnBの値をマ
イナスにすることにより優れた物性のポリエステ
ルを繊維となるが、この値が小さ過ぎる場合は、
表面側の強度がやや低くなり過ぎて繊維全体の強
度がやや低くなる傾向が表われてくるので、ΔnA
−ΔnBの値は−10×10-3以下とならない様に加熱
延伸条件を制御する必要がある。
次に上記の様な特性を有するポリエステル繊維
の製造法について簡単に説明するが、本発明はも
とより下記の方法に限定される訳ではない。本発
明のポリエステル繊維の製造に当たつては紡糸延
伸工程、特に延伸工程が重要である。即ち、例え
ば固有粘度が0.58以上のポリエステル溶融紡糸し
て得た複屈折率0.002〜0.060の未延伸糸を紡糸に
連続して、又は一旦巻取つた後延伸する際に、未
延伸糸第1供給ローラと100℃以下に維持された
未延伸糸第2供給ローラとの間において、1.10倍
以下の予備延伸を行い、次いで第1延伸ローラと
の間において全延伸倍率40%以上の第1段延伸を
行うのが良く、その際未延伸糸第2供給ローラと
第1延伸ローラとの間に高温加圧蒸気噴出ノズル
を設け、ノズル温度を200℃以上にして高温蒸気
を噴出させ、高温加圧蒸気噴出ノズル付近に延伸
点を固定させる。更に第2段延伸を行う際に、第
1延伸ローラと第2延伸ローラとの間に設けられ
た雰囲気温度170〜420℃のスリツトヒーター(糸
条走行路としてスリツトを設けた加熱装置で、核
スリツト中に非接触状態で糸条を走行させながら
加熱するもの:雰囲気温度とは該スリツト内の温
度を言う)中を糸条が0.3秒以上滞在できる様に
通過せしめ、しかる後、第2延伸ローラに供す
る。その際、スリツトヒーター中に温度勾配を設
け、糸条入口の雰囲気温度を170℃以上、出口雰
囲気温度を420℃以下とし、且つ200〜420℃の雰
囲気に糸条が0.3秒以上滞在できる様に糸条を通
過させることが好ましい。又、2段延伸終了後、
一旦巻取ることなく連続的に、あるいは一旦巻取
つた後に、230〜165℃で10%以下のリラツクス処
理を行うことにより、寸法安定性を更に向上させ
ることも可能である。
本発明の繊維は、ゴム等の補強用に供するとき
は、通常マルチフイラメントの形態で用いられる
が、本発明の繊維の用途は格別制限されるもので
はなく、従つて繊維の形態も、ロービングヤー
ン、スフ、チヨツプドストランド等であつても良
い。本発明の繊維は、タイヤコード、特に高重量
車輛用のラジアル構造タイヤにおけるカーカスコ
ードならびにその他のVベルト、平ベルト、歯付
ベルト等の補強コード等のゴム類の補強コードに
好適に用いられる。もちろん本発明の用途は上記
に限られるものではなく、従来のポリエステル繊
維と全く同様に用いられる。以下に本発明の繊維
の構造の特定や物性の測定に用いられる主なパラ
メータの測定法について述べる。
<固有粘度の測定法>
75重量%のP−クロロフエノールと25重量%の
テトラクロルエタンからなる混合溶剤中で測定す
る。
重合体を室温において溶剤中に溶解し且つ粘度
の測定をオストワルドーフエンスケ毛細粘度計中
で30℃において行なう。
固有粘度は、溶液粘度の溶媒粘度に対する比の
自然対数を溶液100ml当りの重合体のグラム数で
表わした重合体溶液の濃度によつて除した値が濃
度ゼロに近づくときの極限値である。
<複屈折率(Δn)の測定法>
ニコン偏光顕微鏡POH型ライツ社ペレツクコ
ンペンセーターを用い、光源としてはスペクトル
光源溶起動装置(東芝SLS−3−B型)を用いた
(Na光源)。5〜6mm長の繊維軸に対し45°の角度
に切断した試料を、切断面を上にして、スライド
グラス上に載せる。試料スライドグラスを回転載
物台にのせ、試料が偏光子に対して45°になる様、
回転載物台を回転させて調節し、アナライザーを
挿入し暗視界とした後、コンペンセーターを30に
して縞数を数える(n個)。コンペンセーターを
右ネジ方向にまわして試料が最初に暗くなる点の
コンペンセーターの目盛a、コンペンセーターを
左ネジ方向にまわして試料が最初に一番暗くなる
点のコンペンセーターの目盛bを測定した後(い
ずれも1/10目盛まで読む)、コンペンセーターを
30にもどしてアナライザーをはずし、試料の直径
dを測定し、下記の式にもとづき複屈折率(Δn)
を算出する(測定数20個の平均値)。
Δn=Γ/d(Γ:レターデーシヨン、=nλ0+ε)
……〔4〕
λ0=589.3mμ
ε:ライツ社のコンペンセーターの説明書のC/
10000とiより求める
i=(a−b)(:コンペンセーターの読みの差)
<繊維断面内のΔn分布の測定法>
透過定量型干渉顕微鏡を使用して得られる中心
屈折率(n⊥、0、n、0)及び外層屈折率
(n⊥、0.9、n、0.9)の値によつて、本発明
の繊維の特異な分子配向が明らかとなり、本発明
の繊維の優れた強度との関連を示すことができ
る。透過定量型干渉顕微鏡(例えば東独カールツ
アイスイエナ社製干渉顕微鏡インターフアコ)を
使用して得られる干渉縞法によつて、繊維の側面
から観察した平均屈折率の分布を測定することが
できる。この方法は円形断面を有する繊維に適用
することができる。繊維の屈折率は、繊維軸の平
行方向に振動している偏光に対する屈折率(n
)と繊維軸の垂直方向に振動している偏光に対
する屈折率(n⊥)によつて特徴づけられる。こ
こに説明する測定は全て光源としてキセノンラン
プを用い、偏光下、干渉フイルター波長544nm
の緑色光線を使用して得られる屈折率(nおよ
びn⊥)を用いて実施される。以下nの測定及
びn⊥より求められるn、0とn、0.9につ
いて詳細に説明するが、n⊥(n⊥、03n⊥、
0.9)に試験される繊維は光学的にスラツトなス
ライドグラス及びカバーグラスを使用し、0.2〜
1波長の範囲内の干渉縞のずれを与える屈折率
(nE)をもつ繊維に対して不活性の封入剤中に浸
漬する。封入剤の屈折率(nE)は緑色光線(波長
λ=544nm)を光源としてアツベの屈折計を用
いて測定した20℃における値であるこの封入剤は
たとえば流動パラフインとα−ブロムナフタリン
の混合液より1.48〜1.65の屈折率を有するものが
調製できる。この封入剤中に1本の繊維を浸漬す
る。この干渉縞のパターンを写真撮影し、1000倍
〜2000倍に拡大して解析する。第1図に略示した
如く繊維の封入剤の屈折率をnE、繊維のS′−S″間
の平均屈折率をn、S′−S″間の厚みをt、使用
光線の波長をλ、バツクグランドの平行干渉縞の
間隔(1λに相当)Dn′、繊維による干渉志縞のず
れをdとすると、光路差Lは
L=dn/Dn λ=(n−nE)t
で表わされる。試料の屈折率をnSとすると、封入
液の屈折率は、nS<nE=n1
nS>nE=n2
の2種のものを用いて第1図に示すような干渉縞
のパターンを評価する。
L1=d1/D1λ=(n−n1)t
L2=d2/D2λ(n−n2)t
n=L1n2−L2n1/R1−R2 ……〔5〕
従つて〔5〕式にもとづいて繊維の中心から外
周までの角位置での光路差から、各位置の繊維の
平均屈折率(n)の分布を求めることができ
る。厚みtは得られる繊維が円型断面と仮定して
計算によつて求めることができる。しかしながら
製造条件の変動や製造後のアクシデントによつ
て、円形断面になつていない場合も考えられる。
このような不都合を除くため、測定する個所は繊
維軸を対称軸として干渉縞のずれが左右対称にな
つている部分を使用することが適当である。測定
は繊維の半径をRとすると0〜0.9Rの間を0.1R
の間隔で行ない、各位置の平均の屈折率を求める
ことができる。同様にしてn⊥の分布も求められ
るので複屈折率分布は
Δn(r/R)=n、r/R−n⊥、r/R
……〔6〕
より求められる。Δn(r/R)は少なくとも3本
のフイラメント、好適には5〜10本のフイラメン
トについて測定したものを平均して得られる。
<繊維の強進度特性の測定法>
東洋ボールドウイン社製テンシロンを用い、試
料長(ゲージ長)100mm、伸長速度=100%/分、
記録速度500mm/分、初荷重1/30g/dの条件で
単繊維のS−S曲線を測定し切断強度(g/d)、
切断伸度(%)および初期弾性率(g/d)を算
出した。初期弾性率は、S−S曲線の原点付近の
最大勾配より算出した。各特性値の算出に関し、
少なくとも5本のフイラメント、好適には10〜20
本のフイラメントについて測定したものを平均し
て得られる。
<小角X線回折による繊維長周期の測定法>
小角X線散乱パターンの測定は、例えば理学電
機社製X線発生装置(RU−3H型)を用いて行な
う。測定には管電圧45KV、管電流70mA、銅対
陰極、ニツケルフイルターで単色化したCuKα
(λx=1.5418Å)を使用する。サンプルホルダー
に繊維試料を単糸同士が互いに平行になるように
取り付ける。試料の厚さは0.5〜1.0mm位になるよ
うにするのが適当である。この平行に配列した繊
維の繊維軸に垂直にX線を入射させ、理学電機射
製PSPC(Position Sensitive Proportional
Counter)システムを用いて測定する。本システ
ムの概要は、[Polmer Journal、vol.13、501
(1981)]に詳しく紹介されている。
測定条件は0.3mm〓×0.2mm〓中ピンホールコリメ
ータを用い、
試料とプローブ間距離:400mm
MCA(マルチチヤンネルアナライザー)
測定チヤンネル数:256
測定時間:600秒
とした。データの処理は、測定散乱強度から空気
散乱強度を差し引いたものを移動平均処理により
求め、その強度最大位置を読みとることにより、
長周期小角散乱角度2αから、下記〔7〕式に従
い、繊維長周期を算出する[第2図A,B参照:
図中1は試料、2はPSPCプローブ、3はポジシ
ヨン・アナライザー、4はMCA、5は表示部を
夫々示す]。
α=λx/2sinα ……〔7〕
λx=1.5418Å
移動平均処理は、次式に従つて算出する。
I(S)N=i=N+K
〓i=N+K
I(S)1/2K+1
ただし、上式中、I(S)N及びI(S)iは、それ
ぞれチヤンネルナンバーN及びiの測定散乱強度
(空気散乱強度を差し引いた強度)、Kは移動平均
の採用点数(ここではK=7)、N−K>0、N
+K≦256
<見掛けの結晶サイズ:ACS>
広角X線回折図における赤道回折曲線の(100)
面の回折強度の半価巾よりScherrerの式を用いて
算出[詳細は丸善株式会社発行「X線結晶学」
(仁田勇監修)上巻第140頁参照]。
Scherrerの式とは、次式で表わされる。
ACS=0.9λ/B2−α2cosθ ……〔8〕
ただし、上式中、λはX線の波長(1.5418Å)、
Bは半価巾(rad)、αは補正角(6.98×
10-3rad)、θは回折角(度)を示す。
本発明の実施例において用いたX線は、管電圧
45KV、管電流70mA、銅対陰極、NIフイルタ
ー、波長1.5418Åであり、デイフラクトメーター
として理学電機社製のSG−7型ゴニオメーター、
X線発生装置としてローターフレツクスRU−3H
型を使用した。
<配合角(OA)の測定法>
繊維の配向角(OA)の測定は、例えば地理電
機社製X線発生装置(RU−3H)、繊維測定装置
(FS−3)、ゴニオメーター(SG−7)及びシン
チレーシヨンカウンタを用いて実施する。測定に
はニツケルフイルターで単色化したCuKα(波長
λ=1.5418Å)を使用する。
配向角の測定は(100)面反射の2θを使用する。
使用される反射の2θは、赤道線方向の回折強度曲
線から決定される。
X線発生装置は45kv、70mAで運転するもの
とし、繊維測定装置に繊維試料を単糸同士が互い
に平行となるように取り付ける。試料の厚みは
0.5mm位になるようにするのが適当である。
予備実験により決定された2θ値にゴニオメータ
ーをセツトする。この平行に配列した繊維の繊維
軸に垂直にX線を入射させる(ビーム垂直透過
法)。方位角方向を−80°〜+30°走査し、シンチ
レーシヨンカウンターで回折強度を記録紙に記録
する。さらに−180°と+180°の回折強度を記録す
る。
この時、スキヤニングスピード4°/min、チヤ
ートスピード1.0cm/min、タイムコンスタント
2秒あるいは5秒、コリメーター1mm〓、レシー
ビングはスリツト縦横とも1°である。
得られた回折強度曲線から配向角を求めるに
は、±180°で得られる回折強度の平均値を取り、
水平線を引く。ピークの頂点から基線に垂線をお
ろし、その高さの中点を求める。中点を通る水平
線を引く。この水平線と回折強度曲線の交点間の
距離を測定し、この値を角度(゜)に換算した値
を配向角(OA)とする。
<力学温度分散>
東洋側器社製Rheovibronを使用し、初糸長4
cm、昇温速度2℃/分、測定時の正弦周波数110
Hzの条件で測定し、損失正接tanδ=E′/E″が最
大となる温度(Tα)を求める。
ただし、上式中E′は貯蔵弾性率(dyne/cm2)、
E″は損失弾性率(dyne/cm2)である。
[詳細は、Memoirs of the Faculty of
Engineering Kyushu Universitv、vol.23、41
(1963)参照]
複素弾性率Eは次式で算出される。
1E1=2.0×1/A・D×109×L/S ……
[Field of Industrial Application] The present invention relates to a new polyester fiber, which has excellent strength and fatigue resistance particularly for reinforcing rubber, etc., or a single yarn having excellent strength and low elongation as a sewing thread. It relates to polyester fibers with a small denier. [Prior Art] The polyester that is the raw material for the fiber intended in the present invention is one in which 85 mol% or more, preferably 95 mol% or more of the constituent units are ethylene terephthalate, and other constituents that can be mixed in a small amount. The unit is diethylene glycol, carbon number is 1~
10 other polyethylene glycols, hexahydro-p-xylylene glycol, isophthalic acid, dibenzoic acid, p-terphenyl-4,4'-dicarboxylic acid, aromatic dicarboxylic acids such as hexahydroterephthalic acid, fats such as adipic acid group dicarboxylic acids,
Examples include hydroxy acids such as hydroxyacetic acid,
Such a polyester material is made into fibers by a normal melt spinning method. Examples of stretching heat treatment methods for imparting excellent physical properties to polyester fibers such as those mentioned above for use in reinforcing rubber products include Japanese Patent Publications Nos. 41-7892 and 48-1966.
The method disclosed in Japanese Patent Application Laid-open No. 53-1367 is known. However, when the present inventors conducted various studies on the physical properties and structure of conventional polyester fibers, the following facts were confirmed. That is, the distribution of birefringence within the fiber cross section of polyethylene terephthalate fibers made into fibers by the usual spinning and drawing method tends to be higher in the outer layer than in the inner layer.
The cutting strength is only about 9.5g/d at most. In addition, the birefringence within the cross section of the fiber has a distribution in which it increases from the inner layer to the outer layer, which is a factor that inhibits spinnability and stretchability in the spinning and drawing processes. It is thought that [Problems to be Solved by the Invention] Therefore, as a result of intensive research on spinning and drawing techniques, the following knowledge was obtained. In other words, if the stretching stress can be concentrated in the center of the yarn by, for example, stretching while heating the yarn surface locally during the stretching process, the stretching deformation pattern will be very mild and the maximum stretching can be achieved. The medium ratio can be increased compared to ordinary stretching methods. In addition, the phenomenon that ``drawing stress concentrates on the surface layer of the yarn, causing strain defects, and the fiber strength is significantly lower than the theoretical strength'', which has been pointed out with conventional drawn yarns, is suppressed, and the final fiber The internal microstructure is the superstretched structure proposed by Clark et al. [References: WNTaylor.Jr., ESClark,
Polym.Eng.Sci., 18, 518 (1978). ], making it possible to obtain polyethylene terephthalate fibers that have superior tensile strength and breaking strength compared to conventional high-strength fibers for industrial materials. On the other hand, as seen in JP-A No. 51-15021, in the case of a thick denier polyester monofilament with a single filament denier of 1000d or more, except for the low orientation part of the polymer chain segments near the surface of the filament, the Although it is known that the method is suitable for low denier monofilaments as clearly stated in the published specification, it is not suitable for thick denier monofilaments. It is not possible to give equivalent properties. Furthermore, the cutting strength of the monofilament described in this publication is at most 8.4 g/
d, and is completely different from the low denier, high strength filament as intended by the present invention. The present invention was completed as a result of further research based on the above knowledge, and its purpose is to create a fine denier fiber that has even better tensile strength and breaking strength than conventional high-strength fibers for industrial materials. The aim is to provide high-strength polyester fibers. [Means for Solving the Problems] The composition of the polyester fiber according to the present invention that can solve the above problems has an intrinsic viscosity of 0.50 or more, preferably 0.58 to 1.0, and a structural unit of 85 % or more (preferably 95% or more) consists of an ethylene component and a tephthalic acid component, and the birefringence within the fiber cross section satisfies the following formula [1] (preferably [2] formula) -10×10 -3 <Δn A −Δn B <0……[1] −10×10 -3 <Δn A −Δn B ≦−1.0×10 -3
...[2] However, Δn A : Birefringence of the fiber at the position of r/R=0.9 Δn B : Birefringence of the fiber at the position of r/R=0.0 R: Radius of the fiber cross section r: Center of the fiber cross section Distance from the axis Further, the single fiber denier is 100 denier or less (more preferably 35 denier or less), the birefringence Δ of the fiber is 195 × 10 -3 or more, the fiber long period by small-angle X-ray diffraction is 170〓 or more, The temperature (Tα) at which the specific gravity is 1.390 or more, the dry heat shrinkage rate is 15% or less, the cutting strength is 10 g/d or more, and the loss tangent (Tanδ), which is the mechanical property of the fiber (measured value at 110 c/s), is maximum. is 160°
The gist lies in the above. [Function] The polyester fiber of the present invention has an inverted distribution of birefringence within the fiber cross section compared to ordinary thermoplastic polymer fibers, and the inner layer has a higher birefringence than the outer fiber layer. It has a unique birefringence distribution. In addition, the fiber long period is 170〓 or more, which is longer than ordinary high-strength polyester fibers, the cutting elongation is 10% or less, the fiber birefringence Δn is 195×10 -3 or more, and it has a wide angle The blend angle of the (100) plane determined by X-ray diffraction is 8° or less, which indicates a very high degree of crystal orientation, and the microstructure also tends to correspond to an elongated structure. In addition, the specific gravity is 0.390 or higher, the constant length temperature rise thermal stress peak temperature is 210°C or higher, and the dry heat shrinkage rate SHD is 15% or lower, indicating physical properties that indicate sufficient stretching treatment. In addition, the cutting strength DT of the fiber, which should be the most important practical performance, is
The strength is 10 g/d or more, which is significantly improved compared to the strength of conventional high-strength polyester fibers, which is at most 9.5 g/d. From the above, it can be said that the high-strength polyester fiber of the present invention has a completely new microstructure compared to conventional high-strength polyester fibers. Moreover, there is no need to particularly increase the molecular weight of the material itself, and the intrinsic viscosity is 0.51 or higher.
Preferably, a value of about 0.58 to 1.0 is sufficient.
Of course, it is preferable that the molecular weight of the polymer be higher, but the most important feature of the polyester fiber of the present invention is that it has an improved microstructure. Polyester fibers containing polyethylene terephthalate as a main component are widely used as clothing and industrial fibers, and one of their major uses is as rubber reinforcing materials mainly for tire cords. A method of producing such rubber-reinforcing polyester fibers is a method of using high molecular weight polyester (USP 2880057, French Patent No. 1261056,
53-1367), a method using thick denier monofilament (Japanese Patent Application Laid-Open No. 51-15021), a method in which high molecular weight polyester is spun and then multi-stage stretched (USP 3651198), a method in which cooling solidification occurs during spinning. etc. have been proposed. However, like the polyester fiber of the present invention, a low denier filament can be used to create a high-strength fiber by providing a unique birefringence distribution in the cross section of the fiber in which the inner layer has a higher birefringence than the outer layer. No idea has ever been proposed to satisfy this requirement. The above-mentioned unique microstructure is caused by P-chlorophenol/tetrachloroethane=3/1 (weight ratio)
Intrinsic viscosity measured at 30°C in a solvent of 1.50 or more, preferably 0.65 to 1.20, more preferably 0.58 to 1.00
This is effectively achieved when using a polyester in which at least 85% of the structural units are composed of polyethylene terephthalate, and particularly remarkable effects are exhibited in increasing strength and improving fatigue resistance. This is because in the case of polyester fibers whose main component is polyethylene terephthalate, in the conventional method, the fiber cross-sectional birefringence distribution of low-denier, high-strength filaments tends to be higher in the fiber outer layer than in the inner layer. This is thought to be due to the fact that it was difficult to increase the number of tie molecular chains, which substantially contribute to high strength because the threadability and stretchability were inhibited. In addition, in the present invention, the single fiber denier is 100d.
Hereinafter, it also has specificity in that it is preferably 35 d or less. This is because when the single fiber denier becomes large, it becomes difficult to develop a uniform stretching stress concentration in the inner layer portion of the yarn, and this becomes a factor that inhibits the stretchability. The degree of crystal orientation of the conventionally known high-strength polyester filament is the orientation angle (OA) of the (100) plane of 10° or more, and the degree of crystal orientation fc (formula [3] below) fc = 180−OA/180× 100 (%) ... [3] is less than 95%, whereas in the case of the high-strength polyester fiber of the present invention, the orientation angle of the (100) plane is less than 8°, and when expressed in terms of crystal blending degree (fc). It has an extremely high crystal orientation degree of 95% or more. Another major feature of the polyester of the present invention is that the constant length heating thermal stress peak temperature, which is the measure of the drawing heat history, is 210° C. or higher. Especially when the peak temperature is 210
If it is less than 0.degree. C., it will be difficult to develop the unique distribution of birefringence within the fiber cross section, which is a feature of the present invention. When using high-strength fibers for industrial materials, especially as rubber reinforcing materials mainly for tire cords, mechanical properties at high temperatures are one of the most important factors for practical performance, but evaluating mechanical properties at high temperatures is quite difficult. However, even if tests are actually conducted, problems such as polymer deterioration during measurement tend to occur, resulting in problems with measurement accuracy and reproducibility. The present inventors evaluated the temperature dependence of dynamic viscoelasticity and mechanical temperature dispersion characteristics as a measure representative of the mechanical properties of fibers at high temperatures under a sinusoidal strain of 110 c/s. As a result, the temperature (Tα) at which the loss tangent (Tanδ) is maximum is less than 160°C at most in the case of ordinary high-strength polyester fibers, but the temperature (Tα) at which the loss tangent (Tanδ) is maximum is 160°C.
It was confirmed that these values were as high as above. Tα
indicates the rigidity of the polymer in the amorphous part, and the higher Tα, the greater the binding force in the non-quality part;
This means that molecular motion due to thermal stimulation is suppressed to higher temperatures, and the degree of decrease in mechanical properties at high temperatures is small. Therefore, it can be said that the high-strength polyester fiber of the present invention has better mechanical properties at high temperatures than conventionally known high-strength polyester fibers. In particular, the polyester fiber of the present invention has little strength loss when exposed to high temperatures, so when it is used as a rubber reinforcing material for tire cords, for example, the rubber is heated and vulcanized with the fiber embedded. It also has the advantage that the strength of the fibers does not deteriorate much even when the fibers are heated, and maintains a high reinforcing effect. Next, to explain more specifically the birefringence distribution within the fiber cross section according to the present invention, -10×10 -3 <Δn A −Δn B <0 ... [1] Preferably -10×10 -3 <Δn A −Δn B ≦−1.0×10 -3
...[2] [However, Δn A and Δn B are as described above] are selected. In formulas [1] and [2], Δn A is Δn of the outer layer of the yarn, and Δn B is Δn of the inner layer of the yarn.
The polyester fiber of the present invention has a very unique microstructure in which the outer yarn layer has a smaller Δn than the inner layer. In the present invention, as mentioned above, by making the value of Δn A - Δn B negative, polyester with excellent physical properties is made into a fiber, but if this value is too small,
There is a tendency for the strength of the surface side to become a little too low and the strength of the entire fiber to be a little low, so Δn A
It is necessary to control the heating and stretching conditions so that the value of -Δn B does not become less than -10×10 -3 . Next, a method for producing polyester fibers having the above characteristics will be briefly explained, but the present invention is not limited to the following method. In producing the polyester fiber of the present invention, the spinning and drawing process, especially the drawing process, is important. That is, for example, when undrawn yarn with a birefringence of 0.002 to 0.060 obtained by melt-spinning a polyester with an intrinsic viscosity of 0.58 or more is drawn continuously after spinning or once wound and then stretched, the first supply of undrawn yarn is performed. Preliminary stretching of 1.10 times or less is performed between the roller and the undrawn yarn second supply roller maintained at 100°C or less, and then first stage stretching is performed between the roller and the first stretching roller at a total stretching ratio of 40% or more. In this case, a high-temperature pressurized steam jet nozzle is installed between the undrawn yarn second supply roller and the first drawing roller, and the nozzle temperature is set to 200°C or higher to jet high-temperature steam. Fix the stretching point near the steam jet nozzle. Furthermore, when performing the second stage drawing, a slit heater (a heating device provided with a slit as a thread running path) with an ambient temperature of 170 to 420°C was installed between the first drawing roller and the second drawing roller. The thread is heated while running through the core slit in a non-contact state (atmospheric temperature refers to the temperature inside the slit). Provided to stretching rollers. At that time, a temperature gradient is created in the slit heater so that the atmospheric temperature at the yarn entrance is 170°C or higher and the exit atmospheric temperature is 420°C or lower, and the yarn is kept in an atmosphere of 200 to 420°C for 0.3 seconds or more. It is preferable to pass the yarn through the thread. Also, after the second stage stretching,
It is also possible to further improve the dimensional stability by performing a relaxation treatment of 10% or less at 230 to 165° C. either continuously without winding or after winding. When the fiber of the present invention is used for reinforcing rubber etc., it is usually used in the form of a multifilament, but the use of the fiber of the present invention is not particularly limited, and therefore the form of the fiber may also be a roving yarn. , short, chopped strands, etc. may be used. The fibers of the present invention are suitably used for tire cords, particularly carcass cords in radial structure tires for heavy vehicles, and reinforcing cords for rubber such as reinforcing cords for other V-belts, flat belts, toothed belts, and the like. Of course, the uses of the present invention are not limited to the above, and can be used in exactly the same way as conventional polyester fibers. Below, methods for measuring the main parameters used to identify the structure and measure the physical properties of the fibers of the present invention will be described. <Measurement method of intrinsic viscosity> Measurement is performed in a mixed solvent consisting of 75% by weight of P-chlorophenol and 25% by weight of tetrachloroethane. The polymer is dissolved in the solvent at room temperature and the viscosity measurements are carried out in an Ostwaldoffenske capillary viscometer at 30°C. Intrinsic viscosity is the limit value at which the natural logarithm of the ratio of solution viscosity to solvent viscosity divided by the concentration of the polymer solution in grams of polymer per 100 ml of solution approaches zero concentration. <Method for Measuring Birefringence (Δn)> A Nikon polarizing microscope POH model Leitz Pellec compensator was used, and a spectral light source fusion starter (Toshiba SLS-3-B model) was used as a light source (Na light source). A sample cut at an angle of 45° to the fiber axis with a length of 5 to 6 mm is placed on a glass slide with the cut side facing up. Place the sample slide glass on the rotating stage so that the sample is at a 45° angle to the polarizer.
After adjusting the rotary stage by rotating it and inserting the analyzer to obtain a dark field, set the compensator to 30 and count the number of stripes (n pieces). Turn the compensator clockwise to measure the point at which the sample first becomes darkest (a), and turn the compensator counterclockwise to measure the point at which the sample first becomes darkest (compensator scale "b"). After (read up to 1/10 scale in both cases), turn off the compensator.
30, remove the analyzer, measure the diameter d of the sample, and calculate the birefringence (Δn) based on the following formula.
Calculate (average value of 20 measurements). Δn=Γ/d (Γ: retardation, = nλ 0 +ε)
...[4] λ 0 = 589.3 mμ ε: C/ of Leitz compensator manual
10000 and i = (a-b) (: difference in compensator reading) <Measurement method of Δn distribution within the fiber cross section> Central refractive index (n⊥, 0, n, 0) and outer layer refractive index (n⊥, 0.9, n, 0.9) reveal the unique molecular orientation of the fibers of the present invention, which is associated with the superior strength of the fibers of the present invention. can be shown. The distribution of the average refractive index observed from the side surface of the fiber can be measured by the interference fringe method obtained using a transmission quantitative interference microscope (for example, Interfaco interference microscope manufactured by Carl Zeiss Jena, East Germany). This method can be applied to fibers with a circular cross section. The refractive index of the fiber is the refractive index (n
) and the refractive index (n⊥) for polarized light vibrating perpendicular to the fiber axis. All measurements described here used a xenon lamp as the light source, under polarized light, and an interference filter wavelength of 544 nm.
is carried out using the refractive index (n and n⊥) obtained using green light. The measurement of n and n, 0 and n, 0.9 obtained from n⊥ will be explained in detail below.
Fibers tested at 0.9) are tested using optically slatted glass slides and coverslips.
The fibers are immersed in an inert encapsulant with a refractive index (n E ) that gives a fringe shift within one wavelength. The refractive index (n E ) of the mounting medium is the value measured at 20°C using an Atsube refractometer using green light (wavelength λ = 544 nm) as a light source.This mounting medium is, for example, a mixture of liquid paraffin and α-bromnaphthalene. One with a refractive index of 1.48 to 1.65 can be prepared from a liquid. A single fiber is immersed in this mounting medium. This interference fringe pattern is photographed, magnified 1,000 to 2,000 times, and analyzed. As shown schematically in Figure 1, the refractive index of the fiber encapsulant is n E , the average refractive index between S' and S'' of the fiber is n, the thickness between S' and S'' is t, and the wavelength of the light beam used is λ, the distance between the background parallel interference fringes (corresponding to 1λ) Dn', and the deviation of the interference fringes due to the fibers as d, the optical path difference L is expressed as L=dn/Dn λ=(n-n E )t It will be done. When the refractive index of the sample is n S , the refractive index of the filled liquid is n S < n E = n 1 n S > n E = n 2 . Evaluate the pattern. L 1 = d 1 /D 1 λ=(n-n 1 )t L 2 =d 2 /D 2 λ(n-n 2 )t n=L 1 n 2 −L 2 n 1 /R 1 −R 2 ... [5] Therefore, based on the formula [5], the distribution of the average refractive index (n) of the fiber at each position can be determined from the optical path difference at the angular position from the center to the outer periphery of the fiber. The thickness t can be calculated by assuming that the obtained fiber has a circular cross section. However, due to variations in manufacturing conditions or accidents after manufacturing, there may be cases where the cross section is not circular.
In order to eliminate such inconveniences, it is appropriate to use a portion to be measured where the displacement of the interference fringes is symmetrical with the fiber axis as the axis of symmetry. When the radius of the fiber is R, the measurement is 0.1R between 0 and 0.9R.
The average refractive index of each position can be obtained by performing the refractive index at intervals of . The distribution of n⊥ can be found in the same way, so the birefringence distribution is Δn(r/R)=n, r/R−n⊥, r/R
...[6] Required from. Δn(r/R) is obtained by averaging measurements made on at least 3 filaments, preferably 5 to 10 filaments. <Measurement method of fiber stiffness characteristics> Using Tensilon manufactured by Toyo Baldwin, sample length (gauge length) 100 mm, elongation speed = 100%/min,
The S-S curve of a single fiber was measured at a recording speed of 500 mm/min and an initial load of 1/30 g/d, and the cutting strength (g/d) was determined.
Cutting elongation (%) and initial elastic modulus (g/d) were calculated. The initial elastic modulus was calculated from the maximum slope near the origin of the SS curve. Regarding the calculation of each characteristic value,
at least 5 filaments, preferably 10-20
It is obtained by averaging the measurements made on the filaments of the book. <Measurement method of fiber long period by small-angle X-ray diffraction> The measurement of the small-angle X-ray scattering pattern is performed using, for example, an X-ray generator manufactured by Rigaku Corporation (RU-3H model). For measurement, tube voltage 45KV, tube current 70mA, copper anticathode, CuKα made monochromatic with a nickel filter.
(λx=1.5418Å) is used. Attach the fiber sample to the sample holder so that the single threads are parallel to each other. It is appropriate that the thickness of the sample be approximately 0.5 to 1.0 mm. X-rays are incident perpendicularly to the fiber axes of these fibers arranged in parallel, and
Counter) system. An overview of this system can be found in [Polmer Journal, vol.13, 501
(1981)]. The measurement conditions were as follows: 0.3 mm x 0.2 mm medium pinhole collimator, distance between sample and probe: 400 mm, MCA (multichannel analyzer), number of measurement channels: 256, and measurement time: 600 seconds. Data processing is performed by subtracting the air scattering intensity from the measured scattering intensity, calculating it by moving average processing, and reading the maximum intensity position.
From the long period small angle scattering angle 2α, calculate the fiber long period according to the following formula [7] [see Figure 2 A and B:
In the figure, 1 is a sample, 2 is a PSPC probe, 3 is a position analyzer, 4 is an MCA, and 5 is a display section]. α=λx/2sinα...[7] λx=1.5418Å The moving average processing is calculated according to the following formula. I(S) N = i=N+K 〓 i=N+K I(S) 1 /2K+1 However, in the above formula, I(S) N and I(S) i are the channel numbers N and i, respectively. Measured scattering intensity (intensity minus air scattering intensity), K is the number of points adopted for the moving average (here K = 7), N-K>0, N
+K≦256 <Apparent crystal size: ACS> (100) of the equatorial diffraction curve in a wide-angle X-ray diffraction diagram
Calculated using Scherrer's formula from the half-value width of the diffraction intensity of the surface [For details, see "X-ray Crystallography" published by Maruzen Co., Ltd.
(Refer to page 140 of Volume 1, supervised by Isamu Nita). Scherrer's equation is expressed by the following equation. ACS=0.9λ/B 2 −α 2 cosθ ...[8] However, in the above formula, λ is the wavelength of X-rays (1.5418Å),
B is the half width (rad), α is the correction angle (6.98×
10 -3 rad), θ indicates the diffraction angle (degrees). The X-rays used in the examples of the present invention have a tube voltage of
45KV, tube current 70mA, copper anticathode, NI filter, wavelength 1.5418Å, and SG-7 type goniometer manufactured by Rigaku Denki as a diffractometer.
Rotorflex RU-3H as an X-ray generator
I used a mold. <Measurement method of blending angle (OA)> Fiber orientation angle (OA) can be measured using, for example, an X-ray generator (RU-3H) manufactured by Geodenki, a fiber measuring device (FS-3), or a goniometer (SG-3). 7) and using a scintillation counter. For measurement, CuKα (wavelength λ = 1.5418 Å) made monochromatic with a nickel filter is used. The orientation angle is measured using 2θ of (100) plane reflection.
The 2θ of reflection used is determined from the equatorial diffraction intensity curve. The X-ray generator shall be operated at 45 kV and 70 mA, and the fiber sample shall be attached to the fiber measuring device so that the single yarns are parallel to each other. The thickness of the sample is
It is appropriate to set it to about 0.5mm. Set the goniometer to the 2θ value determined by preliminary experiments. X-rays are incident perpendicularly to the fiber axes of the fibers arranged in parallel (beam perpendicular transmission method). The azimuthal direction is scanned from -80° to +30°, and the diffraction intensity is recorded on recording paper using a scintillation counter. Furthermore, record the diffraction intensities at −180° and +180°. At this time, the scanning speed is 4°/min, the chart speed is 1.0 cm/min, the time constant is 2 or 5 seconds, the collimator is 1 mm, and the receiving angle is 1° in both the length and width of the slit. To find the orientation angle from the obtained diffraction intensity curve, take the average value of the diffraction intensities obtained at ±180°,
Draw a horizontal line. Drop a perpendicular line from the top of the peak to the baseline and find the midpoint of its height. Draw a horizontal line through the midpoint. The distance between the intersection of this horizontal line and the diffraction intensity curve is measured, and this value is converted into an angle (°), which is defined as the orientation angle (OA). <Mechanical temperature dispersion> Using Rheovibron manufactured by Toyo Saiki Co., Ltd., the initial thread length is 4.
cm, heating rate 2℃/min, sine frequency 110 during measurement
Hz, and find the temperature (Tα) at which the loss tangent tanδ=E′/E″ is maximum. However, in the above equation, E′ is the storage modulus (dyne/cm 2 ),
E″ is the loss modulus (dyne/cm 2 ). [For details, see Memoirs of the Faculty of
Engineering Kyushu University, vol.23, 41
(1963)] The complex modulus of elasticity E is calculated using the following formula. 1E1=2.0×1/A・D×10 9 ×L/S ……
〔9〕
ただし、
A:tanδ測定時のアンブリチユードフアクター
(Ampl:Factor)による係数(第1表参照)
D:Dynamic Corce Dial値
L:試料長(cm)
S:試料断面積(cm2)[9] However, A: Coefficient due to the amplification factor (Ampl: Factor) during tanδ measurement (see Table 1) D: Dynamic Corce Dial value L: Sample length (cm) S: Sample cross-sectional area (cm 2 )
【表】
損失弾性率E″は
E″=1E1sinδ ……〔10〕
により算出される。
<単糸デニール>
JIS−L1073(1977)に従つて測定。
<乾熱収縮率>
160℃でJIS−L1073(1977)に従つて測定。
<比重>
n−ヘプタンと四塩化炭素よりなる密度勾配管
を作成し、30℃±0.1℃に調温された密度勾配管
中に十分に脱泡した試料を入れ、5時間放置後の
密度勾配管中の試料位置を、密度勾配管の目盛り
で読みとつた値を、標準ガラスロートによる密度
勾配管目盛〜比重キヤリプレーシヨングラフから
比重値に換算し、n=4で測定。比重値は原則と
して小数点以下4桁まで読む。
<定長昇温熱応力ピーク温度>
試長4.5cm、昇温速度20℃/分、初荷重0.05
g/dの条件で、室温より溶断温度までの熱収縮
応力を測定し、熱応力が最大となる温度を求め
る。
[詳細はTexttile Research Journal、vol.47782
(1977)参照。]
<後加工性…加硫処理による強力保持率>
1000Dの延伸糸を夫々撚数49×49(回/10cm)
の双糸コードとし、これをバルナツクス社製
「ValcabondE」(レゾルシンおよびP−クロルフ
エノールとホルムアルデヒドの反応物)を含む
RFL液で処理する。デイツプ条件は、乾燥150℃
×60sec、熱処理240℃×120sec、ストレツチ率
3.0%とする。このタイヤコードをゴム中に埋め
込み、ゴムの外側から金型に挟み付けた後、
1000Dの双糸コードに対して600gの加重をかけ、
160℃で3時間ゴムの加硫を行なつた後冷却し、
コードをゴムから取り出して強力を測定する。
以下実施例を挙げて本発明の構成及び作用効果
を具体的に説明する。尚実験例中「部」及び
「%」とあるのは特記しない限り、「重量部」及び
「重量%」を意味するものとする。
実施例
第2表(1)、(2)に示す固有粘度のポリエチレンテ
レフタレートを原料とし、同表に示す条件で紡糸
を行い、同表に示す含屈折率の未延伸糸を得た。
紡糸にあたつては、未延伸糸引取り前に適量の紡
糸油剤を糸条表面に付着させた。
得られた未延伸糸を第3表(1)、(2)に示す条件で
延伸し、第4表(1)、(2)に示す糸質の延伸糸を得
た。第4表(1)、(2)中に従来例として、市販の高強
力グレードのタイヤコード用ポリエステル繊維の
糸質を併記する。[Table] Loss elastic modulus E'' is calculated by E''=1E1sinδ...[10]. <Single thread denier> Measured according to JIS-L1073 (1977). <Dry heat shrinkage rate> Measured at 160℃ according to JIS-L1073 (1977). <Specific Gravity> Create a density gradient tube made of n-heptane and carbon tetrachloride, place a sufficiently degassed sample into the density gradient tube whose temperature is controlled to 30℃±0.1℃, and leave it for 5 hours. The value obtained by reading the sample position in the tube on the scale of the density gradient tube was converted into a specific gravity value from the density gradient tube scale to specific gravity calibration graph using a standard glass funnel, and the value was measured at n=4. As a general rule, read specific gravity values to four decimal places. <Constant length heating thermal stress peak temperature> Test length 4.5cm, heating rate 20℃/min, initial load 0.05
The thermal contraction stress is measured from room temperature to the melting temperature under the conditions of g/d, and the temperature at which the thermal stress is maximum is determined. [Details in Textile Research Journal, vol.47782
(1977). ] <Post-processability...Toughness retention rate by vulcanization treatment> Number of twists of each 1000D drawn yarn is 49 x 49 (twice/10cm)
This is a twin thread cord containing "ValcabondE" (a reaction product of resorcinol and P-chlorophenol and formaldehyde) manufactured by Valnatux.
Treat with RFL solution. Deep conditions are drying at 150°C.
×60sec, heat treatment 240℃×120sec, stretch rate
The rate shall be 3.0%. After embedding this tire cord in the rubber and sandwiching it between the molds from the outside of the rubber,
Applying a load of 600g to a 1000D double thread cord,
After vulcanizing the rubber at 160℃ for 3 hours, it was cooled.
Remove the cord from the rubber and measure its strength. The structure and effects of the present invention will be specifically explained below with reference to Examples. In the experimental examples, "parts" and "%" mean "parts by weight" and "% by weight" unless otherwise specified. Examples Using polyethylene terephthalate having the intrinsic viscosities shown in Table 2 (1) and (2) as raw materials, spinning was performed under the conditions shown in the table to obtain undrawn yarns having the refractive index shown in the table.
During spinning, an appropriate amount of spinning oil was applied to the surface of the yarn before taking off the undrawn yarn. The obtained undrawn yarn was drawn under the conditions shown in Table 3 (1) and (2) to obtain drawn yarn having the quality shown in Table 4 (1) and (2). Tables 4 (1) and (2) also list the yarn quality of commercially available high-strength grade polyester fibers for tire cords as conventional examples.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
第2〜4表より次の様に考えることができる。
実施例1〜6:何れも本発明の規定要件を満たす
実施例であり、比較例および従来材に比べて非
常に優れた切断強度を有しており、しかも後加
工性の項からも明らかである様に、加熱時の強
力保持率が80〜90%と非常に高く、タイヤコー
ド用等として非常に優れたものであることが分
かる。
比較例1:繊維全体の△nおよび「△nA−△nB」
の値が本発明の規定要件を外れており、且つ
Tαも低いため強度が乏しく、加熱時の強力保
持率も劣悪である。
比較例2:繊維全体の△nおよび「△nA−△nB」
の値は一応本発明の規定要件を満たしている
が、用いたポリエチレンテレフタレートの固有
粘度が0.50未満である比較例であり、繊維長周
期が規定要件を満たしておらず、切断強度もや
や不十分あり、加熱時の強力保持率も乏しい。
比較例3〜6:加熱延伸条件等を種々変化させた
比較例であるが、いずれも従来材と同様に繊維
全体の△nが低く且つ「△nA−△nB」の値がプ
ラスを示すと共にTαも低いため、切断強度お
よび加熱時の強力保持率が低い。
比較例7:繊維の複屈折率が低く、また「△nA−
△nB」の値がその好ましい値である「10×10-3
以上」という範囲から外れ、Tαも低いため表
層部の強度が乏しくなり、繊維全体としての強
度は低く且つ加熱時の強力保持率も非常に低く
なつている。
次に上記実験で得た繊維のうち実施例1および
比較例1で得たものを選択し、JIS L 1017の方
法に準拠してタイヤコードとしての特性を比較し
た。結果を従来材(同前)を用いた場合の結果と
共に第5表に示す。[Table] From Tables 2 to 4, the following can be considered. Examples 1 to 6: All of these examples meet the specified requirements of the present invention, and have extremely superior cutting strength compared to comparative examples and conventional materials, which is also clear from the post-processability section. It can be seen that the strength retention rate during heating is extremely high at 80 to 90%, making it an excellent product for use in tire cords, etc. Comparative example 1: △n of the entire fiber and “△n A −△n B ”
The value of is outside the specified requirements of the present invention, and
Since Tα is also low, the strength is poor, and the strength retention rate during heating is also poor. Comparative example 2: △n of the entire fiber and “△n A −△n B ”
Although the value of is a comparative example in which the intrinsic viscosity of the polyethylene terephthalate used is less than 0.50, the fiber length period does not meet the specified requirements, and the cutting strength is also somewhat insufficient. However, the strength retention rate during heating is also poor. Comparative Examples 3 to 6: These are comparative examples in which the heating stretching conditions etc. were varied, but in all cases the △n of the entire fiber was low and the value of ``△n A - △n B '' was positive, similar to the conventional material. As the Tα is also low, the cutting strength and strength retention rate during heating are low. Comparative Example 7: The birefringence of the fiber is low, and “△n A −
The value of △n B is the preferred value of 10×10 -3
Since the fiber is out of the above range and Tα is low, the strength of the surface layer is poor, the strength of the fiber as a whole is low, and the strength retention rate during heating is also very low. Next, among the fibers obtained in the above experiment, those obtained in Example 1 and Comparative Example 1 were selected and their properties as tire cords were compared in accordance with the method of JIS L 1017. The results are shown in Table 5 together with the results when the conventional material (same as above) was used.
【表】【table】
【表】
第5表からも明らかである様に、本発明繊維
は、比較繊維および従来繊維に比べて、強力およ
び疲労強度の卓越したタイヤーコードを提供し得
るものである。[Table] As is clear from Table 5, the fibers of the present invention can provide tire cords with superior strength and fatigue strength compared to comparative fibers and conventional fibers.
第1図Aは本発明の繊維を干渉顕微鏡で横方向
から観察したときに見られる干渉縞を示す模式
図、同Bは繊維断面の模式図、第2図AはPSPC
システムによる小角X線回折測定における試料及
びフイルム面等の配置を示す模式図、同Bは本発
明繊維の小角X線回折パターンを示す模式図であ
る。
Figure 1A is a schematic diagram showing the interference fringes seen when the fiber of the present invention is observed from the lateral direction with an interference microscope, Figure 1B is a schematic diagram of the cross section of the fiber, and Figure 2A is a PSPC
B is a schematic diagram showing the arrangement of a sample, film surface, etc. in small-angle X-ray diffraction measurement using the system, and B is a schematic diagram showing the small-angle X-ray diffraction pattern of the fiber of the present invention.
Claims (1)
ロロエタン=3/1(重量比)の溶媒中、30℃で
測定した値]が0.50以上で、繰り返し単位の85モ
ル%以上がエチレンテレフタレートよりなるポリ
エステルを繊維素材とし、且つ繊維断面内におけ
る複屈折率が下記[1]式を満足し、 −10×10-3<△nA−△nB<0 但し △nA:r/R=0.9の位置における繊維の複屈折
率 △nB:r/R=0.0の位置における繊維の複屈折
率 R:繊維断面の半径 r:繊維断面の中心軸からの距離 且つ単糸デニールが100デニール以下であり、更
に繊維の複屈折率△nが195×10-3以上、小角X
線回折による繊維長周期が170〓以上、比重が
1.390以上、乾熱収縮率が15%以下、切断強度が
10g/d以上、繊維の力学温度分散特性値
(110c/sにおける測定値)である損失正接
(Tanδ)が最大となる温度(Tα)が160°以上で
あることを特徴とするポリエステル繊維。 2 特許請求の範囲第1項において、繊維素材の
固有粘度が0.65〜1.20であるポリエステル繊維。 3 特許請求の範囲第1または2項において、
(△nA−△nB)が−1.0×10-3以下であるポリエス
テル繊維。 4 特許請求の範囲第1〜3項のいずれかにおい
て、広角X線回折により求められる(100)面の
配向角が8度以下であるポリエステル繊維。 5 特許請求の範囲第1〜4項のいずれかにおい
て、繊維の定長昇温熱応力ピーク温度が210℃以
上であるポリエステル繊維。 6 特許請求の範囲第1〜5項のいずれかにおい
て、繊維の単糸デニールが35デニール以下である
ポリエステル繊維。[Scope of Claims] 1. Intrinsic viscosity [value measured at 30°C in a solvent of P-chlorophenol/tetrachloroethane = 3/1 (weight ratio)] is 0.50 or more, and 85 mol% or more of the repeating units are ethylene. The fiber material is polyester made of terephthalate, and the birefringence in the cross section of the fiber satisfies the following formula [1], −10×10 -3 <△n A −△n B <0 where △n A :r/ Birefringence index of the fiber at the position of R=0.9 △n B : Birefringence index of the fiber at the position of r/R=0.0 R: Radius of the fiber cross section r: Distance from the central axis of the fiber cross section and single yarn denier of 100 denier or less, and the birefringence △n of the fiber is 195×10 -3 or more, small angle
The fiber long period by line diffraction is 170〓 or more, and the specific gravity is
1.390 or more, dry heat shrinkage rate is 15% or less, cutting strength is
10 g/d or more, and the temperature (Tα) at which the loss tangent (Tan δ), which is the mechanical temperature dispersion characteristic value of the fiber (measured value at 110 c/s), is maximum is 160° or more. 2. The polyester fiber according to claim 1, wherein the fiber material has an intrinsic viscosity of 0.65 to 1.20. 3 In claim 1 or 2,
A polyester fiber whose (Δn A −Δn B ) is −1.0×10 −3 or less. 4. The polyester fiber according to any one of claims 1 to 3, wherein the orientation angle of the (100) plane determined by wide-angle X-ray diffraction is 8 degrees or less. 5. The polyester fiber according to any one of claims 1 to 4, wherein the fiber has a constant length heating thermal stress peak temperature of 210°C or higher. 6. The polyester fiber according to any one of claims 1 to 5, wherein the fiber has a single filament denier of 35 denier or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11040082A JPS591714A (en) | 1982-06-25 | 1982-06-25 | Polyester fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11040082A JPS591714A (en) | 1982-06-25 | 1982-06-25 | Polyester fiber |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS591714A JPS591714A (en) | 1984-01-07 |
JPH0350002B2 true JPH0350002B2 (en) | 1991-07-31 |
Family
ID=14534839
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11040082A Granted JPS591714A (en) | 1982-06-25 | 1982-06-25 | Polyester fiber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS591714A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ID846B (en) * | 1991-12-13 | 1996-08-01 | Kolon Inc | FIBER YARN, POLYESTER TIRE THREAD AND HOW TO PRODUCE IT |
KR100954873B1 (en) * | 2007-12-28 | 2010-04-28 | 주식회사 효성 | High-strength Polyethyleneterephthalate fiber and its manufacturing method |
JP5243121B2 (en) * | 2008-07-09 | 2013-07-24 | 帝人株式会社 | Polyethylene naphthalate fiber for speaker diaphragm |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5115021A (en) * | 1974-06-17 | 1976-02-06 | Du Pont |
-
1982
- 1982-06-25 JP JP11040082A patent/JPS591714A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5115021A (en) * | 1974-06-17 | 1976-02-06 | Du Pont |
Also Published As
Publication number | Publication date |
---|---|
JPS591714A (en) | 1984-01-07 |
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