JPS6245743A - Production of aromatic polyester fiber - Google Patents
Production of aromatic polyester fiberInfo
- Publication number
- JPS6245743A JPS6245743A JP18643185A JP18643185A JPS6245743A JP S6245743 A JPS6245743 A JP S6245743A JP 18643185 A JP18643185 A JP 18643185A JP 18643185 A JP18643185 A JP 18643185A JP S6245743 A JPS6245743 A JP S6245743A
- Authority
- JP
- Japan
- Prior art keywords
- bobbin
- fibers
- aromatic polyester
- heat treatment
- spinning
- 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
Links
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、高強度、高弾性率を有する芳香族ポリエステ
ル繊維の製造法に関する。更に詳しくは、溶融時に光学
異方性を示す芳香族ポリエステルを溶融紡糸して得られ
た繊維を熱処理することにより熱処理時の融着が少ない
高物性の芳香族ポリエステル繊維の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing aromatic polyester fibers having high strength and high modulus of elasticity. More specifically, the present invention relates to a method for producing aromatic polyester fibers with high physical properties that exhibit less fusion during heat treatment by heat-treating fibers obtained by melt-spinning aromatic polyesters that exhibit optical anisotropy when melted.
（従来の技術）
近年、芳香族ポリエステルの中で、溶融時に光学異方性
を有するものを溶融紡糸することにより、高強度、高弾
性率繊維提供の可能性が明らかになってきた。かかる繊
維は、通常溶融紡糸後に熱処理され、この熱処理が、高
強度、高弾性率の性能発現上極めて重要である。かかる
熱処理工程により重合度、結晶化度、配向等が更に高め
られるが、工業上有利な紡糸温度付近の高温下で短時間
処理を施こそうとする場合には、融着し繊維同志が接触
、接着して離れない状態を起こすことが多く、高物性の
発現が妨げられると共に、商品価値の極めて低いものと
なってしまう。(Prior Art) In recent years, it has become clear that among aromatic polyesters, it is possible to provide high-strength, high-modulus fibers by melt-spinning aromatic polyesters that have optical anisotropy when melted. Such fibers are usually heat treated after melt spinning, and this heat treatment is extremely important for achieving high strength and high elastic modulus performance. This heat treatment step further increases the degree of polymerization, crystallinity, orientation, etc., but if the treatment is carried out for a short time at high temperatures near the industrially advantageous spinning temperature, the fibers may fuse and come into contact with each other. They often adhere and cannot be separated, which hinders the development of high physical properties and results in extremely low commercial value.
従来の熱処理は溶融紡糸して得られた繊維をボビンに巻
き取りボビンをつけたまま熱処理していた。そしてこの
ボビンとしては多数の孔を有する円筒状ボビンや該ボビ
ンの側面の一箇所が切り離された形状が提案されていた
。In conventional heat treatment, fibers obtained by melt spinning are wound onto a bobbin and heat treated with the bobbin still attached. As this bobbin, a cylindrical bobbin having a large number of holes or a shape in which a part of the side surface of the bobbin is cut off has been proposed.
しかしボビンをつけたまま熱処理する方法テハ、ボビン
の材質によりエステルの加水分解を惹起するものや、ボ
ビンに接している側と最外側の繊維に物性差を生じたり
、また収縮を充分吸収できず、融着抑制効果が不充分で
あったりするなどの問題があった。However, heat treatment with the bobbin attached may cause ester hydrolysis depending on the material of the bobbin, or may cause differences in physical properties between the fibers on the side in contact with the bobbin and the outermost fibers, or may not absorb shrinkage sufficiently. , there were problems such as insufficient fusion suppression effect.
（発明が解決しようとする問題点）
本発明の主要な目的は、熱処理時に融着が少なく、高強
度、高弾性率を発現し且つ商品価値の高い芳香族ポリエ
ステル繊維の製造法を提供することである。(Problems to be Solved by the Invention) The main object of the present invention is to provide a method for producing an aromatic polyester fiber that exhibits low fusion during heat treatment, exhibits high strength and high modulus of elasticity, and has high commercial value. It is.
（問題点を解決するための手段）
上述した本発明の目的は、溶融時に光学異方性を示す芳
香族ポリエステルを溶融紡糸し、得られた繊維をボビン
に巻き取った後、ボビンを取り除き繊維のみを熱処理す
ることにより、工業的有利に達成される。(Means for Solving the Problems) The object of the present invention described above is to melt-spun an aromatic polyester that exhibits optical anisotropy when melted, wind the obtained fibers around a bobbin, and then remove the bobbin and spin the fibers. This can be achieved industrially advantageously by heat-treating only.
すなわち溶融時に光学異方性を示す芳香族ポリエステル
を溶融紡糸して得られる繊維は、紡糸後でも引張り弾性
率が高い為巻き取り時に用いたボビンを取り除いても形
崩れせず、そのままの形状を保ちしかも熱処理によって
も何ら形崩れしないためボビンを取り除いた状態で良好
な熱処理が可能であり、ボビンの材質による加水分解の
懸念や内外層の物性差、熱処理時の収縮に伴う融着問題
、さらにそれによる物性低下の問題なく効果的に芳香族
ポリエステル繊維を製造できる。以下本発明を詳述する
。In other words, the fiber obtained by melt-spinning aromatic polyester that exhibits optical anisotropy when melted has a high tensile modulus even after spinning, so it does not lose its shape even when the bobbin used for winding is removed. In addition, it does not lose its shape even during heat treatment, so it is possible to perform good heat treatment with the bobbin removed, and there are concerns about hydrolysis due to the material of the bobbin, physical property differences between the inner and outer layers, and problems with fusion due to shrinkage during heat treatment. Aromatic polyester fibers can be effectively produced without the problem of deterioration of physical properties due to this. The present invention will be explained in detail below.
本発明における溶融時に異方性を示す芳香族ポリエステ
ルとは、９０°直交した２枚の偏光板の間にある加熱試
料台上にポリエステル試料粉末を置いて昇温しでいった
時に、流動可能な温度域において光を透過しうる性質を
有するものをいう。In the present invention, the aromatic polyester that exhibits anisotropy when melted refers to the temperature at which it can flow when the polyester sample powder is placed on a heated sample stand between two polarizing plates crossed at 90° and heated. A substance that has the property of being able to transmit light within a certain range.
このような芳香族ポリエステルは、特公昭５６−１８０
１６号や特公昭５５−２０００８号等に示される芳香族
ジカルボン酸、芳香族ジオール及び／又は芳香族ヒドロ
キシカルボン酸やこれらの誘導体から成るもので、場合
により、これらと脂環族ジカルボン酸、脂環族ジオール
、脂肪族ジオールやこれらの誘導体との共重合体も含ま
れる。Such aromatic polyester
It consists of aromatic dicarboxylic acids, aromatic diols and/or aromatic hydroxycarboxylic acids shown in No. 16 and Japanese Patent Publication No. 55-20008, etc., and their derivatives. Copolymers with cyclic diols, aliphatic diols, and derivatives thereof are also included.
ここで芳香族ジカルボン酸としてはテレフタル酸、イソ
フタル酸、４ 、４’−ジカルボキシジフェニル、２．
６−ジカルボキシナフタレン、１，２−ビス（４−カル
ボキシフェノキシ）エタン等や、これらのアルキル、ア
リール、アルコキシ、ハロゲン基の核置換体が、また芳
香族ジオールとしてはヒドロキノン、レゾルシン、４
、４’−ジヒドロキシジフェニル、４ 、４’−ジヒド
ロキシベンゾフェノン、４．４−ジヒドロキシジフェニ
ルメタン、４゜４−ジヒドロキシジフェニルエタン、２
，２−ヒス（４−ヒドロキシフェニル）プロパン、４．
４′−ジヒドロキシジフェニルエーテル、４．４−ジヒ
ドロキシフェニルスルホン、４゜４′−ジヒドロキシジ
フェニルスルフィド、２゜６−ジヒドロキシナフタレン
、１．５−ジヒドロキシナフタレン等や、これらのアル
キル、アリール、アルコキシ、ハロゲン基の核置換体が
、更に芳香族ヒドロキシカルボン酸としてはｐ−ヒドロ
キシ安息香酸、ｍ−ヒドロキシ安息香酸、２−ヒドロキ
シナフタレン−〇−カルボン酸、１−ヒドロキシナフタ
レン−５−カルボン酸等や、これらのアルキル、アリー
ル、アルコキシ、ハロゲン基の核置換体が挙げられる。Here, the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 4,4'-dicarboxydiphenyl, 2.
6-dicarboxynaphthalene, 1,2-bis(4-carboxyphenoxy)ethane, etc., and nuclear substituted products of these alkyl, aryl, alkoxy, and halogen groups, and aromatic diols such as hydroquinone, resorcinol, and
, 4'-dihydroxydiphenyl, 4,4'-dihydroxybenzophenone, 4.4-dihydroxydiphenylmethane, 4゜4-dihydroxydiphenylethane, 2
, 2-his(4-hydroxyphenyl)propane, 4.
4'-dihydroxydiphenyl ether, 4,4-dihydroxyphenyl sulfone, 4'-4'-dihydroxydiphenyl sulfide, 2'-6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, etc., and their alkyl, aryl, alkoxy, and halogen groups. The nuclear substituted product may further be an aromatic hydroxycarboxylic acid such as p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxynaphthalene-〇-carboxylic acid, 1-hydroxynaphthalene-5-carboxylic acid, etc., or an alkyl thereof. , aryl, alkoxy, and halogen group substituted.
また、脂環族ジカルボン酸としてはｔｒａｎｓ−１，４
−ジカルボキシシクロヘキサン、ｃｌｓ−１，４−ジカ
ルボキシシクロヘキサン等や、これらのアルキル、アリ
ール、ハロゲン基の置換体が、また脂環族及び脂肪族ジ
オールとしてはｔｒａｎｓ −１、４−ジヒドロキシシ
クロヘキサン、ｃｉｓ−１，４−ジヒドロキシシクロヘ
キサン、エチレングリコール、１゜４−ブタンジオール
、キシリレンジオール等が挙げられる。In addition, as the alicyclic dicarboxylic acid, trans-1,4
-dicarboxycyclohexane, cls-1,4-dicarboxycyclohexane, etc., and substituted products of these with alkyl, aryl, and halogen groups; as alicyclic and aliphatic diols, trans -1,4-dihydroxycyclohexane, cis -1,4-dihydroxycyclohexane, ethylene glycol, 1°4-butanediol, xylylene diol and the like.
これらの組合せの内で特に好ましい芳香族ポリエステル
としては、例えば、
（１）ｐ−ヒドロキシ安息香酸残基４０ル７０〜３０モ
ルチと芳香族ジオール残基１５〜３０モルチからなるコ
ポリエステル、
（２） テレフタル酸及び／又はイソフタル酸とクロ
ルヒドロキノン、フェニルヒドロキノン及び／又はヒド
ロキノンから成るコポリエステル、
（３）ｐ−ヒドロキシ安息香酸残基２０ル８０−カルボ
ン酸残基２０〜８０モルチから成るコポリエステルなど
を挙げることができる。これらの出発原料を用い本発明
の目的とするポリエステルを製造するには、そのままで
、あるいは脂肪族又は芳香族モノカルボン酸又はそれら
の誘導体、脂肪族アルコール又はフェノール類又はそれ
らの誘導体等によるエステル化により重縮合反応を行な
う。Among these combinations, particularly preferred aromatic polyesters include (1) copolyesters consisting of 40 to 30 moles of p-hydroxybenzoic acid residues and 15 to 30 moles of aromatic diol residues; (2) Copolyesters consisting of terephthalic acid and/or isophthalic acid and chlorohydroquinone, phenylhydroquinone and/or hydroquinone, (3) Copolyesters consisting of 20 to 80 moles of p-hydroxybenzoic acid residues and 80-carboxylic acid residues, etc. can be mentioned. In order to produce the polyester that is the object of the present invention using these starting materials, they can be used as they are, or they can be esterified with aliphatic or aromatic monocarboxylic acids or their derivatives, aliphatic alcohols, phenols, or their derivatives, etc. A polycondensation reaction is carried out.
重縮合反応法としては既知の塊状重合、溶液重合、懸濁
重合法等を採用することができ、１５０〜３５０℃で、
常圧又は１０〜０．１ｔｏｒｒの減圧下にＳｂ 、 Ｔ
ｉ 、 Ｇｅ化合物等の重合触媒、リン系化合物等の安
定剤、Ｔｘ０２ｐＣａＣＯ 、 タルク等の充填剤
等を場合により添加して行なうことができる。As the polycondensation reaction method, known bulk polymerization, solution polymerization, suspension polymerization, etc. can be adopted.
Sb, T under normal pressure or reduced pressure of 10 to 0.1 torr
1, a polymerization catalyst such as a Ge compound, a stabilizer such as a phosphorus compound, a filler such as Tx02pCaCO, talc, etc. can be added as necessary.
得られたポリマーはそのままで、あるいは粉体状で不活
性気体中、又は減圧下に熱処理して紡糸用試料とする。The obtained polymer is used as it is or in powder form and heat-treated in an inert gas or under reduced pressure to prepare a sample for spinning.
あるいは一度押出機により造粒して用いることもできる
。Alternatively, it can be used after being granulated once using an extruder.
本発明における芳香族ポリエステルには紡糸に適した分
子量範囲が存在すると考えられるが、組成や構造によっ
ては均一に溶解しうる溶剤がなかったり、分子量測定法
の精度がないという問題があり、本発明に適した芳香族
ポリエステルの規格として使丸ない。Although it is thought that the aromatic polyester used in the present invention has a molecular weight range suitable for spinning, there are problems such as the lack of a solvent that can uniformly dissolve it depending on the composition and structure, and the lack of precision in the molecular weight measurement method. There is no standard for aromatic polyester suitable for use.
そこで本発明者らは溶融紡糸条件に適する分子量に対応
する°物°性値として「流動温度」という指標を導入し
た。即ち、島津製作所製のフローテスターＣＦＴ −
５００を用い、径１間、長さ１０票のノズルで圧力１０
０ Ｑ／ａｓ２の状態で芳香族ポリエステル試料を４℃
／ｍｉｎで昇温したとき、試料がノズルを通って流動し
、且ツ４８，０００ ｐｏｉｓｅの見かけ粘度を与える
温度として「流動温度」を定義した。Therefore, the present inventors introduced an index called "flow temperature" as a physical property value corresponding to the molecular weight suitable for melt spinning conditions. That is, the flow tester CFT- made by Shimadzu Corporation.
500, the pressure is 10 with a nozzle with a diameter of 1 and a length of 10.
An aromatic polyester sample was heated at 4°C in a state of 0 Q/as2.
The "flow temperature" was defined as the temperature at which the sample would flow through the nozzle and give an apparent viscosity of 48,000 poise when heated at 1/min.
本発明の溶融紡糸に適した芳香族ポリエステルの「流動
温度」は２５０〜３８０℃、好ましくは２８０〜３５０
℃である。これらの範囲外では紡糸時に糸切れや発泡を
惹起したり、生成繊維の物性も十分でない。The "flowing temperature" of the aromatic polyester suitable for melt spinning of the present invention is 250 to 380°C, preferably 280 to 350°C.
It is ℃. Outside these ranges, yarn breakage or foaming may occur during spinning, and the physical properties of the resulting fibers may not be sufficient.
本発明の溶融紡糸装置としては、加熱制御機構を備えた
プランジャー、スクリュー等の溶融部、ギヤポンプ等の
計量部、紡糸口金を含む紡糸頭部を備えたものであれば
、どのようなものでも使用することができる。The melt spinning device of the present invention may be any device as long as it is equipped with a spinning head including a plunger with a heating control mechanism, a melting section such as a screw, a measuring section such as a gear pump, and a spinneret. can be used.
本発明において溶融紡糸に適した温度は２８０〜４２０
℃で、より好ましくは３００〜均一化が不十分であった
り、逆に高温であると分解発泡による糸切れがおこった
りする。In the present invention, the temperature suitable for melt spinning is 280 to 420.
℃, more preferably 300° C., or the uniformity may be insufficient, or conversely, if the temperature is high, thread breakage may occur due to decomposition and foaming.
上記のようにして溶融紡糸して得られた繊維はボビンに
巻きとられるが、この時、本発明に主張するように、繊
維をボビンに巻いてから、ボビンを取り除いて繊維を熱
処理するわけである。ボビンを取り外す方法としては、
ボビンそのものがボビンの回転方向と直角な方向に切り
欠きをもつものを用いて、繊維の巻き取り後ボビンを変
形又は収縮して除いたり、ボビン上に金属箔や、紙、プ
ラスチックフィルム、金網等のシート状物を巻いてこの
上に繊維を巻き、繊維とこれらのシート状物をボビンか
ら取り外し、さらに繊維からシ−ト状物を取り本発明の
試料とする方法等がある。又、−皮繊維を巻きとった後
、以上の様なボビンに巻きかえて、諺本発明の通り実行
し熱処理することもできる。The fibers obtained by melt spinning as described above are wound around a bobbin, but at this time, as claimed in the present invention, the fibers are wound around the bobbin, then the bobbin is removed, and the fibers are heat-treated. be. To remove the bobbin,
Use a bobbin that has a notch in the direction perpendicular to the direction of rotation of the bobbin, and remove it by deforming or shrinking the bobbin after winding the fiber, or place metal foil, paper, plastic film, wire mesh, etc. on the bobbin. There are methods such as winding a sheet-like material, winding fibers thereon, removing the fibers and the sheet-like material from the bobbin, and then taking a sheet-like material from the fibers and using it as a sample of the present invention. Furthermore, after the skin fibers are wound up, they can be re-wound onto a bobbin as described above and heat treated according to the method of the present invention.
繊維のボビン上での巻き密度としては、通常のフィラメ
ントのそれがＱ、！３．ｐ／ｃｍ３以上であるのに対し
、０．１６〜０．５．Ｆ／ａｍ” の範囲内に設定す
ることが好ましく、かかる巻き密度が本発明の上限を越
える場合には、融着抑制効果が不十分となると共に、熱
処理時に重合、架橋、分解等の反応に伴なって発生する
生成物等の拡散、揮発が不十分となるため物性及びその
均一性を低下させたり、また前記下限を下回る場合には
、形崩れを惹起し、ハンドリング時の損傷が大きくなる
と共に、生産性も低下するので工業上好ましくない。な
お、上記巻き密度の調整は、繊維の物性（特に伸度、弾
性率）や全繊維繊度、繊維束の供給速度、或はスピンド
ルの駆動方式、巻き取り比、巻き取り張力等の巻き取り
機のタイプ及びその操作条件などを適宜勘案、調整する
ことにより達成することができる。The winding density of the fiber on the bobbin is that of a normal filament, Q! 3. p/cm3 or more, whereas 0.16 to 0.5. If the winding density exceeds the upper limit of the present invention, the effect of suppressing fusion will be insufficient and reactions such as polymerization, crosslinking, decomposition, etc. will occur during heat treatment. Diffusion and volatilization of the resulting products, etc. will be insufficient, resulting in a decrease in physical properties and their uniformity, and if it is below the above lower limit, the product will lose its shape and become more susceptible to damage during handling. At the same time, productivity also decreases, which is not desirable from an industrial perspective.The above-mentioned adjustment of the winding density depends on the physical properties of the fibers (especially elongation and modulus of elasticity), the total fiber fineness, the feeding speed of the fiber bundle, or the drive system of the spindle. This can be achieved by appropriately considering and adjusting the type of winder such as winding ratio, winding tension, and its operating conditions.
熱処理は２８０〜４００℃の温度で概ね０．５〜５０時
間施すことが望ましく、かかる熱処理条件の採用により
本発明の目的を一層有利に達成することができる。なお
、かかる熱処理時の雰囲気としては、不活性気体雰囲気
か、１００Ｉ！ｌｌＨｇ以下の真空度の真空が好ましい
。The heat treatment is preferably performed at a temperature of 280 to 400°C for about 0.5 to 50 hours, and by adopting such heat treatment conditions, the object of the present invention can be achieved more advantageously. The atmosphere during the heat treatment may be an inert gas atmosphere or 100I! A vacuum with a degree of vacuum of 11Hg or less is preferable.
なお、上記熱処理時における融着を軽減するための油剤
処理等の前処理、物性の一層の向上のための熱処理前及
び／又は後における延伸等の各工程を、適宜組み合せる
ことができる。Note that pretreatment such as oil treatment to reduce fusion during the heat treatment and stretching before and/or after heat treatment to further improve physical properties can be combined as appropriate.
（作用および効果）
上述した本発明の技術手段を採用することにより熱処理
時における局部的加熱による融着の発生や物性不均一、
或は熱処理時に発生するガス等の反応生成物に伴なう繊
維の欠陥部形式や融着、更には熱処理時における繊維の
収縮に伴なう繊維束間の圧迫によって惹起される融着や
変形等々の問題が解消され、融着が少なく、高物性で且
つ商品価値の高い芳香族ポリエステル繊維を工業的有利
に製造し得る。(Operations and Effects) By adopting the above-mentioned technical means of the present invention, occurrence of fusion due to local heating during heat treatment, non-uniformity of physical properties,
Alternatively, defects in fibers and fusion caused by reaction products such as gas generated during heat treatment, and fusion and deformation caused by compression between fiber bundles due to fiber contraction during heat treatment. These problems are solved, and aromatic polyester fibers with less fusion, high physical properties, and high commercial value can be industrially advantageously produced.
すなわち繊維の物性向上を促進させる熱処理本来の効果
を工業的規模においても十分に発揮させ得、以て商品価
値の高い高強度、高弾性率を有する芳香族ポリエステル
繊維を工業的有利に製造する手段を提供し得た点が本発
明の特筆すべき効果であり、かくして得られる繊維はタ
イヤコード、ローブ、ケーブル、ＦＲＰ 、ＦＲＴＰ
、スピーカーコーン、安全着、テンシ冒ンメンバー等の
各種用途分野に用いることができる。In other words, a means for producing aromatic polyester fibers having high strength and high modulus of elasticity with high commercial value, in an industrially advantageous manner, by which the inherent effect of heat treatment, which promotes the improvement of the physical properties of fibers, can be fully exhibited even on an industrial scale. A noteworthy effect of the present invention is that the fibers thus obtained can be used in tire cords, lobes, cables, FRP, FRTP.
It can be used in various fields such as speaker cones, safety clothing, and tension members.
（実施例）
以下に本発明の理解を容易にするため実施例を示すが、
これらはあくまで例示的なものであり、本発明の要旨は
、これらにより限定されるものではない。(Example) Examples are shown below to facilitate understanding of the present invention.
These are merely illustrative, and the gist of the present invention is not limited thereto.
なお、例中の繊維の引張り試験はインストロン社万能試
験機Ｎ１１１３０を用い、試料間隔２０ｍ、引張り速度
０．５ ｍ ／ ｍｊｎで測定したものであり、試料数
は２２本で、最高と最低を除く平均値を示した。The fiber tensile test in the example was conducted using Instron's universal testing machine N11130, with a sample interval of 20 m and a tensile speed of 0.5 m/mjn. The number of samples was 22, and the highest and lowest were measured. The average value excluding the above is shown.
また融着度（ｆ）は熱処理後繊維束を２０ｍｍ長さに切
断した試料を、ヤマト科学社製ブレンソニック２２０を
用い、水中で２０分間超音波を当てて分散させ、水中に
分散した単糸及び繊維片（２〜数本の単糸が融着したも
の）の合計数（ｎｌを求め、下式により算出した。The degree of fusion (f) was determined by dispersing a sample of a heat-treated fiber bundle cut into 20 mm length in water by applying ultrasonic waves for 20 minutes using Bren Sonic 220 manufactured by Yamato Scientific Co., Ltd. and the total number (nl) of fiber pieces (two to several single yarns fused together) and calculated by the following formula.
なお、かかる値は、熱処理後チーズから無作為に１０個
採取した試材について測定した値の平均値である。In addition, this value is the average value of the values measured for 10 samples randomly taken from the cheese after heat treatment.
口
光学異方性の測定は加熱ステージ上に試料を置いて、偏
光下、２５°Ｃ／ｍｉｎ で昇温しで肉眼観察により行
なった。The optical anisotropy was measured by placing the sample on a heating stage, raising the temperature at 25°C/min under polarized light, and observing it with the naked eye.
参考例
ｐ−アセトキシ安息香酸７．２０）ｆ（４０モル）、テ
レフタル酸２．４９ｒｌＦ（１５モル）、イソフタル酸
０．８３即（５モル） 、４ 、４’−ジアセトキシジ
フェニル５．４５即（２０，２モル）をくし型攪拌翼を
もつ重合槽に仕込み、窒素ガス雰囲気下で攪拌しながら
昇温し、３３０℃で３時間重合した。この間、生成する
酢酸を除去し、強力な攪拌で重合を行ない、その後徐々
に冷却し、２００℃で重合体を系外へ取出した。Reference examples p-acetoxybenzoic acid 7.20) f (40 mol), terephthalic acid 2.49 rlF (15 mol), isophthalic acid 0.83 (5 mol), 4,4'-diacetoxydiphenyl 5.45 mol (20.2 mol) was charged into a polymerization tank equipped with comb-shaped stirring blades, and the temperature was raised while stirring in a nitrogen gas atmosphere, followed by polymerization at 330° C. for 3 hours. During this time, the acetic acid produced was removed and polymerization was carried out with strong stirring, after which it was gradually cooled and the polymer was taken out of the system at 200°C.
重合体の収量はｉｏ、ｓｓ ｘで理論収量の９７．８チ
であった。これを線用ミクロン社のハンマーミルで粉砕
し２．５間以下の粒子とした。これをロータリーキルン
中で窒素雰囲気下に２８０℃で５時間処理したところ「
流動温度」が３２６℃となった。３５０℃以上で光学異
方性が観察された。The yield of polymer was 97.8 inches of the theoretical yield in io, ss x. This was pulverized using a hammer mill manufactured by Line Micron Co., Ltd. to obtain particles of 2.5 mm or less in size. When this was treated in a rotary kiln at 280°C under a nitrogen atmosphere for 5 hours,
The flow temperature was 326°C. Optical anisotropy was observed above 350°C.
実施例１〜７および比較例１〜３
参考例のポリエステルを、３０順径のスクヤ
リュー、溶融体計量用のギ２ポンプ、沖過機及び紡糸口
金を有する紡糸頭からなるスクリュー押出型溶融紡糸装
置を用いて溶融紡糸を行なった。紡糸口金は、孔径０．
ＩＩＩＷ１１／ｄ■２．３００孔数であり、紡糸温度は
３６５℃であ量吐出し、糸条は３００ｍ／分で下記に示
す（ａ）。Examples 1 to 7 and Comparative Examples 1 to 3 The polyester of the reference example was spun using a screw extrusion type melt spinning device consisting of a 30 diameter screw screw, a two-pump pump for measuring the melt, an offshore filter, and a spinning head with a spinneret. Melt spinning was performed using The spinneret has a pore size of 0.
IIIW11/d■2.The number of holes is 300, the spinning temperature is 365° C., the amount is discharged, and the yarn is 300 m/min as shown below (a).
（ｂ）のボビンに巻き取った。（約５００Ｊｌ／ボビン
）
ｆａｔ Ａｌ！製０．５ ｒｉｍ厚で外側直径４５
ｒｕｍ Ｘ長さ２５０ｍ、切り欠ｌｋｍ約４ｍを有する
ボビン（ｂｌ Ａｌ！製０．５ ｍ厚で外側直径８５
ｍＸ長さ２５０ｍ、切り欠き幅約８ｍを有するボビン巻
き取りに際しては、巻き取り比、巻き取り張力（コンペ
ンセーターアームの荷重）及び接圧を変化させて下記第
１表に示すように巻き密度を変化させた。It was wound onto the bobbin shown in (b). (approx. 500Jl/bobbin) fat Al! Made of 0.5 rim thickness and outer diameter 45
A bobbin with a rum x length of 250m and a notch of approximately 4m (bl Al! made with a thickness of 0.5m and an outer diameter of 85m).
When winding a bobbin with a length of 250 m and a notch width of approximately 8 m, the winding density was adjusted as shown in Table 1 below by changing the winding ratio, winding tension (load on the compensator arm), and contact pressure. Changed.
このようにして得られた繊維は平均３ｄ。The fibers thus obtained have an average diameter of 3 d.
引張強度３．ｓ、ｐ／ｄ、伸度０．８％、弾性率４８０
．５ｒ ／ ｄであった。Tensile strength 3. s, p/d, elongation 0.8%, elastic modulus 480
．． It was 5r/d.
上記のように巻き取られた繊維は、各々ボビンを取り除
き円筒状の繊維のみをＮ２中３２０℃×３時間の熱処理
を施した。The bobbin of each of the fibers wound up as described above was removed, and only the cylindrical fibers were heat-treated in N2 at 320° C. for 3 hours.
得られた繊維の引張強度を測定した結果を下記第１表に
併記する。The results of measuring the tensile strength of the obtained fibers are also shown in Table 1 below.
第 １ 表
（注） 比較例：巻き取り時に用いたＭ製のボビンをつ
けたままで熱処理して傅られた繊維
上表より、本発明の手段（Ｎｌｌ−７）を採用すること
により、融着が殆どなく、高物性の芳香族ポリエステル
繊維を製造し得る事実が明瞭に理解される。なお、比較
例（陽８〜著しく低下している。Table 1 (Note) Comparative example: From the table above, fibers were heat-treated with the M bobbin used for winding still attached. It is clearly understood that aromatic polyester fibers with high physical properties can be produced with almost no oxidation. In addition, the comparative example (positive 8 - significantly decreased).
Claims (3)
溶融紡糸して得られた繊維をボビンに巻き取った後、ボ
ビンを取り除き繊維のみを熱処理することを特徴とする
芳香族ポリエステル繊維の製造法(1) Production of aromatic polyester fiber, which is characterized in that the fiber obtained by melt-spinning aromatic polyester that exhibits optical anisotropy when melted is wound around a bobbin, and then the bobbin is removed and only the fiber is heat-treated. law
＾３であることを特徴とする特許請求の範囲第１項記載
の製造法(2) Winding density on the bobbin is 0.16 to 0.5 g/cm
The manufacturing method according to claim 1, characterized in that ^3.
理することを特徴とする特許請求の範囲第１項記載の製
造法(3) The manufacturing method according to claim 1, characterized in that heat treatment is performed at a temperature of 280 to 400°C for 0.5 to 50 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60186431A JP2565676B2 (en) | 1985-08-23 | 1985-08-23 | Aromatic polyester fiber manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60186431A JP2565676B2 (en) | 1985-08-23 | 1985-08-23 | Aromatic polyester fiber manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6245743A true JPS6245743A (en) | 1987-02-27 |
| JP2565676B2 JP2565676B2 (en) | 1996-12-18 |
Family
ID=16188312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60186431A Expired - Fee Related JP2565676B2 (en) | 1985-08-23 | 1985-08-23 | Aromatic polyester fiber manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2565676B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2594668A1 (en) * | 2007-02-28 | 2013-05-22 | Toray Industries, Inc. | Liquid crystalline polyester fiber and process for production of the same |
| WO2013099863A1 (en) | 2011-12-27 | 2013-07-04 | 東レ株式会社 | Liquid-crystalline polyester multifilament |
| JP2018040078A (en) * | 2016-09-07 | 2018-03-15 | 東レ株式会社 | Liquid crystal polyester multifilament |
| WO2019021978A1 (en) * | 2017-07-24 | 2019-01-31 | 株式会社クラレ | Liquid crystalline polyester fiber and method for producing same |
| EP3751040A4 (en) * | 2018-02-06 | 2021-11-17 | Kuraray Co., Ltd. | Filamentary tape and composite material including said tape |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4872393A (en) * | 1971-12-28 | 1973-09-29 | ||
| JPS50157619A (en) * | 1974-05-10 | 1975-12-19 | ||
| JPS6088119A (en) * | 1983-10-13 | 1985-05-17 | Toray Ind Inc | Yarn for polyester fiber like animal hair and its preparation |
-
1985
- 1985-08-23 JP JP60186431A patent/JP2565676B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4872393A (en) * | 1971-12-28 | 1973-09-29 | ||
| JPS50157619A (en) * | 1974-05-10 | 1975-12-19 | ||
| JPS6088119A (en) * | 1983-10-13 | 1985-05-17 | Toray Ind Inc | Yarn for polyester fiber like animal hair and its preparation |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2594668A1 (en) * | 2007-02-28 | 2013-05-22 | Toray Industries, Inc. | Liquid crystalline polyester fiber and process for production of the same |
| WO2013099863A1 (en) | 2011-12-27 | 2013-07-04 | 東レ株式会社 | Liquid-crystalline polyester multifilament |
| JP2018040078A (en) * | 2016-09-07 | 2018-03-15 | 東レ株式会社 | Liquid crystal polyester multifilament |
| WO2019021978A1 (en) * | 2017-07-24 | 2019-01-31 | 株式会社クラレ | Liquid crystalline polyester fiber and method for producing same |
| US11686017B2 (en) | 2017-07-24 | 2023-06-27 | Kuraray Co., Ltd. | Liquid crystalline polyester fiber and method for producing the same |
| EP3751040A4 (en) * | 2018-02-06 | 2021-11-17 | Kuraray Co., Ltd. | Filamentary tape and composite material including said tape |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2565676B2 (en) | 1996-12-18 |
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