JP2002155479A - Method for dyeing wholly aromatic polyamide fiber - Google Patents

Method for dyeing wholly aromatic polyamide fiber

Info

Publication number
JP2002155479A
JP2002155479A JP2000344938A JP2000344938A JP2002155479A JP 2002155479 A JP2002155479 A JP 2002155479A JP 2000344938 A JP2000344938 A JP 2000344938A JP 2000344938 A JP2000344938 A JP 2000344938A JP 2002155479 A JP2002155479 A JP 2002155479A
Authority
JP
Japan
Prior art keywords
dyeing
aromatic polyamide
polyamide fiber
wholly aromatic
flame retardant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2000344938A
Other languages
Japanese (ja)
Other versions
JP4624542B2 (en
Inventor
Saoaya Kuroda
幸乙綾 黒田
Yasunori Tatsuoka
康則 立岡
Shigeru Takahashi
茂 高橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Teijin Ltd
Original Assignee
Teijin Ltd
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Filing date
Publication date
Application filed by Teijin Ltd filed Critical Teijin Ltd
Priority to JP2000344938A priority Critical patent/JP4624542B2/en
Publication of JP2002155479A publication Critical patent/JP2002155479A/en
Application granted granted Critical
Publication of JP4624542B2 publication Critical patent/JP4624542B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Artificial Filaments (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Fireproofing Substances (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a method for dyeing a wholly aromatic aramid fiber capable of suppressing a bleedout of a flame retardant therein into a dyeing liquid and giving both good dyeability and flame retardancy contradictory to each other. SOLUTION: This method for dyeing a wholly, aromatic polyamide fiber containing a flame retardant comprises using a phosphorus-based compound of the formula (I): PO(OR)3 (R is a 1-6 alkyl) in combination with a dye.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、難燃剤を含む全芳
香族ポリアミド繊維の染色方法に関するものであり、更
に詳しくは、難燃剤を含む全芳香族ポリアミド繊維を染
色するに際し、燐系化合物を染色助剤として併用するこ
とにより、難燃性の低下が防止可能な、全芳香族ポリア
ミド繊維の染色方法に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing a wholly aromatic polyamide fiber containing a flame retardant, and more particularly, to a method for dyeing a wholly aromatic polyamide fiber containing a flame retardant with a phosphorus compound. The present invention relates to a method for dyeing wholly aromatic polyamide fibers, which can prevent a decrease in flame retardancy when used as a dyeing assistant.

【0002】[0002]

【従来の技術】全芳香族ポリアミド(以下アラミドと略
記)繊維にはコーネックス、ノーメックスに代表される
メタ系アラミド繊維とテクノーラ、ケブラー、トワロン
に代表されるパラ系アラミド繊維とがある。
2. Description of the Related Art Wholly aromatic polyamide (hereinafter abbreviated as aramid) fibers include meta-aramid fibers represented by Conex and Nomex and para-aramid fibers represented by Technora, Kevlar and Twaron.

【0003】これらのアラミド繊維は、ナイロン6、ナ
イロン66などの従来から広く使用されている脂肪族ポ
リアミド繊維に比較して、剛直な分子構造と高い結晶性
のために耐熱性、耐炎性(難燃性)などの熱的性質、並
びに耐薬品性、強力な耐放射線性、電気特性などの安全
性に優れた性質を有している。従ってバグフィルターな
どの産業資材用やカーテンなどのインテリア用、耐炎性
(難燃性)や耐熱性を必要とする防護服などの衣料用と
して広く使用されている。
These aramid fibers have a rigid molecular structure and high crystallinity compared to conventionally widely used aliphatic polyamide fibers such as nylon 6, nylon 66, etc., so that they have heat resistance and flame resistance. Flammability) and safety properties such as chemical resistance, strong radiation resistance, and electrical properties. Therefore, it is widely used for industrial materials such as bag filters, interiors such as curtains, and clothing such as protective clothing requiring flame resistance (flame retardancy) and heat resistance.

【0004】また、消防士が消火作業中に着用する繊維
としては、従来より不燃性のアスベスト繊維、ガラス繊
維などが使われていたが、環境問題や、動き易さの観点
から近年では、アラミド繊維が使用されるようになって
きており、特に、防炎性を重視する場合はメタ系アラミ
ド繊維が好ましく使用される。
As a fiber worn by firefighters during a fire fighting operation, incombustible asbestos fiber, glass fiber, and the like have been used, but in recent years, aramid fibers have been used from the viewpoint of environmental problems and ease of movement. Fibers have come to be used. Particularly, when importance is placed on flame resistance, meta-aramid fibers are preferably used.

【0005】しかしながら、メタ系アラミド繊維は、分
子鎖が剛直で且つ高結晶性であるため、後加工における
染色が難しいという欠点を有しており、これを解決する
ため、極性溶媒やキャリアーで前処理した後染色する方
法などが提案されているが、該方法は作業環境が悪化す
る等の問題があり、実用化には至っていない。
However, the meta-aramid fiber has a drawback that it is difficult to dye in post-processing because the molecular chain is rigid and has high crystallinity. A method of dyeing after treatment has been proposed, but this method has problems such as deterioration of working environment and has not been put to practical use.

【0006】一方、特開平8−81827号公報には、
アルキルベンゼンスルフォン酸オニウム塩を添加するこ
とにより、メタ系アラミド繊維の染色性を向上させる方
法が開示されている。
On the other hand, JP-A-8-81827 discloses that
A method for improving the dyeability of meta-aramid fibers by adding an onium alkylbenzene sulfonate is disclosed.

【0007】ところが、メタ系アラミド繊維にアルキル
ベンゼンスルホン酸オニウム塩を含有させると、メタ系
アラミド繊維の最大の特徴である防炎性が阻害されると
いう問題が発生するため、通常、このような場合には難
燃剤を同時に含有させるが、一般に難燃剤は染色液中に
ブリードアウトし易いので、染色されたメタ系アラミド
繊維においては、充分な難燃性付与効果が発現しないと
いう問題があった。
However, when an onium alkylbenzenesulfonate is added to the meta-aramid fiber, a problem arises in that the flame resistance, which is the most characteristic feature of the meta-aramid fiber, is impaired. Contains a flame retardant at the same time. However, since the flame retardant generally tends to bleed out into the dyeing solution, there has been a problem that the dyed meta-aramid fiber does not exhibit a sufficient flame retardancy-imparting effect.

【0008】[0008]

【発明が解決しようとする課題】本発明の目的は、上記
従来技術の有する問題点を解消し、染色性と難燃性とい
う相反する性質が共に良好なアラミド繊維、就中メタ系
アラミド繊維の染色方法を提供することにある。
SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide an aramid fiber, particularly a meta-aramid fiber, which is excellent in both contradictory properties of dyeability and flame retardancy. It is to provide a dyeing method.

【0009】[0009]

【課題を解決するための手段】本発明者らは上記目的を
達成するために鋭意検討した結果、難燃剤を含むアラミ
ド繊維を染色する際、特定の構造を有する燐系化合物を
染色助剤として併用するとき、難燃剤添加の効果が最大
限に発揮されることを究明した。
Means for Solving the Problems As a result of extensive studies to achieve the above object, the present inventors have found that when dyeing aramid fibers containing a flame retardant, a phosphorus compound having a specific structure is used as a dyeing aid. It was clarified that the effect of adding a flame retardant was maximized when used in combination.

【0010】かくして本発明によれば、難燃剤を含む全
芳香族ポリアミド繊維を染色するに際し、下記式(I)
で表す燐系化合物を染色助剤として併用することを特徴
とする全芳香族ポリアミド繊維の染色方法が提供され
る。
Thus, according to the present invention, when dyeing a wholly aromatic polyamide fiber containing a flame retardant, the following formula (I)
A method for dyeing wholly aromatic polyamide fibers, characterized in that a phosphorus compound represented by the formula (1) is used in combination as a dyeing aid.

【0011】[0011]

【化2】 Embedded image

【0012】[0012]

【発明の実施の形態】本発明におけるアラミド繊維と
は、アミド結合が芳香族に直結した全芳香族ポリアミド
を主たる構成成分とするもので、例えば下記モノマーを
組み合わせて重縮合することにより得られるポリマーを
言う。 (1)芳香族多価アミンと芳香族多価カルボン酸ハライ
ド (2)芳香族多価アミンと芳香族多価カルボン酸エステ
ル (3)芳香族多価アミンと芳香族多価カルボン酸 (4)芳香族多価イソシアネートと芳香族多価カルボン
BEST MODE FOR CARRYING OUT THE INVENTION The aramid fiber in the present invention is composed mainly of a wholly aromatic polyamide in which an amide bond is directly connected to an aromatic, and is, for example, a polymer obtained by polycondensing a combination of the following monomers. Say (1) Aromatic polyamine and aromatic polycarboxylic acid halide (2) Aromatic polyamine and aromatic polycarboxylic acid ester (3) Aromatic polyamine and aromatic polycarboxylic acid (4) Aromatic polyisocyanate and aromatic polycarboxylic acid

【0013】具体的には、メタフェニンレンジアミンと
イソフタル酸クロライドとを低温溶液重合或いは、界面
重合して得たポリメタフェニレンイソフタルアミドを主
成分とするメタ−メタ結合のアラミド繊維(例えば、帝
人(株)製コーネックスなど)が好ましく例示され、中で
も、特開平8−81827号公報に開示された、メタ系
アラミド繊維にアルキルベンゼンスルホン酸オニウム塩
が含有されてなる易染性メタ系アラミド繊維を用いれ
ば、本発明の効果がより顕著に発現するので好適であ
る。
More specifically, meta-meta-bonded aramid fibers mainly composed of polymetaphenylene isophthalamide obtained by low-temperature solution polymerization or interfacial polymerization of metaphenin diamine and isophthalic chloride (for example, Preferred examples are Conex manufactured by Teijin Limited. Among them, the easily dyeable meta-aramid fiber in which the meta-aramid fiber contains an alkylbenzene sulfonate onium salt is disclosed in JP-A-8-81827. Is preferred because the effects of the present invention are more remarkably exhibited.

【0014】かかるアルキルベンゼンスルホン酸オニウ
ム塩としては、ドデシルベンゼンスルホン酸テトラブチ
ルホスホニウム塩の他、下記式に示すドデシルベンゼン
スルホン酸トリブチルベンジルアンモニウム塩等を好ま
しいものとして挙げることができる。
Preferred examples of the onium alkylbenzenesulfonate include tetrabutylphosphonium dodecylbenzenesulfonate and tributylbenzylammonium dodecylbenzenesulfonate represented by the following formula.

【0015】[0015]

【化3】 Embedded image

【0016】つまり、前述のように、アルキルベンゼン
スルホン酸オニウム塩を含有するメタ系アラミド繊維
は、防炎性が阻害されるという問題が発生するため、通
常、下記式で示されるハロゲン化燐酸エステル系難燃剤
等の難燃剤を同時に含有させる。
That is, as described above, a meta-aramid fiber containing an onium alkylbenzenesulfonate has a problem in that the flame resistance is impaired. Therefore, a halogenated phosphoric ester-based fiber represented by the following formula is usually used. A flame retardant such as a flame retardant is simultaneously contained.

【0017】[0017]

【化4】 Embedded image

【0018】ここで、ハロゲン化燐酸エステル中のRは
炭素数2〜6、好ましくは炭素数2〜3のハロゲン化ア
ルキル基を表すが、ハロゲン原子は塩素又は臭素を示
し、ハロゲン化アルキル基中のハロゲンの置換数は1で
も2以上であってもよい。中でも、2−クロロエチル
基、2−クロロプロピル基が、抗菌性、難燃性及び洗濯
耐久性をより高レベルにする効果が期待出来るので好ま
しい。Xは直接結合又は炭素数1〜4のアルキレン基を
表す。また、nは0〜10の整数であり、なかでも特に
2〜4の範囲の整数が好ましい。
Here, R in the halogenated phosphoric ester represents a halogenated alkyl group having 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms, wherein the halogen atom represents chlorine or bromine. May be 1 or 2 or more. Among them, a 2-chloroethyl group and a 2-chloropropyl group are preferable because the antibacterial properties, the flame retardancy, and the effects of increasing the washing durability can be expected. X represents a direct bond or an alkylene group having 1 to 4 carbon atoms. Further, n is an integer of 0 to 10, particularly preferably an integer of 2 to 4.

【0019】ところが、上記のような難燃剤は、染色時
に染液中にブリードアウトし易く、せっかく難燃剤を含
有させても染色後は脱落してしまうので、充分な難燃性
を付与することができなかった。
However, the above-mentioned flame retardants are liable to bleed out into the dyeing liquor at the time of dyeing and fall off after dyeing even if the flame retardant is contained, so that sufficient flame retardancy must be imparted. Could not.

【0020】本発明者らは、この難燃剤のブリードアウ
ト現象について鋭意検討した結果、上記のような難燃剤
を含むアラミド繊維を染色する際、下記式で表される燐
系化合物を染色助剤として染液中に存在させるとき、難
燃剤のブリードアウトが抑制されて、染色後のアラミド
繊維に充分な難燃性を付与できることを究明した。
The present inventors have conducted intensive studies on the bleed-out phenomenon of the flame retardant. As a result, when dyeing the above-described aramid fiber containing the flame retardant, the phosphorus-based compound represented by the following formula was used as a dyeing aid. Bleed out of the flame retardant was suppressed when it was present in the dyeing liquor, and it was clarified that sufficient flame retardancy can be imparted to the aramid fiber after dyeing.

【0021】[0021]

【化5】 Embedded image

【0022】中でも、Rの炭素原子数が4である場合に
本発明の効果が顕著に発現し、具体的にはトリイソブチ
ルホスファートを最も好ましいものとして挙げることが
出来る。
Among them, when the number of carbon atoms of R is 4, the effect of the present invention is remarkably exhibited, and specifically, triisobutyl phosphate can be mentioned as the most preferable one.

【0023】即ち、易染剤であるアルキルベンゼンスル
ホン酸オニウム塩と、ハロゲン化燐酸エステル系難燃剤
等の難燃剤とを含有するメタ系アラミド繊維を染色する
に際し、上記の燐系化合物を染色助剤として染液中に存
在させれば、難燃剤の脱落が防止され、従来は両立が不
可能であった、染色性と難燃性という相反する性質が共
に良好なメタ系アラミド繊維が得られるのである。
That is, when dyeing a meta-aramid fiber containing an alkylbenzenesulfonic acid onium salt as an easy dye and a flame retardant such as a halogenated phosphate ester flame retardant, the above-mentioned phosphorus compound is used as a dyeing aid. As it is present in the dyeing liquor, the flame-retardant is prevented from falling off, and a meta-aramid fiber having both good dyeing properties and flame-retardant properties, which were conventionally incompatible, can be obtained. is there.

【0024】この際、燐系化合物をイソプロパノール中
に分散させた状態で使用すると、本発明の効果がさらに
顕著になる上、染色時の消泡効果も奏される。
At this time, when the phosphorus compound is used in a state of being dispersed in isopropanol, the effect of the present invention becomes more remarkable, and the defoaming effect at the time of dyeing is also exhibited.

【0025】この理由の詳細は不明であるが、イソプロ
パノールが繊維間空隙への浸透剤として寄与すると共
に、消泡効果も併せ持つためであると思われる。
Although the details of this reason are not clear, it is considered that isopropanol not only contributes as a penetrant to the interfiber space but also has an antifoaming effect.

【0026】上記燐系化合物の染色助剤としての使用量
は、0.1〜1ml/lの範囲が好ましく、0.2〜
0.5ml/lの範囲が特に好ましい。該使用量が0.
1ml/l未満では、本発明の効果が充分に奏されない
場合があり、一方、該使用量が1ml/lを超えると、
染色機(通常は液流染色機)が缶体汚染される場合があ
る。
The amount of the phosphorus compound used as a dyeing aid is preferably in the range of 0.1 to 1 ml / l,
A range of 0.5 ml / l is particularly preferred. The amount used is 0.
When the amount is less than 1 ml / l, the effect of the present invention may not be sufficiently exhibited. On the other hand, when the amount exceeds 1 ml / l,
A dyeing machine (usually a jet dyeing machine) may be contaminated in a can.

【0027】また、染色温度は、110℃以上150℃
以下が好ましく120℃以上がより好ましい。染色温度
が110℃未満の場合は、アラミド繊維の染色性が不十
分になる場合がある。染色温度は高いほど染色性(染着
性)が高まるものの、染料の分解や、アラミド繊維と他
の素材を複合している場合には他の素材の劣化の問題が
発生することもあるので、必ずしも高温にすればするほ
ど良いわけではなく、高々140℃程度であることが好
ましい。
The dyeing temperature is 110 ° C. or more and 150 ° C.
The following is preferable and 120 degreeC or more is more preferable. When the dyeing temperature is lower than 110 ° C., the dyeability of the aramid fiber may be insufficient. The higher the dyeing temperature, the higher the dyeing properties (dyeing properties), but if the dye is decomposed or the aramid fiber is combined with other materials, the problem of deterioration of other materials may occur. It is not always better to raise the temperature, but it is preferable that the temperature is at most about 140 ° C.

【0028】上記アラミド繊維を染色するに際しては、
繊維の状態で染色しても構わないし、該繊維を紡績糸
条、長繊維糸条、ロープ、織編物或いは不織布などの繊
維構造体に成形した後、染色しても構わない。
In dyeing the aramid fiber,
The fiber may be dyed, or the fiber may be formed into a fibrous structure such as a spun yarn, a long fiber yarn, a rope, a woven or knitted fabric, or a nonwoven fabric, and then dyed.

【0029】また、繊維構造体に成形する際には、アラ
ミド繊維と他の繊維とを混紡、混繊、交織編或いは混綿
することもできる。
When forming into a fibrous structure, aramid fibers and other fibers can be blended, blended, interwoven or knitted.

【0030】アラミド繊維に混合する他の繊維素材には
特に限定はないが、アラミド繊維の防炎性(難燃性)を
生かす上では難燃レーヨン、難燃加工綿、難燃ポリエス
テル、難燃ビニロンなどの難燃素材が好ましい。
The other fiber material mixed with the aramid fiber is not particularly limited. However, in order to make use of the flame resistance (flame retardancy) of the aramid fiber, flame retardant rayon, flame retardant processed cotton, flame retardant polyester, flame retardant Flame-retardant materials such as vinylon are preferred.

【0031】更に、上記アラミド繊維には、本発明の目
的を損なわない範囲内で紫外線吸収剤、安定剤、酸化防
止剤、帯電防止剤、蛍光増白剤、触媒、着色剤、無機微
粒子などを添加しても良い。
Further, the above-mentioned aramid fiber may contain an ultraviolet absorber, a stabilizer, an antioxidant, an antistatic agent, a fluorescent brightener, a catalyst, a colorant, inorganic fine particles and the like within a range not to impair the object of the present invention. It may be added.

【0032】上記アラミド繊維を染色する際に使用する
染料は、カチオン染料が好ましい。ここで、カチオン染
料とは水に可溶性で、塩基性を示す基を有する水溶性染
料をいい、アクリル繊維、天然繊維或いはカチオン可染
型ポリエステル繊維等の染色に多く用いられているもの
で、具体的にはジ及びトリアクリルメタン系、キノンイ
ミン(アジン、オキサジン、チアジン)系、キサンテン
系、メチン系(ポリメチン、アザメチン)、複素環アゾ
系(チアゾールアゾ、トリアゾールアゾ、ベンゾチアゾ
ールアゾ)、アントラキノン系などのカチオン染料があ
る。また、最近では塩基性基を封鎖することにより水分
散型にしたカチオン染料もあるが、両者とも用いること
が出来る。
The dye used for dyeing the aramid fiber is preferably a cationic dye. Here, the cationic dye refers to a water-soluble dye having a group that is soluble in water and has a basic property, and is widely used for dyeing acrylic fibers, natural fibers, or cationic dyeable polyester fibers. Specifically, di- and triacrylmethane-based, quinone imine (azine, oxazine, thiazine) -based, xanthene-based, methine-based (polymethine, azamethine), heterocyclic azo-based (thiazoleazo, triazoleazo, benzothiazoleazo), anthraquinone-based, etc. Of cationic dyes. Further, recently, some cationic dyes have been made water-dispersible by blocking a basic group, but both can be used.

【0033】[0033]

【実施例】以下、実施例により本発明を更に詳細に説明
する。尚、実施例中に記載の被染色物の評価は下記の方
法に従って行った。
The present invention will be described in more detail with reference to the following examples. In addition, evaluation of the to-be-dyed thing described in the Example was performed according to the following method.

【0034】(1)染色性 マクベス カラーアイ(Macbeth COLOR-EYE)モデルCE
−3100を用いて測定を行い、明度指数L*で表現し
た。明度指数L*は、JIS Z 8701(2度視野X
YZ系による色の表示方法)又はJIS Z 8728
(10度視野XYZ系による色の表示方法)に規定する
三刺激値のYを用いて、次式より求められるものであ
る。
(1) Dyeability Macbeth COLOR-EYE model CE
The measurement was performed using -3100, and expressed by a lightness index L *. The lightness index L * is JIS Z 8701 (2 degree field of view X
YZ color display method) or JIS Z 8728
Using the tristimulus value Y specified in (color display method using 10-degree visual field XYZ system), it can be obtained from the following equation.

【0035】[0035]

【数1】 (Equation 1)

【0036】明度指数L*は数値が小さいほど濃染化さ
れていることを示す。
The smaller the value of the lightness index L *, the deeper the color.

【0037】(2)防炎性(難燃性) JIS K 7201に準拠し、LOI(限界酸素指数)で
表した。LOI≧27の場合、防炎性(難燃性)に優れ
ていると言われている。
(2) Flame Retardancy (Flame Retardancy) Based on JIS K 7201, it was expressed by LOI (Limited Oxygen Index). When LOI ≧ 27, it is said to be excellent in flame resistance (flame retardancy).

【0038】(3)繊維中の難燃剤含有量 (株)リガク製蛍光X線分析装置を用い、濃度既知の縮合
型ハロゲン化燐酸エステルの標準サンプルから検量線を
作成して、繊維中の燐原子の濃度を求めた。この燐原子
が総て縮合型ハロゲン化燐酸エステルに由来するものと
して、難燃剤の含有量を換算計算して求めた。また、次
式により難燃剤保持率を算出し、ブリードアウト抑制効
果の指標とした。
(3) Flame retardant content in fiber Using a fluorescent X-ray analyzer manufactured by Rigaku Co., Ltd., a calibration curve was prepared from a standard sample of a condensed halogenated phosphoric ester having a known concentration, and the phosphorus content in the fiber was measured. The atomic concentration was determined. Assuming that all of the phosphorus atoms were derived from the condensed halogenated phosphoric ester, the content of the flame retardant was calculated and calculated. Further, the flame retardant retention rate was calculated by the following equation, and was used as an index of the bleed-out suppression effect.

【0039】[0039]

【数2】 (Equation 2)

【0040】[実施例1]IV1.35dl/gのポリ
−m−フェニレンイソフタルアミド30gをN−メチル
−2−ピロリドン110gに溶解し、さらに3.6gの
ドデシルベンゼンスルフォン酸トリブチルベンジルアン
モニウム塩と1.0gのトリス(βクロロプロピル)ホ
スフェートとを混合溶解し、減圧脱泡して紡糸ドープと
した。
Example 1 IV 1.35 dl / g of poly-m-phenyleneisophthalamide (30 g) was dissolved in N-methyl-2-pyrrolidone (110 g), and 3.6 g of tributylbenzylammonium dodecylbenzenesulfonate and 1 g 0.0 g of tris (β-chloropropyl) phosphate was mixed and dissolved, and defoamed under reduced pressure to obtain a spinning dope.

【0041】このドープを85℃に加温し、口径0.0
7ミリ、孔数200の紡糸口金から凝固浴中に湿式紡糸
した。凝固浴の組成は、塩化カルシウムが40重量%、
NMPが5重量%、水が55重量%であり、凝固浴の温
度は85℃であった。
The dope was heated to 85 ° C.
It was wet-spun from a spinning nozzle having a diameter of 7 mm and a hole number of 200 into a coagulation bath. The composition of the coagulation bath is 40% by weight calcium chloride,
NMP was 5% by weight, water was 55% by weight, and the temperature of the coagulation bath was 85 ° C.

【0042】この凝固浴中に紡出糸条を約10cm走行
させ6.2m/分の速度で引き出した。該糸条を水洗
し、95℃の温水で3.5倍に延伸して120℃ロール
で乾燥した後、280℃の熱板上で1.1倍に延伸し
て、444dtex/200フィラメントの延伸糸を得
た。全延伸倍率は3.5倍であった。該延伸糸から常法
により紡績糸を得、次いで該紡績糸を製織して平織物
(密度:経42本/in、緯46本/in)を得た。
The spun yarn was run about 10 cm in this coagulation bath and pulled out at a speed of 6.2 m / min. The yarn was washed with water, stretched 3.5 times with hot water at 95 ° C., dried with a roll at 120 ° C., and then stretched 1.1 times on a hot plate at 280 ° C. to stretch 444 dtex / 200 filaments. Yarn was obtained. The total stretching ratio was 3.5 times. A spun yarn was obtained from the drawn yarn by an ordinary method, and then the spun yarn was woven to obtain a plain woven fabric (density: warp 42 / in, weft 46 / in).

【0043】得られた織物を1g/lのスコアロール#
400(花王製)で、80℃で20分間精練し、水洗・
乾燥後、190℃で1分間プレ・セットした。次いで、
下記染浴で常温から2℃/分の速度で昇温し、135℃
で60分間染色した。 ・染料 C.I.Basic Blue 54(Kayacryl Blue GSL-ED(日本化薬製) 4 %owf ・硝酸Na 25 g/l ・酢酸 0.5 cc/l ・染色助剤 (トリイソブチルホスファート) 0.5 cc/l ・浴比 1:30
The obtained woven fabric was score rolled with 1 g / l.
400 (manufactured by Kao), scour at 80 ° C for 20 minutes,
After drying, it was pre-set at 190 ° C. for 1 minute. Then
The temperature is raised at a rate of 2 ° C./min from room temperature in the following dyeing bath to 135 ° C.
For 60 minutes.・ Dye CIBasic Blue 54 (Kayacryl Blue GSL-ED (manufactured by Nippon Kayaku) 4% owf ・ Na nitrate 25 g / l ・ Acetic acid 0.5 cc / l ・ Dyeing aid (triisobutyl phosphate) 0.5 cc / l ・ Bath ratio 1:30

【0044】染色後、染色布帛を取り出し、次いで、染
色された試料を下記洗浄浴で80℃×20分間還元洗浄
した。 ・NaOH 1g/l ・ハイドロサルファイト 1g/l ・アミラジンD (第一工業製薬製、非イオン活性剤) 1g/l 還元洗浄後、十分水洗して乾燥、ファイナル・セット
(180℃×1分間)した。結果を表1に示す。
After dyeing, the dyed fabric was taken out, and then the dyed sample was reduced and washed in a washing bath described below at 80 ° C. for 20 minutes.・ NaOH 1g / l ・ Hydrosulfite 1g / l ・ Amilazine D (Daiichi Kogyo Seiyaku, non-ionic activator) 1g / l After reducing and washing, thoroughly wash with water and dry, final set (180 ° C × 1 minute) did. Table 1 shows the results.

【0045】[実施例2]実施例1において、染色助剤
であるトリイソブチルホスファートをイソプロパノール
中に分散させた状態で使用した以外は、実施例1と同様
に実施した。結果を表1に示す。
Example 2 The procedure of Example 1 was repeated, except that triisobutyl phosphate, a dyeing aid, was used in a state of being dispersed in isopropanol. Table 1 shows the results.

【0046】[比較例1]実施例1において、染色助剤
であるトリイソブチルホスファートを使用しなかった以
外は、実施例1と同様に実施した。結果を表1に示す。
Comparative Example 1 The procedure of Example 1 was repeated, except that triisobutyl phosphate was not used as a dyeing aid. Table 1 shows the results.

【0047】[比較例2]実施例1において、トリイソ
ブチルホスファートに代えてシリコン系の染色助剤(消
泡剤)を使用した以外は実施例1と同様に実施した。結
果を表1に示す。
Comparative Example 2 The procedure of Example 1 was repeated, except that a silicon-based dyeing assistant (antifoaming agent) was used instead of triisobutyl phosphate. Table 1 shows the results.

【0048】[0048]

【表1】 [Table 1]

【0049】[0049]

【発明の効果】本発明によれば、難燃剤の染色液中への
ブリードアウトが抑制され、染色性と難燃性という相反
する性質が共に良好なアラミド繊維、就中メタ系アラミ
ド繊維が得られる。
According to the present invention, bleed-out of a flame retardant into a dyeing solution is suppressed, and aramid fibers, particularly meta-aramid fibers, are obtained, which are excellent in both contradictory properties of dyeability and flame retardancy. Can be

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) // D01F 6/90 331 D01F 6/90 331 (72)発明者 高橋 茂 大阪府茨木市耳原3丁目4番1号 帝人株 式会社大阪研究センター内 Fターム(参考) 3B154 AA08 AB20 BB45 BD02 BE05 BE10 DA03 4H028 AA35 AA37 BA04 BA05 4H057 AA02 BA03 CA31 CA37 CB21 CB23 CC01 CC02 DA01 DA22 4L035 BB03 BB16 BB17 BB69 BB82 BB89 BB91 EE14 EE20 FF10 GG04 JJ25 KK05 MG04 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // D01F 6/90 331 D01F 6/90 331 (72) Inventor Shigeru Takahashi 3-4 Mihara, Ibaraki-shi, Osaka No. 1 Teijin Ltd. Osaka Research Center F-term (reference) 3B154 AA08 AB20 BB45 BD02 BE05 BE10 DA03 4H028 AA35 AA37 BA04 BA05 4H057 AA02 BA03 CA31 CA37 CB21 CB23 CC01 CC02 DA01 DA22 4L035 BB03 BB16 BB17 BB69 FF10 GG04 JJ25 KK05 MG04

Claims (7)

【特許請求の範囲】[Claims] 【請求項1】 難燃剤を含む全芳香族ポリアミド繊維を
染色するに際し、下記式(I)で表す燐系化合物を染色
助剤として併用することを特徴とする全芳香族ポリアミ
ド繊維の染色方法。 【化1】
1. A method for dyeing a wholly aromatic polyamide fiber, which comprises using a phosphorus compound represented by the following formula (I) as a dyeing aid when dyeing a wholly aromatic polyamide fiber containing a flame retardant. Embedded image
【請求項2】 燐系化合物がイソプロパノール中に分散
されている請求項1記載の全芳香族ポリアミド繊維の染
色方法。
2. The method for dyeing a wholly aromatic polyamide fiber according to claim 1, wherein the phosphorus compound is dispersed in isopropanol.
【請求項3】 全芳香族ポリアミド繊維がアルキルベン
ゼンスルホン酸オニウム塩を含む全芳香族ポリアミド繊
維である請求項1又は2記載の全芳香族ポリアミド繊維
の染色方法。
3. The method for dyeing a wholly aromatic polyamide fiber according to claim 1, wherein the wholly aromatic polyamide fiber is a wholly aromatic polyamide fiber containing an onium salt of alkylbenzenesulfonic acid.
【請求項4】 難燃剤が燐酸エステル及び/又は縮合型
燐酸エステル系難燃剤である請求項1、2又は3記載の
全芳香族ポリアミド繊維の染色方法。
4. The method for dyeing a wholly aromatic polyamide fiber according to claim 1, wherein the flame retardant is a phosphate ester and / or a condensed phosphate ester flame retardant.
【請求項5】 全芳香族ポリアミド繊維がメタ系芳香族
ポリアミド繊維である請求項1〜4のいずれか1項に記
載の全芳香族ポリアミド繊維の染色方法。
5. The method for dyeing a wholly aromatic polyamide fiber according to claim 1, wherein the wholly aromatic polyamide fiber is a meta-based aromatic polyamide fiber.
【請求項6】 染色温度が110℃以上である請求項1
〜5のいずれか1項に記載の全芳香族ポリアミド繊維の
染色方法。
6. The dyeing temperature is 110 ° C. or higher.
6. The method for dyeing a wholly aromatic polyamide fiber according to any one of items 5 to 5.
【請求項7】 染色に使用する染料がカチオン染料であ
る請求項1〜6のいずれか1項に記載の全芳香族ポリア
ミド繊維の染色方法。
7. The method for dyeing a wholly aromatic polyamide fiber according to claim 1, wherein the dye used for dyeing is a cationic dye.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009256844A (en) * 2008-04-21 2009-11-05 Teijin Techno Products Ltd Method for dyeing p-aramid fiber, and textile fiber structural product
KR101383087B1 (en) * 2012-11-05 2014-04-08 김상철 Method of dyeing aromatic polyamide fiber

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51109057A (en) * 1975-03-19 1976-09-27 Unitika Ltd NANNENSEINOKAIRYOSARETA HOKOZOKUHORIAMIDOSEIKEIHINNO SEIZOHO
JPS58163722A (en) * 1982-03-16 1983-09-28 Asahi Chem Ind Co Ltd Production of flame-retardant polyamide fiber or film
JPS58203116A (en) * 1982-05-18 1983-11-26 Asahi Chem Ind Co Ltd Flame-retardant poly (p-phenylene terephthalamide) fiber
JPS63145416A (en) * 1986-11-29 1988-06-17 Asahi Chem Ind Co Ltd Para orientation type aramid yarn
JPH0881827A (en) * 1994-09-09 1996-03-26 Teijin Ltd Easily dyeable meta-aromatic polyamide fiber
JPH0995870A (en) * 1995-09-29 1997-04-08 Teijin Ltd Aromatic polyamide-containing dyed textile fabric and dyeing of aromatic polyamide-containing textile fabric
JP2000328364A (en) * 1999-05-17 2000-11-28 Teijin Ltd Easily dyeable, meta type aromatic polyamide fiber

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51109057A (en) * 1975-03-19 1976-09-27 Unitika Ltd NANNENSEINOKAIRYOSARETA HOKOZOKUHORIAMIDOSEIKEIHINNO SEIZOHO
JPS58163722A (en) * 1982-03-16 1983-09-28 Asahi Chem Ind Co Ltd Production of flame-retardant polyamide fiber or film
JPS58203116A (en) * 1982-05-18 1983-11-26 Asahi Chem Ind Co Ltd Flame-retardant poly (p-phenylene terephthalamide) fiber
JPS63145416A (en) * 1986-11-29 1988-06-17 Asahi Chem Ind Co Ltd Para orientation type aramid yarn
JPH0881827A (en) * 1994-09-09 1996-03-26 Teijin Ltd Easily dyeable meta-aromatic polyamide fiber
JPH0995870A (en) * 1995-09-29 1997-04-08 Teijin Ltd Aromatic polyamide-containing dyed textile fabric and dyeing of aromatic polyamide-containing textile fabric
JP2000328364A (en) * 1999-05-17 2000-11-28 Teijin Ltd Easily dyeable, meta type aromatic polyamide fiber

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009256844A (en) * 2008-04-21 2009-11-05 Teijin Techno Products Ltd Method for dyeing p-aramid fiber, and textile fiber structural product
KR101383087B1 (en) * 2012-11-05 2014-04-08 김상철 Method of dyeing aromatic polyamide fiber

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