JP2004316018A - Wholly aromatic polyamide conjugate fiber structure having excellent flame-resistance and method for producing the same - Google Patents
Wholly aromatic polyamide conjugate fiber structure having excellent flame-resistance and method for producing the same Download PDFInfo
- Publication number
- JP2004316018A JP2004316018A JP2003111266A JP2003111266A JP2004316018A JP 2004316018 A JP2004316018 A JP 2004316018A JP 2003111266 A JP2003111266 A JP 2003111266A JP 2003111266 A JP2003111266 A JP 2003111266A JP 2004316018 A JP2004316018 A JP 2004316018A
- Authority
- JP
- Japan
- Prior art keywords
- fiber structure
- wholly aromatic
- aromatic polyamide
- composite fiber
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 149
- 239000004760 aramid Substances 0.000 title claims abstract description 59
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000002667 nucleating agent Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims description 48
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 44
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 22
- 239000001569 carbon dioxide Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 239000004744 fabric Substances 0.000 claims description 14
- 239000006260 foam Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 6
- 238000009958 sewing Methods 0.000 claims description 6
- 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 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000000463 material Substances 0.000 claims 1
- 230000001681 protective effect Effects 0.000 abstract description 7
- 230000035699 permeability Effects 0.000 abstract description 3
- 238000005187 foaming Methods 0.000 description 13
- 229920006231 aramid fiber Polymers 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 239000012530 fluid Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- -1 polymetaphenylene isophthalamide Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920000561 Twaron Polymers 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000271 Kevlar® Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000004762 twaron Substances 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-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
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- LZDHIQDKAYUDND-UHFFFAOYSA-N biphenylene-1,2-diamine Chemical compound C1=CC=C2C3=C(N)C(N)=CC=C3C2=C1 LZDHIQDKAYUDND-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical group NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Manufacturing Of Multi-Layer Textile Fabrics (AREA)
- Woven Fabrics (AREA)
- Professional, Industrial, Or Sporting Protective Garments (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、優れた防炎性を有する全芳香族ポリアミド複合繊維構造体及びその製造方法に関するものであり、さらに詳しくは、繊維内部に独立した微小空孔を有する全芳香族ポリアミド発泡繊維からなる繊維構造体を複合繊維構造体の内層に配することにより、その限界酸素指数（ＬＯＩ：Ｌｉｍｉｔｉｎｇ ｏｘｙｇｅｎ ｉｎｄｅｘ）を３０以上とした全芳香族ポリアミド複合繊維構造体に関するものである。
【０００２】
上記複合繊維構造体は、消防士、飛行士、レースドライバー、電力会社、化学会社など、火災に遭遇する可能性のある作業に従事する人々が着用する衣服に適した複合繊維構造体である。
【０００３】
【従来の技術】
全芳香族ポリアミド（以下アラミドと略記することがある）繊維にはコーネックス、ノーメックスに代表されるメタ系アラミド繊維とテクノーラ、ケブラー、トワロンに代表されるパラ系アラミド繊維とがある。
【０００４】
これらのアラミド繊維は、ナイロン６、ナイロン６６など、従来から広く使用されている脂肪族ポリアミド繊維と比較して、剛直な分子構造と高い結晶性を有しているので、耐熱性、耐炎性（難燃性）などの熱的性質に優れている上、耐薬品性、耐放射線性、電気特性などの安全性にも優れた性質を有している。
【０００５】
従ってアラミド繊維は、耐炎性（難燃性）や耐熱性が必要とされる防護服やバッグフィルターなどの産業資材用、カーテンなどのインテリア用として広く使用されている。
【０００６】
中でも、消防士、飛行士、レースドライバー、電力会社、化学会社など、火災に遭遇する可能性のある作業に従事する人々が着用する高遮熱性の防炎防護衣服を構成する繊維として、環境問題や動き易さ・軽量化などの観点より、従来のアスベスト繊維、ガラス繊維に代わって、アラミド繊維が多く使用されるようになってきた。
【０００７】
しかしながら、上記の防炎防護衣服においては、特開２０００−２１２８１０号公報或いは特開２００１−２１４３１８号公報に示される如く、防炎性を満足するために多層構造体とすることが必須であり、そのため非常に暑い作業環境下では、着用感（吸湿性、透湿性など）が著しく悪く、軽量で快適、且つ高度の防炎性を有する防炎防護衣服を得るには至っていないのが現状である。
【０００８】
【特許文献１】
特開２０００−２１２８１０号公報
【０００９】
【特許文献２】
特開２００１−２１４３１８号公報
【００１０】
【発明が解決しようとする課題】
本発明の目的は、上記従来技術の有する問題点を解消し、着用感（吸湿性、透湿性など）に優れ、軽量で快適、且つ高度の防炎性を有する防炎防護衣服を製造することが可能な複合繊維構造体及びその製造方法を提供することにある。
【００１１】
【課題を解決するための手段】
本発明者らは上記目的を達成するために鋭意検討した結果、複合繊維構造体の内層に、繊維内部に独立した微小空孔を有する全芳香族ポリアミド発泡繊維からなる繊維構造体を配するとき、所望の複合繊維構造体が得られることを究明した。
【００１２】
かくして本発明によれば、（１）繊維内部に独立した微小空孔を有する全芳香族ポリアミド発泡繊維からなる繊維構造体を内層に配し、全芳香族ポリアミド繊維を６０重量％以上含む繊維構造体を外層に配してなる複合繊維構造体であって、該繊維構造体の限界酸素指数（ＬＯＩ：Ｌｉｍｉｔｉｎｇ ｏｘｙｇｅｎ ｉｎｄｅｘ）が３０以上であることを特徴とする優れた防炎性を有する全芳香族ポリアミド複合繊維構造体、及び（２）発泡核剤を繊維に含浸させた後、膨張させて繊維内部に独立した微小空孔を形成させた全芳香族ポリアミド発泡繊維から繊維構造体を形成し、該繊維構造体を全芳香族ポリアミド繊維を６０重量％以上含む繊維構造体の内層側に配して複合繊維構造体を形成させることを特徴とする優れた防炎性を有する全芳香族ポリアミド複合繊維構造体の製造方法が提供される。
【００１３】
【発明の実施の形態】
本発明で使用するアラミド繊維には、前述の如く、メタ系アラミド繊維とパラ系アラミド繊維とがある。ここで、メタ系アラミド繊維とは、主骨格を構成する芳香環がアミド結合によりメタ型に結合されてなるメタ系全芳香族ポリアミドポリマーからなるものであり、ポリマーの全繰返し単位の８５モル％以上がメタフェニレンイソフタルアミド単位であるものが好ましく、中でもポリメタフェニレンイソフタルアミドホモポリマーが好ましい。
【００１４】
全繰返し単位の１５モル％以下、好ましくは５モル％以下で共重合し得る第３成分としては、ジアミン成分として、例えばパラフェニレンジアミン、３，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルエーテル、パラキシリレンジアミン、ビフェニレンジアミン、３，３’−ジクロルベンジジン、３，３’−ジメチルベンジジン、３，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、１，５−ナフタレンジアミン等の芳香族ジアミンが、また酸成分としては、例えばテレフタル酸、ナフタレン−２，６−ジカルボン酸、ナフタレン−２，７−ジカルボン酸等の芳香族ジカルボン酸が挙げられる。また、これらの芳香族ジアミン及び芳香族ジカルボン酸は、その芳香族環の水素原子の一部がハロゲン原子やメチル基等のアルキル基によって置換されていてもよい。
【００１５】
尚、ポリマーの全末端の２０％以上が、アニリン等の一価のジアミンもしくは一価のカルボン酸成分で封鎖されている場合には、特に高温下に長時間保持しても繊維の強力低下が小さくなるので好ましい。
【００１６】
このようなメタ系全芳香族ポリアミドポリマーは、芳香族ジアミンと芳香族ジカルボン酸ジハライドとを、例えば従来公知の界面重合法により製造することができる。ポリマーの重合度としては、Ｎ−メチル−２−ピロリドンを溶媒として０℃で測定した固有粘度（ＩＶ）が０．８〜３．０、特に１．０〜２．０の範囲にあるものが好ましい。
【００１７】
尚、上記メタ系全芳香族ポリアミドポリマーには、機能特性を保持するために難燃剤や紫外線吸収剤が含まれていても良い。この際使用される難燃剤の好ましい例としては、洗濯耐久難燃性を有すると共に、例え燃焼されても有毒ガスの発生を少なくすることができる点から、下記式で示される芳香族縮合型ノンハロゲン化リン酸エステル系難燃剤が挙げられる。
【００１８】
【化１】
また、紫外線吸収剤の好ましい例としては、下記式で示される紫外線吸収剤が挙げられる。
【００２０】
【化２】
更に、これらメタ系全芳香族ポリアミドポリマーからなる繊維には、耐熱、耐炎性や強力保持性などの機能特性を向上させるためにパラ系アラミド繊維を５〜３５重量部均一混合することも好ましい。
【００２２】
一方、パラ系アラミド繊維としては、デュポン社の「ケブラー」や帝人トワロン（株）の「トワロン」に代表されるポリパラフェニレンテレフタルアミド（ＰＰＴＡ）繊維や、ＰＰＴＡと３，４’−オキシジフェニレンテレフタルアミドとの共重合体繊維（帝人（株）製テクノーラ）など、パラフェニレン基を主鎖中に組み込んだパラ系全芳香族ポリアミドポリマーからなるアラミド繊維が例示される。
【００２３】
本発明で使用する、繊維内部に独立した微小空孔を有する全芳香族ポリアミド発泡繊維とは、繊維を構成する全芳香族ポリアミドポリマー中に、略球形の場合はその平均直径が１０μｍ以下程度の独立空孔を有する繊維を言う。該空孔の平均直径が１０μｍを越えると、独立空孔とすることが難しくなると共に、強度低下が起こる場合があるという懸念がある。また、上記空孔は、略球形のほか、凹凸あるいは扁平などの形状変化を有しているものも含まれる。
【００２４】
上記のような独立空孔を有する繊維、及びそれからなる繊維構造体は、例えば、特開２０００−１５４４６３号公報に開示されているが、該公報記載の発明において、独立空孔を有する繊維を使用することの意義は、保温性とクッション性とを付与するためであり、本願の如く、複合繊維構造体に防炎性を付与するものではない。
【００２５】
上記全芳香族ポリアミド発泡繊維は、メタ系ポリアミド繊維であることが好ましい。
【００２６】
上記の全芳香族ポリアミド発泡繊維は、発泡核剤を繊維に含浸させた後、該発泡核剤を膨張させることにより製造することができる。
【００２７】
本発明における発泡核剤としては、繊維構造物に発泡核剤として含浸され、体積が膨張するものであれば特に限定はされず、例えば、高温で体積が膨張するものなどが挙げられる。
【００２８】
この際、発泡核剤をいかに多く浸透させるかが気孔量に影響し、またその後いかに内部エネルギーを変動させるかが気孔特性（量・サイズなど）に影響を与える。
【００２９】
内部エネルギーを変動させる方法としては、温度・圧力・振動などの刺激を与えることなどが挙げられる。このような点から、発泡核剤の例として、例えば二酸化炭素、窒素、アルゴンなどの常温で気体の性質を有する物質、アセトン、塩化メチレン、ジメヒルホルムアミド、メタノールなどの有機溶剤などを挙げることができる。本発明では、含浸性と取り扱いの容易さ（高温高圧での取り扱い性）などの点より二酸化炭素を用いるのが最も望ましい。
【００３０】
具体的には、二酸化炭素を繊維に含浸させ、その後二酸化炭素を発泡核剤として膨張させ発泡させるのであるが、このとき発泡性能を高めるには、発泡核剤の繊維に対する含浸率を３％以上とすることが望ましく、このような高含浸率を得或いは所定の含浸率に制御するためには、発泡核剤の臨界温度および臨界圧力を超えた温度および圧力の条件下で繊維構造物に含浸させることが好ましい。
【００３１】
即ち、二酸化炭素は臨界温度および圧力を超えた温度及び圧力条件下では、超臨界流体という非凝縮性高密度流体であり、流動体の形態を有してはいるが、気相および液相のどちらに属するともいえない状態であり、気体および液体の両特性を有する。即ち、密度は液体と同程度であるにもかかわらず、気体と同程度の運動性を持つため、該超臨界流体は繊維構造物の内部に含浸されやすい特性を有している。この特性は、やや含浸性は低下するものの、亜臨界流体下でも同様であり、高圧状態にある流動体は、数々の非極性の薬剤を溶解可能とし、繊維内部に含浸し得る特性を有する。
【００３２】
このように高い圧力の二酸化炭素中で繊維構造物を処理するには、高圧に耐えるオートクレーブなどに繊維構造物を充填したのち、二酸化炭素を注入し所定の圧力にするなどの方法が適している。
【００３３】
尚、本発明者らは先に、超臨界流体中で繊維構造物を処理することにより、繊維構造物に種々の機能を付与する方法を提案しているが、該方法では繊維内部に独立した微小空孔を形成させることは出来ない。
【００３４】
つまり、本発明においては、二酸化炭素などの発泡核剤を繊維構造物に含浸させた後、該発泡核剤を膨張させることが必要である。その手段としては、温度や圧力を瞬時に大きく変化させたり、振動を与えたりする方法を用い、含浸された発泡核剤の体積を数倍以上に膨張させればよい。
【００３５】
具体的には、二酸化炭素を用いる場合、圧力を急激に低下させる、或いは温度を急激に上昇させるなどの方法を用いればよいが、なかでも５０℃以上の水に繊維構造物を浸漬する方法が、水の熱伝導率が大きく繊維構造物の温度を急速に変化させる（内部エネルギー変動する）のに有利であり望ましい。
【００３６】
本発明においては、上記の全芳香族ポリアミド発泡繊維からなる繊維構造体を内層に配し、メタ系アラミド繊維及び／又はパラ系アラミド繊維を６０重量％以上含む繊維構造体を外層に配して、複合繊維構造体とすることが肝要である。
【００３７】
ここで、メタ系アラミド繊維及び／又はパラ系アラミド繊維を６０重量％以上含む繊維構造体に含まれるその他の繊維としては、ポリエステル繊維が好ましく例示される。
【００３８】
該ポリエステル繊維とは、テレフタル繊維を主たるジカルボン酸成分とし、少なくとも１種類のグリコール、好ましくはエチレングリコール、トリメチレングリコール、テトラメチレングリコールなどから選ばれた少なくとも１種のアルキレングリコールを主たるグリコール成分とするポリエステルからなる繊維を言う。
【００３９】
該ポリエステル繊維は、必要に応じて第三成分が共重合及び／又はブレンド変性されても構わない。また、かかるポリエステル繊維には、必要に応じて任意の添加剤、例えば触媒、着色防止剤、耐熱剤、難燃剤、酸化防止剤、無機粒子などが含まれていても構わない。
【００４０】
さらに、該ポリエステル繊維には、別工程での延伸や熱処理、或いは仮撚・空気交絡等の処理が施されていても良い。
【００４１】
上記ポリエステル繊維の繊維構造体全重量に対する混合比率は０〜４０重量％であることが好ましい。
【００４２】
本発明における複合繊維構造体とは、全芳香族ポリアミド発泡繊維からなる繊維構造体と、メタ系アラミド繊維及び／又はパラ系アラミド繊維を６０重量％以上含む繊維構造体とが複合されて、二層或いは三層以上の多層構造を有している繊維構造体を言う。
【００４３】
複合の方法としては、従来公知の方法が任意に採用できるが、二重織編物或いは三重以上の多重織編物（ラッセル、ダブルラッセル、ダンボールニットなど）とする方法や、上記の各繊維構造体を縫製により結合させる方法などが好ましく例示される。
【００４４】
かくして得られた複合繊維構造体の限界酸素指数（以下ＬＯＩ：Ｌｉｍｉｔｉｎｇ ｏｘｙｇｅｎ ｉｎｄｅｘと称することがある）は３０以上であることが必要である。ＬＯＩが３０未満の場合は、充分な防炎性が得られず、消防士、飛行士、レースドライバー、電力会社、化学会社など、火災に遭遇する可能性のある作業に従事する人々が着用する防炎防護衣服に使用できない。
【００４５】
【実施例】
以下、実施例により本発明をさらに詳しく説明する。
【００４６】
［実施例１］
固有粘度ＩＶが１．３５ｄｌ／ｇのポリ−ｍ−フェニレンイソフタルアミド３０ｇをＮ−メチル−２−ピロリドン１１５ｇに溶解し、また含ハロゲンアルキルフェニルエーテルリン酸エステル５重量％をＮ−メチル−２−ピロリドンに溶解混合し、減圧脱法して紡糸ドープとした。
【００４７】
このドープを８５℃に加温し、口径０．０７ミリ、孔数２００の紡糸口金から凝固浴に湿式紡糸した。凝固浴の組成は、塩化カルシウムが４０重量％、ＮＭＰが５重量％、残りの水は５５重量％であり、該凝固浴の温度は８５℃であった。
【００４８】
この糸条を凝固浴中に約１０ｃｍ走行させ、６．２ｍ／分の速度で引き出した後、該糸条を水洗し、９５℃の温水で３．３倍に延伸して１２０℃のロールで乾燥し、さらに、３００℃の熱板上で１．０倍延伸して４４４ｄｔｅｘ／２００フィラメントの延伸糸を得た。
【００４９】
得られた延伸糸を１００本集束して２万デニールのトウとし、捲縮を付与した後カットして短繊維を得た。得られた繊維の繊度、カット長、強度、伸度はそれぞれ１．９ｄｔｅｘ、５１ｍｍ、４．５ｇ／ｄｔｅｘ、３３．６％であった。
【００５０】
該短繊維を紡績して４０／２の紡績糸とし、次いで該紡績糸を経糸及び緯糸に配して、経／緯それぞれ５５本／ｉｎ×５４本／ｉｎの密度で製織して平織物を得た。
【００５１】
次に該織物を高圧容器に充填し、室温（２７℃）のまま二酸化炭素を容器に注入し、圧力を２０Ｍｐａとし１５分間保持した。その後、二酸化炭素を急速に排出（急減圧）した。この際の織物への二酸化炭素の含浸率を、重量変化より算出したところ約８％であった。
【００５２】
次に該処理布帛を速やかに１００℃に保たれた恒温水槽に３０秒間浸漬して該処理布帛に含浸されている二酸化炭素を急速に膨潤させた。
【００５３】
発泡処理後の織物の空孔の大きさをＳＥＭ観察行なった結果、空孔は概ね球形で独立孔を形成しており、球形からの形状変化の度合いは、球形の縦横の直径比が概ね３以下であった。またその平均直径は０．８μｍであった。
【００５４】
次いで、発泡処理後の平織物を内層に配し、上記発泡処理前の平織物を外層に配して縫製により結合し、複合繊維構造体を得た。該複合繊維構造体のＬＯＩは３２であり、遮熱性に優れたものであった。
【００５５】
［実施例２］
実施例１で使用した、発泡処理後の平織物を内層に配し、下記の平織物を外層に配して縫製により結合し、複合繊維構造体を得た。
【００５６】
即ち、実施例１で使用した、繊度、カット長、強度、伸度がそれぞれ１．９ｄｔｅｘ、５１ｍｍ、４．５ｇ／ｄｔｅｘ、３３．６％のメタ系全芳香族ポリアミド短繊維６０重量％と、ポリエチレンテレフタレートポリマー（酸化チタン量０．０７重量％）を紡糸速度１４００ｍ／分で紡糸し、延伸温度（予熱）６８℃、セット温度１５０℃で３．５倍に延伸した後、常法に従って捲縮を付与し、カットしたポリエステル短繊維４０重量％とを混綿して４０／２の紡績糸とし、次いで該紡績糸を経糸及び緯糸に配して、経／緯それぞれ５５本／ｉｎ×５４本／ｉｎの密度で製織して平織物を得た。
得られた複合繊維構造体のＬＯＩは３３であり、遮熱性に優れたものであった。
【００５７】
［実施例３］
実施例１で使用した、発泡処理前の平織物を高圧容器に充填し、室温（２７℃）のまま二酸化炭素を容器に注入し、圧力を２８Ｍｐａとし１５分間保持した。その後、二酸化炭素を急速に排出（急減圧）した。この際の織物への二酸化炭素の含浸率を、重量変化より算出したところ約１２％であった。
【００５８】
次に該処理布帛を速やかに１００℃に保たれた恒温水槽に３０秒間浸漬して該処理布帛に含浸されている二酸化炭素を急速に膨潤させた。
【００５９】
発泡処理後の織物の空孔の大きさをＳＥＭ観察行なった結果、空孔は概ね球形で独立孔を形成しており、球形からの形状変化の度合いは、球形の縦横の直径比が概ね３以下であった。またその平均直径は０．８μｍであった。
【００６０】
上記方法により得られた発泡処理後の平織物を内層に配し、実施例１で使用した発泡処理前の平織物を外層に配して縫製により結合し、複合繊維構造体を得た。該複合繊維構造体のＬＯＩは３３であり、遮熱性に優れたものであった。
【００６１】
［比較例１］
実施例１において、発泡処理を行なわなかった以外は実施例１と同様に実施し、複合繊維構造体を得た。該複合繊維構造体のＬＯＩは２８であり、充分な遮熱性を有さないものであった。
【００６２】
［比較例２］
実施例２において、発泡処理を行なわなかった以外は実施例２と同様に実施し、複合繊維構造体を得た。該複合繊維構造体のＬＯＩは２６であり、充分な遮熱性を有さないものであった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a wholly aromatic polyamide composite fiber structure having excellent flameproofing properties and a method for producing the same, and more particularly, to a wholly aromatic polyamide foamed fiber having independent micropores inside the fiber. The present invention relates to a wholly aromatic polyamide composite fiber structure having a limiting oxygen index (LOI) of 30 or more by arranging the fiber structure in an inner layer of the composite fiber structure.
[0002]
The composite fiber structure is a composite fiber structure suitable for clothing worn by firefighters, aviators, race drivers, electric power companies, chemical companies, and other people engaged in work that may encounter a fire.
[0003]
[Prior art]
The wholly aromatic polyamide (hereinafter abbreviated as aramid) fibers include meta-aramid fibers represented by Conex and Nomex and para-aramid fibers represented by Technora, Kevlar and Twaron.
[0004]
Since these aramid fibers have a rigid molecular structure and high crystallinity as compared with aliphatic polyamide fibers widely used in the past, such as nylon 6 and nylon 66, heat resistance and flame resistance ( It has excellent thermal properties such as flame retardancy, and also has excellent properties such as chemical resistance, radiation resistance, and electrical properties.
[0005]
Therefore, aramid fibers are widely used for industrial materials such as protective clothing and bag filters that require flame resistance (flame retardancy) and heat resistance, and for interiors such as curtains.
[0006]
Among them, as a fiber constituting high heat-insulating flame-resistant protective clothing worn by firefighters, aviators, race drivers, electric power companies, chemical companies, and other people engaged in work that may encounter fires, environmental problems Aramid fibers have been increasingly used in place of conventional asbestos fibers and glass fibers from the viewpoints of ease of movement and weight reduction.
[0007]
However, in the above-mentioned flameproof protective clothing, as shown in JP-A-2000-212810 or JP-A-2001-214318, it is essential to form a multilayer structure in order to satisfy the flameproofness. Therefore, in a very hot working environment, the wearability (moisture absorption, moisture permeability, etc.) is extremely poor, and it has not yet been possible to obtain flameproof and protective clothing that is lightweight, comfortable, and has high flameproofness. .
[0008]
[Patent Document 1]
JP 2000-212810 A
[Patent Document 2]
JP 2001-214318 A
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to produce a flameproof and protective garment which is excellent in wearing feeling (moisture absorption, moisture permeability, etc.), lightweight, comfortable and has a high degree of flame resistance. It is an object of the present invention to provide a composite fiber structure which can be used and a method for producing the same.
[0011]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, when arranging a fiber structure made of a wholly aromatic polyamide foamed fiber having independent micropores inside the fiber, in the inner layer of the composite fiber structure. It has been found that a desired composite fiber structure can be obtained.
[0012]
Thus, according to the present invention, (1) a fiber structure in which a fiber structure composed of a wholly aromatic polyamide foamed fiber having independent micropores inside the fiber is disposed in an inner layer, and a wholly aromatic polyamide fiber is contained in an amount of 60% by weight or more. Whole fragrance having excellent flame retardancy, characterized in that the fiber structure has a limiting oxygen index (LOI) of 30 or more, which is a composite fiber structure having a body disposed in an outer layer. A fiber structure is formed from an aromatic polyamide composite fiber structure and (2) a wholly aromatic polyamide foamed fiber in which fibers are impregnated with a foaming nucleating agent and then expanded to form independent micropores inside the fiber. A flame retardant element having a superior flame resistance, wherein the fiber structure is arranged on the inner layer side of a fiber structure containing 60% by weight or more of wholly aromatic polyamide fibers to form a composite fiber structure. Method for producing a family polyamide composite fiber structure is provided.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
As described above, the aramid fibers used in the present invention include meta-aramid fibers and para-aramid fibers. Here, the meta-based aramid fiber is a meta-based wholly aromatic polyamide polymer in which the aromatic rings constituting the main skeleton are bonded in a meta-form by an amide bond, and 85 mol% of the total repeating units of the polymer. The above are preferably metaphenylene isophthalamide units, and among them, polymetaphenylene isophthalamide homopolymer is preferred.
[0014]
As the third component which can be copolymerized in an amount of 15 mol% or less, preferably 5 mol% or less of all repeating units, as a diamine component, for example, paraphenylenediamine, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether , Paraxylylenediamine, biphenylenediamine, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,5-naphthalenediamine and the like. The aromatic diamine and the acid component include, for example, aromatic dicarboxylic acids such as terephthalic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-2,7-dicarboxylic acid. In these aromatic diamines and aromatic dicarboxylic acids, a part of hydrogen atoms in the aromatic ring may be substituted by a halogen atom or an alkyl group such as a methyl group.
[0015]
When 20% or more of all the terminals of the polymer are blocked with a monovalent diamine or a monovalent carboxylic acid component such as aniline, the strength of the fiber decreases even when the polymer is kept at a high temperature for a long time. It is preferable because it becomes smaller.
[0016]
Such a meta-based wholly aromatic polyamide polymer can be produced from an aromatic diamine and an aromatic dicarboxylic acid dihalide by, for example, a conventionally known interfacial polymerization method. As the degree of polymerization of the polymer, one having an intrinsic viscosity (IV) measured at 0 ° C. using N-methyl-2-pyrrolidone as a solvent in the range of 0.8 to 3.0, particularly 1.0 to 2.0. preferable.
[0017]
Incidentally, the meta-based wholly aromatic polyamide polymer may contain a flame retardant or an ultraviolet absorber in order to maintain functional properties. Preferred examples of the flame retardant used in this case include aromatic condensed non-halogens represented by the following formula, since they have flame resistance to washing durability and can reduce the generation of toxic gas even if burned. Phosphoric acid ester-based flame retardants.
[0018]
Embedded image
Preferred examples of the ultraviolet absorber include an ultraviolet absorber represented by the following formula.
[0020]
Embedded image
Further, it is also preferable to uniformly mix 5-35 parts by weight of para-aramid fiber with the fiber composed of the meta-based wholly aromatic polyamide polymer in order to improve functional properties such as heat resistance, flame resistance, and strength retention.
[0022]
On the other hand, as para-aramid fibers, polyparaphenylene terephthalamide (PPTA) fibers represented by "Kevlar" of DuPont and "Twaron" of Teijin Twaron Co., Ltd., and PPTA and 3,4'-oxydiphenylene Aramid fibers composed of para-based wholly aromatic polyamide polymer having a paraphenylene group incorporated in the main chain, such as a copolymer fiber with terephthalamide (Technola manufactured by Teijin Limited) are exemplified.
[0023]
The wholly aromatic polyamide foamed fiber having independent micropores inside the fiber used in the present invention is, in the wholly aromatic polyamide polymer constituting the fiber, in the case of a substantially spherical shape, the average diameter is about 10 μm or less. A fiber having independent pores. If the average diameter of the pores exceeds 10 μm, it is difficult to form independent pores, and there is a concern that the strength may decrease. In addition, the above-mentioned holes include not only a substantially spherical shape but also those having a shape change such as unevenness or flatness.
[0024]
Fibers having independent pores as described above and a fiber structure comprising the same are disclosed in, for example, JP-A-2000-154463. In the invention described in the publication, fibers having independent pores are used. The significance of doing so is to provide heat retention and cushioning properties, and does not provide flame retardancy to the composite fiber structure as in the present application.
[0025]
The above-mentioned wholly aromatic polyamide foamed fiber is preferably a meta-based polyamide fiber.
[0026]
The above wholly aromatic polyamide foamed fiber can be produced by impregnating the fiber with a foam nucleating agent and then expanding the foam nucleating agent.
[0027]
The foam nucleating agent in the present invention is not particularly limited as long as the fiber structure is impregnated with the foam nucleating agent and expands in volume, and examples thereof include those which expand in volume at high temperatures.
[0028]
At this time, how much the foaming nucleating agent penetrates affects the pore amount, and how the internal energy is changed thereafter affects the pore characteristics (amount, size, etc.).
[0029]
Examples of a method of changing the internal energy include applying a stimulus such as temperature, pressure, or vibration. From such a point, examples of the foam nucleating agent include, for example, substances having a gaseous property at normal temperature such as carbon dioxide, nitrogen, and argon, and organic solvents such as acetone, methylene chloride, dimethylformamide, and methanol. it can. In the present invention, it is most preferable to use carbon dioxide from the viewpoint of impregnation and ease of handling (handling at high temperature and high pressure).
[0030]
Specifically, the carbon dioxide is impregnated into the fiber, and then the carbon dioxide is expanded and foamed as a foam nucleating agent. At this time, in order to enhance the foaming performance, the impregnation ratio of the foam nucleating agent to the fiber is 3% or more. In order to obtain such a high impregnation rate or to control it to a predetermined impregnation rate, it is necessary to impregnate the fiber structure at a temperature and pressure exceeding the critical temperature and critical pressure of the foam nucleating agent. Preferably.
[0031]
That is, carbon dioxide is a non-condensable high-density fluid called a supercritical fluid under temperature and pressure conditions exceeding the critical temperature and pressure, and although it has the form of a fluid, the gas phase and the liquid phase It cannot be said to belong to any of them, and has both gas and liquid characteristics. In other words, the supercritical fluid has a property that it is easily impregnated into the interior of the fibrous structure because it has the same mobility as a gas even though the density is about the same as a liquid. This property is similar to that under a subcritical fluid, though the impregnating property is slightly lowered. The fluid in a high pressure state is capable of dissolving various nonpolar drugs and has a property of impregnating the inside of the fiber.
[0032]
In order to treat the fibrous structure in carbon dioxide at such a high pressure, a method of filling the fibrous structure in an autoclave or the like that withstands high pressure and then injecting carbon dioxide to a predetermined pressure is suitable. .
[0033]
In addition, the present inventors have previously proposed a method of imparting various functions to the fiber structure by treating the fiber structure in a supercritical fluid. Micropores cannot be formed.
[0034]
That is, in the present invention, it is necessary to expand the foam nucleating agent after impregnating the fiber structure with the foam nucleating agent such as carbon dioxide. As the means, a method of instantaneously changing the temperature and pressure greatly or applying vibration may be used, and the volume of the impregnated foam nucleating agent may be expanded several times or more.
[0035]
Specifically, in the case of using carbon dioxide, a method of rapidly reducing the pressure or a method of rapidly increasing the temperature may be used. Among them, a method of immersing the fibrous structure in water at 50 ° C. or more is particularly preferable. In addition, the thermal conductivity of water is large, which is advantageous and desirable for rapidly changing the temperature of the fibrous structure (internal energy fluctuation).
[0036]
In the present invention, a fibrous structure composed of the above-mentioned wholly aromatic polyamide foamed fibers is disposed in an inner layer, and a fibrous structure containing 60% by weight or more of meta-aramid fibers and / or para-aramid fibers is disposed in an outer layer. It is important to use a composite fiber structure.
[0037]
Here, as another fiber contained in the fibrous structure containing the meta-aramid fiber and / or the para-aramid fiber in an amount of 60% by weight or more, a polyester fiber is preferably exemplified.
[0038]
The polyester fiber has terephthalic fiber as a main dicarboxylic acid component and at least one kind of glycol, preferably at least one kind of alkylene glycol selected from ethylene glycol, trimethylene glycol, tetramethylene glycol and the like as a main glycol component. A fiber made of polyester.
[0039]
The third component of the polyester fiber may be copolymerized and / or blend-modified if necessary. In addition, the polyester fiber may contain optional additives such as a catalyst, a coloring inhibitor, a heat-resistant agent, a flame retardant, an antioxidant, and inorganic particles as needed.
[0040]
Further, the polyester fiber may be subjected to a process such as drawing or heat treatment in another process, or false twisting or air entanglement.
[0041]
The mixing ratio of the polyester fiber to the total weight of the fiber structure is preferably 0 to 40% by weight.
[0042]
The composite fiber structure according to the present invention is a fiber structure comprising a wholly aromatic polyamide foamed fiber and a fiber structure containing at least 60% by weight of meta-aramid fiber and / or para-aramid fiber. A fiber structure having a multilayer structure of three or more layers.
[0043]
As the compounding method, a conventionally known method can be arbitrarily adopted, but a method of forming a double woven knit or a triple or more multiple woven knit (Russell, double Russell, corrugated cardboard knit, etc.), or the above-mentioned respective fiber structures A preferred example is a method of joining by sewing.
[0044]
It is necessary that the composite fiber structure thus obtained has a limiting oxygen index (hereinafter sometimes referred to as LOI: Limiting oxygen index) of 30 or more. If the LOI is less than 30, it will not provide sufficient fire protection and will be worn by firefighters, aviators, race drivers, power companies, chemical companies, and other people engaged in work that may encounter a fire. Cannot be used for fire and protective clothing.
[0045]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0046]
[Example 1]
30 g of poly-m-phenylene isophthalamide having an intrinsic viscosity IV of 1.35 dl / g is dissolved in 115 g of N-methyl-2-pyrrolidone, and 5% by weight of a halogen-containing alkyl phenyl ether phosphate ester is dissolved in N-methyl-2- It was dissolved and mixed with pyrrolidone, and depressurized to give a spinning dope.
[0047]
The dope was heated to 85 ° C. and wet-spun from a spinneret having a diameter of 0.07 mm and a number of holes of 200 into a coagulation bath. The composition of the coagulation bath was 40% by weight of calcium chloride, 5% by weight of NMP, 55% by weight of the remaining water, and the temperature of the coagulation bath was 85 ° C.
[0048]
This yarn is run about 10 cm in a coagulation bath, pulled out at a speed of 6.2 m / min, washed with water, stretched 3.3 times with hot water of 95 ° C, and rolled at 120 ° C with a roll of 120 ° C. It was dried and further stretched 1.0 times on a hot plate at 300 ° C. to obtain a stretched yarn of 444 dtex / 200 filament.
[0049]
100 drawn yarns were bundled into a 20,000-denier tow, crimped and cut to obtain short fibers. The fineness, cut length, strength and elongation of the obtained fiber were 1.9 dtex, 51 mm, 4.5 g / dtex and 33.6%, respectively.
[0050]
The staple fibers are spun into 40/2 spun yarns, and then the spun yarns are arranged into warps and wefts, and woven at a density of 55 / in × 54 / in each of warp / weft to obtain a plain fabric. Obtained.
[0051]
Next, the woven fabric was filled in a high-pressure container, carbon dioxide was injected into the container at room temperature (27 ° C.), the pressure was set to 20 MPa, and the pressure was maintained for 15 minutes. Thereafter, carbon dioxide was rapidly discharged (rapid decompression). At this time, the impregnation rate of carbon dioxide into the woven fabric was calculated from the change in weight, and was about 8%.
[0052]
Next, the treated fabric was immediately immersed in a constant temperature water bath maintained at 100 ° C. for 30 seconds to rapidly swell the carbon dioxide impregnated in the treated fabric.
[0053]
As a result of SEM observation of the size of the pores of the woven fabric after the foaming treatment, the pores were substantially spherical and formed independent pores. It was below. Its average diameter was 0.8 μm.
[0054]
Next, the plain fabric after the foaming treatment was arranged in the inner layer, and the plain fabric before the foaming treatment was arranged in the outer layer and joined by sewing to obtain a composite fiber structure. The composite fiber structure had an LOI of 32 and was excellent in heat insulation.
[0055]
[Example 2]
The plain fabric after the foaming treatment used in Example 1 was arranged on the inner layer, and the following plain fabric was arranged on the outer layer and joined by sewing to obtain a composite fiber structure.
[0056]
That is, the fineness, cut length, strength, and elongation used in Example 1 were 1.9 dtex, 51 mm, 4.5 g / dtex, and 33.6% of meta-based wholly aromatic polyamide short fibers of 60% by weight, respectively. A polyethylene terephthalate polymer (amount of titanium oxide: 0.07% by weight) is spun at a spinning speed of 1400 m / min, stretched 3.5 times at a stretching temperature (preheating) of 68 ° C. and a set temperature of 150 ° C., and then crimped in a usual manner. And 40% by weight of the cut polyester staple fibers are blended to give a spun yarn of 40/2. Then, the spun yarn is arranged on a warp and a weft, and each of the warp / weft is 55 / in × 54 / The plain weave was obtained by weaving at a density of in.
The obtained composite fiber structure had an LOI of 33 and was excellent in heat insulation.
[0057]
[Example 3]
The plain fabric used in Example 1 before the foaming treatment was filled in a high-pressure container, carbon dioxide was injected into the container at room temperature (27 ° C.), the pressure was set to 28 Mpa, and the pressure was maintained for 15 minutes. Thereafter, carbon dioxide was rapidly discharged (rapid decompression). At this time, the impregnation rate of carbon dioxide into the woven fabric was calculated from the change in weight, and was about 12%.
[0058]
Next, the treated fabric was immediately immersed in a constant temperature water bath maintained at 100 ° C. for 30 seconds to rapidly swell the carbon dioxide impregnated in the treated fabric.
[0059]
As a result of SEM observation of the size of the pores of the woven fabric after the foaming treatment, the pores were substantially spherical and formed independent pores. It was below. Its average diameter was 0.8 μm.
[0060]
The plain fabric after the foaming treatment obtained by the above method was arranged in the inner layer, and the plain fabric before the foaming treatment used in Example 1 was arranged in the outer layer and joined by sewing to obtain a composite fiber structure. The composite fiber structure had an LOI of 33 and was excellent in heat insulation.
[0061]
[Comparative Example 1]
A composite fiber structure was obtained in the same manner as in Example 1 except that the foaming treatment was not performed. The composite fiber structure had an LOI of 28 and did not have sufficient heat shielding properties.
[0062]
[Comparative Example 2]
A composite fiber structure was obtained in the same manner as in Example 2 except that the foaming treatment was not performed. The composite fiber structure had an LOI of 26 and did not have sufficient heat shielding properties.
Claims (13)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003111266A JP2004316018A (en) | 2003-04-16 | 2003-04-16 | Wholly aromatic polyamide conjugate fiber structure having excellent flame-resistance and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003111266A JP2004316018A (en) | 2003-04-16 | 2003-04-16 | Wholly aromatic polyamide conjugate fiber structure having excellent flame-resistance and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004316018A true JP2004316018A (en) | 2004-11-11 |
Family
ID=33471869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003111266A Pending JP2004316018A (en) | 2003-04-16 | 2003-04-16 | Wholly aromatic polyamide conjugate fiber structure having excellent flame-resistance and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004316018A (en) |
-
2003
- 2003-04-16 JP JP2003111266A patent/JP2004316018A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6388659B2 (en) | Fabrics and textile products | |
| US11078608B2 (en) | Fabric, method for manufacturing same, and fiber product | |
| JP6839999B2 (en) | Textiles and textiles | |
| EP3779004B1 (en) | Fabric and textile product | |
| JP6975531B2 (en) | Fabrics and textiles | |
| US11160320B2 (en) | Fabric, multilayer structured fabric, and fiber product | |
| JP2018021275A (en) | Laminated cloth and fiber product | |
| JP2004345102A (en) | Fiber structure having excellent flameproof properties and heat barrier properties and its manufacturing method | |
| CN107735521B (en) | Cloth tape and fiber product | |
| JP2020026596A (en) | Fabric and protection product | |
| JP2020002475A (en) | Fabric and textile product | |
| JP2004316018A (en) | Wholly aromatic polyamide conjugate fiber structure having excellent flame-resistance and method for producing the same | |
| KR101457151B1 (en) | Safety Jacket with Excellent Heat-block quality and Moisture Permeability | |
| KR101457140B1 (en) | Safety Jacket with Excellent Moisture Permeability | |
| JP6449616B2 (en) | Fabric and textile product and method for treating fabric | |
| JP2018184686A (en) | Woven fabric and textile product | |
| JP6811632B2 (en) | Fiber products | |
| JP2020026598A (en) | Fabric and protection product | |
| JP2020020057A (en) | Flame-retardant fabric comprising spun-dyed meta-type wholly aromatic polyamide fiber, and laminated protective clothing made of the fabric | |
| JP2022121885A (en) | Fabric, laminated fabric and textile product | |
| JP2020193422A (en) | Two-layered fabric and heat protective clothing made of the same | |
| JP2020016003A (en) | Flame-retardant cloth and laminated flame-retardant cloth and fiber product | |
| JP2023118159A (en) | Fabric and textile product | |
| JP2012102426A (en) | Laminate protective clothing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060313 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080922 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080930 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20090721 |