JP4563925B2 - Method for producing aromatic copolyamide fiber - Google Patents
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本発明は、芳香族コポリアミド繊維の製造方法に関する。より詳しくは、従来の芳香族ポリアミド繊維に比べて、可塑延伸倍率が向上されており、繊維欠陥の非常に少ない芳香族コポリアミドを製造する方法に関するものである。 The present invention relates to a method for producing an aromatic copolyamide fiber. More specifically, the present invention relates to a method for producing an aromatic copolyamide having an improved plastic draw ratio as compared with conventional aromatic polyamide fibers and having very few fiber defects.
従来、芳香族ジカルボン酸成分と芳香族ジアミン成分とからなる芳香族ポリアミド繊維（以下「アラミド繊維」ということがある）、特にパラ型アラミド繊維は、その強度、高弾性率、高耐熱性等の特性を生かして、産業用途及び衣料用途に広く用いられている。 Conventionally, an aromatic polyamide fiber composed of an aromatic dicarboxylic acid component and an aromatic diamine component (hereinafter sometimes referred to as “aramid fiber”), particularly para-aramid fiber, has strength, high elastic modulus, high heat resistance, etc. Taking advantage of its characteristics, it is widely used in industrial and clothing applications.
代表的なパラ型アラミド繊維の例としては、ポリパラフェニレンテレフタルアミド（ＰＰＴＡ）繊維がある。この繊維は多くの利点を有するが、ポリマードープの光学異方性を利用した所謂液晶紡糸法により製造される点で、プロセス上の問題があり、また、繊維性能については、機械的物性のうち強度が必ずしも高くないこと及び伸度が低く靱性が不十分であること等の欠点が見られる。 A typical para-aramid fiber is polyparaphenylene terephthalamide (PPTA) fiber. Although this fiber has many advantages, it has a process problem in that it is manufactured by a so-called liquid crystal spinning method using the optical anisotropy of a polymer dope, and the fiber performance is out of mechanical properties. There are drawbacks such as not necessarily high strength and low elongation and insufficient toughness.
この問題を解消するため、光学異方性を保持したままヘテロ環含有モノマーを導入した芳香族コポリアミドを用いて、機械的物性を向上させようとした芳香族コポリアミド繊維を開発する試みがなされた（下記特許文献１参照）。しかしながら、かかる芳香族コポリアミドは、ポリマー溶液の不安定性等の要因で、安定した性能を発揮することが難しいことがわかった。 In order to solve this problem, an attempt has been made to develop an aromatic copolyamide fiber that is intended to improve mechanical properties using an aromatic copolyamide having a heterocycle-containing monomer introduced while maintaining optical anisotropy. (See Patent Document 1 below). However, it has been found that such an aromatic copolyamide is difficult to exert stable performance due to factors such as instability of the polymer solution.
そこで、公知のアミド系溶媒に対して高い溶解度を有し、容易に紡糸することができ、紡糸した繊維が延伸処理後に高い引っ張り強度と高い初期モジュラスを有する別の芳香族コポリアミド繊維を開発する試みがなされ、例えば、少なくとも下記の化学式（１）及び（２）の反復構造単位を含むヘテロ環含有芳香族コポリアミドであって、アミド系溶媒に対して光学的に等方性の溶液を形成するような芳香族ポリアミドから繊維を製造することが提案されている（下記特許文献２及び特許文献３参照）。しかしながら、これらの特許文献に開示されている芳香族コポリアミド繊維は、引っ張り強度、初期モジュラス等の機械的物性が不十分である。 Therefore, another aromatic copolyamide fiber that has high solubility in known amide solvents, can be easily spun, and the spun fiber has high tensile strength and high initial modulus after the drawing treatment is developed. Attempts have been made to form, for example, heterocycle-containing aromatic copolyamides containing at least repeating structural units of the following chemical formulas (1) and (2), which form an optically isotropic solution with respect to amide solvents. It has been proposed to produce fibers from such aromatic polyamides (see Patent Document 2 and Patent Document 3 below). However, the aromatic copolyamide fibers disclosed in these patent documents have insufficient mechanical properties such as tensile strength and initial modulus.
また、同様に、少なくとも下記の化学式（１）及び（２）の反復構造単位を含む芳香族コポリアミドの未中和ポリマー溶液を紡糸し可塑化延伸することにより、高引っ張り強度、高初期モジュラス等、改善された機械的物性をもつ芳香族コポリアミド繊維が提案されている（例えば、下記非特許文献１参照）。しかしながら、この方法では、ポリマー溶液が未中和であるため、重合時に発生する塩酸を含み、高温下におけるポリマー鎖分解あるいは設備の腐蝕等の問題があるため、工業的に有用な繊維を得ることは難しい。 Similarly, high tensile strength, high initial modulus, and the like are obtained by spinning and plasticizing and stretching an unneutralized polymer solution of an aromatic copolyamide containing at least the repeating structural units of the following chemical formulas (1) and (2). Aromatic copolyamide fibers having improved mechanical properties have been proposed (for example, see Non-Patent Document 1 below). However, in this method, since the polymer solution is unneutralized, it contains hydrochloric acid generated during polymerization, and there are problems such as polymer chain degradation at high temperatures or corrosion of equipment, so that industrially useful fibers can be obtained. Is difficult.
以上のように、現在に至るまで、中和されたポリマー溶液から、従来と同程度もしくはそれ以上の倍率の可塑化延伸によって優れた機械的物性をもつ芳香族コポリアミド繊維を製造する方法は、未だ提案されていないのが実状である。 As described above, until now, a method for producing an aromatic copolyamide fiber having excellent mechanical properties from a neutralized polymer solution by plasticizing and stretching at a magnification equal to or higher than that of the conventional method is as follows. The actual situation has not been proposed yet.
本発明は、従来のアラミド繊維と比較して、高可塑化延伸倍率で延伸することができ、かつ繊維中の欠陥の程度が十分低減され、その結果、引っ張り強度、初期モジュラス等の機械的物性が優れた芳香族コポリアミド繊維の製造方法を提供することを目的とする。 Compared with conventional aramid fibers, the present invention can be drawn at a high plasticization draw ratio, and the degree of defects in the fibers is sufficiently reduced. As a result, mechanical properties such as tensile strength and initial modulus are obtained. An object of the present invention is to provide a method for producing an aromatic copolyamide fiber excellent in.
上述の目的は、下記の化学式（１）、（２）及び（３）の反復構造単位を含むヘテロ環含有芳香族コポリアミドからなり、かつ、該芳香族コポリアミドの構造反覆単位の全量に対し、化学式（２）の反復構造単位を３０〜９５モル％、化学式（３）の反復構造単位を５〜２０モル％含むヘテロ環含有芳香族ポリアミドの中和ドープを紡糸し、得られた芳香族コポリアミド繊維を、アミド系溶媒を含む水溶液からなる延伸浴中で化学式（２）の反復構造単位の含有率が同一でかつ化学式（３）の反復構造単位を含まないヘテロ環含有芳香族コポリアミド繊維の延伸倍率に対して、延伸倍率向上率が１５０〜３００％となる倍率で可塑延伸することを特徴とする、本発明の芳香族コポリアミド繊維の製造方法によって達成される。 The above-mentioned object is composed of a heterocycle-containing aromatic copolyamide containing repeating structural units represented by the following chemical formulas (1), (2) and (3), and is based on the total amount of structural repeat units of the aromatic copolyamide. Spinning a neutralized dope of a heterocyclic ring-containing aromatic polyamide containing 30 to 95 mol% of the repeating structural unit of the chemical formula (2) and 5 to 20 mol% of the repeating structural unit of the chemical formula (3). Heterocyclic ring-containing aromatic copolyamide in which the content of the repeating structural unit of the chemical formula (2) is the same and does not include the repeating structural unit of the chemical formula (3) in the drawing bath composed of an aqueous solution containing an amide solvent. This is achieved by the method for producing an aromatic copolyamide fiber according to the present invention, characterized in that plastic drawing is carried out at a magnification at which the draw ratio improvement rate is 150 to 300% with respect to the draw ratio of the fiber.
なお、上記化学式（１）、（２）及び（３）におけるＡｒ１、Ａｒ２及びＡｒ３は、各々独立した、パラ配位又は平行軸方向に結合基を有する２価の芳香族基であり、Ａｒ１は非置換又は置換された芳香族基、Ａｒ２は非置換の芳香族基、Ａｒ３はハロゲン基で置換された芳香族基である。 Ar 1 , Ar 2 and Ar 3 in the chemical formulas (1), (2) and (3) are each independently a divalent aromatic group having a bonding group in the para-coordinate or parallel axis direction. , Ar 1 is an unsubstituted or substituted aromatic group, Ar 2 is an unsubstituted aromatic group, and Ar 3 is an aromatic group substituted with a halogen group.
本発明でいう芳香族コポリアミドとは、２種以上の２価の芳香族基が直接アミド結合により連結されている繊維形成性ポリマーを総称し、これらの芳香族基において、２個の芳香環同士が直接結合するか、酸素原子、硫黄原子又はアルキレン基を介して結合していてもよく、また、芳香環にメチル基やエチル基等の低級アルキル基、メトキシ基、クロル基等のハロゲン基等を含むものであってもよい。 The aromatic copolyamide referred to in the present invention is a general term for fiber-forming polymers in which two or more kinds of divalent aromatic groups are directly linked by an amide bond. In these aromatic groups, two aromatic rings are used. May be bonded directly to each other or bonded through an oxygen atom, a sulfur atom or an alkylene group, and the aromatic ring is a lower alkyl group such as a methyl group or an ethyl group, or a halogen group such as a methoxy group or a chloro group. Etc. may be included.
本発明の方法では、繊維の製造に使用する芳香族コポリアミドとして、少なくとも上記３種の反復構成単位を（ポリマー繰り返し単位）含む特定の多元共重合体を使用することを一つの特徴としている。該共重合体にあっては、ポリアミド反覆構造単位の全量（１００モル％）のうち、化学式（２）の反復構造単位が３０〜９５モル％、好ましくは５０〜９０モル％、を占め、かつ、化学式（３）の反復構造単位が５〜２０モル％、好ましくは１０〜２０モル％、を占める多元共重合体である。さらに、該多元共重合体は化学式（１）の反復構造単位を５モル％以上含み、かつ以上３種の反復構造単位の合計が実質的に１００モル％となるよう共重合したものが好ましい。かかる芳香族コポリアミドのうちでも、反復構造単位の全量に対し、化学式（１）の反復構造単位を１０〜２０モル％、化学式（２）の反復構造単位を５０〜９０モル％、化学式（３）の反復構造単位を１０〜２０モル％含むコポリアミドが特に好適な結果が得られる。 One feature of the method of the present invention is that a specific multi-component copolymer containing at least the three types of repeating structural units (polymer repeating units) is used as the aromatic copolyamide used in the production of fibers. In the copolymer, among the total amount (100 mol%) of the polyamide repelling structural unit, the repeating structural unit of the chemical formula (2) accounts for 30 to 95 mol%, preferably 50 to 90 mol%, and The multi-component copolymer occupies 5 to 20 mol%, preferably 10 to 20 mol% of the repeating structural unit of the chemical formula (3). Further, the multi-component copolymer is preferably one containing 5 mol% or more of the repeating structural unit of the chemical formula (1) and copolymerized so that the total of the three kinds of repeating structural units is substantially 100 mol%. Among such aromatic copolyamides, the repeating structural unit of the chemical formula (1) is 10 to 20 mol%, the repeating structural unit of the chemical formula (2) is 50 to 90 mol%, the chemical formula (3) with respect to the total amount of the repeating structural units. Copolyamides containing 10 to 20 mol% of repeating structural units) are particularly suitable.
なお、本発明では、目的とする芳香族コポリアミド繊維の特性を本質的に損なわない範囲で、上記反覆構造単位のＡｒ１、Ａｒ２及びＡｒ３の一部（例えば、全体の１０モル％未満）を、メタ型の２価の芳香族基、例えばメタフェニレン基等、に置き替えても差し支えない。 In the present invention, a part of Ar 1 , Ar 2 and Ar 3 of the repetitive structural unit (for example, less than 10 mol% of the whole) within a range that does not substantially impair the characteristics of the target aromatic copolyamide fiber. ) May be replaced with a meta-type divalent aromatic group such as a metaphenylene group.
さらに、本発明の方法では、後に詳述するような重合〜製糸工程を経て芳香族コポリアミド繊維を製造することをもう一つの特徴としている。特に、中和ドープから紡糸した凝固糸を、アミド系溶媒を含む水溶液からなる延伸浴中で、上記化学式（２）の反復構造単位の含有率が同一でかつ化学式（３）の反復構造単位を含まないヘテロ環含有芳香族コポリアミド繊維の延伸倍率に対して、延伸倍率向上率が１５０〜３００％となる倍率で可塑延伸することを必須とするものである。 Furthermore, in the method of the present invention, another feature is that an aromatic copolyamide fiber is produced through a polymerization process to a spinning process as described in detail later. In particular, a coagulated yarn spun from a neutralized dope is used in a drawing bath composed of an aqueous solution containing an amide solvent, and the content of the repeating structural unit of the chemical formula (2) is the same and the repeating structural unit of the chemical formula (3) is the same. It is essential to plastically stretch at a magnification at which the draw ratio improvement rate is 150 to 300% with respect to the draw ratio of the heterocycle-containing aromatic copolyamide fiber not included.
ここで「延伸倍率向上率」とは、上記の化学式（３）の反復構造単位を含まず、かつ、化学式（２）の反復構造単位の含有率（モル％）が同一のヘテロ環含有芳香族コポリアミドからなる対象繊維を、本発明の繊維に適用するのと同じ組成・温度のアミド系水溶液中にて同じ速度で延伸し、断糸や毛羽等が発生せず良好に延伸できる最大の延伸倍率を求め、その延伸倍率に対して１５０％〜３００％に相当する高い延伸倍率をいう。 Here, the “stretch ratio improvement rate” is a heterocycle-containing aromatic that does not include the repeating structural unit represented by the chemical formula (3) and has the same content (mol%) of the repeating structural unit represented by the chemical formula (2). The target fiber made of copolyamide is stretched at the same speed in an amide-based aqueous solution having the same composition and temperature as that applied to the fiber of the present invention, and the maximum stretch that can be satisfactorily stretched without causing yarn breakage or fluff A ratio is obtained, and a high stretch ratio corresponding to 150% to 300% with respect to the stretch ratio.
なお、本発明の方法では、上記可塑延伸の延伸浴としてアミド系溶媒の濃度が３０〜８０重量％の水溶液を使用するのが好ましく、また、可塑延伸後に３００〜５５０℃の温度で熱処理することが好ましい。
かくして、本発明の方法によれば、芳香族コポリアミドのポリマー組成と重合・製糸条件との組合せによって、すぐれた機械的物性の芳香族コポリアミド繊維を良好な生産性にて製造される。
In the method of the present invention, it is preferable to use an aqueous solution having an amide solvent concentration of 30 to 80% by weight as the stretching bath for plastic stretching, and heat treatment at a temperature of 300 to 550 ° C. after plastic stretching. Is preferred.
Thus, according to the method of the present invention, an aromatic copolyamide fiber having excellent mechanical properties can be produced with good productivity by a combination of the polymer composition of the aromatic copolyamide and the polymerization / spinning conditions.
本発明の方法によれば、従来のアラミド繊維に比べ、高い延伸倍率で可塑延伸することができるので、繊維中の欠陥の程度が十分低減され、その結果、引っ張り強度、初期モジュラス等の機械的物性に優れた芳香族コポリアミド繊維を安定した工程調子で製造することが可能となる。 According to the method of the present invention, plastic drawing can be performed at a higher draw ratio than conventional aramid fibers, so that the degree of defects in the fibers is sufficiently reduced, and as a result, mechanical properties such as tensile strength and initial modulus are reduced. Aromatic copolyamide fibers having excellent physical properties can be produced with stable process conditions.
本発明によれば、目的とする高品質の芳香族コポリアミド繊維は、重合及び製糸（すなわち、紡糸・延伸熱処理）の工程を経て製造される。以下、本発明の製造方法を工程順に説明する。 According to the present invention, the desired high-quality aromatic copolyamide fiber is produced through the steps of polymerization and yarn production (that is, spinning / drawing heat treatment). Hereafter, the manufacturing method of this invention is demonstrated in order of a process.
(重合)
本発明の方法において、使用する上記の芳香族コポリアミドは、それ自体公知の溶液重合法により、アミド系溶媒中で、上記化学式（１）（２）及び（３）の反復構造単位を形成し得る芳香族ジカルボン酸クロライドと芳香族ジアミンとを反応せしめてポリマー溶液を得る方法で製造することができる。
(polymerization)
In the method of the present invention, the aromatic copolyamide used forms the repeating structural units of the above chemical formulas (1), (2) and (3) in an amide solvent by a solution polymerization method known per se. The obtained aromatic dicarboxylic acid chloride and aromatic diamine can be reacted to produce a polymer solution.
この際、好適に用いられる芳香族ジカルボン酸ジクロライドとしては、例えば、テレフタル酸ジクロライド、２−クロロテレフタル酸ジクロライド、３−メチルテレフタル酸ジクロライド、４、４’−ビフェニレンジカルボン酸ジクロライド、２，６−ナフタレンジカルボン酸ジクロライド等のパラ又は平行軸方向に官能基を有する（以下、これらを「パラ型」と総称する）芳香族ジカルボン酸ジクロライドが挙げられる。これら非置換又は置換のいずれでもよいが、なかでもテレフタル酸ジクロライドが特に好適である。これらの芳香族ジカルボン酸ジクロライドは単独で使用してもよく、２種以上を併用してもよい。
なお、本発明の目的を損なわない範囲で、上記パラ型の芳香族ジカルボン酸ジクロライドの一部をイソフタル酸ジクロライドのようなメタ型のジカルボン酸クロライドに置き換えても差し支えない。
In this case, examples of the aromatic dicarboxylic acid dichloride preferably used include terephthalic acid dichloride, 2-chloroterephthalic acid dichloride, 3-methylterephthalic acid dichloride, 4,4′-biphenylenedicarboxylic acid dichloride, and 2,6-naphthalene. Examples thereof include aromatic dicarboxylic acid dichlorides having functional groups in the para- or parallel-axis direction such as dicarboxylic acid dichloride (hereinafter collectively referred to as “para-type”). Either unsubstituted or substituted may be used, and terephthalic acid dichloride is particularly preferable. These aromatic dicarboxylic acid dichlorides may be used alone or in combination of two or more.
It should be noted that a part of the para-type aromatic dicarboxylic acid dichloride may be replaced with a meta-type dicarboxylic acid chloride such as isophthalic acid dichloride within a range not impairing the object of the present invention.
一方、芳香族ジアミンとしては、少なくとも３種の芳香族ジアミンが用いられる。第１の芳香族ジアミンは、非置換パラ型芳香族ジアミンから選ばれた１種であり、例えば、パラフェニレンジアミン、４，４’−ビフェニレンジアミン、３，４’−ジアミノジフェニルエーテル等の、従来のパラ型アラミド繊維の製造に用いられるものが好適に使用される。これらは単独で使用してもよく２種以上併用することもできる。かかる非置換パラ型芳香族ジアミンとしては、なかでもパラフェニレンジアミンが特に好適である。なお、本発明の目的を損なわない範囲で、上記パラ型芳香族ジアミンの一部をメタフェニレンジアミンのような非置換メタ型芳香族ジアミンに置き換えても差し支えない。 On the other hand, as the aromatic diamine, at least three kinds of aromatic diamines are used. The first aromatic diamine is one selected from unsubstituted para-type aromatic diamines. For example, conventional aromatic diamines such as paraphenylene diamine, 4,4′-biphenylene diamine, 3,4′-diaminodiphenyl ether, etc. What is used for manufacture of a para-type aramid fiber is used suitably. These may be used alone or in combination of two or more. As such an unsubstituted para-type aromatic diamine, paraphenylenediamine is particularly preferable. It should be noted that a part of the para type aromatic diamine may be replaced with an unsubstituted meta type aromatic diamine such as metaphenylene diamine within the range not impairing the object of the present invention.
第２の芳香族ジアミンは、置換又は非置換のフェニルベンジミダゾール基を有する芳香族ジアミン類から選ばれた１種であり、なかでも入手のし易さ、得られる繊維の優れた引っ張り強度及び初期モジュラス等の点から、５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾールがよい。 The second aromatic diamine is one selected from aromatic diamines having a substituted or unsubstituted phenyl benzimidazole group, and among them, availability, excellent tensile strength of the resulting fiber, and From the viewpoint of the initial modulus and the like, 5 (6) -amino-2- (4-aminophenyl) benzimidazole is preferable.
また、第３の芳香族ジアミンは、ハロゲン置換のパラ型芳香族ジアミンから選ばれた１種であり、例えば、モノクロロパラフェニレンジアミン、ジクロロパラフェニレンジアミン、モノフロロパラフェニレンジアミン、モノブロモパラフェニレンジアミン等が用いられる。この第３の芳香族ジアミンについても、本発明の目的を損なわない範囲で、上記ハロゲン置換のパラ型芳香族ジアミンの一部をモノクロロメタフェニレンジアミンのようなメタ型の置換芳香族ジアミンに代替しても差し支えない。 The third aromatic diamine is one selected from halogen-substituted para-type aromatic diamines, such as monochloroparaphenylenediamine, dichloroparaphenylenediamine, monofluoroparaphenylenediamine, and monobromoparaphenylenediamine. Etc. are used. As for the third aromatic diamine, a part of the halogen-substituted para-type aromatic diamine is replaced with a meta-type substituted aromatic diamine such as monochlorometaphenylene diamine within the range not impairing the object of the present invention. There is no problem.
本発明で繊維を形成する芳香族コポリアミドは、既に述べたとおり、上記化学式（２）のヘテロ環含有反復構造単位の含有率を、該芳香族ポリアミド反覆構造単位の全量に対し３０〜９５モル％、好ましくは５０〜９５モル％の範囲とする。該反復構造単位の含有率が３０モル％未満の場合には重合反応においては反応溶液が濁るという問題が生じ、このような濁ったドープでは紡糸することが困難である。また、上記化学式（３）の反復構造単位の含有率を、該芳香族ポリアミド構造単位の全量に対し５〜２０モル％、好ましくは１０〜２０モル％の範囲とする。該反復構造単位の含有率が５モル％未満の場合には、紡糸した繊維に可塑延伸及び熱処理を施しても繊維中の欠陥の程度が有意に低減しない。また、含有率が２０モル％より多い場合には、紡糸用ポリマー溶液の粘性が大幅に下がるという問題が生じ、紡糸することが困難である。したがって、本発明では、溶液重合に際し、各反応成分の仕込み量を、生成ポリマー中で各反覆構造単位がそれぞれ上記の範囲となるように調整する必要がある。 As described above, the aromatic copolyamide forming the fiber in the present invention has a content of the heterocyclic-containing repeating structural unit of the above chemical formula (2) of 30 to 95 mol based on the total amount of the aromatic polyamide repetitive structural unit. %, Preferably in the range of 50-95 mol%. When the content of the repeating structural unit is less than 30 mol%, there arises a problem that the reaction solution becomes cloudy in the polymerization reaction, and it is difficult to spin with such a cloudy dope. Further, the content of the repeating structural unit represented by the chemical formula (3) is set in the range of 5 to 20 mol%, preferably 10 to 20 mol% with respect to the total amount of the aromatic polyamide structural unit. When the content of the repeating structural unit is less than 5 mol%, the degree of defects in the fiber is not significantly reduced even if the spun fiber is subjected to plastic drawing and heat treatment. On the other hand, when the content is more than 20 mol%, there arises a problem that the viscosity of the spinning polymer solution is greatly lowered, and spinning is difficult. Therefore, in the present invention, in solution polymerization, it is necessary to adjust the amount of each reaction component charged so that each repetitive structural unit is in the above range in the produced polymer.
本発明で重合溶媒として適当なアミド系溶媒としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルイミダゾリジノン等を例示することができるが、特に、芳香族コポリアミドの重合からドープ調製並びに湿式紡糸工程に至るまでの取扱い性や安定性及び害溶媒の毒性等の点から、Ｎ−メチル−２−ピロリドンが好ましい。 Examples of amide solvents suitable as a polymerization solvent in the present invention include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, and the like. N-methyl-2-pyrrolidone is preferable from the viewpoints of handleability and stability from polymerization of aromatic copolyamide to dope preparation and wet spinning process, and toxicity of harmful solvents.
本発明においては、芳香族コポリアミドのアミド系溶媒に対する溶解性を向上させるために、重合の前、途中、終了時等に無機塩を適当量添加することができる。このような無機塩としては、例えば、塩化リチウム、塩化カルシウム等が挙げられる。該無機塩の添加量は３〜１０重量％が好ましい。添加量が１０重量％を越えると無機塩をアミド系溶媒に対し全量溶解させることが困難となり、添加量が３重量％未満の場合には、溶解性向上の効果が不十分となるので、好ましくない。 In the present invention, in order to improve the solubility of the aromatic copolyamide in the amide solvent, an appropriate amount of an inorganic salt can be added before, during or at the end of polymerization. Examples of such inorganic salts include lithium chloride and calcium chloride. The amount of the inorganic salt added is preferably 3 to 10% by weight. If the addition amount exceeds 10% by weight, it is difficult to dissolve the entire amount of the inorganic salt in the amide solvent, and if the addition amount is less than 3% by weight, the effect of improving the solubility becomes insufficient. Absent.
重合反応終了後の溶液には、反応で生成した塩酸を含むため、塩基性の無機化合物、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、酸化カルシウム等を添加し中和する。中和したポリマー溶液中には中和反応で生じた塩化カルシウム等の無機塩が含まれることがあるが、該無機塩はそのまま溶解性向上に寄与するので、無機塩濃度が過剰にならない限り、除去する必要はない。
重合反応において生成するポリマーの溶媒に対する濃度は重要である。均質な高重合度のポリマーを得るには生成ポリマー濃度として１０重量％以下が好ましい。とりわけ３〜８重量％の濃度範囲が品質の安定したポリマーを得るのに好都合である。
Since the solution after completion of the polymerization reaction contains hydrochloric acid generated by the reaction, a basic inorganic compound such as sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide or the like is added for neutralization. The neutralized polymer solution may contain an inorganic salt such as calcium chloride generated by the neutralization reaction, but the inorganic salt contributes to improving the solubility as it is, so unless the inorganic salt concentration becomes excessive, There is no need to remove it.
The concentration of the polymer produced in the polymerization reaction with respect to the solvent is important. In order to obtain a homogeneous polymer having a high degree of polymerization, the concentration of the produced polymer is preferably 10% by weight or less. In particular, a concentration range of 3-8% by weight is advantageous for obtaining a stable polymer.
（製糸）
溶液重合により得られた上記芳香族コポリアミドのドープは、そのまま、あるいはポリマー濃度を適宜調整後、公知の芳香族ポリアミド繊維の紡糸方法に従って凝固液中に押し出され、凝固糸となる。紡糸用ドープには、必要に応じ、着色剤、難燃剤、安定剤等の添加剤を含んでもよい。紡糸工程では、紡糸口金直下にエアーギャップと呼ばれる短い空間を設け、この空間を通過した未凝固繊維（ポリマードープ）を直ちに凝固液中に導入する方法が好ましいが、通常の湿式紡糸でも差し支えない。
(Yarn making)
The above-mentioned aromatic copolyamide dope obtained by solution polymerization is extruded as it is or after appropriately adjusting the polymer concentration into a coagulating liquid according to a known spinning method of aromatic polyamide fibers to form a coagulated yarn. The spinning dope may contain additives such as a colorant, a flame retardant, and a stabilizer as necessary. In the spinning process, a method of providing a short space called an air gap immediately below the spinneret and immediately introducing uncoagulated fibers (polymer dope) that has passed through this space into the coagulating liquid is preferred, but ordinary wet spinning may also be used.
凝固液は、一般に、アミド系溶媒と水との２成分からなる水溶液で構成される。ここで使用するアミド系溶媒としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルイミダゾリジノン等が使用可能であるが、取扱い性、安定性及び該溶媒の毒性等の点から、Ｎ−メチル−２−ピロリドンが特に好ましく使用される。 The coagulation liquid is generally composed of an aqueous solution composed of two components of an amide solvent and water. As the amide solvent used here, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone and the like can be used. N-methyl-2-pyrrolidone is particularly preferably used from the viewpoint of toxicity of the solvent.
凝固液となる水溶液中のアミド系溶媒の濃度は、濃度１０〜５０重量％であることが好ましい。濃度が５０重量％を越えると、紡出した芳香族コポリアミドドープの凝固が進まず、繊維状物同士の密着が発生し、連続的に製糸することが困難となる。また、濃度が１０重量％未満であると、可塑化が十分に進まず、続いて行なわれる可塑延伸時の延伸性が低下するため好ましくない。凝固浴の温度は凝固浴組成と密接な関係があるが、あまり高温にすると紡糸した繊維同士の密着が激しくなる上、作業性も悪くなるため。好適な温度は０〜５０℃である。 The concentration of the amide solvent in the aqueous solution serving as the coagulation liquid is preferably 10 to 50% by weight. When the concentration exceeds 50% by weight, coagulation of the spun aromatic copolyamide dope does not progress, and the close contact between the fibrous materials occurs, making continuous yarn production difficult. On the other hand, if the concentration is less than 10% by weight, the plasticization does not proceed sufficiently, and the stretchability during the subsequent plastic stretching is lowered, which is not preferable. The temperature of the coagulation bath has a close relationship with the composition of the coagulation bath, but if the temperature is too high, the close contact between the spun fibers becomes severe and the workability also deteriorates. The preferred temperature is 0-50 ° C.
本発明においては、紡糸用ドープが光学的等方性であり、かつ中和されているため、紡糸性が良好で、安定かつ円滑な紡糸を行うことができ、設備の腐食等の問題も生じない。
凝固浴から引き取られた芳香族コポリアミド糸条は、延伸浴中で特定の延伸倍率に可塑延伸される。すなわち、本発明で採用する延伸倍率は、上記化学式（２）の反復構造単位の含有比率が同一でかつ化学式（３）の反復構造単位を含まないヘテロ環含有芳香族コポリアミド繊維の延伸倍率に対する延伸倍率向上率が１５０〜３００％となる倍率とする。延伸倍率がこれより小さいときは、繊維内部に欠陥が残り、所望の機械的物性を有する繊維が得られないばかりでなく、延伸倍率が低いため生産性も低下する。一方、延伸倍率が過大になると延伸時に断糸や毛羽が発生する。
In the present invention, since the spinning dope is optically isotropic and neutralized, the spinnability is good, stable and smooth spinning can be performed, and problems such as corrosion of equipment also occur. Absent.
The aromatic copolyamide yarn taken from the coagulation bath is plastic-drawn at a specific draw ratio in the drawing bath. That is, the draw ratio employed in the present invention is relative to the draw ratio of the heterocycle-containing aromatic copolyamide fiber in which the content ratio of the repeating structural unit of the chemical formula (2) is the same and does not include the repeating structural unit of the chemical formula (3). The magnification at which the stretch ratio improvement rate is 150 to 300%. When the draw ratio is smaller than this, defects remain in the fiber, and not only fibers having desired mechanical properties cannot be obtained, but also the productivity is lowered because the draw ratio is low. On the other hand, if the draw ratio is excessive, yarn breakage and fluff are generated during drawing.
ここで言う「延伸倍率向上率」とは、既に述べたように、上記の化学式（３）の反復構造単位を含まず、かつ化学式（２）の反復構造単位の含有率（モル％）が同一のヘテロ環含有芳香族コポリアミドからなる繊維（対象繊維）を、本発明の繊維に適用する際と同じ組成・温度のアミド系水溶液中にて同じ速度で可塑延伸し、断糸や毛羽（単繊維破断）等が発生せず良好に延伸できる最高の延伸倍率（最大延伸倍率）を求め、その最大延伸倍率に対して１５０％〜３００％に相当する高い延伸倍率をいう。例えば、化学式（３）の反復構造単位を含まずに、化学式（１）及び（２）の反復構造単位のみからなり、かつ化学式（２）の反覆構造単位の含有率が同一の芳香族コポリアミド繊維（対象繊維）の最大延伸倍率が２．０倍のとき、本発明の方法にあっては、その１５０％〜３００％に相当する３．０〜６．０倍の比較的高い倍率で可塑延伸する。本発明において実際に適用する延伸倍率の範囲は、当該繊維を形成するポリマーの組成や延伸浴の組成、温度等によって異なるが、通常、２．３〜４．５倍程度になる。 The “stretch ratio improvement rate” mentioned here does not include the repeating structural unit represented by the chemical formula (3) as described above, and the content (mol%) of the repeating structural unit represented by the chemical formula (2) is the same. Of the heterocycle-containing aromatic copolyamide (target fiber) is plastic-drawn at the same speed in an amide-based aqueous solution having the same composition and temperature as that applied to the fiber of the present invention, and the yarns and fluffs (single fibers) The highest draw ratio (maximum draw ratio) that can be satisfactorily stretched without occurrence of fiber breakage or the like is determined, and refers to a high draw ratio corresponding to 150% to 300% with respect to the maximum draw ratio. For example, an aromatic copolyamide which does not include the repeating structural unit represented by the chemical formula (3), is composed only of the repeating structural units represented by the chemical formulas (1) and (2), and has the same content of the recurring structural unit represented by the chemical formula (2). When the maximum draw ratio of the fiber (target fiber) is 2.0 times, in the method of the present invention, plasticization is performed at a relatively high magnification of 3.0 to 6.0 times corresponding to 150% to 300%. Stretch. The range of the draw ratio actually applied in the present invention varies depending on the composition of the polymer forming the fiber, the composition of the draw bath, the temperature, etc., but is usually about 2.3 to 4.5 times.
本発明では可塑延伸、すなわち繊維を可塑化した状態で延伸を行うため、延伸浴としてアミド系溶媒の水溶液を使用する。ここで用いられるアミド系溶媒としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルイミダゾリジノン等を例示することができるが、なかでもＮ−メチル−２−ピロリドンが好ましい。 In the present invention, an aqueous solution of an amide solvent is used as a drawing bath in order to perform plastic drawing, that is, drawing in a state in which the fiber is plasticized. Examples of the amide solvent used here include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone and the like, among which N-methyl 2-Pyrrolidone is preferred.
延伸浴を構成する水溶液のアミド系溶媒の濃度は３０〜８０重量％が好ましい。濃度が８０重量％を越えると芳香族コポリアミド糸条が該水溶液中に溶解するため、連続的に製糸することが困難となる。また、濃度が３０重量％未満であると繊維の可塑化が十分に進まず、上記延伸倍率を確保することが困難である。該水溶液の温度は、あまり高温にすると繊維同士の密着が激しくなる上、作業性も悪くなるため、０〜５０℃が好適である。 The concentration of the amide solvent in the aqueous solution constituting the stretching bath is preferably 30 to 80% by weight. If the concentration exceeds 80% by weight, the aromatic copolyamide yarn dissolves in the aqueous solution, making continuous yarn production difficult. Further, if the concentration is less than 30% by weight, the plasticization of the fibers does not proceed sufficiently, and it is difficult to ensure the above draw ratio. The temperature of the aqueous solution is preferably 0 to 50 ° C., because if the temperature is too high, the adhesion between the fibers becomes intense and the workability also deteriorates.
延伸に続いて、該芳香族コポリアミド繊維は水洗工程にて溶媒を十分に除去し、乾燥工程にて充分に乾燥したのち熱処理を行う。本発明における繊維の熱処理温度は３００〜５５０℃の範囲が好ましい。熱処理温度が３００℃未満の場合には、繊維が充分に配向結晶化を起こさせることができないために、充分な引っ張り強度、初期モジュラスが得られない。また、熱処理温度が５５０℃を越える場合には、繊維が熱劣化を引き起こすために、充分な引っ張り強度、初期モジュラスが得られない。この熱処理は、定長下又は処理前の原長に対し１５％以内の伸張下又は制限収縮下で行うのが適当である。 Subsequent to stretching, the aromatic copolyamide fiber is sufficiently removed of the solvent in the water washing step and sufficiently dried in the drying step, followed by heat treatment. The heat treatment temperature of the fiber in the present invention is preferably in the range of 300 to 550 ° C. When the heat treatment temperature is less than 300 ° C., the fiber cannot sufficiently cause orientation crystallization, so that sufficient tensile strength and initial modulus cannot be obtained. On the other hand, when the heat treatment temperature exceeds 550 ° C., the fiber causes thermal deterioration, so that sufficient tensile strength and initial modulus cannot be obtained. This heat treatment is suitably carried out under a constant length or under a stretching or restriction shrinkage within 15% of the original length before the treatment.
（得られる繊維）
本発明の方法で得られる芳香族コポリアミド繊維の繊度は、単糸繊度として０．５５〜２２ｄｔｅｘの範囲が好ましく、特に１．６７〜１６．７ｄｔｅｘの範囲が好ましい。単糸繊度が０．５５ｄｔｅｘ未満では製糸工程における毛羽や単糸切れが発生しやすく、また、単糸繊度が２２ｄｔｅｘを超えると撚糸、製網等が困難になるので好ましくない。
(Fiber obtained)
The fineness of the aromatic copolyamide fiber obtained by the method of the present invention is preferably in the range of 0.55 to 22 dtex, and particularly preferably in the range of 1.67 to 16.7 dtex, as the single yarn fineness. If the single yarn fineness is less than 0.55 dtex, fluff and single yarn breakage are likely to occur in the yarn making process, and if the single yarn fineness exceeds 22 dtex, twisting, netting, etc. become difficult.
本発明の方法では、特定組成の芳香族コポリアミド繊維を上述のような条件で製造することによって、繊維中の欠陥が有意に低減し、平均空孔径が３．０ｎｍ以下、好ましくは０．５〜２．８ｎｍ、となり、機械的物性は、引っ張り強度２０ｃＮ／ｄｔｅｘ以上、好ましくは２２〜３０ｃＮ／ｄｔｅｘであり、初期モジュラス５００ｃＮ／ｄｔｅｘ以上、好ましくは６００〜１０００ｃＮ／ｄｔｅｘと良好な値を示し、特に産業用、防護衣料用の資材として有用である。しかも、本発明方法では延伸倍率を大きくとることができるので製糸段階の生産性も向上する。 In the method of the present invention, by producing an aromatic copolyamide fiber having a specific composition under the above-described conditions, defects in the fiber are significantly reduced, and the average pore diameter is 3.0 nm or less, preferably 0.5. The mechanical properties are tensile strength 20 cN / dtex or higher, preferably 22-30 cN / dtex, initial modulus 500 cN / dtex or higher, preferably 600-1000 cN / dtex, showing a good value, It is particularly useful as a material for industrial and protective clothing. Moreover, in the method of the present invention, since the draw ratio can be increased, the productivity in the yarn production stage is also improved.
以下、実施例により本発明を具体的に説明するが、本発明はその説明内容に限定されるものではない。なお、実施例中の各特性値は下記の方法で測定した。
＜粘度（ηｉｎｈ）＞
９８％濃度の濃硫酸中、ポリマー濃度０．５ｇ／ｄｌの溶液について溶液温度３０℃で測定した。
＜繊維中欠陥＞
表１に示す繊維中の欠陥は、小角Ｘ線散乱装置を用いて測定される繊維中の平均空孔径（ｎｍ）によって表示した。測定装置及び測定条件は以下のとおりである。
装置：ＲＩＧＡＫＵ製小角Ｘ線散乱装置（ＲＵ−２００Ｂ）
測定条件：λ（ＣｕＫα）＝０．１５４ｎｍ、４５ｋＶ、７０ｍＡ
解析方法：本測定機器を用いて、小角領域（２θ＜１０°）で測定を行い、散乱光プロファイルから、繊維中の平均空孔径（ｎｍ）を算出した。すなわち、小角Ｘ線散乱の解析からＤｅｂｙｅプロットを行い、Ｄｅｂｙｅプロットから下記の数式により平均孔径（ｎｍ）を求めた。
<Viscosity (ηinh)>
Measurement was made at a solution temperature of 30 ° C. for a solution having a polymer concentration of 0.5 g / dl in 98% concentrated sulfuric acid.
<Defect in fiber>
Defects in the fibers shown in Table 1 were indicated by the average pore diameter (nm) in the fibers measured using a small angle X-ray scattering device. The measurement apparatus and measurement conditions are as follows.
Device: RIGAKU small-angle X-ray scattering device (RU-200B)
Measurement conditions: λ (CuKα) = 0.154 nm, 45 kV, 70 mA
Analysis method: Measurement was performed in a small-angle region (2θ <10 °) using this measuring device, and the average pore diameter (nm) in the fiber was calculated from the scattered light profile. That is, a Debye plot was performed from the analysis of small-angle X-ray scattering, and an average pore diameter (nm) was obtained from the Debye plot by the following formula.
［実施例１］
窒素を内部にフローしている攪拌翼を有する攪拌槽に、Ｎ−メチル−２−ピロリドン（以下、ＮＭＰと略す）１．８４０Ｌを投入した後、十分に乾燥させた塩化カルシウム１６０．０ｇ投入し溶解させた。次いで、パラフェニレンジアミン３．６ｇ（１０モル％）と、５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール５１．８ｇ（７０モル％）と、モノクロロパラフェニレンジアミン９．４ｇ（２０モル％）とを秤量して投入し溶解させた。続いて、テレフタル酸クロライド６６．８ｇ（１００モル％）を投入し、反応せしめて芳香族コポリアミドのポリマー溶液を得た。この生成物に２２．５重量％の水酸化カルシウムを含有するＮＭＰ分散液１０７．５ｇを添加し、中和反応を行ってポリマー溶液を得た。
得られたポリマー溶液から析出せしめたポリマーについて測定した粘度（ηｉｎｈ）は５．５であった。
[Example 1]
After charging 1.840 L of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) into a stirring tank having a stirring blade that is flowing nitrogen, 160.0 g of sufficiently dried calcium chloride is added. Dissolved. Next, 3.6 g (10 mol%) of paraphenylenediamine, 51.8 g (70 mol%) of 5 (6) -amino-2- (4-aminophenyl) benzimidazole, and 9.4 g of monochloroparaphenylenediamine (20 Mol%) was weighed in and dissolved. Subsequently, 66.8 g (100 mol%) of terephthalic acid chloride was added and reacted to obtain a polymer solution of an aromatic copolyamide. To this product, 107.5 g of NMP dispersion containing 22.5% by weight of calcium hydroxide was added and neutralized to obtain a polymer solution.
The viscosity (ηinh) measured for the polymer precipitated from the obtained polymer solution was 5.5.
得られたポリマー溶液（ドープ）を用い、孔径０．１５ｍｍ、孔数２５ホールの紡糸口金から毎分２．５ｃｃの割合で吐出し、エアーギャップと呼ばれる短い空隙部分を通した後、ＮＭＰ濃度３０重量％、温度５０℃の水溶液中に紡出し、６ｍ／分の速度で引き取って、凝固糸を得た。
該凝固糸は、引き続き、温度３０℃、濃度７０重量％のＮＭＰ水溶液中で４．５倍の延伸倍率で可塑延伸を行った。可塑延伸した糸条は水洗、乾燥し、次いで、温度４５０℃下で緊張熱処理を行い、３０．０ｍ／分の速度で巻き取って４２ｄｔｅｘ／２５ｆｉｌの糸条を得た。この結果を表１の実施例１欄に示す。
Using the obtained polymer solution (dope), it was discharged at a rate of 2.5 cc / min from a spinneret having a hole diameter of 0.15 mm and a hole number of 25 holes, and after passing through a short gap portion called an air gap, an NMP concentration of 30 Spinning into an aqueous solution of 50% by weight and a temperature of 50 ° C. was taken up at a speed of 6 m / min to obtain a coagulated yarn.
The coagulated yarn was subsequently subjected to plastic drawing at a draw ratio of 4.5 times in an NMP aqueous solution having a temperature of 30 ° C. and a concentration of 70% by weight. The plastic-drawn yarn was washed with water, dried, then subjected to tension heat treatment at a temperature of 450 ° C., and wound at a speed of 30.0 m / min to obtain a 42 dtex / 25 fil yarn. The results are shown in Example 1 column of Table 1.
［実施例２〜５］
実施例１と同様の製造方法に従い、ジアミン類の添加比率、ＮＭＰ水溶液中での延伸倍率を表１に記載のとおりに変更する以外は、実施例１と同様にして芳香族コポリアミド繊維を製造した。これらの結果を表１の実施例２〜５欄にまとめて示す。
[Examples 2 to 5]
Aromatic copolyamide fibers are produced in the same manner as in Example 1 except that the addition ratio of diamines and the draw ratio in the NMP aqueous solution are changed as shown in Table 1 in accordance with the production method similar to Example 1. did. These results are summarized in the columns of Examples 2 to 5 in Table 1.
［比較例１〜４］
実施例１と同様の製造方法に従い、ジアミン類の添加比率、ＮＭＰ水溶液中での延伸倍率を表１に記載のとおりに本発明の範囲外に変更する以外は、実施例１と同様にして芳香族コポリアミド繊維を製造した。これらの結果を表１の比較例１〜３欄にまとめて示す。なお、比較例１は上記化学式（３）の反復構造単位を含まず、かつ化学式（２）のヘテロ環含有の反復構造単位ジアミン成分のモル％が実施例１と同一のポリマーから得られた繊維を使用した場合の実験例であり、比較例２〜４は各成分の共重合比が本発明で特定した範囲外の実験例である。
[Comparative Examples 1-4]
According to the same production method as in Example 1, the addition ratio of diamines and the draw ratio in NMP aqueous solution were changed to the outside of the scope of the present invention as shown in Table 1, and the fragrance was the same as in Example 1. Group copolyamide fibers were produced. These results are shown together in Comparative Examples 1 to 3 in Table 1. In addition, the comparative example 1 does not contain the repeating structural unit of the said Chemical formula (3), and the fiber whose mol% of the repeating structure unit diamine component of the heterocyclic formula containing the chemical formula (2) was obtained from the same polymer as Example 1 is obtained. The comparative examples 2 to 4 are experimental examples in which the copolymerization ratio of each component is outside the range specified in the present invention.
本発明の方法によれば、中和されたポリマー溶液から十分な可塑化延伸倍率で延伸することができ、かつ繊維中の欠陥の程度が十分低減され、その結果、引っ張り強度、初期モジュラス等の機械的物性に優れた芳香族コポリアミド繊維を製造することができるので、本発明は繊維産業にきわめて有用な発明である。 According to the method of the present invention, the neutralized polymer solution can be stretched at a sufficient plasticizing stretch ratio, and the degree of defects in the fiber is sufficiently reduced. As a result, the tensile strength, initial modulus, etc. Since aromatic copolyamide fibers having excellent mechanical properties can be produced, the present invention is extremely useful for the textile industry.
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| CN102251306B (en) * | 2011-05-23 | 2012-11-21 | 蓝星（成都）新材料有限公司 | High-modulus poly(p-phenylene terephthalamide) (PPTA) fiber and preparation method thereof |
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| JPH05311510A (en) * | 1991-04-11 | 1993-11-22 | Teijin Ltd | Ultrathin aramid yarn and its production |
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| JPH07300534A (en) * | 1994-04-06 | 1995-11-14 | Hoechst Ag | Production of fiber or film from specific molding solution, and fiber or film obtainable thereby |
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| JP2001303365A (en) * | 2000-02-16 | 2001-10-31 | Teijin Ltd | Method for producing meta wholly aromatic polyamide yarn and yarn obtained by the method |
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| JPS52154881A (en) * | 1976-06-17 | 1977-12-22 | Teijin Ltd | Rubber composite reinforced with aromatic polyamide fiber |
| JPH05311510A (en) * | 1991-04-11 | 1993-11-22 | Teijin Ltd | Ultrathin aramid yarn and its production |
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