JPH07102418A - Flame-retardant polyester fiber - Google Patents
Flame-retardant polyester fiberInfo
- Publication number
- JPH07102418A JPH07102418A JP24528693A JP24528693A JPH07102418A JP H07102418 A JPH07102418 A JP H07102418A JP 24528693 A JP24528693 A JP 24528693A JP 24528693 A JP24528693 A JP 24528693A JP H07102418 A JPH07102418 A JP H07102418A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- acid
- polyester
- phosphorus
- diethylene glycol
- 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
Landscapes
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は優れた難燃性と耐光性を
合わせ持ったポリエステル繊維、詳しくはカルボキシホ
スフィン酸で変性され、ジエチレングリコールが４モル
％以下であるポリエステルから得られた難燃性ポリエス
テル繊維に関する。FIELD OF THE INVENTION The present invention relates to a polyester fiber having excellent flame retardancy and light resistance, more specifically, a flame retardant obtained from a polyester modified with carboxyphosphinic acid and having a diethylene glycol content of 4 mol% or less. Regarding polyester fibers.
【０００２】[0002]
【従来の技術】従来よりポリエステル繊維はその優れた
力学物性、易加工性から衣類、インテリア、詰め綿、不
織布、産業用資材等、様々な分野で使用されている。近
年の防災意識の高まりの中で各種素材に対する難燃化の
要求も強くなっており、ポリエステル繊維に関しても難
燃化のために様々な研究が行われている。例えば、ポリ
マー製造時に難燃剤を添加して共重合またはブレンドす
る方法、成型品の製造時に難燃剤を練り込む方法、さら
にはポリエステルからの成型品を後加工し、成型品の表
面あるいは内部までに難燃剤を付着あるいはしみこませ
る方法などが提案されており、繊維の場合にもこれらの
方法が用いられている。2. Description of the Related Art Conventionally, polyester fibers have been used in various fields such as clothes, interiors, stuffed cotton, non-woven fabrics and industrial materials because of their excellent mechanical properties and easy processability. With the recent increase in awareness of disaster prevention, the demand for flame retardancy on various materials is also increasing, and various researches have also been conducted on polyester fibers for flame retardancy. For example, a method of copolymerizing or blending with a flame retardant at the time of polymer production, a method of kneading a flame retardant at the time of production of a molded product, and further post-processing a molded product from polyester to the surface or inside of the molded product. Methods for attaching or impregnating a flame retardant have been proposed, and these methods are also used for fibers.
【０００３】上記の方法のうち、後加工により難燃性を
付与する方法は、風合いが粗雑になったり、洗濯により
難燃剤が脱落して性能が低下したりする欠点がある。ま
た難燃剤を練り込む方法では、製造工程において難燃剤
の滲みだしがおこる欠点がある。それに対しポリマー製
造時に難燃剤を共重合させる方法では上述したような欠
点を克服でき、最も工業的価値が高いものである。この
難燃剤を共重合する方法としては、これまでにも多くの
方法が提案されており、例えば特公昭４９−２２９５８
号公報にはリン化合物としてリン酸エステルをポリエス
テルに共重合することが開示されているが、目的とする
難燃性を付与させる量までリン化合物を配合すると、３
次元化によりポリエステルのゲル化を生じるために、繊
維としたときの物性が著しく低下するという欠点を有し
ている。また特公昭３６−２１０５０号公報、特公昭３
８−９４４７号公報に記載の方法では、リン化合物とし
てホスホン酸またはホスホン酸エステル類を用いている
が、ポリマー製造時にリン化合物の飛散が多く、目的と
するリン量を配合できない。また特公昭５５−４１６１
０号公報記載の方法では、オキサホスファンオキシドと
イタコン酸から誘導したリン化合物を共重合しており、
この化合物を用いた場合上述したような問題は解決でき
るが、リン化合物の構造が複雑な多環構造をとるため、
結晶性が阻害されたり融点が低下したり、また耐熱性や
耐光性が劣ったりする。また合成が煩雑で価格が高くな
り、工業的には問題がある。Of the above-mentioned methods, the method of imparting flame retardancy by post-processing has the drawbacks that the texture becomes rough and that the flame retardant drops off by washing and the performance deteriorates. Further, the method of kneading the flame retardant has a drawback that the flame retardant exudes in the manufacturing process. On the other hand, the method of copolymerizing a flame retardant at the time of polymer production can overcome the above-mentioned drawbacks and has the highest industrial value. As a method of copolymerizing this flame retardant, many methods have been proposed so far, for example, Japanese Patent Publication No. 22958/1974.
The publication discloses copolymerizing a phosphoric acid ester with a polyester as a phosphorus compound. However, when the phosphorus compound is blended to an amount that imparts the desired flame retardancy, 3
Since the polyester gels due to the dimensionalization, it has a drawback that the physical properties of the fiber are remarkably deteriorated. Also, Japanese Examined Patent Publication No. 36-21050 and Japanese Examined Patent Publication No. 3
In the method described in Japanese Patent Application Laid-Open No. 8-9447, phosphonic acid or phosphonic acid esters are used as the phosphorus compound, but the phosphorus compound is often scattered during the production of the polymer, and the target phosphorus amount cannot be blended. In addition, Japanese Examined Japanese Patent Publication 55-4161
In the method described in JP-A-0, the oxaphosphane oxide and the phosphorus compound derived from itaconic acid are copolymerized,
When this compound is used, the above-mentioned problems can be solved, but since the phosphorus compound has a complex polycyclic structure,
Crystallinity is impaired, melting point is lowered, and heat resistance and light resistance are deteriorated. Further, the synthesis is complicated and the price is high, which is industrially problematic.
【０００４】また特公昭５３−１３４７９号公報にはカ
ルボキシホスフィン酸を共重合する方法が開示されてい
る。このカルボキシホスフィン酸を共重合した場合、ポ
リマーのゲル化、リン化合物の飛散といった問題もな
く、価格も比較的安価であり、工業的価値の高いもので
ある。しかし、ホスフィン酸が強い酸であるため得られ
たポリマーは、製造工程で副成するジエチレングリコー
ルの含有率が高くなることが避けられず、このポリマー
を用いて繊維とした場合、耐光性が悪くなるという欠点
がある。したがって難燃剤としてカルボキシホスフィン
酸を用いた難燃性ポリエステル繊維で耐光性に優れた繊
維は得られていないのが実情である。Further, Japanese Patent Publication No. 53-13479 discloses a method of copolymerizing carboxyphosphinic acid. When this carboxyphosphinic acid is copolymerized, there are no problems such as gelation of the polymer and scattering of the phosphorus compound, the price is relatively low, and the industrial value is high. However, since the phosphinic acid is a strong acid, the obtained polymer inevitably has a high content of diethylene glycol, which is a by-product in the manufacturing process, and when this polymer is used as a fiber, the light resistance deteriorates. There is a drawback that. Therefore, the fact is that flame-retardant polyester fibers using carboxyphosphinic acid as a flame retardant have not been obtained with excellent light resistance.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記問題を解
決するためになされたものであって、カルボキシホスフ
ィン酸を難燃剤として用いて、優れた難燃性と耐光性を
合わせ持つポリエステル繊維を提供することを課題とす
るものである。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and uses carboxyphosphinic acid as a flame retardant to produce a polyester fiber having excellent flame retardancy and light resistance. The challenge is to provide.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討した結果、難燃剤としてカル
ボキシホスフィン酸およびその誘導体を用い、ポリマー
中に含まれるジエチレングリコールの量を少なくした難
燃ポリエステルを用いて繊維にすることによって、優れ
た難燃性と耐光性を合わせもった難燃ポリエステル繊維
を得たのである。すなわち本発明の難燃ポリエステル繊
維は、主たる構成単位がエチレンテレフタレートであ
り、下記一般式化２で表されるリン化合物をリン元素と
して０．１〜４．０重量％共重合しているポリエステル
であって、ジエチレングリコールの含有量がジオール成
分の４モル％以下である共重合ポリエステルから形成さ
れる難燃性ポリエステル繊維である。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have used carboxyphosphinic acid and its derivatives as a flame retardant and reduced the amount of diethylene glycol contained in the polymer. By using flame-retardant polyester to form fibers, flame-retardant polyester fibers having excellent flame retardancy and light resistance were obtained. That is, the flame-retardant polyester fiber of the present invention is a polyester in which the main constituent unit is ethylene terephthalate and 0.1 to 4.0% by weight of a phosphorus compound represented by the following general formula 2 is copolymerized as a phosphorus element. It is a flame-retardant polyester fiber formed from a copolyester having a diethylene glycol content of 4 mol% or less of the diol component.
【０００７】[0007]
【化２】 （ただし式中Ｒ1 は炭素原子数１〜１８の１価の有機基
をあらわし、Ｒ2 は水素原子または炭素原子数１〜１８
の１価の有機基を表す。）[Chemical 2] (In the formula, R 1 represents a monovalent organic group having 1 to 18 carbon atoms, and R 2 represents a hydrogen atom or 1 to 18 carbon atoms.
Represents a monovalent organic group. )
【０００８】以下本発明を詳細に説明する。まず本発明
のポリエステル繊維に難燃剤として用いられるリン化合
物としては、（２−カルボキシエチル）メチルホスフィ
ン酸、（２−カルボキシエチル）フェニルホスフィン
酸、（２−メトキシカルボニルエチル）フェニルホスフ
ィン酸、（２−ヒドロキシエトキシカルボニルエチル）
フェニルホスフィン酸、ｐ−（２−カルボキシエチル）
クロロフェニルホスフィン酸、（２−フェノキシカルボ
ニルエチル）ヘキシルホスフィン酸等が挙げられる。こ
のうち特に好ましくは（２−カルボキシエチル）メチル
ホスフィン酸、（２−カルボキシエチル）フェニルホス
フィン酸である。これらリン化合物はポリエステルの製
造時に添加されるが、ホスフィン酸は、その酸性度がカ
ルボン酸に比べて非常に強く、そのためポリエステルの
製造時にエーテル結合を多量に副生してしまう。ポリエ
ステルの主たる構成単位がエチレンテレフタレートの場
合、ジエチレングリコールを多量に副生してしまうので
ある。The present invention will be described in detail below. First, as the phosphorus compound used as the flame retardant in the polyester fiber of the present invention, (2-carboxyethyl) methylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, (2-methoxycarbonylethyl) phenylphosphinic acid, (2 -Hydroxyethoxycarbonylethyl)
Phenylphosphinic acid, p- (2-carboxyethyl)
Examples include chlorophenylphosphinic acid and (2-phenoxycarbonylethyl) hexylphosphinic acid. Of these, (2-carboxyethyl) methylphosphinic acid and (2-carboxyethyl) phenylphosphinic acid are particularly preferable. These phosphorus compounds are added during the production of polyester, and the acidity of phosphinic acid is much stronger than that of carboxylic acid, so that a large amount of ether bonds are by-produced during the production of polyester. When the main constituent unit of polyester is ethylene terephthalate, a large amount of diethylene glycol is produced as a by-product.
【０００９】エーテル結合を多量に含んだポリマーを繊
維にした場合、問題となるのは耐光性である。本発明の
難燃性ポリエステル繊維では、エーテル結合をもつジエ
チレングリコールの量を４モル％以下に抑制したポリエ
ステルを用いることにより、優れた難燃性と耐光性を合
わせ持つことが可能となったのである。ジエチレングリ
コール含有量が４モル％を超えると、繊維に成形した場
合、耐光性が劣るだけでなく、収縮率が大きくなり、融
点が低下したりするため寸法安定性が悪くなったり、着
色したりするという問題があるので好ましくない。When a polymer containing a large amount of ether bonds is used as a fiber, the problem is light resistance. In the flame-retardant polyester fiber of the present invention, by using the polyester in which the amount of diethylene glycol having an ether bond is suppressed to 4 mol% or less, it becomes possible to have both excellent flame retardancy and light resistance. . When the content of diethylene glycol exceeds 4 mol%, when formed into a fiber, not only the light resistance is deteriorated, but also the shrinkage ratio is increased and the melting point is lowered, so that the dimensional stability is deteriorated or the coloring occurs. It is not preferable because there is a problem.
【００１０】本発明において使用されるリン化合物はポ
リマー中のリン原子含有量が０．１〜４．０重量％とな
るように添加される。好ましくは０．３〜１．０重量％
である。リン化合物の添加量がこの範囲より少ない場合
には充分な難燃性能を発現せず、また逆に多い場合に
は、ポリエステル本来がもつ物理的性質を損なうだけで
なく、ポリエステル繊維を製造する際の操業性も低下す
るので好ましくない。The phosphorus compound used in the present invention is added so that the phosphorus atom content in the polymer is 0.1 to 4.0% by weight. Preferably 0.3-1.0% by weight
Is. When the addition amount of the phosphorus compound is less than this range, sufficient flame retardant performance is not exhibited, and when the addition amount is large, not only the physical properties inherent to the polyester are impaired, but also when the polyester fiber is produced. Is also not preferable because the operability of is also reduced.
【００１１】本発明において主たる構成単位がエチレン
テレフタレートであるポリエステルとは、反復構成単位
の７０モル％以上がエチレンテレフタレートであり、原
料成分としてはテレフタル酸またはテレフタル酸ジメチ
ルとエチレングリコールである。共重合成分としては前
記一般式化２で表したリン化合物を用いるが、その他に
イソフタル酸、２，６−ナフタレンジカルボン酸、５−
ナトリウムスルホイソフタル酸等の芳香族ジカルボン
酸、アジピン酸、セバシン酸、アゼライン酸、ヘキサヒ
ドロテレフタル酸等の脂肪族ジカルボン酸、トリメチレ
ングリコール、テトラメチレングリコール、ネオペンチ
ルグリコール、１，４−シクロヘキサンジオール等のグ
リコールまたはこれらの混合物を用いることも可能であ
る。In the present invention, the polyester whose main constituent unit is ethylene terephthalate is ethylene terephthalate in which 70 mol% or more of the repeating constituent unit is ethylene terephthalate, and the raw material components are terephthalic acid or dimethyl terephthalate and ethylene glycol. As the copolymerization component, the phosphorus compound represented by the general formula 2 is used, but in addition, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-
Aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, adipic acid, sebacic acid, azelaic acid, aliphatic dicarboxylic acids such as hexahydroterephthalic acid, trimethylene glycol, tetramethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, etc. It is also possible to use glycols or mixtures thereof.
【００１２】本発明において、ジエチレングリコール含
有量を４モル％以下にする方法としては、例えば、前記
一般式化２で示されるリン化合物を予め塩基性有機化合
物で中和しておく方法が挙げられ、塩基性有機化合物と
してはトリエチルアミン、シクロヘキシルアミン、トリ
ーｎ−ブチルアミン、ピリジン、アニリン等のアミン化
合物、トリエチルアミン酢酸塩、ピリジン酢酸塩等の有
機酢酸塩、ジメチルアセトアミド、ジメチルホルムアミ
ド等のカルボン酸アミドが挙げられる。In the present invention, examples of the method for reducing the content of diethylene glycol to 4 mol% or less include a method of previously neutralizing the phosphorus compound represented by the general formula 2 with a basic organic compound, Examples of the basic organic compound include amine compounds such as triethylamine, cyclohexylamine, tri-n-butylamine, pyridine and aniline, organic acetates such as triethylamine acetate and pyridine acetate, and carboxylic acid amides such as dimethylacetamide and dimethylformamide. .
【００１３】本発明で使用される難燃性ポリエステル
は、例えば以下の方法で製造される。まず前記一般式化
２で表されるリン化合物を塩基性有機化合物と反応させ
たあとで、テレフタル酸、エチレングリコールと共に常
圧または加圧下、２００〜２５０℃でエステル化反応を
行い、さらに三酸化アンチモンを重合触媒として用い
て、１ｍｍＨｇ以下の高真空下、２５０〜３００℃で重
縮合反応を行う事により固有粘度０．５以上、ジエチレ
ングリコールの含有量４モル％以下のポリエステルを得
ることができる。なお通常に用いられている艶消し剤や
カーボンブラック等の顔料、可塑剤、安定剤、静電剤を
添加してもよい。The flame-retardant polyester used in the present invention is produced, for example, by the following method. First, the phosphorus compound represented by the general formula 2 is reacted with a basic organic compound, and then an esterification reaction is performed with terephthalic acid and ethylene glycol at 200 to 250 ° C. under normal pressure or pressure, and further trioxidation is performed. A polyester having an intrinsic viscosity of 0.5 or more and a diethylene glycol content of 4 mol% or less can be obtained by performing a polycondensation reaction at 250 to 300 ° C. under high vacuum of 1 mmHg or less using antimony as a polymerization catalyst. In addition, commonly used matting agents, pigments such as carbon black, plasticizers, stabilizers and electrostatic agents may be added.
【００１４】本発明において上記難燃性ポリエステルを
用いて繊維を製造する方法としては、従来公知の方法を
採用することができる。紡糸速度は一般的に用いられる
７００〜２０００ｍ／分あるいはＰＯＹ領域といわれる
２０００〜４０００ｍ／分でもよい。用途により、仮
撚、捲縮を施してよく、繊維の断面形状も丸、三角、中
空など自由である。また他のポリエステル、ポリエチレ
ン等との複合紡糸も可能である。In the present invention, a conventionally known method can be adopted as a method for producing a fiber using the flame-retardant polyester. The spinning speed may be 700 to 2000 m / min which is generally used, or 2000 to 4000 m / min which is referred to as the POY region. Depending on the application, false twisting or crimping may be applied, and the cross-sectional shape of the fiber may be round, triangular, hollow, or the like. Further, composite spinning with other polyester, polyethylene, etc. is also possible.
【００１５】[0015]
【作用】以上詳述したように本発明の繊維は、前記化２
で示すカルボキシホスフィン酸を難燃剤として用いるこ
とにより優れた難燃性能を有し、かつジエチレングリコ
ールの含有量の少ないポリマーを繊維とすることにより
耐光性も改善された難燃ポリエステル繊維である。従来
カルボキシホスフィン酸を共重合するとＰ−Ｏ−Ｃ結合
の弱さのため、耐光性がやや悪くなり、さらにジエチレ
ングリコールの副生が繊維の耐光性を一層悪化させてい
たが、本発明によりジエチレングリコールの含有量を抑
えることができた理由としては、リン化合物を予め塩基
性有機化合物で中和しておき、製造工程における酸の影
響が少なくできたためと思われる。As described in detail above, the fiber of the present invention is
Is a flame-retardant polyester fiber having excellent flame-retardant performance by using carboxyphosphinic acid as a flame-retardant and having improved light resistance by using a polymer having a low diethylene glycol content. Conventionally, when carboxyphosphinic acid is copolymerized, the light resistance is slightly deteriorated due to the weak P—O—C bond, and the by-product of diethylene glycol further deteriorates the light resistance of the fiber. It is considered that the reason why the content could be suppressed is that the phosphorus compound was previously neutralized with a basic organic compound, and the influence of acid in the production process could be reduced.
【００１６】[0016]
【実施例】以下に実施例を用いて本発明をより具体的に
説明するが、本発明はこれに限定されるものではない。
なお実施例中、部とあるのは重量部を、パーセントとあ
るのは重量パーセントを意味し、固有粘度はフェノール
−１，１，２，２−テトラクロロエタン混合溶媒中（重
量比３：２）３０℃で測定した値より求めたものであ
る。ジエチレングリコール（ＤＥＧ）の含有量はポリマ
ー中の全グリコール単位中のＤＥＧのモル％で表した。
難燃性はＪＩＳＬ−１０９１ Ｄ法に準じて評価した。
また耐光性は紫外線時間照射前後の糸の強力保持率で評
価した。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the examples, “part” means “part by weight” and “percent” means “weight%”, and the intrinsic viscosity is in a phenol-1,1,2,2-tetrachloroethane mixed solvent (weight ratio 3: 2). It is obtained from the value measured at 30 ° C. The content of diethylene glycol (DEG) was expressed as mol% of DEG in all glycol units in the polymer.
Flame retardancy was evaluated according to JIS L-1091 D method.
The light resistance was evaluated by the tenacity retention rate of the yarn before and after irradiation with ultraviolet rays.
【００１７】実施例１ 撹拌機、温度計、滴下ロートのついた４つ口フラスコ
に、（２−カルボキシエチル）フェニルホスフィン酸６
２部と１００部のエチレングリコールを仕込み、５０〜
６０℃に加熱して溶解した。さらに、トリエチルアミン
５９部を滴下ロートより温度を５０℃以下に保ちながら
滴下して反応させた。次に、撹拌機、蒸留塔、圧力調整
器をそなえたステンレス製オートクレーブにテレフタル
酸１２３６部、エチレングリコール９５５部、及び上記
反応で得たリン化合物のエチレングリコール溶液を仕込
み、さらに三酸化アンチモンを０．５５部、トリエチル
アミン１１部加えて、２３０℃、ゲージ圧２．５ｋｇ／
ｃｍ2でエステル化により生成する水を系外に逐次除去
しながら２時間エステル化反応を行った。続いて１時間
で系の温度を２７５℃まで昇温してこの間に系の圧力を
徐々に減じて０．１ｍｍＨｇとし、この条件下で２時間
重縮合を行った。得られたポリマーの〔η〕は０．６３
でリン含有量は５９８０ｐｐｍ、ＤＥＧ含有量は２．４
％であった。このポリマーを常法により、紡糸、延伸し
て得た糸の耐炎回数は５回、耐光性は７９％であった。Example 1 (2-carboxyethyl) phenylphosphinic acid 6 was placed in a four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel.
Charge 2 parts and 100 parts of ethylene glycol, 50 ~
It melt | dissolved by heating at 60 degreeC. Furthermore, 59 parts of triethylamine was added dropwise from a dropping funnel while maintaining the temperature at 50 ° C. or lower to react. Next, 1236 parts of terephthalic acid, 955 parts of ethylene glycol, and an ethylene glycol solution of the phosphorus compound obtained by the above reaction were charged into a stainless steel autoclave equipped with a stirrer, a distillation column, and a pressure regulator, and antimony trioxide was added to 0%. 0.55 parts, 11 parts of triethylamine are added, and the temperature is 230 ° C. and the gauge pressure is 2.5 kg /
The esterification reaction was carried out for 2 hours while successively removing the water generated by the esterification at cm 2 from the system. Subsequently, the temperature of the system was raised to 275 ° C. in 1 hour, during which the system pressure was gradually reduced to 0.1 mmHg, and polycondensation was carried out for 2 hours under these conditions. [Η] of the obtained polymer was 0.63.
The phosphorus content was 5980 ppm, and the DEG content was 2.4.
%Met. The yarn obtained by spinning and drawing this polymer by a conventional method had a flame resistance number of 5 and a light resistance of 79%.
【００１８】比較例１ 撹拌機、蒸留塔、圧力調整器をそなえたステンレス製オ
ートクレーブにテレフタル酸１２３６部、エチレングリ
コール１０５５部、（２−カルボキシエチル）フェニル
ホスフィン酸６２部を仕込み、さらに三酸化アンチモン
を０．５５部、トリエチルアミン１１部加えて、２３０
℃、ゲージ圧２．５ｋｇ／ｃｍ2 でエステル化により生
成する水を系外に逐次除去しながら２時間エステル化反
応を行った。続いて１時間で系の温度を２７５℃まで昇
温してこの間に系の圧力を徐々に減じて０．１ｍｍＨｇ
とし、この条件下で２時間重縮合を行った。得られたポ
リマーの〔η〕は０．６４でリン含有量は５９４０ｐｐ
ｍ、ＤＥＧ含有量は５．４％であった。このポリマーを
常法により、紡糸、延伸して得た糸の耐炎回数は５回、
耐光性は６２％であった。Comparative Example 1 A stainless steel autoclave equipped with a stirrer, a distillation column and a pressure regulator was charged with 1236 parts of terephthalic acid, 1055 parts of ethylene glycol and 62 parts of (2-carboxyethyl) phenylphosphinic acid, and further antimony trioxide. 0.55 parts and triethylamine 11 parts,
The esterification reaction was carried out for 2 hours while successively removing the water produced by the esterification from the system at 0 ° C. and a gauge pressure of 2.5 kg / cm 2 . Subsequently, the temperature of the system was raised to 275 ° C. in 1 hour, and the pressure of the system was gradually reduced during this time to 0.1 mmHg.
And polycondensation was performed for 2 hours under these conditions. The obtained polymer [η] was 0.64 and the phosphorus content was 5940 pp.
The m and DEG contents were 5.4%. The yarn obtained by spinning and drawing this polymer by a conventional method has a flame resistance number of 5 times.
The light resistance was 62%.
【００１９】実施例２〜４、比較例２〜４ 実施例１において、難燃剤を表１に示す化合物に変更し
た以外はそれぞれ実施例１と同様にしてポリマーを製造
し、紡糸、延伸して難燃性、耐光性を評価した。その結
果を表１に併記する。Examples 2 to 4 and Comparative Examples 2 to 4 Polymers were produced, spun and stretched in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the flame retardant. The flame resistance and light resistance were evaluated. The results are also shown in Table 1.
【００２０】[0020]
【表１】 表中ＤＥＧは、ジエチレングリコールを示す。[Table 1] DEG in the table represents diethylene glycol.
【００２１】[0021]
【発明の効果】表１より明らかなように、ＤＥＧ含有量
が低い繊維は耐光性が７７％以上もあり、かつ難燃性も
優れていることが判る。以上、従来では難燃剤として有
用であるカルボキシホスフィン酸を用いると、耐光性が
悪く実用化できなかったという欠点を、本発明により解
決することができ、その用途を拡大することができるの
で、産業界に寄与すること大である。As is clear from Table 1, fibers having a low DEG content have a light resistance of 77% or more and are excellent in flame retardancy. As described above, when carboxyphosphinic acid, which is conventionally useful as a flame retardant, is used, the disadvantage that the light resistance is poor and cannot be put into practical use can be solved by the present invention, and its application can be expanded. It is a great contribution to the world.
Claims (1)
であり、下記一般式化１で表されるリン化合物をリン元
素として０．１〜４．０重量％共重合しているポリエス
テルであって、ジエチレングリコールの含有量がジオー
ル成分の４モル％以下であるポリエステルから形成され
ることを特徴とする難燃性ポリエステル繊維。 【化１】 （ただし式中Ｒ1 は炭素原子数１〜１８の１価の有機基
を表し、Ｒ2 は水素原子または炭素原子数１〜１８の１
価の有機基を表す。）1. A polyester which comprises ethylene terephthalate as a main constituent unit and which is copolymerized with a phosphorus compound represented by the following general formula 1 as a phosphorus element in an amount of 0.1 to 4.0% by weight. A flame-retardant polyester fiber, which is formed from a polyester having a content of 4 mol% or less of a diol component. [Chemical 1] (In the formula, R 1 represents a monovalent organic group having 1 to 18 carbon atoms, and R 2 represents a hydrogen atom or 1 having 1 to 18 carbon atoms.
Represents a valent organic group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24528693A JP3169104B2 (en) | 1993-09-30 | 1993-09-30 | Flame retardant polyester fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24528693A JP3169104B2 (en) | 1993-09-30 | 1993-09-30 | Flame retardant polyester fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07102418A true JPH07102418A (en) | 1995-04-18 |
| JP3169104B2 JP3169104B2 (en) | 2001-05-21 |
Family
ID=17131411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24528693A Expired - Lifetime JP3169104B2 (en) | 1993-09-30 | 1993-09-30 | Flame retardant polyester fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3169104B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005056646A1 (en) * | 2003-12-09 | 2005-06-23 | Toyo Boseki Kabushiki Kaisha | Thermoplastic resin composition for masterbatch, process for producing molding material comprising the same, thermoplastic resin composition obtained with the same, and process for producing the composition |
| JP2005273043A (en) * | 2004-03-23 | 2005-10-06 | Nippon Ester Co Ltd | Flame-retardant cationically dyeable polyester fiber |
| EP1832596A1 (en) * | 2006-03-07 | 2007-09-12 | Clariant International Ltd. | Compounds of mono-carboxyl functionalised dialkylphosphine acids and other components |
| JP2008127570A (en) * | 2006-11-22 | 2008-06-05 | Hyosung Corp | Method for producing flame-retardant polyester polymer, polymer produced thereby and fiber produced therefrom |
| CN101851811A (en) * | 2010-06-03 | 2010-10-06 | 江阴博伦化纤有限公司 | Method for preparing flame-retardant and anti-dripping polyester fiber |
| JP2011106071A (en) * | 2009-11-19 | 2011-06-02 | Teijin Fibers Ltd | Polyester fiber |
| JP2016160429A (en) * | 2015-03-03 | 2016-09-05 | 東レ株式会社 | Manufacturing method of flame retardant polyester composition |
| JP2018532895A (en) * | 2015-12-29 | 2018-11-08 | 江蘇恒力化繊股▲ふん▼有限公司 | Flame retardant polyester fiber and method for producing the same |
-
1993
- 1993-09-30 JP JP24528693A patent/JP3169104B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005056646A1 (en) * | 2003-12-09 | 2005-06-23 | Toyo Boseki Kabushiki Kaisha | Thermoplastic resin composition for masterbatch, process for producing molding material comprising the same, thermoplastic resin composition obtained with the same, and process for producing the composition |
| TWI408159B (en) * | 2003-12-09 | 2013-09-11 | Toyo Boseki | Thermoplastic resin composition for masterbatch, process for producing molded article thereof, thermoplastic resin composition using it, and process for producing it |
| JP2005273043A (en) * | 2004-03-23 | 2005-10-06 | Nippon Ester Co Ltd | Flame-retardant cationically dyeable polyester fiber |
| EP1832596A1 (en) * | 2006-03-07 | 2007-09-12 | Clariant International Ltd. | Compounds of mono-carboxyl functionalised dialkylphosphine acids and other components |
| US7485745B2 (en) | 2006-03-07 | 2009-02-03 | Clariant International Ltd. | Mixtures composed of monocarboxy-functionalized dialkylphosphinic esters and of further components |
| JP2008127570A (en) * | 2006-11-22 | 2008-06-05 | Hyosung Corp | Method for producing flame-retardant polyester polymer, polymer produced thereby and fiber produced therefrom |
| DE102007056179B4 (en) * | 2006-11-22 | 2017-11-09 | Hyosung Corp. | A process for producing a flameproof polyester polymer, polyester polymers prepared therefrom and fibers made using the polyester polymer |
| JP2011106071A (en) * | 2009-11-19 | 2011-06-02 | Teijin Fibers Ltd | Polyester fiber |
| CN101851811A (en) * | 2010-06-03 | 2010-10-06 | 江阴博伦化纤有限公司 | Method for preparing flame-retardant and anti-dripping polyester fiber |
| JP2016160429A (en) * | 2015-03-03 | 2016-09-05 | 東レ株式会社 | Manufacturing method of flame retardant polyester composition |
| JP2018532895A (en) * | 2015-12-29 | 2018-11-08 | 江蘇恒力化繊股▲ふん▼有限公司 | Flame retardant polyester fiber and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3169104B2 (en) | 2001-05-21 |
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