JP2011202308A - Para-type whole aromatic copolyamide fiber and method for producing the same - Google Patents
Para-type whole aromatic copolyamide fiber and method for producing the same Download PDFInfo
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- aromatic copolyamide
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 95
- 239000000835 fiber Substances 0.000 title claims abstract description 88
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000009987 spinning Methods 0.000 claims abstract description 34
- 239000004744 fabric Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 20
- 238000005345 coagulation Methods 0.000 claims description 16
- 230000015271 coagulation Effects 0.000 claims description 16
- 238000002166 wet spinning Methods 0.000 claims description 4
- 230000000704 physical effect Effects 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 description 35
- 238000005259 measurement Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 238000005452 bending Methods 0.000 description 10
- 150000004984 aromatic diamines Chemical class 0.000 description 9
- -1 polyparaphenylene terephthalamide Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- DEZBTHJZUVXZOL-UHFFFAOYSA-N 1,4-dichlorocyclohexa-2,5-diene-1,4-diamine Chemical compound ClC1(C=CC(C=C1)(N)Cl)N DEZBTHJZUVXZOL-UHFFFAOYSA-N 0.000 description 1
- MSWAXXJAPIGEGZ-UHFFFAOYSA-N 2-chlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(Cl)=C1 MSWAXXJAPIGEGZ-UHFFFAOYSA-N 0.000 description 1
- NTNUPCREDHXJEL-UHFFFAOYSA-N 2-methylbenzene-1,4-dicarbonyl chloride Chemical compound CC1=CC(C(Cl)=O)=CC=C1C(Cl)=O NTNUPCREDHXJEL-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- NZZGQZMNFCTNAM-UHFFFAOYSA-N naphthalene-2,6-dicarbonyl chloride Chemical compound C1=C(C(Cl)=O)C=CC2=CC(C(=O)Cl)=CC=C21 NZZGQZMNFCTNAM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000007868 post-polymerization treatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
Description
本発明は、パラ型全芳香族コポリアミド繊維および当該繊維を含む布帛、ならびに当該繊維の製造方法に関する。さらに詳しくは、単糸繊度が細くとも、引張強度などの機械的物性に優れたパラ型全芳香族コポリアミド繊維および当該繊維を含む布帛、ならびに当該繊維の製造方法に関する。 The present invention relates to a para-type wholly aromatic copolyamide fiber, a fabric containing the fiber, and a method for producing the fiber. More specifically, the present invention relates to a para-type wholly aromatic copolyamide fiber excellent in mechanical properties such as tensile strength even if the single yarn fineness is small, a fabric containing the fiber, and a method for producing the fiber.
従来、芳香族ジカルボン酸成分と芳香族ジアミン成分とを主成分としてなるパラ型全芳香族ポリアミド繊維は、その強度、高弾性率、高耐熱性等の特徴を有することから、様々な産業資材用途や、防弾・防刃材といった防護衣料用途等で幅広く用いられている。 Conventionally, para-type wholly aromatic polyamide fibers mainly composed of an aromatic dicarboxylic acid component and an aromatic diamine component have characteristics such as strength, high elastic modulus, high heat resistance, etc. It is widely used for protective clothing such as bulletproof and blade-proof materials.
代表的なパラ型全芳香族ポリアミド繊維としては、例えば、ポリパラフェニレンテレフタルアミド（以下ＰＰＴＡと記す）繊維が知られている。ＰＰＴＡ繊維は、前述の特徴を持ち、幅広く使用されている。しかし一方で、ＰＰＴＡポリマーは汎用の有機溶剤に不溶であるため、溶媒に濃硫酸を使用したポリマードープを用いなければならないという問題があった。また、繊維物性としても、引張強度や耐薬品性、耐光性等が十分に高いものではなく、さらに、擦過等により容易に繊維がフィブリル化する等、幾つかの問題があった。 As a typical para type wholly aromatic polyamide fiber, for example, polyparaphenylene terephthalamide (hereinafter referred to as PPTA) fiber is known. PPTA fibers have the aforementioned characteristics and are widely used. However, on the other hand, since PPTA polymer is insoluble in general-purpose organic solvents, there is a problem that a polymer dope using concentrated sulfuric acid as a solvent must be used. Further, the physical properties of the fiber are not sufficiently high in tensile strength, chemical resistance, light resistance and the like, and there are some problems such that the fiber is easily fibrillated by rubbing or the like.
そこで、前述の問題を解消するために、汎用のアミド系溶媒に対して高い溶解性を示し、これにより濃硫酸を用いることなく紡糸でき、且つ製糸工程における熱延伸や熱処理等により、高い引張強度や耐薬品性、耐光性、耐フィブリル性を有するパラ型全芳香族コポリアミド繊維の製造方法の開発がなされている。 Therefore, in order to solve the above-mentioned problems, it exhibits high solubility in a general-purpose amide solvent, so that it can be spun without using concentrated sulfuric acid, and high tensile strength can be obtained by hot drawing or heat treatment in the yarn making process. In addition, methods for producing para-type wholly aromatic copolyamide fibers having chemical resistance, light resistance, and fibril resistance have been developed.
このようなパラ型全芳香族コポリアミド繊維は、一般に等方性のポリマードープを口金から吐出し、凝固、水洗、乾燥、熱延伸等の工程を経て得られるものであり、その製糸条件は、得られる繊維の機械的物性等の特性に関わっている。 Such a para-type wholly aromatic copolyamide fiber is generally obtained by discharging an isotropic polymer dope from a die and undergoing processes such as coagulation, water washing, drying, and hot drawing. It is related to properties such as mechanical properties of the resulting fiber.
特許文献１および２には、等方性のポリマードープを用いた様々な分子構造を有するパラ型全芳香族コポリアミド繊維の製造方法が報告されている。しかしながら、等方性のポリマードープを用いて得られるパラ型全芳香族コポリアミド繊維は、その高い機械的物性が故に繊維自身が剛直であり、このため、屈曲や結節に弱く、さらにこれを布帛等に用いた場合には、柔軟性が低いという問題があった。 Patent Documents 1 and 2 report methods for producing para-type wholly aromatic copolyamide fibers having various molecular structures using an isotropic polymer dope. However, the para-type wholly aromatic copolyamide fiber obtained by using an isotropic polymer dope is rigid because of its high mechanical properties, and is therefore weak against bending and knots. When used for the above, there is a problem that flexibility is low.
本発明は、かかる従来技術を背景になされたものであり、その目的とするところは、パラ型全芳香族コポリアミド繊維の高い機械的物性を維持しつつ、耐結節性や柔軟性に優れた単糸繊度の小さいパラ型全芳香族コポリアミド繊維を提供することにある。 The present invention has been made against the background of such prior art, and the object of the present invention is excellent in knot resistance and flexibility while maintaining the high mechanical properties of para-type wholly aromatic copolyamide fibers. The object is to provide a para-type wholly aromatic copolyamide fiber having a small single yarn fineness.
本発明者は、上記課題を解決するため鋭意検討を行った。そして、バンドルとしての繊維の耐結節性が単糸繊度に大きく影響しており、また、同等の引張強度を有している繊維であっても、単糸繊度がある一定値以下となる場合において耐結節性が改善することを見出した。さらに、高い引張強度と単糸繊度をある一定値以下とすることを両立するためには、紡糸ドラフトおよび可塑化延伸倍率の両方を特定の範囲にすればよいことを見出した。そして、このような単糸繊度がある一定値以下である繊維を含む布帛においては、繊度の大きい同等の物性を有する繊維を用いて同じ織構造の布帛を作成した場合と比較して、布帛の柔軟性が向上することを見出し、本発明を完成するに到達した。 The present inventor has intensively studied to solve the above problems. And, the knot resistance of the fiber as a bundle greatly affects the single yarn fineness, and even if the fiber has the same tensile strength, the single yarn fineness is below a certain value. It has been found that the nodule resistance is improved. Furthermore, it has been found that both the spinning draft and the plasticizing draw ratio should be in a specific range in order to achieve both high tensile strength and single yarn fineness below a certain value. And in the cloth containing the fiber whose single yarn fineness is a certain value or less, compared with the case where the cloth of the same woven structure was made using the fiber having the same physical properties with a large fineness, The inventors have found that the flexibility is improved and have reached the completion of the present invention.
すなわち本発明は、下記化学構造式（１）、および下記化学構造式（２）で示される構造反復単位を含むパラ型全芳香族コポリアミド繊維からなり、単糸繊度が１．０ｄｔｅｘ以上１．７ｄｔｅｘ未満であり、引張強度が２９〜４０ｃＮ／ｄｔｅｘであるパラ型全芳香族コポリアミド繊維である。 That is, the present invention comprises a para-type wholly aromatic copolyamide fiber containing a structural repeating unit represented by the following chemical structural formula (1) and the following chemical structural formula (2), and the single yarn fineness is 1.0 dtex or more. It is a para-type wholly aromatic copolyamide fiber having a tensile strength of less than 7 dtex and a tensile strength of 29 to 40 cN / dtex.
また別の本発明は、前述のパラ型全芳香族コポリアミド繊維を含む布帛である。
また別の本発明は、下記化学構造式（１）、および下記化学構造式（２）で示される構造反復単位を含むパラ型全芳香族コポリアミドからなり、単糸繊度が１．０ｄｔｅｘ以上１．７ｄｔｅｘ未満であり、引張強度が２９〜４０ｃＮ／ｄｔｅｘであるパラ型全芳香族コポリアミド繊維の製造方法であって、半乾半湿式法により凝固糸を得る紡糸・凝固工程において、紡糸ドラフトを２〜１０倍の範囲とし、前記凝固糸を可塑化状態で延伸して延伸糸を得る可塑化延伸工程において、延伸倍率を１．３〜２．２倍の範囲とするパラ型全芳香族コポリアミド繊維の製造方法である。
Another aspect of the present invention is a fabric containing the para-type wholly aromatic copolyamide fiber described above.
Another aspect of the present invention comprises a para-type wholly aromatic copolyamide containing structural repeating units represented by the following chemical structural formula (1) and the following chemical structural formula (2), and the single yarn fineness is 1.0 dtex or more and 1 A method for producing a para-type wholly aromatic copolyamide fiber having a tensile strength of less than 0.7 dtex and a tensile strength of 29 to 40 cN / dtex, wherein a spinning draft is obtained in a spinning / coagulation step in which a coagulated yarn is obtained by a semi-dry semi-wet method. A para-type wholly aromatic copolymer having a draw ratio in the range of 1.3 to 2.2 times in a plasticizing drawing step in which the coagulated yarn is drawn in a plasticized state to obtain a drawn yarn in a range of 2 to 10 times. It is a manufacturing method of a polyamide fiber.
本発明のパラ型全芳香族コポリアミド繊維は、単糸繊度が小さくとも、引張強度などの機械的物性に優れ、また、耐結節性等の機械的物性に優れた繊維となる。このため、本発明のパラ型全芳香族コポリアミド繊維は、防弾・防刃材等のといった防護衣料用途や、その他様々な産業資材用途において、非常に有用である。 The para-type wholly aromatic copolyamide fiber of the present invention has excellent mechanical properties such as tensile strength and excellent mechanical properties such as knot resistance even if the single yarn fineness is small. Therefore, the para-type wholly aromatic copolyamide fiber of the present invention is very useful in protective clothing applications such as bulletproof / bladeproof materials and various other industrial material applications.
以下、本発明の実施形態について詳細に説明する。
＜パラ型全芳香族コポリアミド＞
本発明に用いるパラ型全芳香族コポリアミドとは、下記化学構造式（１）、および下記化学構造式（２）で示される構造反復単位からなり、１種類又は２種類以上の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ポリマーであって、一般に公知の方法に従って、アミド系極性溶媒中で、芳香族ジカルボン酸ジクロライドと芳香族ジアミンの重縮合反応により得られる。このとき、該芳香族基は２個の芳香族環が酸素、硫黄、アルキル基で結合されたものであっても特に差し支えない。また、これらの２価の芳香環は、非置換またはメチル基やメチル基等の低級アルキル基や、メトキシ基、または塩素基等のハロゲン基で置換されたものであっても、複素環等が結合されたものであっても特に差し支えはなく、その置換基の種類や置換基の数は特に限定されるものではない。
Hereinafter, embodiments of the present invention will be described in detail.
<Para-type wholly aromatic copolyamide>
The para-type wholly aromatic copolyamide used in the present invention is composed of structural repeating units represented by the following chemical structural formula (1) and the following chemical structural formula (2), and one kind or two or more kinds of divalent fragrances. It is a polymer in which a group is directly linked by an amide bond, and is generally obtained by a polycondensation reaction of an aromatic dicarboxylic acid dichloride and an aromatic diamine in an amide polar solvent according to a known method. In this case, the aromatic group may be one in which two aromatic rings are bonded with oxygen, sulfur, or an alkyl group. These divalent aromatic rings may be unsubstituted or substituted with a lower alkyl group such as a methyl group or a methyl group, or a halogen group such as a methoxy group or a chlorine group. Even if it is bonded, there is no particular limitation, and the type of substituent and the number of substituents are not particularly limited.
本発明においては、上記化学構造式（１）の構造反復単位の含有量が、上記化学構造式（１）および上記化学構造式（２）の構造反復単位の合計に対して、１０〜７０モル％であることが、曳糸性や得られる繊維の機械的物性等の面から好ましい。さらに好ましくは１５〜６０モル％、最も好ましくは２０〜５０モル％の範囲である。 In the present invention, the content of the structural repeating unit of the chemical structural formula (1) is 10 to 70 mol based on the total of the structural repeating units of the chemical structural formula (1) and the chemical structural formula (2). % Is preferred from the standpoints of spinnability and mechanical properties of the resulting fiber. More preferably, it is 15-60 mol%, Most preferably, it is the range of 20-50 mol%.
［パラ型全芳香族コポリアミドの原料］
〔芳香族ジカルボン酸ジクロライド〕
本発明に用いられるパラ型全芳香族コポリアミドの原料とな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’−ビフェニル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が挙げられる。これらの中では、汎用性や繊維の機械的物性等の面から、テレフタル酸ジクロライドが最も好ましい。またこれら芳香族ジカルボン酸ジクロライドは、１種類のみを用いても、あるいは、２種類以上を併用してもよく、その場合の組成比は特に限定されるものではない。
[Raw material of para-type wholly aromatic copolyamide]
[Aromatic dicarboxylic acid dichloride]
Examples of the aromatic dicarboxylic acid dichloride used as a raw material for the para-type wholly aromatic copolyamide used in the present invention include terephthalic acid dichloride, 2-chloroterephthalic acid dichloride, 3-methylterephthalic acid dichloride, and 4,4′-biphenyl. Examples thereof include dicarboxylic acid dichloride and 2,6-naphthalenedicarboxylic acid dichloride. Among these, terephthalic acid dichloride is most preferable from the viewpoints of versatility and mechanical properties of fibers. These aromatic dicarboxylic acid dichlorides may be used alone or in combination of two or more, and the composition ratio in that case is not particularly limited.
〔芳香族ジアミン〕
本発明に用いられるパラ型全芳香族コポリアミドの原料となる芳香族ジアミンとしては、例えば、パラフェニレンジアミン、５−アミノ−２−（４−アミノフェニレン）ベンズイミダゾール、パラ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、１，４−ジクロロパラフェニレンジアミン等が挙げられる。本発明においては、これらに限定されるものではなく、芳香環に置換基がついていたり、その他複素環等がついていたりしても差し支えない。
[Aromatic diamine]
Examples of the aromatic diamine used as a raw material for the para-type wholly aromatic copolyamide used in the present invention include paraphenylenediamine, 5-amino-2- (4-aminophenylene) benzimidazole, parabiphenylenediamine, and 3,4. Examples include '-diaminodiphenyl ether and 1,4-dichloroparaphenylenediamine. In the present invention, the aromatic ring is not limited to these, and the aromatic ring may have a substituent or other heterocyclic ring.
本発明に用いられるパラ型全芳香族コポリアミドの原料としては、上記化学構造式（１）で示される構造反復単位と上記化学構造式（２）で示される構造反復単位とをそれぞれ構成するため、少なくとも２種類以上の芳香族ジアミンを用いる。その組み合わせとしては、汎用性や繊維の機械的物性、曳糸性等の面からパラフェニレンジアミンと５−アミノ−２−（４−アミノフェニレン）ベンズイミダゾールの組み合わせが最も好ましい。その組成比は特に限定されるものではないが、全芳香族ジアミン量に対して、パラフェニレンジアミンを１０〜７０モル％、５−アミノ−２−（４−アミノフェニレン）ベンズイミダゾールを３０〜９０モル％とすることが好ましく、さらに好ましくは、パラフェニレンジアミンを１５〜６０モル％、５−アミノ−２−（４−アミノフェニレン）ベンズイミダゾールを４０〜８５モル％、最も好ましくは、パラフェニレンジアミンを２０〜５０モル％、５−アミノ−２−（４−アミノフェニレン）ベンズイミダゾールを５０〜８０モル％とする範囲である。 As a raw material of the para type wholly aromatic copolyamide used in the present invention, a structural repeating unit represented by the chemical structural formula (1) and a structural repeating unit represented by the chemical structural formula (2) are respectively configured. At least two kinds of aromatic diamines are used. As the combination, the combination of paraphenylenediamine and 5-amino-2- (4-aminophenylene) benzimidazole is most preferable from the viewpoints of versatility, mechanical properties of fibers, and spinnability. The composition ratio is not particularly limited, but 10 to 70 mol% of paraphenylenediamine and 30 to 90 of 5-amino-2- (4-aminophenylene) benzimidazole with respect to the total aromatic diamine amount. Preferably, the molar ratio is 15% to 60% by mole, more preferably 40 to 85% by mole, and most preferably paraphenylenediamine is 5-amino-2- (4-aminophenylene) benzimidazole. Is 20 to 50 mol%, and 5-amino-2- (4-aminophenylene) benzimidazole is 50 to 80 mol%.
［パラ型全芳香族コポリアミドの製造方法］
〔パラ型全芳香族コポリアミドの重合〕
本発明に用いられるパラ型全芳香族コポリアミドの重合にあたっては、アミド系極性溶媒を重合溶媒として、これに、例えば、パラフェニレンジアミンおよび５−アミノ−２−（４−アミノフェニレン）ベンズイミダゾール等の芳香族ジアミン、例えば、テレフタル酸ジクロライド等の芳香族ジカルボン酸ジクロライドをそれぞれ溶解させ、公知の方法による重縮合反応を行う。
[Method for producing para-type wholly aromatic copolyamide]
[Polymerization of para-type wholly aromatic copolyamide]
In the polymerization of the para type wholly aromatic copolyamide used in the present invention, an amide polar solvent is used as a polymerization solvent, and examples thereof include paraphenylenediamine and 5-amino-2- (4-aminophenylene) benzimidazole. Each of the aromatic diamines, for example, aromatic dicarboxylic acid dichlorides such as terephthalic acid dichloride is dissolved, and a polycondensation reaction is performed by a known method.
用いられるアミド系溶媒としては、例えば、Ｎ−メチル−２−ピロリドン（以下ＮＭＰと記す）、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルイミダゾリジノン等が挙げられるが、汎用性、有害性、取り扱い性、パラ型全芳香族コポリアミドポリマーに対する溶解性等の観点から、ＮＭＰが最も好ましい。 Examples of the amide solvent used include N-methyl-2-pyrrolidone (hereinafter referred to as NMP), N, N-dimethylformamide, N, N-dimethylacetamide, dimethylimidazolidinone and the like. NMP is most preferable from the viewpoints of toxicity, handleability, solubility in para-type wholly aromatic copolyamide polymer, and the like.
〔中和反応〕
反応終了後、重縮合反応により系内に塩酸が発生し系内が酸性になるため、中和する目的で、水酸化カルシウム等のアルカリを添加する。アルカリの添加量は、アルカリの種類や芳香族ジアミンと芳香族ジカルボン酸ジクロライドの添加量により異なるが、水酸化カルシウムを用いる場合、芳香族ジカルボン酸ジクロライドに対して９５〜１００モル％の添加量とすることが好ましい。水酸化カルシウムが９５モル％未満の場合には、十分に中和を行うことができず、系内は依然として酸性を示し、解重合の原因になるため好ましくない。また１００モル％を超える場合には、系内がアルカリを示し、同じく解重合の原因となり好ましくない。
中和反応により発生する塩化カルシウムは、生成したポリマーの溶媒への溶解を高める溶解助剤として、そのまま用いることができる。このため、系内から除去する必要はない。
[Neutralization reaction]
After completion of the reaction, hydrochloric acid is generated in the system by the polycondensation reaction and the system becomes acidic. For the purpose of neutralization, an alkali such as calcium hydroxide is added. The amount of alkali added varies depending on the type of alkali and the amount of aromatic diamine and aromatic dicarboxylic acid dichloride, but when calcium hydroxide is used, the amount added is 95 to 100 mol% with respect to the aromatic dicarboxylic acid dichloride. It is preferable to do. When calcium hydroxide is less than 95 mol%, neutralization cannot be carried out sufficiently, and the inside of the system still shows acidity, causing depolymerization. On the other hand, when it exceeds 100 mol%, the inside of the system shows alkali, which is also undesirable because it causes depolymerization.
Calcium chloride generated by the neutralization reaction can be used as it is as a dissolution aid for enhancing the dissolution of the produced polymer in a solvent. For this reason, it is not necessary to remove from the system.
〔重合後処理等〕
得られたパラ型全芳香族コポリアミドポリマーは、ＮＭＰ等のアミド系極性溶媒に溶解した等方性のポリマー溶液であり、単離することなくそのまま、製糸工程で用いることができる。ただし、パラ型全芳香族コポリアミドポリマーの濃度は、ポリマー溶液の粘度や安定性に著しく影響し、ひいては、後の製糸工程における曵糸性等に大きく影響する。このため、ポリマー濃度は、２〜１０質量％の範囲に調整することが好ましい。ポリマー濃度や粘度調整をするためには、得られたポリマー溶液にＮＭＰ等のアミド系極性溶媒を適量添加することができる。
[Post-polymerization treatment, etc.]
The obtained para-type wholly aromatic copolyamide polymer is an isotropic polymer solution dissolved in an amide polar solvent such as NMP, and can be used as it is in the spinning process without isolation. However, the concentration of the para-type wholly aromatic copolyamide polymer significantly affects the viscosity and stability of the polymer solution, and consequently greatly affects the spinnability and the like in the subsequent spinning process. For this reason, it is preferable to adjust a polymer concentration in the range of 2-10 mass%. In order to adjust the polymer concentration and viscosity, an appropriate amount of an amide polar solvent such as NMP can be added to the obtained polymer solution.
＜パラ型全芳香族コポリアミド繊維の製糸＞
次に、本発明のパラ型全芳香族コポリアミド繊維の製造方法について説明する。製糸にあたっては、パラ型全芳香族コポリアミドのポリマードープを用いる。
本発明における「ポリマードープ」とは、パラ型全芳香族コポリアミドポリマーを溶解可能な溶媒に溶解したポリマー溶液を指し、ポリマーが溶媒に溶解した状態で液晶を形成しておらず、ポリマー分子が特定の規則性を持たず無秩序に溶媒中に溶解しているポリマー溶液である。したがって、芳香族ジカルボン酸ジクロライドと芳香族ジアミンの重縮合反応の際に用いる溶媒が、パラ型全芳香族コポリアミドポリマーに対しても良溶媒である場合には、重縮合反応後のポリマーを単離することなく、そのままポリマードープとして用いることができる。
<Threading of para-type wholly aromatic copolyamide fiber>
Next, the manufacturing method of the para type wholly aromatic copolyamide fiber of this invention is demonstrated. For the yarn production, a polymer dope of para-type wholly aromatic copolyamide is used.
“Polymer dope” in the present invention refers to a polymer solution in which a para-type wholly aromatic copolyamide polymer is dissolved in a solvent that can be dissolved. In the state in which the polymer is dissolved in the solvent, no liquid crystal is formed. It is a polymer solution that has no specific regularity and is dissolved in a solvent randomly. Therefore, if the solvent used in the polycondensation reaction of the aromatic dicarboxylic acid dichloride and the aromatic diamine is a good solvent for the para-type wholly aromatic copolyamide polymer, the polymer after the polycondensation reaction is simply used. It can be used as a polymer dope without separation.
また、ポリマードープの調製にあたっては、ポリマーの溶媒への溶解性を高める目的で無機塩を溶解助剤として用いることもできる。この無機塩としては、例えば、塩化カルシウム、塩化リチウム等が挙げられるが、これらに限定されるものではない。ポリマードープに対する無機塩の添加量としては、特に限定されるものではないが、ポリマー溶解性向上の効果や、無機塩の溶媒への溶解性、曳糸性、得られる繊維の機械的物性等の観点から、ポリマードープ質量に対して３〜１０質量％とすることが好ましい。 In preparing the polymer dope, an inorganic salt can also be used as a dissolution aid for the purpose of enhancing the solubility of the polymer in the solvent. Examples of the inorganic salt include, but are not limited to, calcium chloride and lithium chloride. The amount of the inorganic salt added to the polymer dope is not particularly limited, but the effect of improving the polymer solubility, the solubility of the inorganic salt in the solvent, the spinnability, the mechanical properties of the resulting fiber, etc. From a viewpoint, it is preferable to set it as 3-10 mass% with respect to polymer dope mass.
［紡糸・凝固工程］
製糸にあたっては、先ず、公知の半乾半湿式紡糸法または湿式紡糸法を適用し、紡糸口金からエアギャップを介して前述したポリマードープを凝固液中に吐出して凝固させ、凝固糸を得る紡糸・凝固工程を実施する。
[Spinning and coagulation process]
In spinning, first, a known semi-dry semi-wet spinning method or wet spinning method is applied, and the polymer dope described above is discharged from a spinneret through an air gap into a coagulating liquid to coagulate to obtain a coagulated yarn.・ Implement a solidification process.
〔紡糸口金の孔径〕
この際に用いる紡糸口金の孔径は特に限定されるものではないが、吐出安定性や曳糸性等の観点から、０．０５〜０．３ｍｍとすることが好ましく、さらに好ましくは０．１〜０．２５ｍｍの範囲である。
[Spinner hole diameter]
The hole diameter of the spinneret used at this time is not particularly limited, but is preferably 0.05 to 0.3 mm, more preferably 0.1 to 0.1 mm, from the viewpoints of discharge stability and spinnability. The range is 0.25 mm.
〔紡糸ドラフト〕
ここで言う「紡糸ドラフト」とは、ポリマードープが紡糸口金から吐出される際の線速度に対する、凝固工程後に配置した引き取りローラーでの引き取り速度の割合を意味する。本発明においては、紡糸・凝固工程における紡糸ドラフトを、２〜１０倍とすることが必須である。紡糸ドラフトが２倍未満の場合には、後の可塑化延伸工程での延伸倍率を上げたとしても、目標とする単糸繊度や引張強度を達成することが困難である。一方、紡糸ドラフトが１０倍を超える場合には、後述する可塑化延伸工程において、目標の可塑化倍率の到達が困難になるばかりでなく、十分に凝固していない段階での延伸となるため、強度への寄与が小さいために、目標の強度到達が困難となる。さらに、凝固工程において単糸切れや断糸等が発生し、工程通過性等が非常に悪化する。
本発明においては、紡糸ドラフトを２．５〜９倍の範囲とすることがより好ましく、３〜８倍の範囲とすることが最も好ましい。
[Spinning draft]
Here, “spinning draft” means the ratio of the take-up speed at the take-up roller disposed after the coagulation step to the linear speed when the polymer dope is discharged from the spinneret. In the present invention, it is essential that the spinning draft in the spinning / coagulation step is 2 to 10 times. When the spinning draft is less than 2 times, it is difficult to achieve the target single yarn fineness and tensile strength even if the draw ratio in the subsequent plasticizing drawing step is increased. On the other hand, if the spinning draft exceeds 10 times, not only will it be difficult to reach the target plasticization ratio in the plasticizing and stretching step described later, but it will be stretched at a stage where it has not sufficiently solidified, Since the contribution to the strength is small, it is difficult to reach the target strength. Furthermore, single yarn breakage, yarn breakage, etc. occur in the coagulation process, and process passability and the like are extremely deteriorated.
In the present invention, the spinning draft is more preferably 2.5 to 9 times, and most preferably 3 to 8 times.
［可塑化延伸工程］
本発明においては、紡糸・凝固工程を経て凝固糸を得た後、最終的なパラ型全芳香族コポリアミド繊維を得るまでの任意の製造箇所において、得られた繊維束を延伸に付す延伸工程を実施する。延伸としては、得られた凝固糸を高濃度のＮＭＰ水溶液中で可塑化状態として延伸を行う、可塑化延伸工程を実施する。
[Plasticization stretching process]
In the present invention, after obtaining a coagulated yarn through a spinning / coagulation step, a drawing step in which the obtained fiber bundle is subjected to drawing at any production site until the final para-type wholly aromatic copolyamide fiber is obtained. To implement. As the stretching, a plasticizing stretching step is performed in which the obtained coagulated yarn is stretched in a plasticized state in a high concentration NMP aqueous solution.
本発明においては、可塑化延伸工程における可塑化延伸倍率を１．３〜２．２倍の範囲とすることが必須である。可塑化延伸倍率が１．３倍未満の場合には、目標とする単糸繊度並びに引張強度の達成が困難でなる。一方、可塑化延伸倍率が２．２倍を超える場合には、可塑化延伸工程における単糸切れや断糸が多発し、工程通過性が著しく悪化する。
本発明においては、可塑化延伸倍率を１．３５〜２．１倍の範囲とすることがより好ましく、１．４〜２．０倍の範囲とすることが最も好ましい。
In the present invention, it is essential that the plasticizing draw ratio in the plasticizing drawing step is in the range of 1.3 to 2.2 times. When the plasticizing draw ratio is less than 1.3, it is difficult to achieve the target single yarn fineness and tensile strength. On the other hand, when the plasticizing draw ratio exceeds 2.2 times, single yarn breakage and yarn breakage frequently occur in the plasticizing drawing step, and the process passability is remarkably deteriorated.
In the present invention, the plasticizing draw ratio is more preferably 1.35 to 2.1 times, and most preferably 1.4 to 2.0 times.
［その他の工程］
本発明においては、上記紡糸・凝固工程および可塑化延伸工程を実施すれば、製糸におけるその他の工程は特に限定されるものではない。例えば、水洗工程、乾燥工程、熱処理工程、巻取工程等を経て、最終的にパラ型全芳香族コポリアミド繊維を得ることができる。その際、使用する用途等に応じて油剤や加工剤等を付与しても特に差し支えない。なお、各工程における条件は特に限定されるものではなく、公知の工程条件を基に、曳糸性や工程通過性、得られる繊維の品位や機械的物性等の観点から、適宜調整することができる。
[Other processes]
In the present invention, if the spinning / coagulating step and the plasticizing / drawing step are carried out, the other steps in the yarn production are not particularly limited. For example, a para-type wholly aromatic copolyamide fiber can be finally obtained through a washing step, a drying step, a heat treatment step, a winding step, and the like. At that time, an oil agent, a processing agent, or the like may be applied depending on the intended use. The conditions in each step are not particularly limited, and can be appropriately adjusted from the viewpoints of stringiness, processability, fiber quality and mechanical properties obtained based on known process conditions. it can.
＜パラ型全芳香族コポリアミド繊維の物性＞
本発明の製造方法によって得られるパラ型全芳香族コポリアミド繊維は、単糸繊度が１．０ｄｔｅｘ以上１．７ｄｔｅｘ未満、より好ましくは１．１ｄｔｅｘ以上１．６５ｄｔｅｘ未満、最も好ましくは１．２ｄｔｅｘ以上１．６ｄｔｅｘ未満であり、且つ引張強度が２９〜４０ｃＮ／ｄｔｅｘ、より好ましくは２９．５〜３９ｃＮ／ｄｔｅｘ、最も好ましくは３０〜３８ｃＮ／ｄｔｅｘの繊維となる。
<Physical properties of para-type wholly aromatic copolyamide fiber>
The para-type wholly aromatic copolyamide fiber obtained by the production method of the present invention has a single yarn fineness of 1.0 dtex or more and less than 1.7 dtex, more preferably 1.1 dtex or more and less than 1.65 dtex, most preferably 1.2 dtex or more. The fiber has a tensile strength of less than 1.6 dtex and a tensile strength of 29 to 40 cN / dtex, more preferably 29.5 to 39 cN / dtex, and most preferably 30 to 38 cN / dtex.
＜パラ型全芳香族コポリアミド繊維を含む布帛＞
本発明においては、前述のパラ型全芳香族コポリアミド繊維を用いて、用途や目的に応じて布帛を作製する。布帛の作製方法や構造等は特に限定されるものではなく、公知の織機をそのまま用いることができる。織機の種類や製織条件、また織構造等は用途や目的等に応じて、適宜調整することができる。
<Cloth containing para-type wholly aromatic copolyamide fiber>
In the present invention, a fabric is produced using the above-described para-type wholly aromatic copolyamide fiber according to the purpose and purpose. The production method and structure of the fabric are not particularly limited, and a known loom can be used as it is. The type of loom, the weaving conditions, the woven structure, and the like can be appropriately adjusted according to the use and purpose.
以下、本発明を実施例等によりさらに具体的に説明するが、本発明は、その要旨を超えない限り、これに何等限定されるものではない。 EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, this invention is not limited to this unless it exceeds the summary.
＜測定・評価方法＞
実施例および比較例においては、下記の項目について、下記の方法によって測定・評価を行った。
<Measurement and evaluation method>
In Examples and Comparative Examples, the following items were measured and evaluated by the following methods.
（１）繊維の繊度
得られた繊維を、公知の検尺機を用いて１００ｍ巻き取り、その質量を測定した。得られた質量に１００を乗じた値を１００００ｍあたりの繊度（ｄｔｅｘ）として算出した。
(1) Fineness of fiber The obtained fiber was wound up by 100 m using a known measuring machine, and its mass was measured. A value obtained by multiplying the obtained mass by 100 was calculated as a fineness (dtex) per 10,000 m.
（２）平均単糸繊度
オートバイブロ式繊度測定器（サーチ株式会社製、商品名：ＤＥＮＩＣＯＮ、型式：ＤＣ−２１Ｂ）により、以下の条件で単糸繊度の測定を行い、その平均値を平均単糸繊度とした。
［測定条件］
温度 ：室温
試験片 ：７０ｍｍ
荷重 ：０．１ｇ
測定周波数 ：１８００Ｈｚ
測定本数 ：２０
(2) Average single yarn fineness The single yarn fineness was measured under the following conditions with a motorcycle bro type fineness measuring instrument (trade name: DENICON, model: DC-21B, manufactured by Search Corporation). The yarn fineness was set.
[Measurement condition]
Temperature: Room temperature Test piece: 70mm
Load: 0.1g
Measurement frequency: 1800Hz
Number of measurements: 20
（３）繊維の引張強度
引張試験機（ＩＮＳＴＲＯＮ社製、商品名：ＩＮＳＴＲＯＮ、型式：５５６５型）により、糸試験用チャックを用いて、ＡＳＴＭ Ｄ８８５の手順に基づき、以下の条件で測定を実施した。
［測定条件］
温度 ：室温
試験片 ：７５ｃｍ
撚り係数 ：１
試験速度 ：２５０ｍｍ／分
チャック間距離 ：５００ｍｍ
(3) Tensile strength of fiber Using a tensile tester (manufactured by INSTRON, trade name: INSTRON, model: 5565 type), measurement was performed under the following conditions using a yarn test chuck based on the procedure of ASTM D885. .
[Measurement condition]
Temperature: Room temperature Test piece: 75cm
Twist factor: 1
Test speed: 250 mm / min Chuck distance: 500 mm
（４）繊維の結節強度
引張試験機（ＩＮＳＴＲＯＮ社製、商品名：ＩＮＳＴＲＯＮ、型式：５５６５型）により、糸試験用チャックを用いて、ＪＩＳ Ｌ１０１３の手順に基づき、以下の条件で測定を実施した。
［測定条件］
温度 ：室温
試験片 ：７５ｃｍ
撚り係数 ：１
試験速度 ：２５０ｍｍ／分
チャック間距離 ：５００ｍｍ
(4) Knot strength of fiber Using a tensile tester (manufactured by INSTRON, trade name: INSTRON, model: 5565 type), a yarn test chuck was used and measurement was performed under the following conditions based on the procedure of JIS L1013. .
[Measurement condition]
Temperature: Room temperature Test piece: 75cm
Twist factor: 1
Test speed: 250 mm / min Chuck distance: 500 mm
（５）強度保持率
（３）の引張強度、および（４）の結節強度の測定結果を用いて、引張強度に対する強度保持率を下記式（Ａ）により算出した。
(5) Strength retention The strength retention with respect to the tensile strength was calculated by the following formula (A) using the measurement results of the tensile strength of (3) and the knot strength of (4).
（６）布帛の柔軟性
純曲げ試験機（カトーテック株式会社製、商品名：自動化純曲げ試験機、型式：ＫＥＳ−ＦＢ２）を用いて、ＫＥＳ曲げ硬さ（ｇｆ・ｃｍ２／ｃｍ）測定の手順に基づき、以下の条件で測定を実施した。
［測定条件］
温度 ：室温
試験片 ：２０ｃｍ×２０ｃｍ
曲げ速度 ：０．５ｃｍ-1／秒
曲率範囲 ：−２．５〜２．５ｃｍ-1
(6) Flexibility of fabric KES bending hardness (gf · cm 2 / cm) measurement using a pure bending tester (manufactured by Kato Tech Co., Ltd., trade name: automated pure bending tester, model: KES-FB2) Based on the procedure, the measurement was carried out under the following conditions.
[Measurement condition]
Temperature: Room temperature Test piece: 20cm x 20cm
Bending speed: 0.5 cm −1 / sec Curvature range: −2.5 to 2.5 cm −1
＜実施例１＞
［パラ型全芳香族コポリアミドの製造］
公知の方法により、ＮＭＰに溶解したパラフェニレンジアミン１６質量部と５−アミノ−２−（４−アミノフェニレン）ベンズイミダゾール７８質量部に、テレフタル酸ジクロライド１００質量部を添加し、重縮合反応を行い、パラ型全芳香族コポリアミドポリマードープを得た。このときのポリマー濃度は５質量％、ポリマーの極限粘度（ＩＶ）は５．２２であった。
<Example 1>
[Production of para-type wholly aromatic copolyamide]
By a known method, 100 parts by mass of terephthalic acid dichloride is added to 16 parts by mass of paraphenylenediamine and 78 parts by mass of 5-amino-2- (4-aminophenylene) benzimidazole dissolved in NMP, and a polycondensation reaction is performed. A para-type wholly aromatic copolyamide polymer dope was obtained. At this time, the polymer concentration was 5% by mass, and the intrinsic viscosity (IV) of the polymer was 5.22.
［パラ型全芳香族コポリアミド繊維の製造］
次に、穴径０．２ｍｍ、穴数が３００の紡糸口金を１０５℃に加熱した後、１０５℃に加熱したポリマードープを吐出し、半乾半湿式法により１０ｍｍのエアギャップを介して、ＮＭＰ濃度が４０質量％、５０℃の水溶液で満たした凝固浴を通過させ、凝固糸を得た。なおこの紡糸・凝固工程における紡糸ドラフトは５．２とした。
引き続き、得られた凝固糸を、ＮＭＰ濃度が７０質量％、２０℃の水溶液で満たした可塑化浴に通過させて繊維を可塑化状態にし、次いで可塑化延伸を行った。このときの可塑化延伸倍率は、１．６５倍とした。
その後、十分に水洗し、２００℃の乾燥ローラーにて乾燥を行い、熱処理を行う前の基糸を得た。
[Production of para-type wholly aromatic copolyamide fiber]
Next, after heating a spinneret having a hole diameter of 0.2 mm and a hole number of 300 to 105 ° C., the polymer dope heated to 105 ° C. is discharged, and the NMP is passed through an air gap of 10 mm by a semi-dry semi-wet method. The solution was passed through a coagulation bath filled with an aqueous solution having a concentration of 40% by mass and 50 ° C. to obtain a coagulated yarn. The spinning draft in this spinning / coagulation step was set to 5.2.
Subsequently, the obtained coagulated yarn was passed through a plasticizing bath filled with an aqueous solution having an NMP concentration of 70% by mass and 20 ° C. to bring the fiber into a plasticized state, and then subjected to plasticizing drawing. The plasticizing draw ratio at this time was 1.65 times.
Thereafter, it was sufficiently washed with water, dried with a drying roller at 200 ° C., and a base yarn before heat treatment was obtained.
次いで、得られた基糸を、非接触熱処理装置を用いて、炉内酸素濃度＝１５０ｐｐｍ、炉内温度＝４６０℃、張力＝２．５ｍＮ／ｄｔｅｘにて熱処理を行い、最後にワインダーで巻き取ることにより、パラ型全芳香族コポリアミド繊維を得た。
得られたパラ型全芳香族コポリアミド繊維は、繊度が４７５ｄｔｅｘ、フィラメント数が３００、平均単糸繊度が１．５８ｄｔｅｘであった。得られた繊維の引張強度、結節強度および強度保持率を表１に示す。
続いて、得られたパラ型全芳香族コポリアミド繊維を用い、公知のレピア織機を用いて平織りの布帛を製織した。得られた布帛の織構造は、経糸＝３０本／ｉｎｃｈ、緯糸＝３０本／ｉｎｃｈ、目付け＝１１８ｇ／ｍ２であった。得られた布帛の柔軟性（ＫＥＳ曲げ硬さ）を測定した結果を、表１に示す。
Next, the obtained base yarn is heat-treated at a furnace oxygen concentration = 150 ppm, furnace temperature = 460 ° C., tension = 2.5 mN / dtex using a non-contact heat treatment apparatus, and finally wound with a winder. As a result, para-type wholly aromatic copolyamide fibers were obtained.
The obtained para-type wholly aromatic copolyamide fiber had a fineness of 475 dtex, a filament count of 300, and an average single yarn fineness of 1.58 dtex. Table 1 shows the tensile strength, knot strength and strength retention of the obtained fiber.
Subsequently, using the obtained para-type wholly aromatic copolyamide fiber, a plain weave fabric was woven using a known rapier loom. The resulting fabric had a woven structure of warp = 30 / inch, weft = 30 / inch, basis weight = 118 g / m 2 . Table 1 shows the results of measuring the flexibility (KES bending hardness) of the obtained fabric.
＜実施例２＞
紡糸・凝固工程における紡糸ドラフトを２．７、可塑化延伸倍率を２．０倍とした以外は、実施例１と同じ手法により、パラ型全芳香族コポリアミド繊維を得た。得られた繊維は、繊度が４９５ｄｔｅｘ、フィラメント数が３００、平均単糸繊度が１．６５ｄｔｅｘであった。得られたパラ型全芳香族コポリアミド繊維の引張強度、結節強度および強度保持率を、表１に示す。
続いて、得られたパラ型全芳香族コポリアミド繊維を用いて、経糸＝２９．５本／ｉｎｃｈ、緯糸＝２９．５本／ｉｎｃｈとした以外は、実施例１と同じ手法により平織りの布帛を作製した。得られた布帛の目付けは、１２０ｇ／ｍ２であった。また、布帛の柔軟性（ＫＥＳ曲げ硬さ）の測定結果を、表１に示す。
<Example 2>
Para-type wholly aromatic copolyamide fibers were obtained in the same manner as in Example 1 except that the spinning draft in the spinning / coagulation step was 2.7 and the plasticizing draw ratio was 2.0 times. The obtained fiber had a fineness of 495 dtex, a filament count of 300, and an average single yarn fineness of 1.65 dtex. Table 1 shows the tensile strength, knot strength and strength retention of the obtained para-type wholly aromatic copolyamide fiber.
Subsequently, a plain weave fabric was obtained in the same manner as in Example 1 except that the obtained para-type wholly aromatic copolyamide fiber was used with warp = 29.5 / inch and weft = 29.5 / inch. Was made. The basis weight of the obtained fabric was 120 g / m 2 . Table 1 shows the measurement results of the flexibility (KES bending hardness) of the fabric.
＜実施例３＞
紡糸・凝固工程における紡糸ドラフトを７．５、可塑化延伸倍率を１．３５倍とした以外は、実施例１と同じ手法により、パラ型全芳香族コポリアミド繊維を得た。得られた繊維は、繊度が４４２ｄｔｅｘ、フィラメント数が３００、平均単糸繊度が１．４７ｄｔｅｘであった。得られたパラ型全芳香族コポリアミド繊維の引張強度、結節強度および強度保持率を、表１に示す。
続いて、得られたパラ型全芳香族コポリアミド繊維を用いて、経糸＝３１本／ｉｎｃｈ、緯糸＝３１本／ｉｎｃｈとした以外は、実施例１と同じ手法により平織りの布帛を作製した。得られた布帛の目付けは、１１７ｇ／ｍ２であった。また、布帛の柔軟性（ＫＥＳ曲げ硬さ）の測定結果を、表１に示す。
<Example 3>
Para-type wholly aromatic copolyamide fibers were obtained in the same manner as in Example 1 except that the spinning draft in the spinning / coagulation step was 7.5 and the plasticizing draw ratio was 1.35 times. The obtained fiber had a fineness of 442 dtex, a filament count of 300, and an average single yarn fineness of 1.47 dtex. Table 1 shows the tensile strength, knot strength and strength retention of the obtained para-type wholly aromatic copolyamide fiber.
Subsequently, using the obtained para-type wholly aromatic copolyamide fiber, a plain weave fabric was produced in the same manner as in Example 1, except that warp = 31 / inch and weft = 31 / inch. The basis weight of the obtained fabric was 117 g / m 2 . Table 1 shows the measurement results of the flexibility (KES bending hardness) of the fabric.
＜比較例１＞
紡糸・凝固工程における紡糸ドラフトを１．５、可塑化延伸倍率を１．３５倍とした以外は、実施例１と同じ手法により、パラ型全芳香族コポリアミド繊維を得た。得られた繊維は、繊度が６３１ｄｔｅｘ、フィラメント数が３００、平均単糸繊度が２．１ｄｔｅｘであった。得られたパラ型全芳香族コポリアミド繊維の引張強度、結節強度および強度保持率を、表１に示す。
続いて、得られたパラ型全芳香族コポリアミド繊維を用いて、経糸＝２６本／ｉｎｃｈ、緯糸＝２６本／ｉｎｃｈとした以外は、実施例１と同じ手法により平織りの布帛を作製した。得られた布帛の目付けは、１２１ｇ／ｍ２であった。また、布帛の柔軟性（ＫＥＳ曲げ硬さ）の測定結果を、表１に示す。
<Comparative Example 1>
Para-type wholly aromatic copolyamide fibers were obtained in the same manner as in Example 1 except that the spinning draft in the spinning / coagulation step was 1.5 and the plasticizing draw ratio was 1.35 times. The obtained fiber had a fineness of 631 dtex, a filament count of 300, and an average single yarn fineness of 2.1 dtex. Table 1 shows the tensile strength, knot strength and strength retention of the obtained para-type wholly aromatic copolyamide fiber.
Subsequently, a plain weave fabric was produced in the same manner as in Example 1 except that the obtained para-type wholly aromatic copolyamide fiber was used with warp = 26 / inch and weft = 26 / inch. The basis weight of the obtained fabric was 121 g / m 2 . Table 1 shows the measurement results of the flexibility (KES bending hardness) of the fabric.
＜比較例２＞
穴径０．２ｍｍ、穴径が２００の紡糸口金を用い、紡糸・凝固工程における紡糸ドラフトを１．５、可塑化延伸倍率を１．１倍とした以外は、実施例１と同じ手法により、パラ型全芳香族コポリアミド繊維を得た。得られた繊維は、繊度が４７２ｄｔｅｘ、フィラメント数が２００、平均単糸繊度が２．３６ｄｔｅｘであった。得られたパラ型全芳香族コポリアミド繊維の引張強度、結節強度および強度保持率を、表１に示す。
続いて、得られたパラ型全芳香族コポリアミド繊維を用いて、経糸＝３０本／ｉｎｃｈ、緯糸＝３０本／ｉｎｃｈとした以外は、実施例１と同じ手法により平織りの布帛を作製した。得られた布帛の目付けは、１１８ｇ／ｍ２であった。また、布帛の柔軟性（ＫＥＳ曲げ硬さ）の測定結果を、表１に示す。
<Comparative example 2>
Using a spinneret with a hole diameter of 0.2 mm and a hole diameter of 200, except that the spinning draft in the spinning / coagulation step was 1.5 and the plasticizing draw ratio was 1.1 times, the same method as in Example 1, Para-type wholly aromatic copolyamide fiber was obtained. The obtained fiber had a fineness of 472 dtex, a filament count of 200, and an average single yarn fineness of 2.36 dtex. Table 1 shows the tensile strength, knot strength and strength retention of the obtained para-type wholly aromatic copolyamide fiber.
Subsequently, a plain weave fabric was produced in the same manner as in Example 1 except that the obtained para-type wholly aromatic copolyamide fiber was used with warp = 30 / inch and weft = 30 / inch. Weight per unit area of the resulting fabric was 118 g / m 2. Table 1 shows the measurement results of the flexibility (KES bending hardness) of the fabric.
＜比較例３＞
紡糸・凝固工程における紡糸ドラフトを１１．２、可塑化延伸倍率を１．２５倍とした以外は、実施例１と同じ手法により、パラ型全芳香族コポリアミド繊維の作製を試みたが、可塑化延伸工程において断糸が多発し、糸の採取ができなかった。
<Comparative Example 3>
An attempt was made to produce para-type wholly aromatic copolyamide fibers by the same method as in Example 1, except that the spinning draft in the spinning / coagulation step was 11.2 and the plasticizing draw ratio was 1.25 times. During the drawing and drawing process, yarn breakage occurred frequently, and the yarn could not be collected.
＜比較例４＞
紡糸・凝固工程における紡糸ドラフトを５．２、可塑化延伸倍率を２．４倍とした以外は、実施例１と同じ手法により、パラ型全芳香族コポリアミド繊維の作製を試みたが、可塑化延伸工程において断糸が多発し、糸の採取ができなかった。
<Comparative example 4>
An attempt was made to produce a para-type wholly aromatic copolyamide fiber by the same method as in Example 1 except that the spinning draft in the spinning and coagulation process was 5.2 and the plasticizing draw ratio was 2.4 times. During the drawing and drawing process, yarn breakage occurred frequently, and the yarn could not be collected.
本発明のパラ型全芳香族ポリアミド繊維は、単糸繊度が細くとも、引張強度などの機械的物性に優れ、また、耐結節性等の機械的物性に優れた高強度の繊維となる。このため、本発明のパラ型全芳香族コポリアミド繊維は、防弾・防刃材等のといった防護衣料用途や、その他様々な産業資材用途において、非常に有用である。 The para-type wholly aromatic polyamide fiber of the present invention is a high-strength fiber excellent in mechanical properties such as tensile strength and mechanical properties such as knot resistance, even if the single yarn fineness is small. Therefore, the para-type wholly aromatic copolyamide fiber of the present invention is very useful in protective clothing applications such as bulletproof / bladeproof materials and various other industrial material applications.
Claims (4)
半乾半湿式紡糸法または湿式紡糸により凝固糸を得る紡糸・凝固工程において、紡糸ドラフトを２〜１０倍の範囲とし、
前記凝固糸を可塑化状態で延伸して延伸糸を得る可塑化延伸工程において、延伸倍率を１．３〜２．２倍の範囲とするパラ型全芳香族コポリアミド繊維の製造方法。
In the spinning / coagulation step of obtaining a coagulated yarn by semi-dry semi-wet spinning method or wet spinning, the spinning draft is in the range of 2 to 10 times,
A method for producing a para-type wholly aromatic copolyamide fiber in which a draw ratio is in a range of 1.3 to 2.2 times in a plasticizing drawing step of drawing the coagulated yarn in a plasticized state to obtain a drawn yarn.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104040054A (en) * | 2012-01-11 | 2014-09-10 | 纳幕尔杜邦公司 | Aramid copolymer yarn having low residual sulfur |
| JP2015504986A (en) * | 2012-01-11 | 2015-02-16 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Sulfur and alkali metal containing imidazole fibers with ion-bonded halides |
| JP2015504985A (en) * | 2012-01-11 | 2015-02-16 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Sulfur-containing imidazole fiber with ion-bonded halide |
| JP2015506421A (en) * | 2012-01-11 | 2015-03-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Method for removing sulfur from fibers using halogen salt ion exchange |
| JP2015506422A (en) * | 2012-01-11 | 2015-03-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Method for removing sulfur from fibers using a weak base |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61194208A (en) * | 1985-02-18 | 1986-08-28 | Teijin Ltd | Production of polyamide multifilament |
| JPS6399321A (en) * | 1986-10-16 | 1988-04-30 | Asahi Chem Ind Co Ltd | Production of poly-p-phenylene terephthalamide based fiber |
| JP2922327B2 (en) * | 1991-04-11 | 1999-07-19 | 帝人株式会社 | Extra fine aramid fiber |
| WO2008012925A1 (en) * | 2006-07-26 | 2008-01-31 | Teijin Techno Products Limited | Aromatic polyamide fiber and process for producing the same and protective clothing using said aromatic polyamide fiber |
| WO2008075751A1 (en) * | 2006-12-15 | 2008-06-26 | Teijin Techno Products Limited | Heterocyclic ring-containing aromatic polyamide fiber, method for producing the same, fabric comprising the fiber, fiber-reinforced composite material reinforced with the fiber |
| JP2008156801A (en) * | 2006-12-26 | 2008-07-10 | Teijin Techno Products Ltd | Ultra fine meta-type wholly aromatic polyamide fibers and method for producing the same |
-
2010
- 2010-03-25 JP JP2010070183A patent/JP2011202308A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61194208A (en) * | 1985-02-18 | 1986-08-28 | Teijin Ltd | Production of polyamide multifilament |
| JPS6399321A (en) * | 1986-10-16 | 1988-04-30 | Asahi Chem Ind Co Ltd | Production of poly-p-phenylene terephthalamide based fiber |
| JP2922327B2 (en) * | 1991-04-11 | 1999-07-19 | 帝人株式会社 | Extra fine aramid fiber |
| WO2008012925A1 (en) * | 2006-07-26 | 2008-01-31 | Teijin Techno Products Limited | Aromatic polyamide fiber and process for producing the same and protective clothing using said aromatic polyamide fiber |
| WO2008075751A1 (en) * | 2006-12-15 | 2008-06-26 | Teijin Techno Products Limited | Heterocyclic ring-containing aromatic polyamide fiber, method for producing the same, fabric comprising the fiber, fiber-reinforced composite material reinforced with the fiber |
| JP2008156801A (en) * | 2006-12-26 | 2008-07-10 | Teijin Techno Products Ltd | Ultra fine meta-type wholly aromatic polyamide fibers and method for producing the same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104040054A (en) * | 2012-01-11 | 2014-09-10 | 纳幕尔杜邦公司 | Aramid copolymer yarn having low residual sulfur |
| KR20140111695A (en) * | 2012-01-11 | 2014-09-19 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Aramid copolymer yarn having low residual sulfur |
| JP2015504986A (en) * | 2012-01-11 | 2015-02-16 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Sulfur and alkali metal containing imidazole fibers with ion-bonded halides |
| JP2015504985A (en) * | 2012-01-11 | 2015-02-16 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Sulfur-containing imidazole fiber with ion-bonded halide |
| JP2015506421A (en) * | 2012-01-11 | 2015-03-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Method for removing sulfur from fibers using halogen salt ion exchange |
| JP2015506422A (en) * | 2012-01-11 | 2015-03-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Method for removing sulfur from fibers using a weak base |
| JP2015510047A (en) * | 2012-01-11 | 2015-04-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Aramid copolymer yarn with low residual sulfur |
| KR101923762B1 (en) | 2012-01-11 | 2018-11-29 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Aramid copolymer yarn having low residual sulfur |
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