JPH04100915A - Polyphenylene sulfide fiber and its production - Google Patents
Polyphenylene sulfide fiber and its productionInfo
- Publication number
- JPH04100915A JPH04100915A JP21610990A JP21610990A JPH04100915A JP H04100915 A JPH04100915 A JP H04100915A JP 21610990 A JP21610990 A JP 21610990A JP 21610990 A JP21610990 A JP 21610990A JP H04100915 A JPH04100915 A JP H04100915A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene sulfide
- molecular weight
- fiber
- heat
- temperature
- 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.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 24
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 23
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 238000009826 distribution Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 230000009477 glass transition Effects 0.000 abstract description 2
- 208000018747 cerebellar ataxia with neuropathy and bilateral vestibular areflexia syndrome Diseases 0.000 abstract 1
- 239000011810 insulating material Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、耐熱性・耐薬品性を有するポリフェニレンサ
ルファイド繊維とその製造方法に関するもので、更に詳
しくは、強度等の繊維特性が優れ、毛羽や欠点が少ない
ポリフェニレンサルファイド繊維とその製造方法に関す
る。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to polyphenylene sulfide fibers having heat resistance and chemical resistance and a method for producing the same. The present invention relates to a polyphenylene sulfide fiber with few defects and drawbacks, and a method for producing the same.
（従来の技術）
ポリフェニレンサルファイドよりなる繊維は耐熱性、耐
酸化性、耐燃性、耐薬品性などの優れた性質を有するの
で、工業用フィルターや防護服等過酷な条件下で使用す
る繊維製品の素材として有望であることが知られている
。(Prior art) Fibers made of polyphenylene sulfide have excellent properties such as heat resistance, oxidation resistance, flame resistance, and chemical resistance, so they are suitable for textile products used under harsh conditions such as industrial filters and protective clothing. It is known to be a promising material.
ポリフェニレンサルファイドの繊維化技術に関しては例
えば特公昭５２−３６０９号公報、特開昭５７−１４３
５１８号公報、同５８−３１１１２号公報等の各公報に
開示されているが、これらの方法で得られる繊維は、強
度の低いものしか得られず、また紡糸時に糸切れし易す
い等、操業性にも問題があった。Regarding the fiberization technology of polyphenylene sulfide, for example, Japanese Patent Publication No. 52-3609 and Japanese Patent Application Laid-open No. 57-143
Although the fibers obtained by these methods are disclosed in various publications such as Publication No. 518 and Publication No. 58-31112, the fibers obtained by these methods have only low strength, and the fibers are easy to break during spinning, making it difficult to operate. There were also problems with sexuality.
（発明が解決しようとする課題）
本発明においては、ポリフェニレンサルファイド製であ
っても高強度で、欠点の少なくかつ繊維化の諸工程にお
いて色々なトラブルが生ずることのないポリフェニレン
サルファイド繊維を製造する方法について検討した。(Problems to be Solved by the Invention) The present invention provides a method for producing polyphenylene sulfide fibers that have high strength even if they are made of polyphenylene sulfide, have few defects, and do not cause various troubles during the fiberization process. We considered this.
（課題を解決するための手段）
上記課題を解決するために鋭意検討を重ねた結果、繊維
特性と製糸性とを両立させるには、ポリフェニレンサル
ファイドの分子量分布、特に低分子量成分の含有率が大
きく関与していることを見い出した。つまり、分子量分
布が狭く、低分子成分の含有率が一定量以下のポリフェ
ニレンサルファイドを用いる時、前述の課題を解決され
ることを見い出したのである。(Means for solving the problem) As a result of intensive studies to solve the above problem, we found that in order to achieve both fiber properties and spinnability, the molecular weight distribution of polyphenylene sulfide, especially the content of low molecular weight components, must be large. found to be involved. In other words, it has been found that the above-mentioned problems can be solved when polyphenylene sulfide having a narrow molecular weight distribution and a content of low molecular weight components is below a certain level.
かくして、本発明は以下の構成からなる。Thus, the present invention consists of the following configuration.
（１） 重量平均分子量（門−） ２００００〜１０
００００、分子量分布（Ｍｗ／Ｍｎ） １０以下である
ポリフェニレンサルファイド重合体からなる繊維。(1) Weight average molecular weight (class-) 20000-10
0000, a fiber made of a polyphenylene sulfide polymer having a molecular weight distribution (Mw/Mn) of 10 or less.
（２） 重量平均分子Ｍ（石） ２００００−１（１
００００、分子量分布（Ｍｗ ／ Ｍｎ ） １０以下
であり、−６−が１０００以下ノオリゴマー重量分率が
５％以下のポリフェニレンサルファイド重合体を口金温
度２７０〜３１０℃の口金より紡糸し、次いで延伸、熱
処理することを特徴とするポリフェニレンサルファイド
繊維の製造法。(2) Weight average molecule M (stone) 20000-1 (1
A polyphenylene sulfide polymer having a molecular weight distribution (Mw/Mn) of 10 or less and a -6- of 1000 or less and an oligomer weight fraction of 5% or less is spun from a spindle at a spindle temperature of 270 to 310°C, then stretched, A method for producing polyphenylene sulfide fiber, which is characterized by heat treatment.
以下本発明について、詳細に説明する。The present invention will be explained in detail below.
本発明におけるポリフェニレンサルファイドとは、たと
えば多ハロ置換ヘンゼンとアルカリ金属サルファイドと
を有機極性溶媒中で反応せしめることによって得られる
重合体であり、代表的にはたとえば米国特許第３３５４
１２９号明細書に詳しく述べられているものが使用でき
る。The polyphenylene sulfide in the present invention is a polymer obtained by, for example, reacting a polyhalo-substituted Hensen with an alkali metal sulfide in an organic polar solvent, and is typically a polymer obtained by, for example, US Pat.
Those detailed in the '129 specification can be used.
本発明のポリフェニレンサルファイド繊維を得るために
は、２０，０００〜１００，０００の重量平均分子量（
門−）を有し、分子量分布（Ｍｗ ／ Ｍｎ ）が１０
以下であり、Ｍｗ＜１０００のオリゴマー含有率が５％
以下のポリフェニレンサルファイドを使用する。五が２
０．０００以下の時は製糸性が悪く強度の高い繊維力得
られない。またーｈ−がｉｏｏ、ｏｏｏ以上の時は、溶
融押出が困難となる。In order to obtain the polyphenylene sulfide fiber of the present invention, a weight average molecular weight of 20,000 to 100,000 (
) and has a molecular weight distribution (Mw/Mn) of 10
or less, and the oligomer content with Mw<1000 is 5%
Use the following polyphenylene sulfide. Five is two
When it is less than 0.000, the spinning property is poor and high strength fiber strength cannot be obtained. Moreover, when -h- is more than ioo or ooo, melt extrusion becomes difficult.
さらに分子量分布（Ｍｗ ／ Ｍｎ ）が１０以上の時
には延伸性が悪くなる欠点を有し、Ｍｗ ＜ １０００
のオリゴマー含有率が５％の時には、加熱熔融時の劣化
が著しく糸切れの原因になりやすく、長時間の操業が困
難である。Furthermore, when the molecular weight distribution (Mw/Mn) is 10 or more, it has the disadvantage of poor stretchability, and when Mw < 1000
When the oligomer content is 5%, the deterioration during heating and melting is significant and easily causes thread breakage, making long-term operation difficult.
上記のポリフェニレンサルファイドを２７０〜３００゛
Ｃの範囲の紡糸温度で紡糸する。紡糸温度が２７０℃以
下の時はフィルターでの目詰りによるノズルパック圧上
昇性が著しく、３００℃以上の時はポリマーの劣化が生
ずるため本発明の目的とする繊維が得られない。The polyphenylene sulfide described above is spun at a spinning temperature in the range of 270-300°C. When the spinning temperature is below 270°C, the nozzle pack pressure increases significantly due to filter clogging, and when it is above 300°C, polymer deterioration occurs, making it impossible to obtain the fiber targeted by the present invention.
また延伸温度はポリフェニレンサルファイドのガラス転
移温度±２０゛Ｃ１好ましくは５１０℃であり、延伸倍
率は２．０〜４．０、好ましくは２．５〜３．５である
。The stretching temperature is ±20° C1, preferably 510° C., the glass transition temperature of polyphenylene sulfide, and the stretching ratio is 2.0 to 4.0, preferably 2.5 to 3.5.
さらに熱処理は１６０〜１８０’Ｃで１〜１０秒間緊張
下で行う。上記条件で延伸および熱処理することによっ
て複屈折０．１５０〜０．３００で、強度３．５ ｇ
／ ｄ以上、伸度３０％以上という物性値を有する繊維
を得ることができる。また特に延伸後の熱処理は繊維の
結晶化制御のために重要である。Further heat treatment is performed at 160-180'C for 1-10 seconds under tension. By stretching and heat-treating under the above conditions, the birefringence is 0.150-0.300 and the strength is 3.5 g.
It is possible to obtain fibers having physical property values of /d or more and elongation of 30% or more. Furthermore, heat treatment after stretching is particularly important for controlling fiber crystallization.
以上のようにして得られたポリフェニレンサルファイド
繊維は、強度３．５ｇ／ｄ以上、伸度３０％以上といっ
た高物性でかつ欠点の少ないという特性を有する。The polyphenylene sulfide fiber obtained as described above has high physical properties such as strength of 3.5 g/d or more and elongation of 30% or more, and has few defects.
尚本発明における分子量分布、オリゴマー含有率は以下
のようにして求めた。The molecular weight distribution and oligomer content in the present invention were determined as follows.
（分子量分布）
以下に示す条件でＧＰＣ測定を行い、■、■、耳／Ｍｎ
を算出した。(Molecular weight distribution) GPC measurement was performed under the conditions shown below.
was calculated.
装置 ポンプ： ５１０型（１４ａ ｔｅｒｓ社製）イ
ンジェクター： Ｌ１２に型（）
検出器＝９４５型液体クロマトグラフ用ＦＩＤ（Ｔｒａ
ｃｏｒ Ｉｎｓｔｒｕｍｅｎｔｓ社製）データ処理：
Ｍ７４０型データモジュール（Ｗａｔｅｒｓ社製）
カラム： ５ｈｏｄｅｘ ＡＴ−８０Ｍ条件 溶 媒
＝１−クロロナフタレン測定温度：２２０℃
（オリゴマー含有率）
上述の分子量分布測定における分子量分布曲線よりポリ
スチレン換算の分子ｉｉ Ｍｗ ＜ １０００の割合を
計算した。Equipment Pump: Model 510 (manufactured by 14Aters) Injector: Model L12 () Detector: Model 945 FID for liquid chromatograph (Tra
Cor Instruments) Data processing:
M740 type data module (manufactured by Waters) Column: 5hodex AT-80M conditions Solvent
=1-chloronaphthalene measurement temperature: 220°C (oligomer content) The proportion of molecules ii Mw < 1000 in terms of polystyrene was calculated from the molecular weight distribution curve in the above-mentioned molecular weight distribution measurement.
（実施例）
［ポリマーの重合］
１リツトルのＮ−メチルピロリドン（ＮＭＰ）および７
２６．６グラムのＮａ２Ｓ・９Ｈ２０をガラスフラスコ
に入れ、水和水が蒸発するまでかきまぜながら加熱する
。これにｐ−ジクロロヘンゼン４４１ｇを加え、２２７
℃で１７時間加熱する。(Example) [Polymerization of polymer] 1 liter of N-methylpyrrolidone (NMP) and 7
26.6 grams of Na2S.9H20 are placed in a glass flask and heated with stirring until the water of hydration evaporates. Add 441 g of p-dichlorohenzene to this, and add 227 g of p-dichlorohenzene.
Heat at ℃ for 17 hours.
反応容器より重合体を取り出し、メタノールと水を用い
て各２回洗浄する。乾燥すると２８５ｇのポリフェニレ
ンサルファイドを得る。これをポリマーＡとする。ポリ
マーＡをさらにメタノールと水を用いて、洗浄を５回繰
り返したものをポリマーＢ、１０回繰り返したものをポ
リマーＣとする。The polymer is taken out from the reaction vessel and washed twice each with methanol and water. After drying, 285 g of polyphenylene sulfide is obtained. This is called Polymer A. Polymer A was washed 5 times with methanol and water to obtain Polymer B, and polymer C was obtained by washing 10 times.
重合温度を２３８℃１重合時間を８時間に変更した以外
はポリマーＡと同様にして、ポリマーＤを得る。ポリマ
ーＤをさらにメタノールと水を用いて洗浄を１０回繰り
返し、ポリマーＥを得る。Polymer D was obtained in the same manner as Polymer A except that the polymerization temperature was changed to 238° C. and the polymerization time was changed to 8 hours. Polymer D is further washed 10 times using methanol and water to obtain Polymer E.
ポリマーＡ・〜Ｅの写／…、と５＜１０００の含有率を
表−１に示す。Table 1 shows the contents of Polymers A, -E, and 5<1000.
〔紡糸・延伸］
Ａ−Ｅのポリマーを３１０℃で溶融押出し、孔径０．４
１ｍφ、ホール数３０個を有し２９０℃に加熱した紡糸
口金より吐出量４５ｇ／分で吐出させる。吐出された糸
状は、冷却固化させ、油剤を付与させた後、捲取った。[Spinning/Stretching] Polymers A-E were melt extruded at 310°C, pore size 0.4
It is discharged from a spinneret having a diameter of 1 m and 30 holes and heated to 290° C. at a discharge rate of 45 g/min. The discharged filament was cooled and solidified, coated with an oil agent, and then wound up.
次ムこ得られた未延伸糸を表面温度９０゛Ｃに加熱した
ローラーを使用し、３．０の延伸倍率で行い２００℃の
ホットプレートで熱セットを行った。Next, the obtained undrawn yarn was drawn at a stretching ratio of 3.0 using a roller heated to a surface temperature of 90°C and heat set on a hot plate at 200°C.
表−２に実施例１と比較例１〜５の可紡性と操業性を示
す。また表−３に得られた繊維の特性を示す。Table 2 shows the spinnability and operability of Example 1 and Comparative Examples 1 to 5. Furthermore, Table 3 shows the properties of the obtained fibers.
表−１
表−２
（発明の効果）
本発明は以上のように構成されているので本発明の高巻
縮・低収縮性ステーブル繊維は繊維としての強度その他
の緒特性に優れている他、耐熱性および耐薬品性に優れ
でおり、寸法安定性にも優れているので例えば工業用フ
ィルター、抄紙用カンバス、電気絶縁材料あるいは防護
服等過酷な条件下でも使用に耐え得る繊維製品の素材と
して有用なものである。Table 1 Table 2 (Effects of the Invention) Since the present invention is constructed as described above, the high crimping/low shrinkage stable fiber of the present invention has excellent strength and other properties as a fiber. It has excellent heat resistance, chemical resistance, and dimensional stability, so it is a material for textile products that can withstand use even under harsh conditions, such as industrial filters, papermaking canvas, electrical insulation materials, and protective clothing. It is useful as a.
表−３ 特許出願人 東洋紡績株式会社Table-3 Patent applicant: Toyobo Co., Ltd.
Claims (2)
０００、分子量分布（＠Ｍｗ＠／＠Ｍｎ＠）１０以下で
あるポリフェニレンサルファイド重合体からなる繊維。(1) Weight average molecular weight (@Mw@) 20000-100
000, a fiber made of a polyphenylene sulfide polymer having a molecular weight distribution (@Mw@/@Mn@) of 10 or less.
０００、分子量分布（＠Ｍｗ＠／＠Ｍｎ＠）１０以下で
あり、＠Ｍｗ＠が１０００以下のオリゴマー重量分率が
５％以下のポリフェニレンサルファイド重合体を口金温
度２７０〜３１０℃の口金より紡糸し、次いで延伸、熱
処理することを特徴とするポリフェニレンサルファィド
繊維の製造法。(2) Weight average molecular weight (@Mw@) 20000-100
000, a molecular weight distribution (@Mw@/@Mn@) of 10 or less, @Mw@ of 1000 or less, and an oligomer weight fraction of 5% or less is spun using a spindle at a spindle temperature of 270 to 310°C. , followed by stretching and heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21610990A JPH04100915A (en) | 1990-08-15 | 1990-08-15 | Polyphenylene sulfide fiber and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21610990A JPH04100915A (en) | 1990-08-15 | 1990-08-15 | Polyphenylene sulfide fiber and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04100915A true JPH04100915A (en) | 1992-04-02 |
Family
ID=16683385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21610990A Pending JPH04100915A (en) | 1990-08-15 | 1990-08-15 | Polyphenylene sulfide fiber and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04100915A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009270219A (en) * | 2008-05-07 | 2009-11-19 | Toyobo Co Ltd | Polyphenylene sulfide fiber excellent in forming processability |
| WO2015182523A1 (en) * | 2014-05-30 | 2015-12-03 | 東レ株式会社 | Polyphenylene sulfide fibers, and manufacturing method therefor |
-
1990
- 1990-08-15 JP JP21610990A patent/JPH04100915A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009270219A (en) * | 2008-05-07 | 2009-11-19 | Toyobo Co Ltd | Polyphenylene sulfide fiber excellent in forming processability |
| WO2015182523A1 (en) * | 2014-05-30 | 2015-12-03 | 東レ株式会社 | Polyphenylene sulfide fibers, and manufacturing method therefor |
| CN106460240A (en) * | 2014-05-30 | 2017-02-22 | 东丽株式会社 | Polyphenylene sulfide fibers, and manufacturing method therefor |
| JPWO2015182523A1 (en) * | 2014-05-30 | 2017-04-20 | 東レ株式会社 | Polyphenylene sulfide fiber and method for producing the same |
| AU2015267804B2 (en) * | 2014-05-30 | 2018-07-05 | Toray Industries, Inc. | Polyphenylene sulfide fibers, and manufacturing method therefor |
| US10138577B2 (en) | 2014-05-30 | 2018-11-27 | Toray Industries, Inc. | Polyphenylene sulfide fibers, and manufacturing method therefor |
| TWI651343B (en) * | 2014-05-30 | 2019-02-21 | 日商東麗股份有限公司 | Poly-stretched benzene-sulfur fiber and manufacturing method thereof |
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