JPS5951604B2 - Manufacturing method of flame retardant polyamide fiber - Google Patents
Manufacturing method of flame retardant polyamide fiberInfo
- Publication number
- JPS5951604B2 JPS5951604B2 JP1279177A JP1279177A JPS5951604B2 JP S5951604 B2 JPS5951604 B2 JP S5951604B2 JP 1279177 A JP1279177 A JP 1279177A JP 1279177 A JP1279177 A JP 1279177A JP S5951604 B2 JPS5951604 B2 JP S5951604B2
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- Prior art keywords
- polyamide
- acid
- manufacturing
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- stretching
- 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.)
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Description
【発明の詳細な説明】 本発明は難燃性ポリアミド繊維の製造法に関する。[Detailed description of the invention] The present invention relates to a method for producing flame-retardant polyamide fibers.
ポリアミド、特にナイロン6、ナイロン66は機械的特
性に優れ染色性が良好で外観の美しい所から繊維その他
の成型材料として広く利用されている。Polyamides, especially nylon 6 and nylon 66, are widely used as fibers and other molding materials because of their excellent mechanical properties, good dyeability, and beautiful appearance.
しかしながらポリアミドは燃焼し易いという欠点を有し
ており、このためその用途が限定されている。従来、ポ
リアミドに難燃性を付与する方法として、ポリアミドの
成型品、例えばポリアミド繊維の表面をチオ尿素の如き
難燃化剤で処理する方法が知られている。However, polyamides have the disadvantage of being easily combustible, which limits their use. Conventionally, as a method of imparting flame retardancy to polyamide, a method has been known in which the surface of a polyamide molded article, for example, polyamide fiber, is treated with a flame retardant such as thiourea.
しかしながらかかる方法で十分な難燃性効果を得るには
、難燃化剤の付着量を多くする必要があり、そのため製
品の外観や風合が著しく損われるばかりか難燃効果も耐
久性に乏しいという欠点を有する。かかる欠点をなくす
方法としてポリアミドの成型前に難燃化剤をポリアミド
に内部添加せしめる試みが種々提案されている。However, in order to obtain a sufficient flame retardant effect using this method, it is necessary to increase the amount of flame retardant applied, which not only significantly impairs the appearance and texture of the product, but also causes poor durability of the flame retardant effect. It has the following drawback. As a method of eliminating such drawbacks, various attempts have been made to add flame retardants internally to polyamide before molding the polyamide.
しかしながら従来提案された難燃化剤はポリアミドに対
する難燃効果が十分でなく、且つその効果を向上させる
には多量の添加を必要とする。しかも難燃化剤の多くは
ポリアミドとの反応性を有するために難燃化剤の多量の
添加は、ポリアミドの著しい分解、発泡、ゲル化、着色
等の好ましくない現象を伴い、ポリアミド本来の物性や
商品的価値が著しく損われる。例えば特公昭47−38
546号公報には、ポリアミドの難燃化剤として核ブロ
ム化ジフエニル化合物が記載され、該化合物は耐熱性に
優れ、ポリアミドと混合加熱してもポリアミドを劣化せ
しめることが殆んどないとしているが、本発明者等の追
試によれば、核ブロム化ジフエニル化合物の中、例えば
ヘキサプロムジフエニルエーテルをナイロン6に10重
量%配合し溶融紡糸した場合、ナイロン6を劣化させる
事は、他のハロゲン化合物と比較して確かに少ないが、
それでも未変性ナイロン6に比べるとその色調は黄色味
に着色しておりまた得られた糸の難燃性も不十分であつ
た。However, the flame retardants that have been proposed so far do not have a sufficient flame retardant effect on polyamides, and require a large amount of addition to improve the effect. Moreover, since many flame retardants have reactivity with polyamide, adding a large amount of flame retardant is accompanied by undesirable phenomena such as significant decomposition, foaming, gelation, and coloring of polyamide, and the inherent physical properties of polyamide and the commercial value is significantly impaired. For example, special public service
Publication No. 546 describes a nuclear brominated diphenyl compound as a flame retardant for polyamide, and it is said that this compound has excellent heat resistance and hardly deteriorates the polyamide even when mixed with polyamide and heated. According to additional experiments conducted by the present inventors, when nylon 6 is melt-spun with 10% by weight of hexaprom diphenyl ether among nuclear brominated diphenyl compounds, the deterioration of nylon 6 is caused by other halogens. Although it is certainly less compared to compounds,
Even so, the color tone was yellowish compared to unmodified nylon 6, and the flame retardancy of the obtained thread was also insufficient.
一方難燃化剤としてきわめて多量(15〜30重量%)
の上述の如き核ハロゲン化芳香族化合物を配合されたポ
リアミドは、比較的良好なる難燃性を示すが、この方法
ではポリアミド本来の物性や商品的価置が損われ、また
コストアツプも大きい。On the other hand, extremely large amounts (15-30% by weight) are used as flame retardants.
Polyamide blended with the above-mentioned nuclear halogenated aromatic compound exhibits relatively good flame retardancy, but this method impairs the inherent physical properties and commercial value of the polyamide, and also increases cost.
更にはこの種のポリアミドは、その燃焼時に有毒なハロ
ゲン系ガスを多量に発生するというきわめて大きな欠陥
を有している。これらの欠陥を補うべく、ハロゲン系難
燃化剤の配合量を減らし、しかもより高い難燃性を付与
するために、金属酸化物などの難燃助剤が種々検討され
ている。Furthermore, this type of polyamide has a very serious defect in that it generates a large amount of toxic halogen gas when it is burned. In order to compensate for these deficiencies, various flame retardant aids such as metal oxides have been investigated in order to reduce the amount of halogen flame retardant and to provide higher flame retardancy.
例えば、酸化アンチモンはハロゲン系難燃化剤の難燃助
剤としては著名である。しかしこの方法ではポリアミド
に不溶な酸化アンチモンを数%以上配合する事になり、
繊維化に際し技術的に大きな障害となる。即ち酸化アン
チモンが凝集して溶融紡糸口金バツクの目ずまりを生じ
たり、あるいは糸中の節となつて紡糸糸切れ、延伸糸切
れが多発する原因となり、実質上繊維化は非常に困難で
ある。以上の如く、従来知られているポリアミドの難燃
化剤は種々の欠点を有しており、特に繊維化する場合に
は困難度が飛躍的に増大するため末だ実用化された例は
ないのが現状である。For example, antimony oxide is well known as a flame retardant aid for halogen flame retardants. However, this method requires adding several percent or more of insoluble antimony oxide to the polyamide.
This is a major technical obstacle in fiberization. That is, antimony oxide aggregates and causes clogging of the melt spinneret bag, or forms knots in the yarn, causing frequent spun yarn breakage and drawn yarn breakage, making it virtually difficult to make fibers. . As mentioned above, the conventionally known flame retardants for polyamides have various drawbacks, and the degree of difficulty increases dramatically when converting them into fibers, so they have never been put to practical use. is the current situation.
本発明の目的はか・る従来技術の諸欠陥を克服し、ポリ
アミド本来の優れた諸物性を何ら損うことなく、しかも
少量の難燃化剤の配合により優れた難燃性能を有するポ
リアミド繊維を提供するにあり、他の目的は、か・るポ
リアミド繊維を工業的容易且つ安価に製造する方法を提
供するためにある。The purpose of the present invention is to overcome the various deficiencies of the prior art, and to produce polyamide fibers that have excellent flame retardant performance by incorporating a small amount of flame retardant without impairing the original excellent physical properties of polyamide. Another object of the present invention is to provide a method for manufacturing polyamide fibers industrially easily and inexpensively.
即ち本発明はポリアミドに一般式(1)
〔式中Xは塩素及び/または臭素、YはR,ORまたは
0R″0R(Rは炭素数1〜10のアルキル基、アリー
ル基または核ハロゲン化アリール基或いは炭素数7〜1
6のアラルキル基または核ハロゲン化アラルキル基、但
しハロゲンは塩素及び/または臭素、R″は炭素数1〜
6のアルキレン基)、1は2〜6の整数、mはOまたは
1である。That is, the present invention provides a polyamide with the general formula (1) [wherein Group or carbon number 7-1
6 aralkyl group or nuclear halogenated aralkyl group, provided that halogen is chlorine and/or bromine, and R'' has 1 to 1 carbon atoms.
6 alkylene group), 1 is an integer of 2 to 6, and m is O or 1.
〕で示される少なくとも一種の核ハロゲン化芳香族化合
物を得られるポリアミド繊維重量に対して、0.5〜1
5%、並びにコハタ酸、アジピン酸、セバシン酸、アゼ
ライン酸、テレフタル酸、イソフタル酸及びヘキサヒド
ロフタル酸から成る群より選ばれた少なくとも一種のカ
ルボン酸化合物を得られるポリアミド繊維重量に対して
0.5〜4%の割合で添加し、溶融紡糸後、50〜14
0℃の温度で熱延伸して成る難燃性ポリアミド繊維の製
造法にある。本発明に用いられるポリアミドは、通常の
合成線状ポリアミドを意味し、例えばナイロン6,ナイ
ロン10,ナイロン11,ナイロン12,ナイロン66
,ナイロン610及びこれらを主成分とする共重合ポリ
アミド等が挙げられるが、中でもナイロン6及びナイロ
ン66が好ましく適用される。] 0.5 to 1% based on the weight of the polyamide fiber from which at least one type of nuclear halogenated aromatic compound is obtained.
5%, and at least one carboxylic acid compound selected from the group consisting of succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid and hexahydrophthalic acid, based on the weight of the polyamide fiber obtained. Added at a ratio of 5 to 4%, after melt spinning, 50 to 14%
A method for producing flame-retardant polyamide fibers by hot stretching at a temperature of 0°C. The polyamide used in the present invention means ordinary synthetic linear polyamides, such as nylon 6, nylon 10, nylon 11, nylon 12, nylon 66.
, nylon 610, and copolyamides containing these as main components, among which nylon 6 and nylon 66 are preferably used.
本発明に用いられる核ハロゲン化芳香族化合物は前記一
般式(1)で示される。かかる核ハロゲン化芳香族化合
物としては、例えばトリブロムベンゼン、トリブロムト
ルエン、テトラブロムベンゼン、ペンタブロムベンゼン
、ペンタブロムエチルベンゼン、ペンタブロムトルエン
、ヘキサブロムベンゼン、ペンタブロム−n−デシルベ
ンゼン、トリクロルトルエン、テトラクロルベンゼン、
ペンタクロルベンゼン、ペンタクロルトルエン、へキサ
クロルベンゼン、ペンタクロルエチルベンゼン、テトラ
クロルエチルベンゼン、等の核ハロゲン化ベンゼン誘導
体、テトラプロムジフエニルエーテル、ペンタプロムジ
フエニルエーテル、ヘキサプロムジフエニルエーテル、
デカプロムジフニニルエーテル、トリプロムジクロルジ
フエニルエーテル、デカクロルジフエニルエーテル、ペ
ンタプロムペンタクロルジフエニルエーテル等の核ハロ
ゲン化ジフエニルエーテル誘導体、ペンタプロムジフエ
ニル、へキサクロルジフエニル、ヘキサプロムジフエニ
ル、デカプロムジフエニル、デカクロルジフエニル、4
−メチルーノナプロムジフエニル、4−n−デシルーノ
ナプロムジフエニル等の核ハロゲン化ジフエニル誘導体
、ペンタプロムジフエニルメタン、デカプロムジフエニ
ルメタン、デカブロム−1,10−ジフエニルデカン等
の核ハロゲン化ジフエニルアルキル誘導体、ベンジルオ
キシペンタクロルベンゼン、1,2−ジ(2’,4’,
6’一トリプロムフエノキシ)エタン、1,6−ジ(2
’,4’,6’一トリプロムフエノキシ)へキサン等が
挙げられる。これらの中でも付与する難燃性能等の点か
ら、核臭素化合物が好ましく、特にへキサブロムベンゼ
ン、ペンタブロムトルエン、ペンタプロムエチルベンゼ
ン、ペンタプロムベンゼン、テトラブロムベンゼン、ト
リブロムトルエン、ジフエニルエーテル臭化物(臭素付
加数4 〜10)、ビフエニル臭化物(臭素付加数4
〜10)が好ましい。一方本発明に用いられるカルボン
酸化合物としては前記したコハク酸、アジピン酸、セバ
シン酸、アゼライン酸、テレフタル酸、イソフタル酸、
へキサヒドロフタル酸等が挙げられるが、中でもコハク
酸及びへキサヒドロフタル酸が好ましい化合物である。The nuclear halogenated aromatic compound used in the present invention is represented by the general formula (1). Examples of such nuclear halogenated aromatic compounds include tribromobenzene, tribromotoluene, tetrabromobenzene, pentabromobenzene, pentabromoethylbenzene, pentabromotoluene, hexabromobenzene, pentabromo-n-decylbenzene, trichlorotoluene, and tetrabromobenzene. Chlorbenzene,
Nuclear halogenated benzene derivatives such as pentachlorobenzene, pentachlorotoluene, hexachlorobenzene, pentachloroethylbenzene, tetrachloroethylbenzene, tetraprom diphenyl ether, pentaprom diphenyl ether, hexaprom diphenyl ether,
Nuclear halogenated diphenyl ether derivatives such as decaprom diphenyl ether, triprom dichloro diphenyl ether, decachlor diphenyl ether, pentaprom pentachlor diphenyl ether, pentaprom diphenyl, hexachlor diphenyl, hexaprom diphenyl enyl, decapromdiphenyl, decachlordiphenyl, 4
- Nuclear halogenated diphenyl derivatives such as methyl nonaprom diphenyl and 4-n-decyl nonaprom diphenyl, nuclear halogenation such as pentaprom diphenylmethane, decaprom diphenylmethane, decabrom-1,10-diphenyldecane, etc. Diphenylalkyl derivative, benzyloxypentachlorobenzene, 1,2-di(2',4',
6'-tripromephenoxy)ethane, 1,6-di(2
Examples include ',4',6'-tripromephenoxy)hexane. Among these, nuclear bromine compounds are preferred from the viewpoint of imparting flame retardant properties, and in particular hexabromobenzene, pentabromotoluene, pentapromoethylbenzene, pentapromobenzene, tetrabromobenzene, tribromotoluene, diphenyl ether bromide ( 4 to 10), biphenyl bromide (bromine number 4 to 10), biphenyl bromide (bromine number 4 to 10),
~10) are preferred. On the other hand, the carboxylic acid compounds used in the present invention include the above-mentioned succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid,
Examples include hexahydrophthalic acid, among which succinic acid and hexahydrophthalic acid are preferred.
上記両化合物の添加量は、ポリアミド繊維の使用目的に
よつて適宜選択できる。The amounts of both of the above compounds added can be appropriately selected depending on the intended use of the polyamide fiber.
一般に添加量が多くなるほど難燃性能は増大するが、紡
出延伸時の操業性並びに繊維製品の品質に悪影響を及ぼ
さない範囲内で添加しなければならず、通常得られるポ
リアミド繊維に対して、核ハロゲン化芳香族化合物は0
.5〜15重量%、またカルボン酸化合物は0.5〜
4重量%の範囲で使用すればよい。カルボン酸化合物の
添加量が0.5〜 4重量%の範囲内にあつても核ハロ
ゲン化芳香族化合物が0.5重量%未満の場合は繊維の
難燃性能が十分ではなく、逆に15重量%より多い場合
は紡出性、延伸性の低下、製品糸の色調の悪化、製品糸
の燃焼時における多量のハロゲンガスの発生などがあり
好ましくない。また核ハロゲン化芳香族化合物が0.5
〜15重量%の範囲内であつてもカルボン酸化合物が0
.5重量%未満では難燃性能等が十分に付与されず、逆
に4重量%より多い場合は、紡出性、延伸性が低下する
ので好ましくない。かかる見地からより好ましい範囲は
、核ハロゲン化芳香族化合物が1〜7重量%、カルボン
酸化合物が0.7〜 2重量%であり、特に核ハロゲン
化芳香族化合物はl〜4重量%が好ましい。本発明方法
は上記核ハロゲン化芳香族化合物とカルボン酸化合物を
ポリアミドに添加して溶融紡糸する。Generally, the flame retardant performance increases as the amount added increases, but it must be added within a range that does not adversely affect the operability during spinning and drawing and the quality of textile products. Nuclear halogenated aromatic compounds are 0
.. 5 to 15% by weight, and the carboxylic acid compound is 0.5 to 15% by weight.
It may be used within a range of 4% by weight. Even if the amount of carboxylic acid compound added is within the range of 0.5 to 4% by weight, if the amount of nuclear halogenated aromatic compound is less than 0.5% by weight, the flame retardant performance of the fiber is not sufficient, and conversely, the flame retardant performance of the fiber is insufficient. If the amount is more than % by weight, it is not preferable because spinnability and drawability are reduced, the color tone of the product yarn is deteriorated, and a large amount of halogen gas is generated when the product yarn is burned. In addition, the nuclear halogenated aromatic compound is 0.5
Even within the range of ~15% by weight, the carboxylic acid compound is 0.
.. If it is less than 5% by weight, flame retardant properties etc. will not be sufficiently imparted, and if it is more than 4% by weight, spinnability and stretchability will deteriorate, which is not preferable. From this point of view, a more preferable range is 1 to 7% by weight of the nuclear halogenated aromatic compound and 0.7 to 2% by weight of the carboxylic acid compound, and particularly preferably 1 to 4% by weight of the nuclear halogenated aromatic compound. . In the method of the present invention, the above-mentioned nuclear halogenated aromatic compound and carboxylic acid compound are added to polyamide and melt-spun.
添加する時期は、ポリアミドをチツプ化後が好ましい。
重合前、重合中もしくは重合終了時に添加するとポリア
ミドの着色等、好ましくない現象がみられることがある
。前記両化合物をポリアミドに添加する方法は特に制限
されない。The timing of addition is preferably after the polyamide is turned into chips.
If added before, during or at the end of polymerization, undesirable phenomena such as coloring of the polyamide may occur. The method of adding both of the above compounds to the polyamide is not particularly limited.
例えば回転ドラムに所定のポリアミドと該両化合物を投
入して混合、或いはミキサーでポリアミドと該両化合物
を混合して得られた混合物を公知のエクストルーダー或
いは格子型溶融装置等で溶融混練後紡出する事ができる
。また該両化合物を予め高濃度でポリアミドに混合、溶
融させてマスターチツプを作成し、次に所定の濃度にな
るように通常のポリアミドチツプを混合希釈して紡出す
る事も可能である。何れの方法においても、混合は十分
均一となる迄行う必要がある。For example, a specified polyamide and both compounds are put into a rotating drum and mixed, or the mixture obtained by mixing the polyamide and both compounds in a mixer is melt-kneaded using a known extruder or grid-type melting device, and then spun. I can do that. It is also possible to prepare a master chip by mixing and melting both of these compounds in polyamide at a high concentration, and then mixing and diluting ordinary polyamide chips to a predetermined concentration and spinning. In either method, it is necessary to mix until the mixture is sufficiently uniform.
混合が不十分な場合には溶融紡糸の工程において糸切れ
等のトラブルが生じる上に、得られるポリアミド繊維の
品質の均一性が低下する。従つてポリアミドと該両化合
物とを溶融状態で混合する時間としては、溶融紡糸工程
を含めて合計5分間以上を必要とする。しかし余りにも
長時間をかけるとポリアミドの物性変化が無視できない
程度に増大するので溶融混合時間は最大1時間とするべ
きである。溶融紡糸の方法としては従来公知の溶融紡糸
法が採用できる。If the mixing is insufficient, troubles such as yarn breakage may occur during the melt spinning process, and the quality of the resulting polyamide fibers will be less uniform. Therefore, a total of 5 minutes or more is required for mixing the polyamide and both compounds in a molten state, including the melt spinning step. However, if the mixing time is too long, changes in the physical properties of the polyamide will increase to a non-negligible extent, so the melt mixing time should be at most 1 hour. As the melt spinning method, a conventionally known melt spinning method can be adopted.
即ち、例えば前記核ハロゲン化芳香族化合物とカルボン
酸化合物をポリアミドチツプと混合したエクストルーダ
一で溶融してギヤポンプで計量した後口金より押し出し
て糸条となし捲取る方法がある。この際ポリアミドを溶
融した後スタテイツタミキサ一(例えば特殊械化工業株
式会社製1SGミキサー)などの混練装置で混練した後
紡糸する方法なども可能である。紡糸温度は使用するポ
リアミド及び該両化合物の種類や添加量により任意に選
ぶ事ができるが、一般にはポリアミドの融点以上融点+
80℃以下の範囲が望ましい。好ましくはポリアミドの
融点+(10〜50℃)の範囲である。以上の方法で溶
融紡糸した後、得られたポリアミド未延伸糸を延伸倍率
11以上、好ましくは、30以上で延伸する。That is, for example, there is a method in which the nuclear halogenated aromatic compound and the carboxylic acid compound are mixed with polyamide chips, melted in an extruder, metered with a gear pump, extruded from a spinneret, and then formed into a thread and wound up. At this time, it is also possible to melt the polyamide, knead it in a kneading device such as a static mixer (for example, 1SG mixer manufactured by Tokushu Kaika Kogyo Co., Ltd.), and then spin it. The spinning temperature can be arbitrarily selected depending on the polyamide used and the type and amount of both compounds added, but generally the spinning temperature is higher than the melting point of the polyamide.
A range of 80°C or less is desirable. Preferably, the range is the melting point of polyamide + (10 to 50°C). After melt spinning by the above method, the obtained undrawn polyamide yarn is drawn at a draw ratio of 11 or more, preferably 30 or more.
延伸に際しては50℃〜140℃の範囲で熱延伸する方
法が、延伸糸切れ防止や品質の安定の為に好都合である
。熱延伸法としてはホツトピン延伸、熱ローラー延伸な
どがあるが、ホツトピン延伸が、特に好ましい方法であ
る。本発明方法によれば極めて容易に、優れた難燃性を
有し、しかもポリアミド本来の優れた諸特性を何ら低下
せしめることのない難燃性ポリアミド繊維を得ることが
できる。本発明では前記カルボン酸化合物を併用する事
により、核ハロゲン化芳香族化合物の配合量が従来に比
して非常に少なくてもよいため、コスト的にも有利で、
又紡出性にも問題が見られず、得られる繊維の耐光性、
白度等も十分満足のできるものである。更に該ポリアミ
ド繊維の燃焼時に、有毒なハロゲン系ガスの発生を大巾
に低下せしめることも可能である。本発明方法において
ポリアミドに第3成分、例えば艶消剤、酸化防止剤、熱
安定剤、耐光剤、帯電防止剤、着色剤、螢光増白剤を添
加する事は何ら差し支えない。以下実施例により本発明
を詳細に説明する。When drawing, a method of hot drawing at a temperature in the range of 50° C. to 140° C. is convenient for preventing drawn yarn breakage and stabilizing quality. Examples of hot stretching methods include hot pin stretching and hot roller stretching, but hot pin stretching is particularly preferred. According to the method of the present invention, flame-retardant polyamide fibers having excellent flame retardancy and without degrading the original excellent properties of polyamide can be obtained very easily. In the present invention, by using the above-mentioned carboxylic acid compound in combination, the amount of the nuclear halogenated aromatic compound to be blended can be much smaller than in the past, which is advantageous in terms of cost.
In addition, there were no problems with spinnability, and the light resistance of the resulting fibers was
The whiteness etc. are also sufficiently satisfactory. Furthermore, it is also possible to greatly reduce the generation of toxic halogen gases during combustion of the polyamide fibers. In the method of the present invention, there is no problem in adding third components to the polyamide, such as matting agents, antioxidants, heat stabilizers, light stabilizers, antistatic agents, colorants, and fluorescent brighteners. The present invention will be explained in detail below with reference to Examples.
尚実施例中相対粘度〔ηRel〕は濃硫酸1%濃度にな
る様にポリアミドを溶解し、25℃においてオストワル
ド粘度計にて測定した値をもつて示した。難燃性の評価
は以下の測定法に従つて限界酸素指数(以下L,O,I
と略称する)及び45゜コイル法による接炎回数で示し
た。J(a) L,O,Iの測定法
布サンプルはJIS−K−7201−1972A法−2
号に準じてL,O,Iを測定した。In the Examples, the relative viscosity [ηRel] is the value measured by an Ostwald viscometer at 25° C. after dissolving the polyamide in concentrated sulfuric acid to a concentration of 1%. Flame retardancy is evaluated using the limiting oxygen index (L, O, I) according to the following measurement method.
) and the number of times of flame contact using the 45° coil method. J(a) L, O, I measurement method Fabric sample is JIS-K-7201-1972A method-2
L, O, and I were measured according to No.
糸サンプルについては試験する繊維から重さ0.5g、
長さ100mm、撚り数10の撚棒を作成し、中心に針
金を挿入して、燃焼円筒の中央底部に垂直に保持し同様
に測定を行なつた。(b) 45゜コイル法による接炎
回数の測定法布サンプルはJIS−L−1091−19
71D法に準じて接炎回数を測定した。For yarn samples, weigh 0.5 g from the fiber to be tested;
A twisted rod with a length of 100 mm and a twist number of 10 was prepared, a wire was inserted into the center, and the rod was held vertically at the center bottom of a combustion cylinder and measurements were made in the same manner. (b) Method for measuring the number of times of flame contact using the 45° coil method The cloth sample is based on JIS-L-1091-19.
The number of flame contacts was measured according to the 71D method.
糸サンプルについては試験する繊維から重さ1g、長さ
100mm、撚り数10の撚棒を作成し、この撚棒を0
.5mmφのステンレス鋼線よりなる直径10mm、コ
イルピツチ2mm、長さ150mmのコイル内に挿入し
45度の角度に保持して、炎の長さ45mmのミタロバ
ーナ一にて下端に10秒接炎して燃焼させ、炎が消える
と位置をずらして再び同様に下端に接炎する。かくして
撚棒の10cmが燃焼し尽くすまでの接炎回数を測定し
、5回の平均値で示した。また相溶性の試験方法及び評
価方法は次の通りである。即ち、30mmφ×200m
m試験管に、ポリアミドブライトペレツト約27gと所
定量の化合物を十分混合した後投入する。For yarn samples, a twisted rod with a weight of 1 g, a length of 100 mm, and a number of twists of 10 is made from the fiber to be tested, and this twisted rod is
.. Insert it into a coil made of 5mmφ stainless steel wire with a diameter of 10mm, a coil pitch of 2mm, and a length of 150mm, hold it at a 45 degree angle, and burn it by touching the lower end with a Mitaro burner with a flame length of 45mm for 10 seconds. When the flame goes out, shift the position and apply the flame again to the lower end in the same way. In this way, the number of times of flame contact until 10 cm of the twisted rod was completely burnt out was measured, and the average value of the five times was shown. The compatibility test method and evaluation method are as follows. That is, 30mmφ×200m
About 27 g of polyamide brite pellets and a predetermined amount of the compound are thoroughly mixed and then poured into a test tube.
ポリアミドの酸化を防ぐ為に、窒素フローしながら試験
管をポリアミドの融点以上に加熱し内容物を溶融させる
。溶融後攪拌棒にて十分均一混合する。次いでガラス壁
越しに溶融物の状態を肉眼観察し、次の3段階に大別し
て評価した。○=均一に溶解し、ポリマーが透明で油滴
分散物が存在しない。To prevent oxidation of the polyamide, the test tube is heated to a temperature higher than the melting point of the polyamide while flowing nitrogen to melt the contents. After melting, mix thoroughly and uniformly with a stirring rod. Next, the state of the melt was observed with the naked eye through the glass wall, and the evaluation was roughly divided into the following three stages. ◯=uniformly dissolved, the polymer was transparent, and no oil droplet dispersion was present.
△=大部分は溶解しているが、一部の分散物の為にポリ
マーが半透明状である。Δ=Most of the polymer is dissolved, but the polymer is translucent due to some dispersion.
×=ポリマーが不透明であり、未溶解物が多量に分散し
ている。× = Polymer is opaque, and a large amount of undissolved matter is dispersed.
但し、上記3段階の中間に位置する場合は、〇△の如き
中間的な表示を用いた。However, in the case of being located in the middle of the above three stages, an intermediate display such as 〇△ was used.
着色性の評価規準は、次の通りである。The evaluation criteria for colorability are as follows.
即ち、繊維の着色状態を肉眼により次の通り評価した。
◎=全<着色無く、未変性ポリアミドと同等。○=僅か
に着色しているが、未変性ポリアミドに近い。△=未変
性ポリアミドと比較し、明らかに着色が認められる。That is, the colored state of the fibers was visually evaluated as follows.
◎ = All < No coloration, equivalent to unmodified polyamide. ○=Slightly colored, but close to unmodified polyamide. Δ=Coloring is clearly observed compared to unmodified polyamide.
×一未変性ポリアミドと比較し、着色が著しい。×1: Significant coloring compared to unmodified polyamide.
但し、中間的段階に位置する場合は、△×の如き中間的
な表示を用いた。また、可紡性の評価は次の様に行なつ
た。However, if the item is at an intermediate stage, an intermediate symbol such as △× is used. Moreover, evaluation of spinnability was performed as follows.
〇=未変性ナイロン6並みに糸切れが少なく、100万
m当りの糸切れが1回以下。〇 = As few thread breakages as unmodified nylon 6, less than 1 thread breakage per 1 million m.
△=100万m当りの糸切れが5 〜20回程度。△ = Thread breaks approximately 5 to 20 times per million meters.
×=糸切れが多発し、満足な紡出糸が得られない゜
但し、中間的段階に位置する場合は△×の如き中間的な
表示も用いた。× = Yarn breakage occurs frequently and a satisfactory spun yarn cannot be obtained. However, when the yarn is at an intermediate stage, an intermediate indication such as △× is also used.
実施例 l
ナイロン6フルダルチツプ(相対粘度260、水分率0
.08重量%)に、第1表に記載した各種化合物を予め
よく混合し、通常のエクストルーダー型紡糸機を用いて
260℃の温度、紡速600m/分で溶融紡糸した。Example l Nylon 6 full-dull chip (relative viscosity 260, moisture content 0
.. The various compounds listed in Table 1 were thoroughly mixed in advance with 08% by weight) and melt-spun using a conventional extruder-type spinning machine at a temperature of 260° C. and a spinning speed of 600 m/min.
次に90℃の温度で3.4倍に熱延伸(ホツトピン延伸
)して10フイラメントからなる40デニールの繊維を
得た。得られた繊維の燃焼性のテストをL,O,Iの測
定及び45゜コイル法による接炎回数の測定により行な
つた。尚、相溶性、着色性、可紡性等の評価方法は、前
記した通りである。Next, the fiber was hot-stretched (hot-pin-stretched) to 3.4 times at a temperature of 90°C to obtain a 40-denier fiber consisting of 10 filaments. The combustibility of the obtained fibers was tested by measuring L, O, and I, and by measuring the number of flame contacts using a 45° coil method. The evaluation methods for compatibility, colorability, spinnability, etc. are as described above.
結果を第1表に示す。The results are shown in Table 1.
第1表に示した様に、核ハロゲン化芳香族化合物4.0
重量%とカルボン酸化合物1.5重量%をナイロン6チ
ツプにブレンド、紡出した本発明品C應1〜5)は相溶
性、着色性、可紡性には殆んど問題が見られず、その難
燃性能も優れている。As shown in Table 1, nuclear halogenated aromatic compounds 4.0
% by weight and 1.5% by weight of a carboxylic acid compound into nylon 6 chips and spun the products C1 to 5) of the present invention, with almost no problems in compatibility, colorability, and spinnability. , its flame retardant performance is also excellent.
一方應6、f).7、應8は核ハロゲン化芳香族化合物
4重量%のみをプレンド、紡出した場合であるが、これ
らは相溶性、着色性、可紡性などには問題がなかつたが
、肝心の難燃性能向上効果が認められない。またf).
9、應10は核ハロゲン化芳香族化合物4重量%と三酸
化アンチモン2重量%を組み合わせた場合であるがこれ
らは相溶性や可紡性が悪く、その難燃効果も未だ不十分
である。應11はペンタブロムトルエンを應7より増量
して10重量%ブレンド、紡出した場合である。黒7に
比べて添加量が増えている為に難燃性能は向上している
ものの、未十分とはいえず、また着色性や可紡性は逆に
悪化した。実施例 2
ナイロン6フルダルチツプ(相対粘度255、水分率0
.09重量%)にコハク酸及びヘキサブロムジフェニル
エーテルを種々の割合で、予めよく混合し、実施例1と
同様の方法で10フイラメントからなる40デニールの
繊維を得た。On the other hand, 6, f). 7 and 8 are cases where only 4% by weight of the nuclear halogenated aromatic compound was blended and spun, and although there were no problems with compatibility, colorability, spinnability, etc., the important flame retardant No performance improvement effect was observed. Also f).
No. 9 and No. 10 are cases in which 4% by weight of a nuclear halogenated aromatic compound and 2% by weight of antimony trioxide are combined, but these have poor compatibility and spinnability, and their flame retardant effect is still insufficient. In case No. 11, the amount of pentabromotoluene was increased from that in case No. 7, and it was blended and spun to 10% by weight. Although the flame retardant performance was improved due to the increased additive amount compared to Black 7, it was still not sufficient, and the colorability and spinnability deteriorated. Example 2 Nylon 6 full dual tip (relative viscosity 255, moisture content 0)
.. 09% by weight), succinic acid and hexabromidiphenyl ether in various proportions were thoroughly mixed in advance, and a 40-denier fiber consisting of 10 filaments was obtained in the same manner as in Example 1.
得られた繊維のL.O.I.の測定及び45゜コイル法
による接炎回数の測定を行なつた。また前記の方法で相
溶性、着色性、可紡性の評価も行なつた。結果を第2表
に示す。第2表め結果からも明らかな様に、コハク酸或
いはへキサプロムジフエニルエーテル単独添加では難燃
性能向上効果は殆んどみられなかつたが、両者を適正添
加量で併用することにより初めてナJイロン6本来の諸
特性を低下することなく優れた難燃性能を有するナイロ
ン6繊維を得ることができた。The L. O. I. The number of flame contacts was measured using the 45° coil method. Compatibility, colorability, and spinnability were also evaluated using the methods described above. The results are shown in Table 2. As is clear from the results in Table 2, when succinic acid or hexaprom diphenyl ether was added alone, almost no flame retardant performance improvement effect was observed, but when both were used together in appropriate amounts, It was possible to obtain nylon 6 fibers having excellent flame retardant performance without degrading the original properties of nylon 6.
実施例 3
ナイロン66チツプ(相対粘度245)に、第3表に記
載した各種化合物を予めよく混合し、実施例1と同様の
方法、但し紡出温度は270℃で10フイラメントから
なる40デニールの繊維を得た。Example 3 Nylon 66 chips (relative viscosity 245) were thoroughly mixed with the various compounds listed in Table 3, and the same method as Example 1 was used except that the spinning temperature was 270°C and a 40 denier film consisting of 10 filaments was prepared. Obtained fiber.
得られた繊維のL.O.I.の測定及び45゜コイル法
による接炎回数の測定を行なつた。また前記の方法で相
溶性、着色性、可紡性の評価も行なつた。結果を第3表
に記載する。第3表の結果からも明らかなように核ハロ
ゲン化芳香族化合物とカルボン酸化合物を併用した本発
明品(遥1〜3)は、優れた難燃性能を有する上に、良
好な諸特性を示したが、核ハロゲン化芳香族化合物単独
の場合(▲4〜6)難燃性能が向上せず、また添加量を
増量すると (’胤9)ポリアミド特性に悪影響を与え
た。The L. O. I. The number of flame contacts was measured using the 45° coil method. Compatibility, colorability, and spinnability were also evaluated using the methods described above. The results are shown in Table 3. As is clear from the results in Table 3, the products of the present invention (Haruka 1 to 3), which use a combination of a nuclear halogenated aromatic compound and a carboxylic acid compound, have excellent flame retardant performance and other good properties. However, when the nuclear halogenated aromatic compound was used alone (▲4 to 6), the flame retardant performance did not improve, and when the amount added was increased ('9), it had an adverse effect on the polyamide properties.
更に公知の難燃助剤である三酸化アンチモンを併用して
も (應7〜8)難燃性能は不十分で、しかも相溶性、
可紡性等の特性も劣化した。実施例 4
ナイロン6セミダブルチツプ(相対粘度2.60、水分
率0.08重量%)にコハタ酸1.3重量%とデカプロ
モビフエニル3.5重量%を予めよく混合し通常のエク
ストルーダ一型紡糸機を用いて260℃の温度、紡速6
00m/分で溶融紡糸した。Furthermore, even if antimony trioxide, a known flame retardant aid, is used in combination (7-8), the flame retardant performance is insufficient, and the compatibility is poor.
Properties such as spinnability also deteriorated. Example 4 Nylon 6 semi-double chips (relative viscosity 2.60, moisture content 0.08% by weight) were thoroughly mixed with 1.3% by weight of succinic acid and 3.5% by weight of decapromobiphenyl in a conventional extruder type 1. Using a spinning machine at a temperature of 260°C and a spinning speed of 6
Melt spinning was performed at 00 m/min.
得られた未延伸糸を用いて第4表の如き各種の延伸方法
で延伸した。但し延伸倍率は全て3.4である。その際
の延伸性及び延伸糸の糸むら(R%)の測定結果につい
て第4表に記す。第4表に記載のように冷延伸ではピン
の有無にかかわらず延伸性が不十分であり、またR%値
も高くピンが有つても未だ不十分である。The obtained undrawn yarn was drawn by various drawing methods as shown in Table 4. However, the stretching ratio is 3.4 in all cases. Table 4 shows the measurement results of stretchability and yarn unevenness (R%) of the drawn yarn. As shown in Table 4, in cold drawing, the drawability is insufficient regardless of the presence or absence of pins, and the R% value is also high and is still insufficient even with pins.
R%値が高いという事は糸の太さが不均一であるという
事であり、部分未延伸の存在が予想され、染色斑などの
問題が生じ易い為に好ましくない事である。熱延伸では
、ホツトピン延伸性、ホツトローラ一延伸ともに延伸性
、R%値は良好である。A high R% value means that the thickness of the yarn is non-uniform, which is not preferable because it is expected that there will be some undrawn parts, which is likely to cause problems such as dyeing spots. In hot stretching, the hot pin stretchability and hot roller single stretching are both good in stretchability and R% value.
しかし延伸温度が40℃では、R%値が高くなる傾向を
示し、延伸性も多少低下するために好ましくない。他方
、延伸温度が150℃ではR%値は良好ではあるが、延
伸性が多少低下し、特に糸が融着を起こし、延伸スター
ト時の糸切れが多発するので、好ましくない。However, when the stretching temperature is 40° C., the R% value tends to increase and the stretchability also decreases to some extent, which is not preferable. On the other hand, when the stretching temperature is 150° C., although the R% value is good, the drawability is somewhat lowered, and in particular, the threads tend to fuse and breakage occurs frequently at the start of drawing, which is not preferable.
従つて熱延伸温度は50〜140℃が好ましい。実施例
5
ナイロン6フルダルチツプ(相対粘度2.70、水分率
0.08重量%)にコハク酸5重量%とペンタプロムエ
チルベンゼン12重量%を予めよく混合し、エダストル
ータ−を使用して250℃で溶融混練し、マスターチツ
プを得た。Therefore, the hot stretching temperature is preferably 50 to 140°C. Example 5 5% by weight of succinic acid and 12% by weight of pentapromethylbenzene were thoroughly mixed in advance with nylon 6 fulldulchip (relative viscosity 2.70, moisture content 0.08% by weight), and melted at 250°C using an Edust router. Kneaded and obtained master chips.
かかるマスターチツプをコハク酸の含有量が1.25重
量%でペンタプロムエチルベンゼンの含有量が3重量%
となるようにナイロン6フルダルチツプ(相対粘度2.
70、水分率0.08重量%)とよく混合しエクストル
ーダ一型紡糸機を使用し255℃の温度、紡速650m
/分で溶融紡糸した。次に約3.3倍に90℃のホツト
ピンで熱延伸して1.0フイラメントからなる40デニ
ールの繊維を得た。この繊維の強度は48g/d、伸度
は35%で未変性ナイロン6普通糸と大差が無かつた。
この繊維を用いて通常の整経、編立を行ない、トリコツ
トサンプルとした。整経、編立時の操業性等の問題点は
特に無く、未変性ナイロン6の場合と同等であつた。ま
た、このトリコツトサンプルに通常の精練、染色を施し
た。染色は分散染色、酸性染色の両者で行なつたが、染
色性は未変性ナイロン6と大差なく良好であつた。得ら
れた染色トリコツト布の難燃性能を評価する為に接炎回
数の測定を行なつた。Such a master chip has a succinic acid content of 1.25% by weight and a pentapromethylbenzene content of 3% by weight.
Nylon 6 full dual tip (relative viscosity 2.
70, moisture content 0.08% by weight) and was mixed well using an extruder type spinning machine at a temperature of 255°C and a spinning speed of 650m.
/min. Next, the fiber was hot-stretched by about 3.3 times using a hot pin at 90° C. to obtain a 40-denier fiber consisting of 1.0 filament. The strength of this fiber was 48 g/d and the elongation was 35%, which was not much different from that of unmodified nylon 6 ordinary yarn.
This fiber was subjected to normal warping and knitting to obtain a tricot sample. There were no particular problems with workability during warping and knitting, and the results were comparable to those of unmodified nylon 6. Further, this tricot sample was subjected to usual scouring and dyeing. Dyeing was carried out by both dispersion dyeing and acid dyeing, and the dyeability was good with no major difference from unmodified nylon 6. In order to evaluate the flame retardant performance of the obtained dyed tricot cloth, the number of times it was exposed to flame was measured.
Claims (1)
中Xは塩素及び/又は臭素、YはR、ORまたはOR′
OR(Rは炭素数1〜10のアルキル基、アリール基ま
たは核ハロゲン化アリール基或いは炭素数7〜16のア
ラルキル基または核ハロゲン化アラルキル基、坦しハロ
ゲンは塩素及び/または臭素、R′は炭素数1〜6のア
ルキレン基)、lは2〜6の整数、mは0または1であ
る。 〕で示される少なくとも一種の核ハロゲン化芳香族化合
物を得られるポリアミド繊維重量に対して0.5〜15
%、並びにコハク酸、アジピン酸、セバシン酸、アゼラ
イン酸、テレフタル酸、イソフタル酸及びヘキサヒドロ
フタル酸から成る群より選ばれた少なくとも一種のカル
ボン酸化合物を得られるポリアミド繊維重量に対して0
.5〜4%の割合で添加し、溶融紡糸後、50〜140
℃の温度で熱延伸して成る難燃性ポリアミド繊維の製造
法。2 ポリアミドがナイロン6またはナイロン66で
ある特許請求の範囲第1項記載の製造法。 3 一般式(1)で示される核ハロゲン化芳香族化合物
に於いて、ハロゲンが全て臭素である特許請求の範囲第
1項記載の製造法。 4 一般式(1)で示される核ハロゲン化芳香族化合物
がヘキサブロムベンゼン、ペンタブロムトルエン、ペン
タブロムエチルベンゼン、ペンタブロムベンゼン、トリ
ブロムトルエン、臭素付加数4〜10のジフェニルエー
テル臭化物及び臭素付加数4〜10のビフェニル臭化物
から成る群より選ばれた少なくとも一種の化合物である
特許請求の範囲第3項記載の製造法。 5 ポリアミドに一般式(1)で示される核ハロゲン化
芳香族化合物を得られるポリアミド繊維重量に対して1
〜7%添加する特許請求の範囲第1項、第3項または第
4項記載の製造法。 6 カルボン酸化合物がコハク酸及び/またはヘキサヒ
ドロフタル酸である特許請求の範囲第1項記載の製造法
。 7 ポリアミドにカルボン酸化合物を得られるポリアミ
ド繊維重量に対して0.7〜2%添加する特許請求の範
囲第1項または第6項記載の製造法。 8 チップ化後のポリアミドに一般式(1)で示される
核ハロゲン化芳香族化合物並びにカルボン酸化合物を添
加する特許請求の範囲第1項記載の製造法。 9 熱延伸がホットピン延伸または熱ローラー延伸であ
る特許請求の範囲第1項記載の製造法。 10 熱延伸がホットピン延伸である特許請求の範囲第
9項記載の製造法。[Claims] 1 Polyamide has the general formula (1) ▲ Numerical formula, chemical formula, table, etc. ▼ ... (1) [In the formula, X is chlorine and/or bromine, Y is R, OR or OR'
OR (R is an alkyl group, aryl group, or nuclear halogenated aryl group having 1 to 10 carbon atoms, or an aralkyl group or halogenated aralkyl group having 7 to 16 carbon atoms, and the carrier halogen is chlorine and/or bromine; R' is (alkylene group having 1 to 6 carbon atoms), 1 is an integer of 2 to 6, and m is 0 or 1. ] 0.5 to 15 based on the weight of the polyamide fiber obtained from at least one type of nuclear halogenated aromatic compound
%, and at least one carboxylic acid compound selected from the group consisting of succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid and hexahydrophthalic acid.
.. Added at a ratio of 5 to 4%, after melt spinning, 50 to 140
A method for producing flame-retardant polyamide fibers by hot stretching at a temperature of ℃. 2. The manufacturing method according to claim 1, wherein the polyamide is nylon 6 or nylon 66. 3. The production method according to claim 1, wherein in the nuclear halogenated aromatic compound represented by general formula (1), all halogens are bromine. 4 The nuclear halogenated aromatic compound represented by the general formula (1) is hexabromobenzene, pentabromotoluene, pentabromoethylbenzene, pentabromobenzene, tribromotoluene, diphenyl ether bromide with a bromine addition number of 4 to 10, and a bromine addition number 4 The manufacturing method according to claim 3, which is at least one compound selected from the group consisting of -10 biphenyl bromides. 5 1 for the weight of the polyamide fiber from which the nuclear halogenated aromatic compound represented by the general formula (1) is obtained in the polyamide
The manufacturing method according to claim 1, 3, or 4, wherein ~7% is added. 6. The production method according to claim 1, wherein the carboxylic acid compound is succinic acid and/or hexahydrophthalic acid. 7. The manufacturing method according to claim 1 or 6, wherein the carboxylic acid compound is added to the polyamide in an amount of 0.7 to 2% based on the weight of the polyamide fiber obtained. 8. The manufacturing method according to claim 1, wherein a nuclear halogenated aromatic compound represented by general formula (1) and a carboxylic acid compound are added to the polyamide after chipping. 9. The manufacturing method according to claim 1, wherein the hot stretching is hot pin stretching or hot roller stretching. 10. The manufacturing method according to claim 9, wherein the hot stretching is hot pin stretching.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1279177A JPS5951604B2 (en) | 1977-02-07 | 1977-02-07 | Manufacturing method of flame retardant polyamide fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1279177A JPS5951604B2 (en) | 1977-02-07 | 1977-02-07 | Manufacturing method of flame retardant polyamide fiber |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5398417A JPS5398417A (en) | 1978-08-28 |
JPS5951604B2 true JPS5951604B2 (en) | 1984-12-14 |
Family
ID=11815213
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1279177A Expired JPS5951604B2 (en) | 1977-02-07 | 1977-02-07 | Manufacturing method of flame retardant polyamide fiber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5951604B2 (en) |
-
1977
- 1977-02-07 JP JP1279177A patent/JPS5951604B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS5398417A (en) | 1978-08-28 |
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