JP2010261133A - Laminated protective suit - Google Patents
Laminated protective suit Download PDFInfo
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- JP2010261133A JP2010261133A JP2009114784A JP2009114784A JP2010261133A JP 2010261133 A JP2010261133 A JP 2010261133A JP 2009114784 A JP2009114784 A JP 2009114784A JP 2009114784 A JP2009114784 A JP 2009114784A JP 2010261133 A JP2010261133 A JP 2010261133A
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- fabric
- aromatic polyamide
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- 230000001681 protective effect Effects 0.000 title claims abstract description 67
- 239000000835 fiber Substances 0.000 claims abstract description 155
- 239000004744 fabric Substances 0.000 claims abstract description 108
- 239000004760 aramid Substances 0.000 claims abstract description 73
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 73
- 238000004043 dyeing Methods 0.000 claims description 88
- 239000010410 layer Substances 0.000 claims description 38
- -1 polytetrafluoroethylene Polymers 0.000 claims description 28
- 239000002344 surface layer Substances 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 9
- 239000005871 repellent Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 67
- 230000008569 process Effects 0.000 abstract description 29
- 238000010438 heat treatment Methods 0.000 abstract description 26
- 239000004033 plastic Substances 0.000 abstract description 20
- 229920003023 plastic Polymers 0.000 abstract description 20
- 239000000975 dye Substances 0.000 abstract description 16
- 238000005406 washing Methods 0.000 abstract description 14
- 230000002040 relaxant effect Effects 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 description 35
- 239000000243 solution Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 26
- 238000009987 spinning Methods 0.000 description 25
- 238000005259 measurement Methods 0.000 description 22
- 238000005345 coagulation Methods 0.000 description 16
- 230000015271 coagulation Effects 0.000 description 16
- 239000002759 woven fabric Substances 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 7
- 238000000691 measurement method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical group NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- IRBICNVNOXDYKS-UHFFFAOYSA-N 1-chlorocyclohexa-3,5-diene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(Cl)(C(Cl)=O)C1 IRBICNVNOXDYKS-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- LKGQTURGJNTDLR-UHFFFAOYSA-N 2-chlorobenzene-1,3-diamine Chemical compound NC1=CC=CC(N)=C1Cl LKGQTURGJNTDLR-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- LVGKZTVMAHRVFR-UHFFFAOYSA-N 4-(phenoxazine-10-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C2OC2=CC=CC=C21 LVGKZTVMAHRVFR-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000544 Gore-Tex Polymers 0.000 description 1
- 229920006282 Phenolic fiber Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 229920003071 Polyclar® Polymers 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- YAZXITQPRUBWGP-UHFFFAOYSA-N benzene-1,3-dicarbonyl bromide Chemical compound BrC(=O)C1=CC=CC(C(Br)=O)=C1 YAZXITQPRUBWGP-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920006376 polybenzimidazole fiber Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000007447 staining method Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Abstract
Description
本発明は、積層布帛からなる防護服に関する。より詳しくは、染色性が良好であるとともに、繊維の強度、および、熱収縮安定性に優れた、メタ型全芳香族ポリアミド繊維を含む易染色性布帛を含む積層防護服に関する。 The present invention relates to a protective garment comprising a laminated fabric. More specifically, the present invention relates to a laminated protective garment including an easily dyeable fabric containing a meta-type wholly aromatic polyamide fiber, which has good dyeability and excellent fiber strength and heat shrinkage stability.
ポリメタフェニレンテレフタルアミド繊維等のメタ型全芳香族ポリアミド繊維は、分子骨格のほとんどが芳香族環から構成されているため、優れた耐熱性と寸法安定性を発現する。これらの特性を活かして、メタ型全芳香族ポリアミド繊維は、消防士が消火作業中に着用する耐熱防護服を構成する繊維として、好適に使用されている。 Meta-type wholly aromatic polyamide fibers such as polymetaphenylene terephthalamide fiber exhibit excellent heat resistance and dimensional stability because most of the molecular skeleton is composed of aromatic rings. Taking advantage of these characteristics, meta-type wholly aromatic polyamide fibers are suitably used as fibers constituting heat-resistant protective clothing worn by firefighters during fire fighting operations.
そして、防護服の分野においては、耐熱性や寸法安定性以外に、視覚性や審美性等の美的観点での特性も必要とされており、特に、着色した繊維が求められていた。さらに、安全性の観点からは、より優れた繊維強度や熱収縮安定性が求められていた。 In the field of protective clothing, in addition to heat resistance and dimensional stability, characteristics from the viewpoint of aesthetics such as visibility and aesthetics are required, and in particular, colored fibers have been demanded. Furthermore, from the viewpoint of safety, more excellent fiber strength and heat shrinkage stability have been demanded.
加えて、近年、耐熱性防護服に関しては遮熱性の評価方法について標準化がなされ、輻射熱はもとより、伝導熱にも注目した評価方法が確立された（試験法番号：ＩＳＯ９１５１）。そして、この評価方法による基準をクリアするにあたり、すなわち、熱伝導を遅延させるにあたっては、防護服内に大量の空気層を作ることが効果的である。 In addition, in recent years, with respect to heat-resistant protective clothing, standardization has been made on the method for evaluating heat shielding properties, and an evaluation method focusing on conduction heat as well as radiant heat has been established (test method number: ISO 9151). And in clearing the standard by this evaluation method, that is, in delaying heat conduction, it is effective to create a large amount of air layer in the protective clothing.
以上のように、耐熱性防護服の要求特性は、より高度なものに変化しており、このため、例えば、表地層、透湿防水性を有する中間層、および遮熱性を有する裏地層からなる３層構造の防護服や、表地層と裏地層との間に充分な量の空気を含有させることで中間層を簡略化した２層構造の防護服が提案されており、昨今では、２層または３層を重ねて縫製した耐熱性防護服が主流となっている（特許文献１参照）。 As described above, the required characteristics of heat-resistant protective clothing have been changed to more advanced ones. For this reason, for example, it consists of a surface layer, a moisture-permeable waterproof intermediate layer, and a heat-insulating lining layer Three-layered protective clothing and two-layered protective clothing in which the intermediate layer is simplified by containing a sufficient amount of air between the outer layer and the lining layer have been proposed. Or the heat-resistant protective clothing which piled up three layers and sewed has become the mainstream (refer patent document 1).
しかしながら、従来の技術では、耐熱性等の機能的特性を満足させつつ、染色性、および、優れた機械的強度と熱寸法安定性とをバランスよく満足させた、メタ型全芳香族ポリアミド繊維を含む易染色性布帛を、少なくとも１層として含む積層防護服は、未だ存在していなかった。 However, in the conventional technology, a meta type wholly aromatic polyamide fiber that satisfies the functional properties such as heat resistance and satisfies a good balance between dyeability and excellent mechanical strength and thermal dimensional stability is provided. There has not yet been a layered protective garment including at least one layer of the easily dyeable fabric.
本発明は、上記背景技術に鑑みてなされたものであり、その目的とするところは、染料に対する染色性に優れ、しかも、繊維の強度、および、熱収縮安定性をバランスよく兼備したメタ型全芳香族ポリアミド繊維を主成分として含む易染色性布帛を、少なくとも１層として含む積層防護服を提供することにある。 The present invention has been made in view of the background art described above, and the object of the present invention is an excellent meta type that has excellent dyeability for dyes, and also has a good balance of fiber strength and heat shrink stability. An object of the present invention is to provide a laminated protective garment including at least one layer of an easily dyeable fabric containing an aromatic polyamide fiber as a main component.
本発明者らは、上記の課題に鑑み鋭意検討を重ねた。その結果、特定倍率範囲での可塑延伸および水洗工程を経た後、乾熱処理前に水蒸気弛緩熱処理を行ったメタ型全芳香族ポリアミド繊維を含む易染色性布帛を、少なくとも１層として用いることにより、上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors have made extensive studies in view of the above problems. As a result, by using a readily dyeable fabric containing a meta-type wholly aromatic polyamide fiber that has undergone a plastic stretching and water washing step in a specific magnification range and then subjected to a steam relaxation heat treatment before a dry heat treatment, as at least one layer, The present inventors have found that the above problems can be solved and have completed the present invention.
すなわち本発明は、積層布帛からなる防護服であって、該積層布帛は、メタ型全芳香族ポリアミド繊維を含む布帛を、少なくとも１層として含むものであり、該メタ型全芳香族ポリアミド繊維は、原繊維の破断強度が２．５ｃＮ／ｄｔｅｘ以上、染色前後の３００℃乾熱収縮率の比が２．５以下であり、染色後の該メタ型全芳香族ポリアミド繊維を含む布帛の明度指数Ｌ＊値が、３０以下である積層防護服である。 That is, the present invention is a protective garment comprising a laminated fabric, and the laminated fabric includes a fabric containing a meta-type wholly aromatic polyamide fiber as at least one layer. The lightness index of the fabric containing the meta-type wholly aromatic polyamide fiber after dyeing, wherein the breaking strength of the fibril is 2.5 cN / dtex or more, the ratio of the 300 ° C. dry heat shrinkage before and after dyeing is 2.5 or less It is a layered protective clothing whose L * value is 30 or less.
本発明の積層防護服は、メタ型全芳香族ポリアミド繊維が本来有する、優れた耐熱性、耐炎性、防炎性を発現するとともに、染料に対する染色性が良好であり、かつ、優れた繊維強度、および、熱収縮安定性を兼ね備える。このため、これらの特性が必要とされる分野における工業的価値は極めて大きく、特に、消防士が消火作業中に着用する耐熱防護服として好適に用いることができる。 The laminated protective garment of the present invention expresses the excellent heat resistance, flame resistance and flameproofness inherent to the meta-type wholly aromatic polyamide fiber, has good dyeability for dyes, and has excellent fiber strength. And heat shrink stability. For this reason, the industrial value in the field | area where these characteristics are required is very large, and can be used suitably especially as a heat-resistant protective clothing which a firefighter wears during a fire fighting operation.
以下、本発明について詳細に説明する。
本発明の積層防護服は、以下に記載する易染色性メタ型全芳香族ポリアミド繊維を含む易染色性布帛を、少なくとも１層として含むものである。
Hereinafter, the present invention will be described in detail.
The layered protective garment of the present invention includes at least one easy-dyeable fabric containing the easy-dyeable meta-type wholly aromatic polyamide fiber described below.
＜易染色性メタ型全芳香族ポリアミド繊維＞
本発明に用いられる易染色性メタ型全芳香族ポリアミド繊維は、以下の特定の物性を兼ね備える。本発明に用いられる易染色性メタ型全芳香族ポリアミド繊維の物性、構成、および、製造方法等について以下に説明する。
<Easily dyeable meta-type wholly aromatic polyamide fiber>
The readily dyeable meta-type wholly aromatic polyamide fiber used in the present invention has the following specific physical properties. The physical properties, configuration, production method and the like of the easily dyeable meta-type wholly aromatic polyamide fiber used in the present invention will be described below.
［易染色性メタ型全芳香族ポリアミド繊維の物性］
〔原繊維の破断強度〕
本発明に用いられる易染色性メタ型全芳香族ポリアミド繊維の原繊維（染色前の繊維）の破断強度は、２．５ｃＮ／ｄｔｅｘ以上である。２．５ｃＮ／ｄｔｅｘ以上であることが必須であり、２．７ｃＮ／ｄｔｅｘ以上であることが好ましく、２．９以上であることがさらに好ましい。破断強度が２．５ｃＮ／ｄｔｅｘ未満である場合には、紡績・染色等の後加工工程の通過性が悪化するため好ましくない。
易染色性メタ型全芳香族ポリアミド繊維の原繊維（染色前の繊維）の破断強度は、後記する製造方法における可塑延伸工程において、延伸倍率を適正化することにより制御することができる。２．５ｃＮ／ｄｔｅｘ以上とするためには、延伸倍率を２．５〜１０．０倍の範囲とすればよい。
[Physical properties of readily dyeable meta-type wholly aromatic polyamide fibers]
[Fracture strength of fibrils]
The breaking strength of the easy-dyeable meta-type wholly aromatic polyamide fiber used in the present invention (fiber before dyeing) is 2.5 cN / dtex or more. It is essential that it is 2.5 cN / dtex or more, preferably 2.7 cN / dtex or more, and more preferably 2.9 or more. When the breaking strength is less than 2.5 cN / dtex, the passability in post-processing steps such as spinning and dyeing deteriorates, which is not preferable.
The breaking strength of the easily dyeable meta-type wholly aromatic polyamide fiber fibrils (fibers before dyeing) can be controlled by optimizing the draw ratio in the plastic drawing step in the production method described later. In order to achieve 2.5 cN / dtex or more, the draw ratio may be in the range of 2.5 to 10.0 times.
なお、本発明における「破断強度」とは、ＪＩＳ Ｌ １０１５に基づき、以下の条件で測定して得られる値をいう。
（測定条件）
つかみ間隔 ：２０ｍｍ
初荷重 ：０．０４４ｃＮ（１／２０ｇ）／ｄｔｅｘ
引張速度 ：２０ｍｍ／分
The “breaking strength” in the present invention refers to a value obtained by measurement under the following conditions based on JIS L 1015.
(Measurement condition)
Grasp interval: 20mm
Initial load: 0.044 cN (1/20 g) / dtex
Tensile speed: 20 mm / min
〔染色前後の３００℃乾熱収縮率の比〕
本発明に用いられる易染色性メタ型全芳香族ポリアミド繊維は、染色前後の３００℃乾熱収縮率（染色前３００℃乾熱収縮率／染色後３００℃乾熱収縮率）の比が２．５以下である。染色前後の３００℃乾熱収縮率の比は、２．５以下であることが必須であり、２．３以下が好ましく、２．２以下がさらに好ましく、２．１以下が最も好ましい。一般に、収縮率の比が２．５を超えて変化する場合には、染色工程で繊維の収縮が起こることから、原繊維構造体の設計が困難となる。
易染色性メタ型全芳香族ポリアミド繊維の染色前後の３００℃乾熱収縮率の比は、後記する製造方法における蒸気処理工程において、弛緩倍率を適正化することにより制御することができる。比を２．５以下とするためには、弛緩倍率を０．６５〜１．０倍の範囲とすればよい。
[Ratio of 300 ° C dry heat shrinkage before and after dyeing]
The easily dyeable meta type wholly aromatic polyamide fiber used in the present invention has a ratio of 300 ° C. dry heat shrinkage before and after dyeing (300 ° C. dry heat shrinkage before dyeing / 300 ° C. dry heat shrinkage after dyeing) of 2. 5 or less. The ratio of the 300 ° C. dry heat shrinkage ratio before and after dyeing is essential to be 2.5 or less, preferably 2.3 or less, more preferably 2.2 or less, and most preferably 2.1 or less. In general, when the ratio of shrinkage ratios exceeds 2.5, fiber shrinkage occurs in the dyeing process, making it difficult to design a fibril structure.
The ratio of the 300 ° C. dry heat shrinkage ratio before and after dyeing of the easily dyeable meta-type wholly aromatic polyamide fiber can be controlled by optimizing the relaxation rate in the steam treatment step in the production method described later. In order to make the ratio 2.5 or less, the relaxation magnification may be in the range of 0.65 to 1.0.
なお、本発明における「３００℃乾熱収縮率」および「染色前後の３００℃乾熱収縮率の比」とは、以下の方法で得られる値をいう。
（３００℃乾熱収縮率）
約３３００ｄｔｅｘのトウに９８ｃＮ（１００ｇ）の荷重を吊るし、互いに３０ｃｍ離れた箇所に印をつける。荷重を除去後、トウを３００℃雰囲気下に１５分間置いた後、印間の長さＬを測定する。測定結果Ｌをもとに、下記式にて得られる値を３００℃乾熱収縮率（％）とする。
３００℃乾熱収縮率（％）＝（３０−Ｌ）／３０×１００
In the present invention, “300 ° C. dry heat shrinkage” and “300 ° C. dry heat shrinkage ratio before and after dyeing” refer to values obtained by the following method.
(300 ° C dry heat shrinkage)
A load of 98 cN (100 g) is hung on a tow of about 3300 dtex, and points 30 cm apart are marked. After removing the load, the tow is placed in an atmosphere of 300 ° C. for 15 minutes, and then the length L between the marks is measured. Based on the measurement result L, the value obtained by the following equation is defined as 300 ° C. dry heat shrinkage (%).
300 ° C. dry heat shrinkage (%) = (30−L) / 30 × 100
（染色前後の３００℃乾熱収縮率の比）
上記の測定・算出法により、原繊維の３００℃乾熱収縮率と染色繊維の３００℃乾熱収縮率とをそれぞれ求める。染色前後の３００℃乾熱収縮率の比は、得られた結果を用いて、下記式にて得られる値とする。
染色前後の３００℃乾熱収縮率比＝原繊維の３００℃乾熱収縮率／染色繊維の３００℃乾熱収縮率
(Ratio of 300 ° C dry heat shrinkage before and after dyeing)
By the measurement / calculation method described above, the 300 ° C. dry heat shrinkage of the original fiber and the 300 ° C. dry heat shrinkage of the dyed fiber are determined. The ratio of the 300 ° C. dry heat shrinkage ratio before and after dyeing is a value obtained by the following equation using the obtained results.
300 ° C. dry heat shrinkage ratio before and after dyeing = 300 ° C. dry heat shrinkage of the original fiber / 300 ° C. dry heat shrinkage of the dyed fiber
なお、本発明における「染色」とは、特に指定されない場合には、以下の染色方法による染色を意味する。
（染色方法）
カチオン染料（日本化薬社製、商品名：Ｋａｙａｃｒｙｌ Ｂｌｕｅ ＧＳＬ−ＥＤ（Ｂ−５４））６％ｏｗｆ、酢酸０．３ｍＬ／Ｌ、硝酸ナトリウム２０ｇ／Ｌ、キャリア剤としてベンジルアルコール７０ｇ／Ｌ、分散剤として染色助剤（明成化学工業社製、商品名：ディスパーＴＬ）０．５ｇ／Ｌを含む染色液を用意する。引き続き、繊維と当該染色液の浴比を１：４０として、１２０℃下６０分間の染色処理を実施する。
The “staining” in the present invention means staining by the following staining method unless otherwise specified.
(Dyeing method)
Cationic dye (Nippon Kayaku Co., Ltd., trade name: Kayacryl Blue GSL-ED (B-54)) 6% owf, acetic acid 0.3 mL / L, sodium nitrate 20 g / L, carrier agent benzyl alcohol 70 g / L, dispersion A dyeing solution containing 0.5 g / L of a dyeing assistant (manufactured by Meisei Chemical Co., Ltd., trade name: Disper TL) is prepared as an agent. Subsequently, the dyeing treatment is performed at 120 ° C. for 60 minutes with the bath ratio of the fiber and the dyeing solution being 1:40.
〔原繊維の３００℃乾熱収縮率〕
本発明に用いられる易染色性メタ型全芳香族ポリアミド繊維は、原繊維（染色前の繊維）の３００℃乾熱収縮率が３．０％以下であることが好ましい。原繊維の３００℃乾熱収縮率は、３．０％以下であることが好ましく、２．９％以下がより好ましく、２．８％以下が特に好ましい。収縮率が３．０％を超える場合には、高温雰囲気下での使用時に製品寸法が変化し、製品の破損が生じる等の問題が発生するため好ましくない。
[300 ° C dry heat shrinkage of fibrils]
The easily dyeable meta-type wholly aromatic polyamide fiber used in the present invention preferably has a fibril (pre-dyeing) 300 ° C. dry heat shrinkage of 3.0% or less. The 300 ° C. dry heat shrinkage of the fibril is preferably 3.0% or less, more preferably 2.9% or less, and particularly preferably 2.8% or less. When the shrinkage rate exceeds 3.0%, it is not preferable because the product dimensions change when used in a high-temperature atmosphere and the product is damaged.
本発明において、易染色性メタ型全芳香族ポリアミド繊維の原繊維の３００℃乾熱収縮率は、後に記載する製造方法における水蒸気弛緩熱処理工程において、弛緩倍率を適正化することにより制御することができる。原繊維の３００℃乾熱収縮率を３．０％以下とするためには、弛緩倍率を０．６５〜１．０とすればよい。 In the present invention, the 300 ° C. dry heat shrinkage rate of the easily dyeable meta-type wholly aromatic polyamide fiber fibrils can be controlled by optimizing the relaxation rate in the steam relaxation heat treatment step in the production method described later. it can. In order to set the 300 ° C. dry heat shrinkage of the fibrils to 3.0% or less, the relaxation ratio may be set to 0.65 to 1.0.
易染色性メタ全型芳香族ポリアミド繊維の原繊維の３００℃乾熱収縮率は、後に記載する製造方法における水蒸気弛緩熱処理工程において、弛緩倍率を適正化することにより制御することができる。原繊維の３００℃乾熱収縮率を３．０％以下とするためには、弛緩倍率を０．６５〜１．０倍の範囲とすればよい。
なお、原繊維の３００℃乾熱収縮率は、上記した３００℃乾熱収縮率の測定方法によって測定する。
The 300 ° C. dry heat shrinkage ratio of the easy-dyeable meta-all-aromatic polyamide fibers can be controlled by optimizing the relaxation rate in the steam relaxation heat treatment step in the production method described later. In order to set the 300 ° C. dry heat shrinkage of the fibrils to 3.0% or less, the relaxation ratio may be in the range of 0.65 to 1.0.
In addition, the 300 degreeC dry heat shrinkage rate of a fibril is measured with the measuring method of the above-mentioned 300 degreeC dry heat shrinkage rate.
＜易染色性メタ型全芳香族ポリアミド繊維を含む易染色性布帛＞
［布帛の構成成分］
本発明の積層防護服の少なくとも１層となる易染色性布帛は、上記の易染色性メタ型全芳香族ポリアミド繊維を含むものである。布帛における易染色性メタ型全芳香族ポリアミド繊維の含有量は、染色性や風合いの観点から繊維の全質量に対して５０質量％以上であり、好ましくは８０質量％以上、さらに好ましくは９０質量％以上、特に好ましくは１００％である。
<Easily Dyeable Fabric Containing Easily Dyeable Meta-type Fully Aromatic Polyamide Fiber>
[Constituent components of fabric]
The easily dyeable fabric which is at least one layer of the laminated protective garment of the present invention contains the above easily dyeable meta type wholly aromatic polyamide fiber. The content of the easily dyeable meta-type wholly aromatic polyamide fiber in the fabric is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass with respect to the total mass of the fiber from the viewpoint of dyeability and texture. % Or more, particularly preferably 100%.
なお、本発明の積層防護服を構成する易染色性布帛において、該易染色性メタ型全芳香族ポリアミド繊維と混合する繊維としては、例えば、ポリベンゾイミダゾール繊維、ポリイミド繊維、ポリアミドイミド繊維、ポリエーテルイミド繊維、ポリアリレート繊維、ポリパラフェニレンベンゾビスオキサゾール繊維、ノボロイド繊維、難燃アクリル繊維、ポリクラール繊維、難燃ポリエステル繊維、難燃綿繊維、難燃ウール繊維、パラ型全芳香族ポリアミド繊維等を例示できる。これらのなかでは、繊維の強度や耐熱性の観点から、パラ型全芳香族ポリアミドが好ましい。 In the easily dyeable fabric constituting the laminated protective garment of the present invention, examples of the fiber mixed with the easily dyeable meta-type wholly aromatic polyamide fiber include polybenzimidazole fiber, polyimide fiber, polyamideimide fiber, poly Etherimide fiber, polyarylate fiber, polyparaphenylene benzobisoxazole fiber, novoloid fiber, flame retardant acrylic fiber, polyclar fiber, flame retardant polyester fiber, flame retardant cotton fiber, flame retardant wool fiber, para type wholly aromatic polyamide fiber, etc. It can be illustrated. Of these, para-type wholly aromatic polyamides are preferable from the viewpoints of fiber strength and heat resistance.
［布帛の形態］
本発明の積層防護服を構成する易染色性布帛の形態は、特に限定されるものではなく、布帛に求められる目的、用途等により適宜選択すればよい。
易染色性メタ型全芳香族ポリアミド繊維以外の繊維を含む場合には、例えば、メタ型全芳香族ポリアミド繊維と混合される繊維とを、常法により混合して紡績糸の形態とした後に、該紡績糸を用いて布帛を形成することが挙げられる。本発明において、易染色性布帛の形態は、織物、編物、不織布等、いずれの形態であってもよい。
[Fabric form]
The form of the easily dyeable fabric constituting the layered protective clothing of the present invention is not particularly limited, and may be appropriately selected depending on the purpose, use, etc. required for the fabric.
When including fibers other than the easily dyeable meta-type wholly aromatic polyamide fiber, for example, after mixing the fiber mixed with the meta-type wholly aromatic polyamide fiber by a conventional method to form a spun yarn, Examples include forming a fabric using the spun yarn. In the present invention, the form of the easily dyeable fabric may be any form such as a woven fabric, a knitted fabric, and a non-woven fabric.
易染色性布帛の目付は、１５０〜３５０ｇ／ｍ２の範囲にあることが好ましい。該目付が１５０ｇ／ｍ２未満の場合には、充分な耐熱性能が得られないおそれがあり、一方で、該目付けが３５０ｇ／ｍ２を越える場合には、防護服にした際に重くなり、着用感が阻害されるため好ましくない。 The basis weight of the easily dyeable fabric is preferably in the range of 150 to 350 g / m 2 . If the basis weight is less than 150 g / m 2 , sufficient heat resistance may not be obtained. On the other hand, if the basis weight exceeds 350 g / m 2 , it becomes heavy when used as protective clothing, Since a feeling of wearing is inhibited, it is not preferred.
［易染色性布帛の物性］
〔染色布帛の明度指数Ｌ＊値〕
本発明に用いられる易染色性布帛は、上記の染色方法で染色した布帛の明度指数Ｌ＊値が３０以下である。明度指数Ｌ＊値が３０を超える場合には、十分な染色性が得られないため好ましくない。
[Physical properties of easily dyeable fabric]
[Lightness index L * value of dyed fabric]
In the easily dyeable fabric used in the present invention, the lightness index L * value of the fabric dyed by the above dyeing method is 30 or less. A lightness index L * value exceeding 30 is not preferable because sufficient dyeability cannot be obtained.
染色布帛の明度指数Ｌ＊値は、後記するメタ型全芳香族ポリアミド繊維の製造方法における水蒸気弛緩熱処理工程において、弛緩倍率を適正化することにより制御することができる。布帛の明度指数Ｌ＊値を３０以下とするためには、弛緩倍率を０．６５〜１．０倍の範囲とすればよい。 The lightness index L * value of the dyed fabric can be controlled by optimizing the relaxation rate in the steam relaxation heat treatment step in the process for producing a meta-type wholly aromatic polyamide fiber described later. In order to set the lightness index L * value of the fabric to 30 or less, the relaxation magnification may be in the range of 0.65 to 1.0.
なお、本発明における「明度指数Ｌ＊値」とは、上記の染色方法で染色した繊維に対して、以下の測定法で測定した値をいう。なお、Ｌ＊は、数値が小さいほど濃染化されていることを示す。
（測定方法）
カラー測色装置（マスベク社製、商品名：マクベスカラーアイ モデルＣＥ−３１００）を用いて、以下の測定条件で測定する。
｛測定条件｝
視野 ：１０度
光源 ：Ｄ６５
波長 ：３６０〜７４０ｎｍ
In addition, the “lightness index L * value” in the present invention refers to a value measured by the following measurement method on the fiber dyed by the above dyeing method. In addition, L * shows that it is deeply dyed, so that a numerical value is small.
(Measuring method)
Measurement is performed under the following measurement conditions using a color measuring device (trade name: Macbeth Color Eye Model CE-3100, manufactured by Masbek).
{Measurement condition}
Field of view: 10 degrees Light source: D65
Wavelength: 360-740 nm
〔染色布帛の染着率〕
本発明の易染色性布帛は、上記の染色方法で染色した布帛の染着率が９０％以上であることが好ましい。染色布帛の染着率は、９０％以上であることが好ましく、９２％以上であることがより好ましい。染色布帛の染着率が９０％未満の場合には、染色工程における染料のロス量が増えることから、染色工程でのコストが増加するため好ましくない。
染色布帛の染着率は、後記するメタ型全芳香族ポリアミド繊維の製造方法における水蒸気弛緩熱処理工程において、弛緩倍率を適正化することにより制御することができる。染色繊維の染着率を９０％以上とするためには、弛緩倍率を０．６５〜１．０倍の範囲とすればよい。
[Dyeing rate of dyed fabric]
The easily dyeable fabric of the present invention preferably has a dyeing rate of 90% or more of the fabric dyed by the above dyeing method. The dyeing rate of the dyed fabric is preferably 90% or more, and more preferably 92% or more. When the dyeing rate of the dyed fabric is less than 90%, the loss amount of the dye in the dyeing process increases, which is not preferable because the cost in the dyeing process increases.
The dyeing rate of the dyed fabric can be controlled by optimizing the relaxation rate in the steam relaxation heat treatment step in the process for producing a meta-type wholly aromatic polyamide fiber described later. In order to set the dyeing rate of the dyed fibers to 90% or more, the relaxation magnification may be in the range of 0.65 to 1.0.
なお、本発明における「染着率」とは、以下の方法によって得られる値をいう。
（染着率）
布帛を染色した染色残液に、この染色残液と同容積のジクロロメタンを加え、残染料を抽出する。引き続き、抽出液について、波長６７０ｎｍ、５４０ｎｍ、５３０ｎｍの吸光度をそれぞれ測定し、あらかじめ染料濃度が既知のジクロロメタン溶液から作成した上記３波長の検量線から抽出液の染料濃度をそれぞれ求め、上記３波長における濃度の平均値を抽出液の染料濃度（Ｃ）とする。染色前の染料濃度（Ｃｏ）を用いて、以下の式にて得られる値を染着率（Ｕ）とする。
染着率（Ｕ）＝（Ｃｏ−Ｃ）／Ｃｏ×１００
The “dyeing rate” in the present invention refers to a value obtained by the following method.
(Dyeing rate)
The same amount of dichloromethane as this dyeing residual liquid is added to the dyeing residual liquid dyeing the fabric to extract the residual dye. Subsequently, with respect to the extract, the absorbance at wavelengths of 670 nm, 540 nm, and 530 nm was measured, respectively, and the dye concentration of the extract was determined from the calibration curve of the above three wavelengths prepared from a dichloromethane solution with a known dye concentration in advance. Let the average value of density | concentration be the dye density | concentration (C) of an extract. Using the dye concentration (Co) before dyeing, the value obtained by the following equation is defined as the dyeing rate (U).
Dyeing rate (U) = (Co−C) / Co × 100
〔染色布帛の限界酸素指数（ＬＯＩ）〕
本発明の易染色性布帛は、上記の染色方法で染色した染色布帛の限界酸素指数（ＬＯＩ））が３０以上であることが好ましい。染色布帛の限界酸素指数（ＬＯＩ）は、３０以上であることが好ましく、３０．５以上がより好ましく、３１．０以上が特に好ましい。限界酸素指数（ＬＯＩ）が３０未満の場合には、高温雰囲気下での使用時に、製品が高熱により着火する恐れがあるため好ましくない。
染色布帛の限界酸素指数（ＬＯＩ）は、後に記載するメタ型全芳香族ポリアミド繊維の製造方法において、残存溶媒量を低減することにより制御することができる。染色繊維の限界酸素指数（ＬＯＩ））を３０以上とするためには、残存溶媒量を０．１％以下とすればよい。
[Limited oxygen index (LOI) of dyed fabric]
The easily dyeable fabric of the present invention preferably has a limiting oxygen index (LOI) of 30 or more of the dyed fabric dyed by the above dyeing method. The limiting oxygen index (LOI) of the dyed fabric is preferably 30 or more, more preferably 30.5 or more, and particularly preferably 31.0 or more. When the limiting oxygen index (LOI) is less than 30, it is not preferable because the product may be ignited by high heat when used in a high temperature atmosphere.
The limiting oxygen index (LOI) of the dyed fabric can be controlled by reducing the amount of residual solvent in the method for producing a meta-type wholly aromatic polyamide fiber described later. In order to set the limiting oxygen index (LOI) of the dyed fiber to 30 or more, the residual solvent amount may be set to 0.1% or less.
なお、本発明における「限界酸素指数（ＬＯＩ）」とは、ＪＩＳ Ｋ７２０１−２のＬＯＩ測定法に基づき、以下の測定条件で測定して得られる値をいう。
（測定条件）
試験片の形 ：Ｖ
寸法 ：１４０ｍｍ×５２ｍｍ
点火手順 ：Ｂ（伝ぱ点火）
酸素濃度間隔：０．２％
The “limit oxygen index (LOI)” in the present invention refers to a value obtained by measurement under the following measurement conditions based on the LOI measurement method of JIS K7201-2.
(Measurement condition)
Specimen shape: V
Dimensions: 140mm x 52mm
Ignition procedure: B (propagation ignition)
Oxygen concentration interval: 0.2%
＜メタ型全芳香族ポリアミドの製造方法＞
本発明に用いられる易染色性メタ型全芳香族ポリアミド繊維の原料となるメタ型全芳香族ポリアミドの製造方法は、特に限定されるものではなく、例えば、メタ型芳香族ジアミン成分とメタ型芳香族ジカルボン酸成分とを原料とした溶液重合や界面重合等により製造することができる。また、本発明の目的を損なわない範囲内で、パラ型等の他の共重合成分が共重合されていてもよい。
<Method for producing meta-type wholly aromatic polyamide>
The production method of the meta-type wholly aromatic polyamide used as a raw material for the easily dyeable meta-type wholly aromatic polyamide fiber used in the present invention is not particularly limited. For example, the meta-type aromatic diamine component and the meta-type aroma It can be produced by solution polymerization, interfacial polymerization or the like using an aromatic dicarboxylic acid component as a raw material. Further, other copolymer components such as a para type may be copolymerized within a range not impairing the object of the present invention.
〔メタ型全芳香族ポリアミドの原料〕
（メタ型芳香族ジアミン成分）
メタ型芳香族ポリアミドの原料となるメタ型芳香族ジアミン成分としては、メタフェニレンジアミン、３，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルスルホン等、および、これらの芳香環にハロゲン、炭素数１〜３のアルキル基等の置換基を有する誘導体、例えば、２，４−トルイレンジアミン、２，６−トルイレンジアミン、２，４−ジアミノクロロベンゼン、２，６−ジアミノクロロベンゼン等を例示することができる。なかでも、メタフェニレンジアミンのみ、または、メタフェニレンジアミンを８５モル％以上、好ましくは９０モル％以上、特に好ましくは９５モル％以上含有する混合ジアミンであることが好ましい。
[Raw material for meta-type wholly aromatic polyamide]
(Meta-type aromatic diamine component)
Examples of the meta-type aromatic diamine component used as a raw material for the meta-type aromatic polyamide include metaphenylene diamine, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, and the like. Examples of derivatives having substituents such as alkyl groups of 1 to 3, such as 2,4-toluylenediamine, 2,6-toluylenediamine, 2,4-diaminochlorobenzene, 2,6-diaminochlorobenzene, etc. be able to. Of these, metaphenylenediamine alone or a mixed diamine containing metaphenylenediamine in an amount of 85 mol% or more, preferably 90 mol% or more, particularly preferably 95 mol% or more is preferable.
（メタ型芳香族ジカルボン酸成分）
メタ型全芳香族ポリアミドの原料となるメタ型芳香族ジカルボン酸成分としては、例えば、メタ型芳香族ジカルボン酸ハライドを挙げることができる。メタ型芳香族ジカルボン酸ハライドとしては、イソフタル酸クロライド、イソフタル酸ブロマイド等のイソフタル酸ハライド、および、これらの芳香環にハロゲン、炭素数１〜３のアルコキシ基等の置換基を有する誘導体、例えば３−クロロイソフタル酸クロライド等を例示することができる。なかでも、イソフタル酸クロライドそのもの、または、イソフタル酸クロライドを８５モル％以上、好ましくは９０モル％以上、特に好ましくは９５モル％以上含有する混合カルボン酸ハライドであることが好ましい。
(Meta-type aromatic dicarboxylic acid component)
Examples of the meta-type aromatic dicarboxylic acid component that is a raw material for the meta-type wholly aromatic polyamide include a meta-type aromatic dicarboxylic acid halide. Examples of the meta-type aromatic dicarboxylic acid halide include isophthalic acid halides such as isophthalic acid chloride and isophthalic acid bromide, and derivatives having substituents such as halogen and alkoxy groups having 1 to 3 carbon atoms on the aromatic ring, such as 3 -Chloroisophthalic acid chloride etc. can be illustrated. Of these, isophthalic acid chloride itself or a mixed carboxylic acid halide containing isophthalic acid chloride in an amount of 85 mol% or more, preferably 90 mol% or more, particularly preferably 95 mol% or more is preferable.
＜易染色性メタ型全芳香族ポリアミド繊維の製造方法＞
本発明に用いられる易染色性メタ型全芳香族ポリアミド繊維は、上記の製造方法によって得られた芳香族ポリアミドを用いて、例えば、以下に説明する紡糸液調製工程、紡糸・凝固工程、可塑延伸浴延伸工程、洗浄工程、弛緩処理工程、熱処理工程を経て製造される。
<Manufacturing method of easily dyeable meta type wholly aromatic polyamide fiber>
The readily dyeable meta-type wholly aromatic polyamide fiber used in the present invention is prepared by using the aromatic polyamide obtained by the above-described production method, for example, a spinning solution preparation step, a spinning / coagulation step, and plastic drawing described below. It is manufactured through a bath stretching process, a washing process, a relaxation process, and a heat treatment process.
なお、本発明において特に好ましく使用されるのは、力学特性、耐熱性、難燃性の観点から、メタフェニレンイソフタルアミド単位を主成分とするメタ型全芳香族ポリアミドである。全繰り返し単位の好ましくは９０モル％以上、さらに好ましくは９５モル％以上、特に好ましくは１００モル％がメタフェニレンイソフタルアミド単位から構成されるメタ型全芳香族ポリアミドであることが望ましい。 In the present invention, a meta-type wholly aromatic polyamide having a metaphenylene isophthalamide unit as a main component is particularly preferably used from the viewpoint of mechanical properties, heat resistance and flame retardancy. It is desirable that the meta-type wholly aromatic polyamide is composed of metaphenylene isophthalamide units, preferably 90 mol% or more, more preferably 95 mol% or more, particularly preferably 100 mol% of all repeating units.
［紡糸液調製工程］
紡糸液調製工程においては、メタ型全芳香族ポリアミドをアミド系溶媒に溶解して、紡糸液（メタ型全芳香族ポリアミド重合体溶液）を調製する。紡糸液の調製にあたっては、通常、アミド系溶媒を用い、使用されるアミド系溶媒としては、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡｃ）等を例示することができる。これらのなかでは溶解性と取扱い安全性の観点から、ＮＭＰまたはＤＭＡｃを用いることが好ましい。
[Spinning liquid preparation process]
In the spinning solution preparation step, the meta type wholly aromatic polyamide is dissolved in an amide solvent to prepare a spinning solution (meta type wholly aromatic polyamide polymer solution). In preparing the spinning solution, an amide solvent is usually used, and examples of the amide solvent used include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and dimethylacetamide (DMAc). be able to. Of these, NMP or DMAc is preferably used from the viewpoints of solubility and handling safety.
溶液濃度としては、次工程である紡糸・凝固工程での凝固速度および重合体の溶解性の観点から、適当な濃度を適宜選択すればよく、例えば、ポリマーがポリメタフェニレンイソフタルアミドで溶媒がＮＭＰの場合には、通常は１０〜３０質量％の範囲とすることが好ましい。 The concentration of the solution may be appropriately selected from the viewpoint of the coagulation rate and the solubility of the polymer in the next spinning and coagulation step. For example, the polymer is polymetaphenylene isophthalamide and the solvent is NMP. In the case of, it is usually preferred to be in the range of 10 to 30% by mass.
［紡糸・凝固工程］
紡糸・凝固工程においては、上記で得られた紡糸液（メタ型全芳香族ポリアミド重合体溶液）を紡出して凝固させる。
紡糸装置としては特に限定されるものではなく、従来公知の湿式紡糸装置を使用することができる。また、安定して湿式紡糸できるものであれば、紡糸口金の紡糸孔数、配列状態、孔形状等は特に制限する必要はなく、例えば、孔数が１０００〜３００００個、紡糸孔径が０．０４〜０．２ｍｍのスフ用の多ホール紡糸口金等を用いてもよい。
[Spinning and coagulation process]
In the spinning / coagulation step, the spinning solution (meta-type wholly aromatic polyamide polymer solution) obtained above is spun and coagulated.
The spinning device is not particularly limited, and a conventionally known wet spinning device can be used. Further, the number of spinning holes, the arrangement state, the hole shape, etc. of the spinneret are not particularly limited as long as they can be stably wet-spun. For example, the number of holes is 1,000 to 30,000, and the spinning hole diameter is 0.04. A multi-hole spinneret for ˜0.2 mm sufu may be used.
また、紡糸口金から紡出する際の紡糸液（メタ型全芳香族ポリアミド重合体溶液）の温度は、２０〜９０℃の範囲が適当である。
凝固浴としても特に限定されるものではなく、従来公知の浴液を使用することができる。例えば、無機塩を含まない水性凝固浴を採用する場合には、ＮＭＰ濃度４０〜７０質量％の水溶液を、浴液の温度２０〜９０℃の範囲として用いることができる。この場合の凝固浴中への繊維の浸漬時間は、０．１〜３０秒の範囲が適当である。
本発明においては、凝固浴の成分あるいは条件を適宜調節することにより、繊維表面に形成されるスキンを薄くすることができ、その結果、染色性をより向上させることができる。
The temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) when spinning from the spinneret is suitably in the range of 20 to 90 ° C.
The coagulation bath is not particularly limited, and a conventionally known bath solution can be used. For example, when an aqueous coagulation bath not containing an inorganic salt is employed, an aqueous solution having an NMP concentration of 40 to 70% by mass can be used as a temperature range of the bath solution of 20 to 90 ° C. In this case, the fiber immersion time in the coagulation bath is suitably in the range of 0.1 to 30 seconds.
In the present invention, by appropriately adjusting the components or conditions of the coagulation bath, the skin formed on the fiber surface can be thinned, and as a result, the dyeability can be further improved.
［可塑延伸浴延伸工程］
可塑延伸浴延伸工程においては、凝固浴にて凝固して得られた繊維が可塑状態にあるうちに、可塑延伸浴中にて繊維を延伸処理する。
可塑延伸浴液としては特に限定されるものではなく、従来公知のものを採用することができる。
延伸倍率は２．５〜１０．０倍の範囲が好ましく、さらに好ましくは２．５〜６．０倍である。本発明においては、可塑延伸浴での延伸により分子鎖配向を上げておくことが、最終的に得られる易染色性繊維の熱収縮安定性および強度のバランスを確保するのに重要である。
[Plastic stretching bath stretching process]
In the plastic drawing bath drawing step, the fiber is drawn in the plastic drawing bath while the fiber obtained by coagulation in the coagulation bath is in a plastic state.
It does not specifically limit as a plastic drawing bath liquid, A conventionally well-known thing can be employ | adopted.
The draw ratio is preferably in the range of 2.5 to 10.0 times, more preferably 2.5 to 6.0 times. In the present invention, raising the molecular chain orientation by stretching in a plastic stretching bath is important for ensuring the balance between heat shrink stability and strength of the easily dyeable fiber finally obtained.
可塑延伸浴中での延伸倍率が２．５倍未満である場合には、２．５ｃＮ／ｄｔｅｘ以上の破断強度であって十分な熱収縮安定性を有する繊維を得ることが困難となる。一方で、延伸倍率が１０．０倍を越える場合には、単糸切れが発生するため、生産安定性が悪くなる。
可塑延伸浴の温度は、２０〜９０℃の範囲が好ましい。温度が２０〜９０℃の範囲にあると、工程調子が良いため好ましい。
When the draw ratio in the plastic drawing bath is less than 2.5 times, it becomes difficult to obtain a fiber having a breaking strength of 2.5 cN / dtex or more and sufficient heat shrink stability. On the other hand, when the draw ratio exceeds 10.0 times, single yarn breakage occurs, resulting in poor production stability.
The temperature of the plastic stretching bath is preferably in the range of 20 to 90 ° C. It is preferable that the temperature is in the range of 20 to 90 ° C. because the process condition is good.
［洗浄工程］
洗浄工程においては、可塑延伸浴にて延伸された繊維を、十分に洗浄する。洗浄は、得られる繊維の品質面に影響を及ぼすことから、多段にて実施することが好ましい。特に、洗浄工程における洗浄浴の温度および洗浄浴液中のアミド系溶媒の濃度は、繊維からのアミド系溶媒の抽出状態および洗浄浴からの水の繊維中への浸入状態に影響を与える。このため、これらを最適な状態とする目的においても、洗浄工程を多段として、温度条件およびアミド系溶媒の濃度条件を制御することが好ましい。
[Washing process]
In the washing step, the fiber drawn in the plastic drawing bath is thoroughly washed. Washing is preferably performed in multiple stages because it affects the quality of the resulting fiber. In particular, the temperature of the cleaning bath in the cleaning step and the concentration of the amide solvent in the cleaning bath liquid affect the state of extraction of the amide solvent from the fibers and the state of penetration of water from the cleaning bath into the fibers. For this reason, it is preferable to control the temperature condition and the concentration condition of the amide solvent by setting the washing process in multiple stages for the purpose of bringing these into an optimum state.
温度条件およびアミド系溶媒の濃度条件については、最終的に得られる繊維の品質を満足できるものであれば特に限定されるものではないが、最初の洗浄浴を６０℃以上の高温とすると、水の繊維中への浸入が一気に起こり、繊維中に巨大なボイドが生成して品質の劣化を招く。このため、最初の洗浄浴は、３０℃以下の低温とすることが好ましい。
繊維中に溶媒が残っている場合には、高温での物性低下や収縮、限界酸素指数（ＬＯＩ）の低下等が生じる。このため、繊維に含まれる溶媒量は、１％以下とすることが好ましく、０．１％以下とすることがより好ましい。
The temperature condition and the concentration condition of the amide solvent are not particularly limited as long as the quality of the finally obtained fiber can be satisfied, but if the initial washing bath is at a high temperature of 60 ° C. or higher, water Intrusion into the fiber occurs at once, and a huge void is formed in the fiber, resulting in deterioration of quality. For this reason, it is preferable that the first washing bath has a low temperature of 30 ° C. or lower.
When the solvent remains in the fiber, the physical properties and shrinkage at a high temperature, the limiting oxygen index (LOI), etc. are reduced. For this reason, the amount of solvent contained in the fiber is preferably 1% or less, and more preferably 0.1% or less.
［水蒸気弛緩熱処理工程］
弛緩熱処理工程においては、洗浄工程において洗浄された繊維を、水蒸気中、好ましくは飽和水蒸気中で弛緩熱処理する。水蒸気中で弛緩熱処理することにより、繊維内部の非晶部分が著しく配向緩和し、染色性が向上するとともに、染色時等の熱による収縮を抑制することができる。
[Water vapor relaxation heat treatment process]
In the relaxation heat treatment step, the fibers washed in the washing step are subjected to relaxation heat treatment in water vapor, preferably saturated water vapor. By performing the relaxation heat treatment in water vapor, the amorphous portion inside the fiber is remarkably relaxed, the dyeability is improved, and shrinkage due to heat during dyeing can be suppressed.
水蒸気弛緩熱処理工程における水蒸気圧力は、１９６〜３９２ｋＰａの範囲とすることが好ましく、２２５〜３６３ｋＰａの範囲とすることがさらに好ましい。弛緩熱処理の水蒸気圧力が１９６ｋＰａ未満の場合には、繊維内部の非晶部分の十分な配向緩和が起きず、目的とする熱収縮安定性を付与することが困難となる。一方で、３９２ｋＰａを越える場合には、熱収縮安定性は付与できるものの、繊維の易染性が大きく低下してしまうため好ましくない。 The water vapor pressure in the water vapor relaxation heat treatment step is preferably in the range of 196 to 392 kPa, and more preferably in the range of 225 to 363 kPa. When the water vapor pressure of the relaxation heat treatment is less than 196 kPa, sufficient orientation relaxation of the amorphous portion inside the fiber does not occur, and it becomes difficult to impart the desired heat shrinkage stability. On the other hand, if it exceeds 392 kPa, heat shrink stability can be imparted, but the fiber dyeability is greatly reduced, which is not preferable.
また、水蒸気弛緩熱処理工程における弛緩倍率は、０．６５〜１．０倍とすることが好ましく、０．６５〜０．９５倍の範囲とすることがさらに好ましい。弛緩倍率がこの範囲を超える場合には、繊維内部の非晶部分の十分な配向緩和が起こらず、目的とする熱収縮安定性を付与することが困難となる。さらに、繊維内部の非晶部分の配向緩和が不十分となるため、染色前後の３００℃乾熱収縮率の比と、染色繊維の明度指数（Ｌ＊値）が大きくなり、本発明の目的を達成することが困難となる。さらには、原繊維の３００℃乾熱収縮率も大きくなり、その結果、染色繊維の染着率が低下する。このため、本発明においては、水蒸気弛緩熱処理工程における弛緩倍率の制御は、極めて重要である。 Moreover, the relaxation ratio in the steam relaxation heat treatment step is preferably 0.65 to 1.0 times, and more preferably 0.65 to 0.95 times. When the relaxation ratio exceeds this range, sufficient orientation relaxation of the amorphous portion inside the fiber does not occur, and it becomes difficult to impart the desired heat shrinkage stability. Furthermore, since the orientation relaxation of the amorphous part inside the fiber becomes insufficient, the ratio of the 300 ° C. dry heat shrinkage before and after dyeing and the lightness index (L * value) of the dyed fiber increase, and the object of the present invention is It becomes difficult to achieve. Furthermore, the 300 ° C. dry heat shrinkage of the fibrils also increases, and as a result, the dyeing rate of the dyed fibers decreases. For this reason, in the present invention, the control of the relaxation rate in the steam relaxation heat treatment step is extremely important.
［乾熱処理工程］
乾熱処理工程においては、水蒸気弛緩熱処理工程を経た繊維を、乾燥・熱処理する。乾熱処理の方法としては特に限定されるものではないが、例えば、熱ローラー、熱板等を用いる方法を挙げることができる。これにより、最終的に、本発明の易染色性メタ型全芳香族ポリアミド繊維を得ることができる。
[Dry heat treatment process]
In the dry heat treatment step, the fiber that has undergone the water vapor relaxation heat treatment step is dried and heat treated. Although it does not specifically limit as a method of dry heat processing, For example, the method of using a hot roller, a hot plate, etc. can be mentioned. Thereby, finally, the easily dyeable meta type wholly aromatic polyamide fiber of the present invention can be obtained.
＜積層防護服＞
本発明の積層防護服は、上述の易染色性メタ型全芳香族ポリアミド繊維を含む布帛を、少なくとも１層として含むものである。
積層防護服の構成としては、特に限定されるものではないが、上記易染色性メタ型全芳香族ポリアミド繊維を含む布帛を、表地層とすることが好ましい。また、例えば、表地層と内層のみからなる二層構造とする場合には、上記の易染色性メタ型全芳香族ポリアミド繊維を含む布帛を表地層とし、内層を、全芳香族ポリアミド繊維を含む耐熱性布帛とすることが好ましい。
<Laminated protective clothing>
The laminated protective garment of the present invention includes at least one layer of the fabric containing the above-described easily dyeable meta-type wholly aromatic polyamide fiber.
Although it does not specifically limit as a structure of laminated protective clothing, It is preferable to make the fabric containing the said easily dyeable meta type wholly aromatic polyamide fiber into a surface layer. Further, for example, in the case of a two-layer structure consisting only of a surface layer and an inner layer, the cloth containing the above easily dyeable meta-type wholly aromatic polyamide fiber is used as a surface layer, and the inner layer includes a wholly aromatic polyamide fiber. It is preferable to use a heat resistant fabric.
特に、本発明の積層防護服としては、表地層と内層のみからなる二層構造であり、該表地層として、前記メタ型全芳香族ポリアミド繊維を含む布帛を用い、該内層として、透湿防水性フィルムの両面に全芳香族ポリアミド繊維からなる織編布が貼り合わされた複合体を用いる構成することが好ましい。 In particular, the laminated protective garment of the present invention has a two-layer structure consisting of only a surface layer and an inner layer. As the surface layer, a fabric containing the meta-type wholly aromatic polyamide fiber is used, and as the inner layer, moisture permeable and waterproof. It is preferable to use a composite in which a woven or knitted fabric made of wholly aromatic polyamide fibers is bonded to both sides of the conductive film.
なお、本発明の積層防護服は、表地層と内層等から構成される複合構造を有するが、各層は相互に接合されている必要はなく、重ね合わして縫合したものであってもよい。また、内層は、ファスナー等を使用して表地層から取り外し可能となるようにし、洗濯が簡単に出来るような構造を有するものとすることもできる。 In addition, although the laminated protective clothing of the present invention has a composite structure composed of a surface layer and an inner layer, each layer does not need to be joined to each other, and may be one that is overlapped and stitched. Further, the inner layer can be detached from the outer layer using a fastener or the like, and can have a structure that can be easily washed.
［表地層］
本発明の積層防護服の表地層は、上記の易染色性メタ型全芳香族ポリアミド繊維を含む布帛であることが好ましい。易染色性メタ型全芳香族ポリアミド繊維の含有量は、染色性や風合いの観点から繊維の全質量に対して５０質量％以上であり、好ましくは８０質量％以上、さらに好ましくは９０質量％以上、特に好ましくは１００％である。
[Surface layer]
It is preferable that the surface layer of the layered protective garment of the present invention is a fabric containing the above easily dyeable meta-type wholly aromatic polyamide fiber. The content of the easily dyeable meta-type wholly aromatic polyamide fiber is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, based on the total mass of the fiber from the viewpoint of dyeability and texture. Particularly preferably, it is 100%.
該表地層には、撥水性加工を施して、耐水性の高い布帛とすることが好ましい。撥水加工は、表地層の両面に施してもよいが、少なくとも、積層防護服の表側面に施されていることが好ましい。撥水性加工を施した布帛を用いてなる防護服は、消火作業の際に空隙部に水が浸入してくるのを防止することができるため、防護服の着用性能を向上させることができる。
該撥水加工としては特に限定されるものではなく、例えば、フッ素系の撥水性樹脂を用いて、公知の方法に従い、コーティング法、スプレー法、あるいは浸漬法等の加工方法によって加工を行うことができる。
It is preferable that the surface layer is subjected to water repellency processing to form a fabric having high water resistance. The water repellent finish may be applied to both surfaces of the surface layer, but is preferably applied to at least the surface side of the laminated protective clothing. Since the protective clothing using the fabric subjected to water repellent processing can prevent water from entering the gap during the fire extinguishing operation, the wearing performance of the protective clothing can be improved.
The water-repellent processing is not particularly limited, and for example, using a fluorine-based water-repellent resin, processing can be performed by a processing method such as a coating method, a spray method, or an immersion method according to a known method. it can.
［内層］
内層としては、全芳香族ポリアミド繊維を含む耐熱性布帛を用いることが好ましい。より好ましくは、透湿防水性を有する薄膜フィルムの両面に全芳香族ポリアミド繊維からなる織編布が貼り合わされた複合体が用いられる。
ここで用いる透湿防水性を有する薄膜フィルムとしては、透湿防水性を有するものであればいずれも使用可能であるが、耐薬品性を兼ね備えたポリテトラフルオロエチレン製の薄膜フィルムを用いることが特に好ましい。
また、透湿防水性を有するフィルムに全芳香族ポリアミド繊維からなる織編布を貼り合わせる方法としては、ラミネート加工が最適に例示される。
[Inner layer]
As the inner layer, it is preferable to use a heat resistant fabric containing wholly aromatic polyamide fibers. More preferably, a composite in which a woven or knitted fabric made of wholly aromatic polyamide fibers is bonded to both surfaces of a thin film having moisture permeability and waterproofness is used.
As the thin film having moisture permeability and waterproofness used here, any film having moisture permeability and waterproofness can be used, but a thin film made of polytetrafluoroethylene having chemical resistance can be used. Particularly preferred.
Further, as a method of bonding a woven or knitted fabric made of wholly aromatic polyamide fiber to a film having moisture permeability and waterproofness, laminating is optimally exemplified.
全芳香族ポリアミド繊維からなる織編布の目付としては、５０〜２００ｇ／ｍ２の範囲とすることが好ましい。織編物の目付が５０ｇ／ｍ２未満の場合には、織編物の強度が低く、また所望の遮熱性が得られないおそれがあり、一方で、該目付が２００ｇ／ｍ２を超える場合には、防護服の重量を増加させ、着用者の動きを阻害するようになるため好ましくない。 The basis weight of the made textile fabric wholly aromatic polyamide fiber is preferably in the range of 50 to 200 g / m 2. If the basis weight of the woven or knitted fabric is less than 50 g / m 2 , the strength of the woven or knitted fabric may be low and the desired heat shielding property may not be obtained. On the other hand, if the basis weight exceeds 200 g / m 2 This is not preferable because the weight of the protective clothing is increased and the movement of the wearer is inhibited.
以下、実施例等を挙げて本発明をさらに具体的に説明するが、本発明は、これらの実施例等によって限定されるものではない。 EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further more concretely, this invention is not limited by these Examples etc.
＜測定方法＞
実施例および比較例における各物性値は、下記の方法で測定した。
［固有粘度（ＩＶ）］
ポリマーを９７％濃硫酸に溶解し、オストワルド粘度計を用い３０℃で測定した。
<Measurement method>
Each physical property value in Examples and Comparative Examples was measured by the following method.
[Intrinsic viscosity (IV)]
The polymer was dissolved in 97% concentrated sulfuric acid and measured at 30 ° C. using an Ostwald viscometer.
［繊度］
ＪＩＳ Ｌ １０１５に基づき、正量繊度のＡ法に準拠した測定を実施し、見掛繊度にて表記した。
[Fineness]
Based on JIS L 1015, the measurement based on the A method of positive fineness was implemented, and it described with the apparent fineness.
［原繊維の破断強度、破断伸度］
ＪＩＳ Ｌ １０１５に基づき、インストロン社製、型番５５６５を用いて、以下の条件で測定した。
（測定条件）
つかみ間隔 ：２０ｍｍ
初荷重 ：０．０４４ｃＮ（１／２０ｇ）／ｄｔｅｘ
引張速度 ：２０ｍｍ／分
[Fracture strength and elongation at break of fibrils]
Based on JIS L1015, it measured on condition of the following using the model number 5565 by Instron.
(Measurement condition)
Grasp interval: 20mm
Initial load: 0.044 cN (1/20 g) / dtex
Tensile speed: 20 mm / min
［３００℃乾熱収縮率］
約３３００ｄｔｅｘのトウに９８ｃＮ（１００ｇ）の荷重を吊るし、互いに３０ｃｍ離れた箇所に印をつける。荷重を除去後、トウを３００℃雰囲気下に１５分間置いた後、印間の長さＬを測定した。測定結果Ｌをもとに、下記式にて得られる値を３００℃乾熱収縮率（％）とした。
３００℃乾熱収縮率（％）＝（３０−Ｌ）／３０×１００
[300 ° C dry heat shrinkage]
A load of 98 cN (100 g) is hung on a tow of about 3300 dtex, and points 30 cm apart are marked. After removing the load, the tow was placed in an atmosphere of 300 ° C. for 15 minutes, and then the length L between the marks was measured. Based on the measurement result L, the value obtained by the following formula was defined as 300 ° C. dry heat shrinkage (%).
300 ° C. dry heat shrinkage (%) = (30−L) / 30 × 100
［染色前後の３００℃乾熱収縮率の比］
上記の測定・算出法により、織物の３００℃乾熱収縮率と染色繊維の３００℃乾熱収縮率とをそれぞれ求めた。得られた結果を用いて、下記式にて得られる値を染色前後の３００℃乾熱収縮率の比とした。
染色前後の３００℃乾熱収縮率比＝織物の３００℃乾熱収縮率／染色織物の３００℃乾熱収縮率
[Ratio of 300 ° C dry heat shrinkage before and after dyeing]
The 300 ° C. dry heat shrinkage rate of the woven fabric and the 300 ° C. dry heat shrinkage rate of the dyed fiber were determined by the above measurement / calculation method. Using the obtained results, the value obtained by the following formula was used as the ratio of 300 ° C. dry heat shrinkage before and after dyeing.
300 ° C. dry heat shrinkage ratio before and after dyeing = 300 ° C. dry heat shrinkage of fabric / 300 ° C. dry heat shrinkage of dyed fabric
［染着率］
布帛を染色した染色残液に、この染色残液と同容積のジクロロメタンを加え、残染料を抽出する。引き続き、抽出液について、波長６７０ｎｍ、５４０ｎｍ、５３０ｎｍの吸光度をそれぞれ測定し、あらかじめ染料濃度が既知のジクロロメタン溶液から作成した上記３波長の検量線から抽出液の染料濃度をそれぞれ求め、上記３波長における濃度の平均値を抽出液の染料濃度（Ｃ）とした。染色前の染料濃度（Ｃｏ）を用いて、以下の式にて得られる値を染着率（Ｕ）とした。
染着率（Ｕ）＝（Ｃｏ−Ｃ）／Ｃｏ×１００
[Dyeing rate]
The same amount of dichloromethane as this dyeing residual liquid is added to the dyeing residual liquid dyeing the fabric to extract the residual dye. Subsequently, with respect to the extract, the absorbance at wavelengths of 670 nm, 540 nm, and 530 nm was measured, respectively, and the dye concentration of the extract was determined from the calibration curve of the above three wavelengths prepared from a dichloromethane solution with a known dye concentration in advance. The average value of the concentration was defined as the dye concentration (C) of the extract. Using the dye concentration (Co) before dyeing, the value obtained by the following formula was used as the dyeing rate (U).
Dyeing rate (U) = (Co−C) / Co × 100
［染色布帛の明度指数Ｌ＊値］
カラー測色装置（マスベク社製、商品名：マクベスカラーアイ モデルＣＥ−３１００）を用いて、以下の測定条件で測定を実施した。なお、Ｌ＊は、数値が小さいほど濃染化されていることを示す。
（測定条件）
視野 ：１０度
光源 ：Ｄ６５
波長 ：３６０〜７４０ｎｍ
[Lightness index L * value of dyed fabric]
Measurement was carried out under the following measurement conditions using a color measuring device (trade name: Macbeth Color Eye Model CE-3100, manufactured by Masbek). In addition, L * shows that it is deeply dyed, so that a numerical value is small.
(Measurement condition)
Field of view: 10 degrees Light source: D65
Wavelength: 360-740 nm
［染色布帛の限界酸素指数（ＬＯＩ）］
ＪＩＳ Ｋ７２０１−２のＬＯＩ測定法に基づき、得られた染色布帛について、以下の測定条件で測定を実施した。
（測定条件）
試験片の形 ：Ｖ
寸法 ：１４０ｍｍ×５２ｍｍ
点火手順 ：Ｂ（伝ぱ点火）
酸素濃度間隔：０．２％
[Limited oxygen index (LOI) of dyed fabric]
Based on the LOI measurement method of JIS K7201-2, the obtained dyed fabric was measured under the following measurement conditions.
(Measurement condition)
Specimen shape: V
Dimensions: 140mm x 52mm
Ignition procedure: B (propagation ignition)
Oxygen concentration interval: 0.2%
［布帛の引張強度］
ＪＩＳ Ｌ１０９６の引張強さＡ法（ストリップ法：ラベルドストリップ法）に基づき、インストロン社製、型番１１２２を用いて、染色前の布帛について以下の測定条件で測定を実施した。
（測定条件）
切断採取時の試験片の大きさ ：幅５．５ｃｍ×長さ３０ｃｍ
試験片の幅 ：５．０ｃｍ
試験片の枚数 ：３枚
測定回数 ：各試験片につき、たて方向およびよこ方向それぞれ３回
つかみ間隔 ：２０ｃｍ
初荷重 ：５０ｇ
引張速度 ：２０ｍｍ／分
[Tensile strength of fabric]
Based on the tensile strength A method (strip method: labeled strip method) of JIS L1096, measurement was performed on the fabric before dyeing using the model number 1122 manufactured by Instron Corporation under the following measurement conditions.
(Measurement condition)
Size of test piece at the time of cutting and sampling: width 5.5 cm × length 30 cm
Specimen width: 5.0 cm
Number of test pieces: 3 Measurement times: 3 times for each test piece in the vertical direction and the horizontal direction Grasp interval: 20 cm
Initial load: 50g
Tensile speed: 20 mm / min
［布帛の染色時収縮率］
布帛のタテ、ヨコのサイズにつき、染色前後にそれぞれ測定し（ｎ＝５）、染色前後の収縮率の平均値を求めた。
[Shrinkage rate during dyeing of fabric]
The vertical and horizontal sizes of the fabric were measured before and after dyeing (n = 5), and the average shrinkage before and after dyeing was determined.
[炎に対する遮熱性]
ＩＳＯ ９１５１に準拠した方法により、２４℃温度上昇試験を行った。具体的には、試験用積層防護服を規定の火炎に暴露し、該積層防護服内の温度上昇が２４℃に達するまでの時間を測定し、炎に対する遮熱性の評価とした。
[Heat insulation against flame]
A temperature increase test at 24 ° C. was performed by a method based on ISO 9151. Specifically, the layered protective garment for test was exposed to a prescribed flame, and the time until the temperature rise in the layered protective garment reached 24 ° C. was measured to evaluate the heat shielding property against the flame.
[放射熱に対する遮熱性]
ＩＳＯ ６９４２；１９９２に準拠した方法により、測定を実施した。具体的には、試験用積層防護服を規定の火炎に暴露し、該積層防護服内の温度上昇が二度火傷に達するまでの時間を測定し、放射熱に対する遮熱性の評価とした。
[Heat insulation against radiant heat]
The measurement was performed by a method according to ISO 6942; 1992. Specifically, the layered protective garment for test was exposed to a prescribed flame, and the time until the temperature inside the layered protective garment reached a second burn was measured, and the heat shielding property against radiant heat was evaluated.
＜実施例１＞
［紡糸液調製工程］
特公昭４７−１０８６３号公報記載の方法に準じた界面重合法により製造した、固有粘度が１．９のポリメタフェニレンイソフタルアミド粉末２０．０質量部を、−１０℃に冷却したＮ−メチル−２−ピロリドン（以下、ＮＭＰと略す）８０．０質量部中に懸濁させ、スラリー状にした。引き続き、懸濁液を６０℃まで昇温して溶解させ、透明なポリマー溶液を得た。
<Example 1>
[Spinning liquid preparation process]
N-methyl-, prepared by interfacial polymerization in accordance with the method described in JP-B-47-10863, 20.0 parts by mass of polymetaphenylene isophthalamide powder having an intrinsic viscosity of 1.9, cooled to −10 ° C. It was suspended in 80.0 parts by mass of 2-pyrrolidone (hereinafter abbreviated as NMP) to form a slurry. Subsequently, the suspension was heated to 60 ° C. and dissolved to obtain a transparent polymer solution.
［紡糸・凝固工程］
得られたポリマー溶液を紡糸原液として、孔径０．０７ｍｍ、孔数１５００の紡糸口金から、４０℃の凝固浴中に吐出して紡糸した。凝固浴の組成は、ＮＭＰが５５質量％、水が４５質量％であり、凝固浴中に糸速７ｍ／分で吐出して紡糸した。
[Spinning and coagulation process]
The obtained polymer solution was spun as a spinning dope from a spinneret having a hole diameter of 0.07 mm and a hole number of 1500 into a coagulation bath at 40 ° C. The composition of the coagulation bath was 55% by mass of NMP and 45% by mass of water, and was spun by discharging into the coagulation bath at a yarn speed of 7 m / min.
［可塑延伸浴延伸工程］
引き続き、温度４０℃の水／ＮＭＰ＝４０／６０（質量％）の組成の可塑延伸浴中にて、５．２倍の延伸倍率で延伸を行った。
[Plastic stretching bath stretching process]
Subsequently, the film was stretched at a stretching ratio of 5.2 times in a plastic stretching bath having a composition of water / NMP = 40/60 (mass%) at a temperature of 40 ° C.
［洗浄工程］
延伸後、２０℃の水／ＮＭＰ＝７０／３０浴（浸漬長１．８ｍ）、２０℃の水浴（浸漬長３．６ｍ）、さらに６０℃の温水浴（浸漬長５．４ｍ）に順次通して、十分に洗浄を行った。
[Washing process]
After stretching, it is sequentially passed through a 20 ° C. water / NMP = 70/30 bath (immersion length 1.8 m), a 20 ° C. water bath (immersion length 3.6 m), and a 60 ° C. warm water bath (immersion length 5.4 m). And thoroughly washed.
［水蒸気弛緩熱処理工程］
洗浄した繊維に対して、飽和水蒸気圧力２９４ｋＰａ下、弛緩倍率０．８０倍にて、約１．０秒間の水蒸気弛緩熱処理を実施した。
[Water vapor relaxation heat treatment process]
The washed fiber was subjected to steam relaxation heat treatment for about 1.0 seconds under a saturation steam pressure of 294 kPa and a relaxation factor of 0.80.
［乾熱処理工程］
弛緩熱処理実施後、表面温度３５０℃の熱ローラーにて延伸倍率１．０倍（定長）にて乾熱処理を施し、ポリメタフェニレンイソフタルアミド繊維を得た。
[Dry heat treatment process]
After the relaxation heat treatment, dry heat treatment was performed at a draw ratio of 1.0 (constant length) with a heat roller having a surface temperature of 350 ° C. to obtain polymetaphenylene isophthalamide fibers.
［原繊維の物性］
得られたポリメタフェニレンイソフタルアミド繊維の物性は、繊度２．２２ｄｔｅｘ、破断強度３．２０ｃＮ／ｄｔｅｘ、破断伸度３５．２％、であった。また、３００℃乾熱収縮率は２．５％であり、優れた熱収縮安定性を示した。原繊維の物性を表１に示す。
[Physical properties of fibrils]
The physical properties of the obtained polymetaphenylene isophthalamide fiber were a fineness of 2.22 dtex, a breaking strength of 3.20 cN / dtex, and a breaking elongation of 35.2%. The 300 ° C. dry heat shrinkage ratio was 2.5%, which showed excellent heat shrink stability. Table 1 shows the physical properties of the fibrils.
［布帛の作製］
得られたポリメタフェニレンイソフタルアミド繊維のトウに、押込捲縮を付与した後、２インチにカットした。引き続き、通常の紡績工程を通して紡績糸（番手：３０／２）を作製し、当該紡績糸から２／１の綾織に織成した織物（目付:２４０ｇ／ｍ２、厚み：０．８ｍｍ）を作製した。公知の方法で精練処理し、布帛表面にある糊剤、油剤を除去した。
[Production of fabric]
The resulting polymetaphenylene isophthalamide fiber tow was subjected to indentation crimping and then cut into 2 inches. Subsequently, a spun yarn (count: 30/2) was produced through a normal spinning process, and a woven fabric (weight per unit: 240 g / m 2 , thickness: 0.8 mm) woven into a 2/1 twill weave was produced from the spun yarn. . Scouring treatment was performed by a known method to remove the paste and oil on the fabric surface.
［布帛の染色工程］
カチオン染料（日本化薬社製、商品名：Ｋａｙａｃｒｙｌ Ｂｌｕｅ ＧＳＬ−ＥＤ（Ｂ−５４））６％ｏｗｆ、酢酸０．３ｍＬ／Ｌ、硝酸ナトリウム２０ｇ／Ｌ、キャリア剤としてベンジルアルコール７０ｇ／Ｌ、分散剤として染色助剤（明成化学工業社製、商品名：ディスパーＴＬ）０．５ｇ／Ｌを含む染色液を用意した。上記で得られた布帛と当該染色液の浴比を１：４０として、１２０℃下６０分間の染色処理を実施した。
染色処理後、ハイドロサルファイト２．０ｇ／Ｌ、アミラジンＤ（第一工業製薬社製、商品名：アミラジンＤ）２．０ｇ／Ｌ、水酸化ナトリウム１．０ｇ／Ｌの割合で含有する処理液を用いて、浴比１：２０で８０℃下２０分間の還元洗浄を実施し、水洗後に乾燥することにより染色布帛を得た。
[Cloth dyeing process]
Cationic dye (Nippon Kayaku Co., Ltd., trade name: Kayacryl Blue GSL-ED (B-54)) 6% owf, acetic acid 0.3 mL / L, sodium nitrate 20 g / L, carrier agent benzyl alcohol 70 g / L, dispersion A dyeing solution containing 0.5 g / L of a dyeing assistant (made by Meisei Chemical Co., Ltd., trade name: Disper TL) was prepared as an agent. The dyeing treatment was carried out at 120 ° C. for 60 minutes with the bath ratio of the fabric obtained above and the dyeing solution being 1:40.
After the dyeing treatment, hydrosulfite 2.0 g / L, amylazine D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: amirazine D) 2.0 g / L, treatment solution containing sodium hydroxide 1.0 g / L Was used for reduction washing at 80 ° C. for 20 minutes at a bath ratio of 1:20, and after washing with water, a dyed fabric was obtained.
［染色布帛等の物性］
染色前後の布帛および染色液を用いて、上記測定方法により、限界酸素指数（ＬＯＩ値）、布帛の引張強度、布帛の染色時収縮率、布帛の明度指数Ｌ＊値、および染着率を評価した。また、染色繊維を引き抜き、染色前後の３００℃乾熱収縮率の比を評価した。
その結果、限界酸素指数（ＬＯＩ値）は３０．５、布帛の引張強度は１２５４Ｎ／５ｃｍ、布帛の染色時収縮率は０．５％、明度指数Ｌ＊は２８．９と良好な布帛物性を示した。また、染着率は９０．５％、染色前後の３００℃乾熱収縮率の比は１．９８であった。結果を表２に示す。
[Physical properties of dyed fabric, etc.]
Using the above-described measurement methods, the critical oxygen index (LOI value), the tensile strength of the fabric, the shrinkage rate during dyeing of the fabric, the lightness index L * value of the fabric, and the dyeing rate are evaluated using the fabric and dyeing solution before and after dyeing. did. Moreover, the dyed fiber was pulled out and the ratio of 300 ° C. dry heat shrinkage before and after dyeing was evaluated.
As a result, the critical oxygen index (LOI value) was 30.5, the tensile strength of the fabric was 1254 N / 5 cm, the shrinkage ratio during dyeing of the fabric was 0.5%, and the lightness index L * was 28.9. Indicated. The dyeing rate was 90.5%, and the ratio of the 300 ° C. dry heat shrinkage before and after dyeing was 1.98. The results are shown in Table 2.
［積層防護服の作製］
（表地層）
上記で得られたポリメタフェニレンイソフタルアミド繊維のトウに、押込捲縮を付与した後、２インチにカットした。引き続き、コポリパラフェニレン・３、４‘オキシジフェニレンテレフタルアミド繊維（帝人テクノプロダクツ（株）製、商標名：テクノーラ）と、混合比率が９０：１０となる割合で混紡した紡績糸（番手：２０／２）を作製した。得られた紡績糸を用いて、２／１の綾織に織成した織物（目付：２８０ｇ／ｍ２、厚み：０．８ｍｍ）作製し、これを表地層とした。
[Production of laminated protective clothing]
(Surface layer)
The tow of the polymetaphenylene isophthalamide fiber obtained above was subjected to indentation crimping and then cut into 2 inches. Subsequently, spun yarn (number: 20) blended with copolyparaphenylene-3, 4 ′ oxydiphenylene terephthalamide fiber (manufactured by Teijin Techno Products Co., Ltd., trade name: Technora) at a mixing ratio of 90:10. / 2) was produced. Using the obtained spun yarn, a woven fabric (weight per unit: 280 g / m 2 , thickness: 0.8 mm) woven into a 2/1 twill weave was prepared, and this was used as a surface layer.
（内層）
透湿防水性のポリテトラフルオロエチレン製フィルム（ジャパンゴアテックス（株）製、目付：３５ｇ／ｍ２）の片面に、上記で得られたポリメタフェニレンイソフタルアミド繊維からなる織布（目付：７５ｇ／ｍ２）を貼り合わせた。フィルムのもう一方の面には、遮熱性を持たせるために、上記で得られたポリメタフェニレンイソフタルアミド繊維の丸編物（目付：１８０ｇ／ｍ２、ハニカムメッシュ構造）を貼り合せ、内層となる複合体を得た。
(Inner layer)
A woven fabric made of the polymetaphenylene isophthalamide fiber obtained above (weight per unit: 75 g) on one side of a moisture-permeable and water-resistant polytetrafluoroethylene film (manufactured by Japan Gore-Tex Co., Ltd., basis weight: 35 g / m 2 ). / M 2 ). On the other side of the film, a circular knitted fabric (weight per unit: 180 g / m 2 , honeycomb mesh structure) of the polymetaphenylene isophthalamide fiber obtained above is bonded to form an inner layer in order to provide heat insulation. A complex was obtained.
（積層工程）
上記で得られた表地層、および内層の２層を重ねて縫合することにより、本発明の積層防護服を得た。得られた積層防護服の評価結果を、表３に示す。
(Lamination process)
The layered protective clothing of the present invention was obtained by overlaying and stitching the two layers of the surface layer and the inner layer obtained above. Table 3 shows the evaluation results of the obtained layered protective clothing.
＜実施例２＞
［紡糸液調製工程］
撹拌装置および原料投入口を備えた反応容器に、Ｎ−メチル−２−ピロリドン（以下、ＮＭＰと略す）８５４．８部を入れ、このＮＭＰ中にメタフェニレンジアミン（以下、ＭＰＤＡと略す）８３．４部を溶解した。さらに、該溶液にイソフタル酸クロライド（以下、ＩＰＣと略す）１５６．９部を徐々に撹拌しながら添加し、反応を実施した。
反応開始から４０分間攪拌を継続した後、水酸化カルシウム粉末を５７．１部添加し、さらに４０分間撹拌した後に反応を終了させた。反応容器から重合溶液を取り出したところ、重合溶液は透明であり、ポリマー濃度は１６％であった。
<Example 2>
[Spinning liquid preparation process]
85.48 parts of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) is placed in a reaction vessel equipped with a stirrer and a raw material inlet, and metaphenylenediamine (hereinafter abbreviated as MPDA) in this NMP. 4 parts were dissolved. Further, 156.9 parts of isophthalic acid chloride (hereinafter abbreviated as IPC) was added to the solution while gradually stirring to carry out the reaction.
After stirring for 40 minutes from the start of the reaction, 57.1 parts of calcium hydroxide powder was added, and the reaction was terminated after stirring for another 40 minutes. When the polymerization solution was taken out from the reaction vessel, the polymerization solution was transparent and the polymer concentration was 16%.
［紡糸・凝固工程、可塑延伸浴延伸工程、洗浄工程、水蒸気弛緩熱処理工程、乾熱処理工程］
得られた重合溶液を紡糸原液とし、可塑延伸浴中延伸倍率を５．３倍、水蒸気弛緩倍率を０．７７倍とした以外は、実施例１と同様にしてポリメタフェニレンイソフタルアミド繊維を得た。
[Spinning / coagulation process, plastic drawing bath drawing process, washing process, steam relaxation heat treatment process, dry heat treatment process]
A polymetaphenylene isophthalamide fiber was obtained in the same manner as in Example 1 except that the obtained polymerization solution was used as a spinning dope and the draw ratio in the plastic draw bath was 5.3 times and the water vapor relaxation ratio was 0.77 times. It was.
［原繊維の物性］
得られたポリメタフェニレンイソフタルアミド繊維の物性は、繊度２．２０ｄｔｅｘ、破断強度３．１１ｃＮ／ｄｔｅｘ、破断伸度３６．９％、３００℃乾熱収縮率２．７％であった。得られた繊維の物性を表１に示す。
[Physical properties of fibrils]
The physical properties of the obtained polymetaphenylene isophthalamide fiber were a fineness of 2.20 dtex, a breaking strength of 3.11 cN / dtex, a breaking elongation of 36.9%, and a 300 ° C. dry heat shrinkage of 2.7%. Table 1 shows the physical properties of the obtained fiber.
［布帛の製造・染色］
引き続き、実施例１と同様に、当該繊維から織物を作製し、その後に染色を実施した。
[Manufacture and dyeing of fabric]
Subsequently, in the same manner as in Example 1, a woven fabric was prepared from the fibers, and then dyeing was performed.
［染色布帛等の物性］
得られた染色織物の物性を、表２に示す。
[Physical properties of dyed fabric, etc.]
Table 2 shows the physical properties of the obtained dyed fabric.
［積層防護服の作製］
（表地層）
上記で得られたポリメタフェニレンイソフタルアミド繊維を用いて、実施例１と同様に、表地層となる織物を作製した。
（積層工程）
実施例１と同一の方法で内層となる複合体を作製し、実施例１と同一の方法により積層防護服を得た。得られた積層防護服の評価結果を、表３に示す。
[Production of laminated protective clothing]
(Surface layer)
Using the polymetaphenylene isophthalamide fiber obtained above, a woven fabric to be a surface layer was produced in the same manner as in Example 1.
(Lamination process)
A composite as an inner layer was produced by the same method as in Example 1, and a laminated protective garment was obtained by the same method as in Example 1. Table 3 shows the evaluation results of the obtained layered protective clothing.
＜実施例３＞
［原繊維の製造］
可塑延伸浴中延伸倍率を５．５倍、水蒸気弛緩倍率を０．６９倍とした以外は、実施例１と同様にしてポリメタフェニレンイソフタルアミド繊維を得た。
<Example 3>
[Manufacture of fibrils]
Polymetaphenylene isophthalamide fibers were obtained in the same manner as in Example 1 except that the draw ratio in the plastic drawing bath was 5.5 times and the water vapor relaxation ratio was 0.69 times.
［原繊維の物性］
得られた繊維の物性は、繊度２．００ｄｔｅｘ、破断強度３．３５ｃＮ／ｄｔｅｘ、破断伸度３３．１％、３００℃乾熱収縮率２．６％であった。得られた繊維の物性を表１に示す。
[Physical properties of fibrils]
The physical properties of the obtained fiber were a fineness of 2.00 dtex, a breaking strength of 3.35 cN / dtex, a breaking elongation of 33.1%, and a 300 ° C. dry heat shrinkage of 2.6%. Table 1 shows the physical properties of the obtained fiber.
［布帛の製造・染色］
引き続き、実施例１と同様に、当該繊維から織物を作製し、その後に染色を実施した。
[Manufacture and dyeing of fabric]
Subsequently, in the same manner as in Example 1, a woven fabric was prepared from the fibers, and then dyeing was performed.
［染色布帛等の物性］
得られた染色織物の物性を、表２に示す。
[Physical properties of dyed fabric, etc.]
Table 2 shows the physical properties of the obtained dyed fabric.
［積層防護服の作製］
（表地層）
上記で得られたポリメタフェニレンイソフタルアミド繊維を用いて、実施例１と同様に、表地層となる織物を作製した。
（積層工程）
実施例１と同一の方法で内層となる複合体を作製し、実施例１と同一の方法により積層防護服を得た。得られた積層防護服の評価結果を、表３に示す。
[Production of laminated protective clothing]
(Surface layer)
Using the polymetaphenylene isophthalamide fiber obtained above, a woven fabric to be a surface layer was produced in the same manner as in Example 1.
(Lamination process)
A composite as an inner layer was produced by the same method as in Example 1, and a laminated protective garment was obtained by the same method as in Example 1. Table 3 shows the evaluation results of the obtained layered protective clothing.
＜比較例１＞
［原繊維の製造］
可塑延伸浴中延伸倍率を５．０倍、水蒸気弛緩倍率を１．０５倍（延伸）とした以外は、実施例３と同様にしてポリメタフェニレンイソフタルアミド繊維を得た。
<Comparative Example 1>
[Manufacture of fibrils]
A polymetaphenylene isophthalamide fiber was obtained in the same manner as in Example 3 except that the draw ratio in the plastic drawing bath was 5.0 times and the water vapor relaxation ratio was 1.05 times (drawn).
［原繊維の物性］
得られた繊維の物性は、繊度２．１２ｄｔｅｘ、破断強度３．４２ｃＮ／ｄｔｅｘ、破断伸度２９．１％、３００℃乾熱収縮率６．７％であった。得られた繊維の物性を表１に示す。
[Physical properties of fibrils]
The physical properties of the obtained fiber were a fineness of 2.12 dtex, a breaking strength of 3.42 cN / dtex, a breaking elongation of 29.1%, and a 300 ° C. dry heat shrinkage of 6.7%. Table 1 shows the physical properties of the obtained fiber.
［布帛の製造・染色］
引き続き、実施例１と同様に、当該繊維から織物を作製し、その後に染色を実施した。
[Manufacture and dyeing of fabric]
Subsequently, in the same manner as in Example 1, a woven fabric was prepared from the fibers, and then dyeing was performed.
［染色織物等の物性］
得られた染色織物の物性を、表２に示す。
[Physical properties of dyed fabrics, etc.]
Table 2 shows the physical properties of the obtained dyed fabric.
［積層防護服の作製］
（表地層）
上記で得られたポリメタフェニレンイソフタルアミド繊維を用いて、実施例１と同様に、表地層となる織物を作製した。
（積層工程）
実施例１と同一の方法で内層となる複合体を作製し、実施例１と同一の方法により積層防護服を得た。得られた積層防護服の評価結果を、表３に示す。
[Production of laminated protective clothing]
(Surface layer)
Using the polymetaphenylene isophthalamide fiber obtained above, a woven fabric to be a surface layer was produced in the same manner as in Example 1.
(Lamination process)
A composite as an inner layer was produced by the same method as in Example 1, and a laminated protective garment was obtained by the same method as in Example 1. Table 3 shows the evaluation results of the obtained layered protective clothing.
＜比較例２＞
［原繊維の製造］
可塑延伸浴中延伸倍率を５．５倍、水蒸気弛緩処理を行わなかった以外は、実施例１と同様にしてポリメタフェニレンイソフタルアミド繊維を得た。
<Comparative example 2>
[Manufacture of fibrils]
A polymetaphenylene isophthalamide fiber was obtained in the same manner as in Example 1 except that the draw ratio in the plastic drawing bath was 5.5 times and the steam relaxation treatment was not performed.
［原繊維の物性］
得られた繊維の物性は、繊度２．０４ｄｔｅｘ、破断強度３．２０ｃＮ／ｄｔｅｘ、破断伸度３３．１％、３００℃乾熱収縮率５．９％であった。得られた繊維の物性を表１に示す。
[Physical properties of fibrils]
The physical properties of the obtained fiber were a fineness of 2.04 dtex, a breaking strength of 3.20 cN / dtex, a breaking elongation of 33.1%, and a 300 ° C. dry heat shrinkage of 5.9%. Table 1 shows the physical properties of the obtained fiber.
［布帛の製造・染色］
引き続き、実施例１と同様に、当該繊維から織物を作製し、その後に染色を実施した。
[Manufacture and dyeing of fabric]
Subsequently, in the same manner as in Example 1, a woven fabric was prepared from the fibers, and then dyeing was performed.
［染色織物等の物性］
得られた染色織物の物性を、表２に示す。
[Physical properties of dyed fabrics, etc.]
Table 2 shows the physical properties of the obtained dyed fabric.
［積層防護服の作製］
（表地層）
上記で得られたポリメタフェニレンイソフタルアミド繊維を用いて、実施例１と同様に、表地層となる織物を作製した。
（積層工程）
実施例１と同一の方法で内層となる複合体を作製し、実施例１と同一の方法により積層防護服を得た。得られた積層防護服の評価結果を、表３に示す。
[Production of laminated protective clothing]
(Surface layer)
Using the polymetaphenylene isophthalamide fiber obtained above, a woven fabric to be a surface layer was produced in the same manner as in Example 1.
(Lamination process)
A composite as an inner layer was produced by the same method as in Example 1, and a laminated protective garment was obtained by the same method as in Example 1. Table 3 shows the evaluation results of the obtained layered protective clothing.
＜比較例３＞
［原繊維の製造］
紡糸液調製工程における溶媒を、ＮＭＰからジメチルアセトアミド（以下、ＤＭＡｃと略す）に変更した以外は、実施例２と同様にして得た重合溶液を紡糸原液とし、特公昭６２−１８４１２７号公報記載の方法に準じて乾式紡糸を行った。乾燥塔を出た繊維をＤＭＡｃ３０質量％の９０℃浴にて４．０倍に延伸し、水蒸気弛緩工程を経ずに８０℃でクリンプ加工を行うことにより、ポリメタフェニレンイソフタルアミド繊維を得た。
<Comparative Example 3>
[Manufacture of fibrils]
A polymerization solution obtained in the same manner as in Example 2 except that the solvent in the spinning solution preparation step was changed from NMP to dimethylacetamide (hereinafter abbreviated as DMAc) was used as a spinning stock solution, and described in JP-B-62-184127. Dry spinning was performed according to the method. The fiber exiting the drying tower was stretched 4.0 times in a 90 ° C. bath of DMAc 30% by mass, and crimped at 80 ° C. without passing through a water vapor relaxation step to obtain polymetaphenylene isophthalamide fiber. .
［原繊維の物性］
得られた繊維の物性は、繊度１．６５ｄｔｅｘ、破断強度３．３０ｃＮ／ｄｔｅｘ、破断伸度５５．５％、３００℃乾熱収縮率１４．９％であった。得られた繊維の物性を表１に示す。
[Physical properties of fibrils]
The physical properties of the obtained fiber were a fineness of 1.65 dtex, a breaking strength of 3.30 cN / dtex, a breaking elongation of 55.5%, and a 300 ° C. dry heat shrinkage of 14.9%. Table 1 shows the physical properties of the obtained fiber.
［布帛の製造・染色］
引き続き、実施例１と同様に、当該繊維から織物を作製し、その後に染色を実施した。
[Manufacture and dyeing of fabric]
Subsequently, in the same manner as in Example 1, a woven fabric was prepared from the fibers, and then dyeing was performed.
［染色織物等の物性］
得られた染色織物の物性を、表２に示す。
[Physical properties of dyed fabrics, etc.]
Table 2 shows the physical properties of the obtained dyed fabric.
［積層防護服の作製］
（表地層）
上記で得られたポリメタフェニレンイソフタルアミド繊維を用いて、実施例１と同様に、表地層となる織物を作製した。
（積層工程）
実施例１と同一の方法で内層となる複合体を作製し、実施例１と同一の方法により積層防護服を得た。得られた積層防護服の評価結果を、表３に示す。
[Production of laminated protective clothing]
(Surface layer)
Using the polymetaphenylene isophthalamide fiber obtained above, a woven fabric to be a surface layer was produced in the same manner as in Example 1.
(Lamination process)
A composite as an inner layer was produced by the same method as in Example 1, and a laminated protective garment was obtained by the same method as in Example 1. Table 3 shows the evaluation results of the obtained layered protective clothing.
Claims (8)
該積層布帛は、メタ型全芳香族ポリアミド繊維を含む布帛を、少なくとも１層として含むものであり、
該メタ型全芳香族ポリアミド繊維は、原繊維の破断強度が２．５ｃＮ／ｄｔｅｘ以上、染色前後の３００℃乾熱収縮率の比が２．５以下であり、
染色後の該メタ型全芳香族ポリアミド繊維を含む布帛の明度指数Ｌ＊値が、３０以下である積層防護服。 A protective clothing made of laminated fabric,
The laminated fabric includes a fabric including a meta-type wholly aromatic polyamide fiber as at least one layer,
The meta-type wholly aromatic polyamide fiber has a breaking strength of fibrils of 2.5 cN / dtex or more, and a ratio of 300 ° C. dry heat shrinkage before and after dyeing is 2.5 or less,
A laminated protective garment in which a lightness index L * value of a fabric containing the meta-type wholly aromatic polyamide fiber after dyeing is 30 or less.
該表地層は、前記メタ型全芳香族ポリアミド繊維を含む布帛であり、
該内層は、透湿防水性フィルムの両面に全芳香族ポリアミド繊維からなる織編布が貼り合わされた複合体である請求項１から４いずれか記載の積層防護服。 The laminated protective garment is a two-layer structure consisting only of a surface layer and an inner layer,
The surface layer is a fabric containing the meta-type wholly aromatic polyamide fiber,
The laminated protective clothing according to any one of claims 1 to 4, wherein the inner layer is a composite in which a woven or knitted fabric made of wholly aromatic polyamide fibers is bonded to both surfaces of a moisture-permeable and waterproof film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009114784A JP2010261133A (en) | 2009-05-11 | 2009-05-11 | Laminated protective suit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009114784A JP2010261133A (en) | 2009-05-11 | 2009-05-11 | Laminated protective suit |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2010261133A true JP2010261133A (en) | 2010-11-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009114784A Pending JP2010261133A (en) | 2009-05-11 | 2009-05-11 | Laminated protective suit |
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| Country | Link |
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| JP (1) | JP2010261133A (en) |
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2009
- 2009-05-11 JP JP2009114784A patent/JP2010261133A/en active Pending
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