JP6873683B2 - Three-layer woven knit and textile products - Google Patents
Three-layer woven knit and textile products Download PDFInfo
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- JP6873683B2 JP6873683B2 JP2016244280A JP2016244280A JP6873683B2 JP 6873683 B2 JP6873683 B2 JP 6873683B2 JP 2016244280 A JP2016244280 A JP 2016244280A JP 2016244280 A JP2016244280 A JP 2016244280A JP 6873683 B2 JP6873683 B2 JP 6873683B2
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- 239000004753 textile Substances 0.000 title claims description 10
- 239000000835 fiber Substances 0.000 claims description 121
- 239000004760 aramid Substances 0.000 claims description 40
- 229920003235 aromatic polyamide Polymers 0.000 claims description 39
- 239000004744 fabric Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 18
- -1 ether ketone Chemical class 0.000 claims description 16
- 238000009940 knitting Methods 0.000 claims description 15
- 230000014759 maintenance of location Effects 0.000 claims description 14
- 239000003063 flame retardant Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 6
- 239000004693 Polybenzimidazole Substances 0.000 claims description 6
- 239000004697 Polyetherimide Substances 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- 229920001230 polyarylate Polymers 0.000 claims description 6
- 229920002480 polybenzimidazole Polymers 0.000 claims description 6
- 229920002577 polybenzoxazole Polymers 0.000 claims description 6
- 229920001601 polyetherimide Polymers 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 6
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 5
- 229920002530 polyetherether ketone Polymers 0.000 claims description 5
- 229920000297 Rayon Polymers 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000002964 rayon Substances 0.000 claims description 4
- 229920002972 Acrylic fiber Polymers 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 claims description 3
- 241001465754 Metazoa Species 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 3
- 229920006221 acetate fiber Polymers 0.000 claims description 3
- 229920006277 melamine fiber Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229920006306 polyurethane fiber Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 3
- 238000009941 weaving Methods 0.000 claims description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 150000001408 amides Chemical class 0.000 description 8
- 238000009987 spinning Methods 0.000 description 8
- 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 7
- 238000002156 mixing Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000012545 processing Methods 0.000 description 5
- 239000013557 residual solvent Substances 0.000 description 5
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical group NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 235000014676 Phragmites communis Nutrition 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 239000002759 woven fabric Substances 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 244000273256 Phragmites communis Species 0.000 description 2
- 229920001494 Technora Polymers 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000004950 technora Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YDYSEBSNAKCEQU-UHFFFAOYSA-N 2,3-diamino-n-phenylbenzamide Chemical compound NC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1N YDYSEBSNAKCEQU-UHFFFAOYSA-N 0.000 description 1
- GOJFAKBEASOYNM-UHFFFAOYSA-N 2-(2-aminophenoxy)aniline Chemical compound NC1=CC=CC=C1OC1=CC=CC=C1N GOJFAKBEASOYNM-UHFFFAOYSA-N 0.000 description 1
- MYEWQUYMRFSJHT-UHFFFAOYSA-N 2-(2-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1N MYEWQUYMRFSJHT-UHFFFAOYSA-N 0.000 description 1
- LNTGGPJSADTYSG-UHFFFAOYSA-N 2-(2-carbonochloridoylphenoxy)benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1OC1=CC=CC=C1C(Cl)=O LNTGGPJSADTYSG-UHFFFAOYSA-N 0.000 description 1
- NJMIRMHNYQIHST-UHFFFAOYSA-M 2-dodecylbenzenesulfonate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O NJMIRMHNYQIHST-UHFFFAOYSA-M 0.000 description 1
- FEIVVAUUAPGMES-UHFFFAOYSA-M 2-dodecylbenzenesulfonate;tetraphenylphosphanium Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 FEIVVAUUAPGMES-UHFFFAOYSA-M 0.000 description 1
- UIWFKZBONQGUDI-UHFFFAOYSA-M 2-dodecylbenzenesulfonate;tributyl(tetradecyl)phosphanium Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC UIWFKZBONQGUDI-UHFFFAOYSA-M 0.000 description 1
- ZHTQTFPMOHHUNM-UHFFFAOYSA-M 2-hexylbenzenesulfonate;tetrabutylphosphanium Chemical compound CCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCC[P+](CCCC)(CCCC)CCCC ZHTQTFPMOHHUNM-UHFFFAOYSA-M 0.000 description 1
- WEEOFHJAGVFCFD-UHFFFAOYSA-N 2-n-chlorobenzene-1,2-diamine Chemical compound NC1=CC=CC=C1NCl WEEOFHJAGVFCFD-UHFFFAOYSA-N 0.000 description 1
- RPKCLSMBVQLWIN-UHFFFAOYSA-N 2-n-methylbenzene-1,2-diamine Chemical compound CNC1=CC=CC=C1N RPKCLSMBVQLWIN-UHFFFAOYSA-N 0.000 description 1
- LHSXSRQUGCHBPG-UHFFFAOYSA-N 4-(aminomethoxy)aniline Chemical compound NCOC1=CC=C(N)C=C1 LHSXSRQUGCHBPG-UHFFFAOYSA-N 0.000 description 1
- IWRVPXDHSLTIOC-UHFFFAOYSA-N 4-phenyldiazenylbenzene-1,3-diamine Chemical compound NC1=CC(N)=CC=C1N=NC1=CC=CC=C1 IWRVPXDHSLTIOC-UHFFFAOYSA-N 0.000 description 1
- HPFMWXQXAHHFAA-UHFFFAOYSA-N 5-chlorobenzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC(Cl)=CC(C(Cl)=O)=C1 HPFMWXQXAHHFAA-UHFFFAOYSA-N 0.000 description 1
- CGXXBHCRXCEKCP-UHFFFAOYSA-N 5-methoxybenzene-1,3-dicarbonyl chloride Chemical compound COC1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 CGXXBHCRXCEKCP-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical class CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 1
- WQGNHOQJJZTLIJ-UHFFFAOYSA-M benzyl(tributyl)azanium;2-dodecylbenzenesulfonate Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O WQGNHOQJJZTLIJ-UHFFFAOYSA-M 0.000 description 1
- ZXKVYIKEMZVNBW-UHFFFAOYSA-M benzyl(tributyl)phosphanium;2-hexylbenzenesulfonate Chemical compound CCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 ZXKVYIKEMZVNBW-UHFFFAOYSA-M 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MPXAYYWSDIKNTP-UHFFFAOYSA-N n-(2-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC=C1N MPXAYYWSDIKNTP-UHFFFAOYSA-N 0.000 description 1
- VIUHYPPHBQZSPF-UHFFFAOYSA-N naphthalene-1,4-dicarbonyl chloride Chemical compound C1=CC=C2C(C(=O)Cl)=CC=C(C(Cl)=O)C2=C1 VIUHYPPHBQZSPF-UHFFFAOYSA-N 0.000 description 1
- NZZGQZMNFCTNAM-UHFFFAOYSA-N naphthalene-2,6-dicarbonyl chloride Chemical compound C1=C(C(Cl)=O)C=CC2=CC(C(=O)Cl)=CC=C21 NZZGQZMNFCTNAM-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005080 phosphorescent agent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical class CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 235000012773 waffles Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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- Knitting Of Fabric (AREA)
- Woven Fabrics (AREA)
- Professional, Industrial, Or Sporting Protective Garments (AREA)
Description
本発明は、難燃性および遮熱性に優れる三層構造織編物および繊維製品に関する。 The present invention relates to a three-layer structure woven knitted fabric and a textile product having excellent flame retardancy and heat shielding properties.
従来、十分なデッドエアを形成する遮熱層を有する耐熱性防護服が提案されている(例えば特許文献1、特許文献2、特許文献3、特許文献4)。
しかしながら、熱収縮率が異なる2種以上の全芳香族ポリアミド繊維を用いたものでは、厚み保持率が低く、遮熱性が低下しやすいという問題があった。また、生地の幅方向の収縮により厚みを発現しているため、十分な厚みが得られず、遮熱性が十分ではないという問題があった。
Conventionally, heat-resistant protective clothing having a heat-shielding layer that forms sufficient dead air has been proposed (for example, Patent Document 1,
However, when two or more kinds of all-aromatic polyamide fibers having different heat shrinkage rates are used, there is a problem that the thickness retention rate is low and the heat shielding property tends to be lowered. Further, since the thickness is developed by the shrinkage of the fabric in the width direction, there is a problem that a sufficient thickness cannot be obtained and the heat shielding property is not sufficient.
本発明は上記の背景に鑑みなされたものであり、その目的は、難燃性および遮熱性に優れる三層構造織編物および繊維製品を提供することにある。 The present invention has been made in view of the above background, and an object of the present invention is to provide a three-layer structure woven knitted fabric and a textile product having excellent flame retardancy and heat shielding properties.
本発明者は上記の課題を達成するため鋭意検討した結果、表裏の地組織部と、表裏の地組織部を連結する連結部とで構成される三層構造織編物において、全芳香族ポリアミド繊維を巧みに配することにより難燃性および遮熱性に優れる三層構造織編物が得られることを見出し、さらに鋭意検討を重ねることにより本発明を完成するに至った。 As a result of diligent studies to achieve the above problems, the present inventor has made a total aromatic polyamide fiber in a three-layer structure woven or knitted fabric composed of a front and back ground structure and a connecting part connecting the front and back ground structures. It was found that a three-layer structure woven or knitted fabric having excellent flame retardancy and heat shielding properties could be obtained by skillfully arranging the above, and further diligent studies led to the completion of the present invention.
かくして、本発明によれば「表裏の地組織部と、表裏の地組織部を連結する連結部とで構成される三層構造織編物であって、
前記連結部に、見掛けヤング率5000kg/mm 2 以上のパラ型全芳香族ポリアミド繊維からなる長繊維が配され、
表裏の地組織部にメタ型全芳香族ポリアミド繊維が配され、
織編物が編物であり、
織編物の厚さが3〜10mmの範囲内であり、
織編物の厚み保持率が40%以上であり、
かつJIS L1091−1992 A−4法により測定した残炎時間が2秒以下であることを特徴とする三層構造織編物。」が提供される。
Thus, according to the present invention, "a three-layer structure woven or knitted fabric composed of a front and back ground structure portion and a connecting portion connecting the front and back ground structure portions.
Long fibers made of para-type total aromatic polyamide fibers having an apparent Young's modulus of 5000 kg / mm 2 or more are arranged at the connecting portion.
Meta-type total aromatic polyamide fibers are arranged on the front and back of the ground structure,
The woven knit is a knit,
The thickness of the woven or knitted fabric is in the range of 3 to 10 mm.
The thickness retention rate of woven and knitted fabrics is 40% or more.
Moreover, a three-layer structure woven knitted fabric characterized in that the residual flame time measured by the JIS L1091-1992 A-4 method is 2 seconds or less. Is provided.
その際、三層構造織編物に全芳香族ポリアミド繊維が織編物重量対比40重量%以上含まれることが好ましい。また、織編物がさらに、全芳香族ポリエステル繊維、ポリベンズオキサゾール(PBO)繊維、ポリベンズイミダゾール(PBI)繊維、ポリベンズチアゾール(PBTZ)繊維、ポリイミド(PI)繊維、ポリスルホンアミド(PSA)繊維、ポリエーテルエーテルケトン(PEEK)繊維、ポリエーテルイミド(PEI)繊維、ポリアリレート(PAr)繊維、メラミン繊維、フェノール繊維、フッ素系繊維、およびポリフェニレンスルフィド(PPS)繊維からなる群より選択されるいずれか1種以上を含むことが好ましい。また、織編物がさらに、セルロース繊維、ポリオレフィン繊維、アクリル繊維、レーヨン繊維、コットン繊維、獣毛繊維、ポリウレタン繊維、ポリ塩化ビニル繊維、ポリ塩化ビニリデン繊維、アセテート繊維およびポリカーボネート繊維からなる群より選択されるいずれか1種以上を含むことが好ましい。 At that time, it is preferable that the three-layer structure woven knit contains 40% by weight or more of the total aromatic polyamide fiber with respect to the weight of the woven knit. In addition, the woven and knitted fabrics are further composed of total aromatic polyester fibers, polybenzoxazole (PBO) fibers, polybenzimidazole (PBI) fibers, polybenzthiazole (PBTZ) fibers, polyimide (PI) fibers, polysulfonamide (PSA) fibers, and the like. Any one selected from the group consisting of polyether ether ketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorofiber, and polyphenylene sulfide (PPS) fiber. It is preferable to contain one or more kinds. In addition, the woven or knitted fabric is further selected from the group consisting of cellulose fibers, polyolefin fibers, acrylic fibers, rayon fibers, cotton fibers, animal hair fibers, polyurethane fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, acetate fibers and polycarbonate fibers. It is preferable to include any one or more of them.
また、本発明によれば、前記の三層構造織編物を用いてなり、防護服、消防防火服、消防活動服、救助服、ワークウェア、警察制服、自衛隊衣服、および軍服からなる群より選択されるいずれかの繊維製品が提供される。 Further, according to the present invention, the above-mentioned three-layer structure woven or knitted fabric is used, and a selection is made from a group consisting of protective clothing, fire-fighting fire-retardant clothing, fire-fighting activity clothing, rescue clothing, work wear, police uniform, self-defense force clothing, and military uniform. Any textile product that is provided is provided.
本発明によれば、難燃性および遮熱性に優れる三層構造織編物および繊維製品が得られる。 According to the present invention, a three-layer structure woven knitted fabric and a textile product having excellent flame retardancy and heat shielding properties can be obtained.
以下、本発明の実施の形態について詳細に説明する。まず、本発明において、全芳香族ポリアミド繊維にはメタ型全芳香族ポリアミド繊維およびパラ型全芳香族ポリアミド繊維が含まれる。
ここで、パラ型全芳香族ポリアミド繊維としては、高い繊維強度を有するポリパラフェニレンテレフタルアミド、あるいは、これに第3成分を共重合した繊維などが好ましい。ポリパラフェニレンテレフタルアミド共重合体の一例としては、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を挙げることができる。市販品では、帝人株式会社製「トワロン」(商標名)、東レ・デュポン株式会社製「ケブラー」(商標名)、帝人株式会社製「テクノーラ」(商標名)などが例示される。
Hereinafter, embodiments of the present invention will be described in detail. First, in the present invention, the total aromatic polyamide fiber includes a meta-type total aromatic polyamide fiber and a para-type total aromatic polyamide fiber.
Here, as the para-type total aromatic polyamide fiber, polyparaphenylene terephthalamide having a high fiber strength, a fiber obtained by copolymerizing a third component with the polyparaphenylene terephthalamide, or the like is preferable. Examples of the polyparaphenylene terephthalamide copolymer include
また、メタ型全芳香族ポリアミド繊維とは、その繰返し単位の85モル%以上がm−フェニレンイソフタルアミドであるポリマーからなる繊維である。かかるメタ型全芳香族ポリアミドは、15モル%未満の範囲内で第3成分を含んだ共重合体であってもさしつかえない。
このようなメタ型全芳香族ポリアミドは、従来から公知の界面重合法により製造することができ、そのポリマーの重合度としては、0.5g/100mlの濃度のN−メチル−2−ピロリドン溶液で測定した固有粘度(I.V.)が1.3〜1.9dl/gの範囲のものが好ましく用いられる。
The meta-type total aromatic polyamide fiber is a fiber made of a polymer in which 85 mol% or more of the repeating unit is m-phenylene isophthalamide. Such a meta-type total aromatic polyamide may be a copolymer containing a third component in the range of less than 15 mol%.
Such a meta-type total aromatic polyamide can be produced by a conventionally known interfacial polymerization method, and the degree of polymerization of the polymer is 0.5 g / 100 ml in an N-methyl-2-pyrrolidone solution. Those having a measured intrinsic viscosity (IV) in the range of 1.3 to 1.9 dl / g are preferably used.
上記メタ型全芳香族ポリアミドにはアルキルベンゼンスルホン酸オニウム塩が含有されていてもよい。アルキルベンゼンスルホン酸オニウム塩としては、ヘキシルベンゼンスルホン酸テトラブチルフォスフォニウム塩、ヘキシルベンゼンスルホン酸トリブチルベンジルフォスフォニウム塩、ドデシルベンゼンスルホン酸テトラフェニルフォスフォニウム塩、ドデシルベンゼンスルホン酸トリブチルテトラデシルフォスフォニウム塩、ドデシルベンゼンスルホン酸テトラブチルフォスフォニウム塩、ドデシルベンゼンスルホン酸トリブチルベンジルアンモニウム塩等の化合物が好ましく例示される。なかでもドデシルベンゼンスルホン酸テトラブチルフォスフォニウム塩、又はドデシルベンゼンスルホン酸トリブチルベンジルアンモニウム塩は、入手しやすく、熱的安定性も良好なうえ、N−メチル−2−ピロリドンに対する溶解度も高いため特に好ましく例示される。 The meta-type total aromatic polyamide may contain an onium salt of alkylbenzene sulfonic acid. Examples of the alkylbenzenesulfonic acid onium salt include hexylbenzenesulfonic acid tetrabutylphosphonium salt, hexylbenzenesulfonic acid tributylbenzylphosphonium salt, dodecylbenzenesulfonic acid tetraphenylphosphonium salt, and dodecylbenzenesulfonic acid tributyltetradecylphosphonium salt. Compounds such as nium salt, tetrabutylphosphonium salt of dodecylbenzenesulfonic acid, and tributylbenzylammonium salt of dodecylbenzenesulfonic acid are preferably exemplified. Among them, dodecylbenzenesulfonic acid tetrabutylphosphonium salt or dodecylbenzenesulfonic acid tributylbenzylammonium salt is particularly easy to obtain, has good thermal stability, and has high solubility in N-methyl-2-pyrrolidone. Preferably exemplified.
上記アルキルベンゼンスルホン酸オニウム塩の含有割合は、十分な染色性の改良効果を得るために、ポリ−m−フェニレンイソフタルアミドに対して2.5モル%以上、好ましくは3.0〜7.0モル%の範囲にあるものが好ましい。
また、ポリ−m−フェニレンイソフタルアミドとアルキルベンゼンスルホン酸オニウム塩を混合する方法としては、溶媒中にポリ−m−フェニレンイソフタルアミドを混合、溶解し、それにアルキルベンゼンスルホン酸オニウム塩を溶媒に溶解する方法などが用いられそのいずれを用いてもよい。このようにして得られたドープは、従来から公知の方法により繊維に形成される。
The content ratio of the alkylbenzene sulfonic acid onium salt is 2.5 mol% or more, preferably 3.0 to 7.0 mol, based on poly-m-phenylene isophthalamide in order to obtain a sufficient effect of improving the stainability. Those in the range of% are preferable.
Further, as a method of mixing poly-m-phenylene isophthalamide and an alkylbenzene sulfonic acid onium salt, a method of mixing and dissolving poly-m-phenylene isophthalamide in a solvent and dissolving the alkylbenzene sulfonic acid onium salt in the solvent. Etc. are used, and any of them may be used. The dope thus obtained is formed into fibers by a conventionally known method.
メタ型全芳香族ポリアミド繊維に用いるポリマーは、染着性や耐変褪色性を向上させる等目的で、下記の式(1)で示される反復構造単位を含む芳香族ポリアミド骨格中に、反復構造の主たる構成単位とは異なる芳香族ジアミン成分、または芳香族ジカルボン酸ハライド成分を、第3成分として芳香族ポリアミドの反復構造単位の全量に対し1〜10mol%となるように共重合させることも可能である。
−(NH−Ar1−NH−CO−Ar1−CO)− ・・・式(1)
ここで、Ar1はメタ配位または平行軸方向以外に結合基を有する2価の芳香族基である。
The polymer used for the meta-type total aromatic polyamide fiber has a repeating structure in an aromatic polyamide skeleton containing a repeating structural unit represented by the following formula (1) for the purpose of improving dyeability and discoloration resistance. It is also possible to copolymerize an aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main constituent unit of the above as a third component so as to be 1 to 10 mol% with respect to the total amount of the repeating structural unit of the aromatic polyamide. Is.
-(NH-Ar1-NH-CO-Ar1-CO) -... Equation (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than the meta-coordination or the parallel axis direction.
また、第3成分として共重合させることも可能であり、式(2)、(3)に示した芳香族ジアミンの具体例としては、例えば、p−フェニレンジアミン、クロロフェニレンジアミン、メチルフェニレンジアミン、アセチルフェニレンジアミン、アミノアニシジン、ベンジジン、ビス(アミノフェニル)エーテル、ビス(アミノフェニル)スルホン、ジアミノベンズアニリド、ジアミノアゾベンゼン等が挙げられる。式(4)、(5)に示すような芳香族ジカルボン酸ジクロライドの具体例としては、例えば、テレフタル酸クロライド、1,4−ナフタレンジカルボン酸クロライド、2,6−ナフタレンジカルボン酸クロライド、4,4’−ビフェニルジカルボン酸クロライド、5−クロルイソフタル酸クロライド、5−メトキシイソフタル酸クロライド、ビス(クロロカルボニルフェニル)エーテルなどが挙げられる。
H2N−Ar2−NH2 ・・・式(2)
H2N−Ar2−Y−Ar2−NH2 ・・・式(3)
XOC−Ar3−COX ・・・式(4)
XOC−Ar3−Y−Ar3−COX ・・・式(5)
Further, it can be copolymerized as a third component, and specific examples of the aromatic diamines represented by the formulas (2) and (3) include, for example, p-phenylenediamine, chlorophenylenediamine, and methylphenylenediamine. Examples thereof include acetylphenylenediamine, aminoanisidine, benzidine, bis (aminophenyl) ether, bis (aminophenyl) sulfone, diaminobenzanilide, diaminoazobenzene and the like. Specific examples of the aromatic dicarboxylic acid dichloride shown in the formulas (4) and (5) include, for example, terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4. '-Biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis (chlorocarbonylphenyl) ether and the like can be mentioned.
H 2 N-Ar2-NH 2 ... Equation (2)
H 2 N-Ar2-Y-Ar2-NH 2 ... Equation (3)
XOC-Ar3-COX ・ ・ ・ Equation (4)
XOC-Ar3-Y-Ar3-COX ・ ・ ・ Equation (5)
ここで、Ar2はAr1とは異なる2価の芳香族基、Ar3はAr1とは異なる2価の芳香族基、Yは酸素原子、硫黄原子、アルキレン基からなる群から選ばれる少なくとも1種の原子又は官能基であり、Xはハロゲン原子を表す。
また、メタ型全芳香族ポリアミド繊維の結晶化度は、染料の吸尽性がよく、より少ない染料でまたは染色条件が弱くても狙いの色に調整し易いという点で、5〜35%であることが好ましい。さらには、染料の表面偏在が起こり難く耐変褪色性も高い点および実用上必要な寸法安定性も確保できる点で15〜25%であることがより好ましい。
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, and Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group. Alternatively, it is a functional group, and X represents a halogen atom.
In addition, the crystallinity of the meta-type total aromatic polyamide fiber is 5 to 35% in that the dye absorbency is good and it is easy to adjust to the target color with less dye or even if the dyeing conditions are weak. It is preferable to have. Further, it is more preferably 15 to 25% in that the surface of the dye is less likely to be unevenly distributed, the discoloration resistance is high, and the dimensional stability required for practical use can be ensured.
また、メタ型全芳香族ポリアミド繊維が難燃剤を含んでいてもよい。用いる難燃剤としては特開平10−251981号公報に記載されたものや、無機系の金属および担体、金属含有担体の表面を被覆したものなどが例示されるが、優れた難燃性を得る上でリン系難燃剤が好ましい。含有量としては繊維重量対比1〜15重量%が好ましい。
また、メタ型全芳香族ポリアミド繊維が、有機染料または有機顔料または無機顔料を含んでいてもよい。
また、メタ型全芳香族ポリアミド繊維の残存溶媒量は、メタ型全芳香族ポリアミド繊維の優れた難燃性能を損なわない点で、0.1重量%以下(好ましくは0.001〜0.1重量%)であることが好ましい。
Further, the meta-type total aromatic polyamide fiber may contain a flame retardant. Examples of the flame retardant to be used include those described in JP-A No. 10-251981, inorganic metals and carriers, and those coated on the surface of a metal-containing carrier. Phosphorus-based flame retardants are preferable. The content is preferably 1 to 15% by weight based on the weight of the fiber.
Further, the meta-type total aromatic polyamide fiber may contain an organic dye or an organic pigment or an inorganic pigment.
Further, the residual solvent amount of the meta-type total aromatic polyamide fiber is 0.1% by weight or less (preferably 0.001 to 0.1) in that the excellent flame retardant performance of the meta-type total aromatic polyamide fiber is not impaired. Weight%) is preferable.
前記メタ型全芳香族ポリアミド繊維は以下の方法により製造することができ、特に後述する方法により、結晶化度や残存溶媒量を上記範囲とすることができる。
メタ型全芳香族ポリアミドポリマーの重合方法としては、特に限定する必要はなく、例えば特公昭35−14399号公報、米国特許第3360595号公報、特公昭47−10863号公報などに記載された溶液重合法、界面重合法を用いてもよい。
The meta-type total aromatic polyamide fiber can be produced by the following method, and in particular, the crystallinity and the amount of residual solvent can be set in the above range by the method described later.
The method for polymerizing the meta-type total aromatic polyamide polymer is not particularly limited, and the solution weights described in, for example, Japanese Patent Publication No. 35-14399, US Pat. No. 3,360,595, and Japanese Patent Publication No. 47-10863 are not particularly limited. A legal or interfacial polymerization method may be used.
紡糸溶液としては、とくに限定する必要はないが、上記溶液重合や界面重合などで得られた、芳香族コポリアミドポリマーを含むアミド系溶媒溶液を用いても良いし、上記重合溶液から該ポリマーを単離し、これをアミド系溶媒に溶解したものを用いても良い。
ここで用いられるアミド系溶媒としては、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチル−2−ピロリドン、ジメチルスルホキシドなどを例示することができるが、とくにN,N−ジメチルアセトアミドが好ましい。
The spinning solution is not particularly limited, but an amide-based solvent solution containing an aromatic copolyamide polymer obtained by the above solution polymerization or interfacial polymerization may be used, or the polymer may be used from the above polymerization solution. It may be isolated and dissolved in an amide solvent.
Examples of the amide-based solvent used here include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like, and in particular, N, N-dimethylacetamide. Is preferable.
上記の通り得られた共重合芳香族ポリアミドポリマー溶液は、さらにアルカリ金属塩又はアルカリ土類金属塩を含むことにより安定化され、より高濃度、低温での使用が可能となり好ましい。好ましくはアルカリ金属塩及びアルカリ土類金属塩がポリマー溶液の全重量に対して1重量%以下、より好ましくは0.1重量%以下である。その際、前記のような難燃剤を含ませてもよい。
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)を凝固液中に紡出して凝固させる。
The copolymerized aromatic polyamide polymer solution obtained as described above is preferably stabilized by further containing an alkali metal salt or an alkaline earth metal salt, and can be used at a higher concentration and a lower temperature. The alkali metal salt and the alkaline earth metal salt are preferably 1% by weight or less, more preferably 0.1% by weight or less, based on the total weight of the polymer solution. At that time, the flame retardant as described above may be included.
In the spinning / coagulation step, the spinning solution (meta-type total aromatic polyamide polymer solution) obtained above is spun into the coagulating solution and coagulated.
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0.05〜0.2mmのスフ用の多ホール紡糸口金等を用いてもよい。
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。
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 need not be particularly limited as long as it can be stably wet-spun. For example, the number of holes is 1000 to 30,000 and the spinning hole diameter is 0.05. A multi-hole spinneret or the like for a rayon of ~ 0.2 mm may be used.
The temperature of the spinning solution (meta-type total aromatic polyamide polymer solution) when spinning from the spinneret is preferably in the range of 20 to 90 ° C.
繊維を得るために用いる凝固浴としては、実質的に無機塩を含まない、アミド系溶媒、好ましくはNMPの濃度が45〜60質量%の水溶液を、浴液の温度10〜50℃の範囲で用いる。アミド系溶媒(好ましくはNMP)の濃度が45質量%未満ではスキンが厚い構造となってしまい、洗浄工程における洗浄効率が低下し、繊維の残存溶媒量を低減させることが困難となる。一方、アミド系溶媒(好ましくはNMP)の濃度が60質量%を超える場合には、繊維内部に至るまで均一な凝固を行うことができず、このためやはり、繊維の残存溶媒量を低減させることが困難となる。なお、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。 As the coagulation bath used to obtain the fibers, an amide-based solvent, preferably an aqueous solution having an NMP concentration of 45 to 60% by mass, which is substantially free of inorganic salts, is used in a bath solution temperature range of 10 to 50 ° C. Use. If the concentration of the amide solvent (preferably NMP) is less than 45% by mass, the skin becomes thick, the cleaning efficiency in the cleaning step is lowered, and it becomes difficult to reduce the amount of residual solvent in the fibers. On the other hand, when the concentration of the amide solvent (preferably NMP) exceeds 60% by mass, uniform coagulation cannot be performed up to the inside of the fiber, and therefore the amount of residual solvent in the fiber is also reduced. Becomes difficult. The time for immersing the fibers in the coagulation bath is appropriately in the range of 0.1 to 30 seconds.
引続き、アミド系溶媒、好ましくはNMPの濃度が45〜60質量%の水溶液であり、浴液の温度を10〜50℃の範囲とした可塑延伸浴中にて、3〜4倍の延伸倍率で延伸を行う。延伸後、10〜30℃のNMPの濃度が20〜40質量%の水溶液、続いて50〜70℃の温水浴を通して十分に洗浄を行う。
洗浄後の繊維は、温度270〜290℃にて乾熱処理を施し、上記の結晶化度および残存溶媒量の範囲を満たすメタ型全芳香族アラミド繊維を得ることができる。
前記メタ型全芳香族アラミド繊維において、繊維は、長繊維(マルチフィラメント)でもよいし短繊維でもよい。特に、他の繊維と混紡する上で繊維長25〜200mmの短繊維が好ましい。また、単繊維繊度としては1〜5dtexの範囲が好ましい。
Subsequently, an amide-based solvent, preferably an aqueous solution having an NMP concentration of 45 to 60% by mass, was used in a plastic stretching bath in which the temperature of the bath liquid was in the range of 10 to 50 ° C., at a stretching ratio of 3 to 4 times. Perform stretching. After stretching, it is thoroughly washed through an aqueous solution having an NMP concentration of 10 to 30 ° C. of 20 to 40% by mass, followed by a warm water bath at 50 to 70 ° C.
The washed fibers are subjected to dry heat treatment at a temperature of 270 to 290 ° C. to obtain meta-type total aromatic aramid fibers that satisfy the above ranges of crystallinity and residual solvent amount.
In the meta-type total aromatic aramid fiber, the fiber may be a long fiber (multifilament) or a short fiber. In particular, short fibers having a fiber length of 25 to 200 mm are preferable for blending with other fibers. The single fiber fineness is preferably in the range of 1 to 5 dtex.
本発明の三層構造織編物は、表裏の地組織部と、表裏の地組織部を連結する連結部とで構成される三層構造織編物であり、全芳香族ポリアミド繊維を含む。
ここで、優れた難燃性を得る上で、三層構造織編物に全芳香族ポリアミド繊維が三層構造織編物重量対比40重量%以上(より好ましくは70〜100重量%)含まれることが好ましい。
The three-layer structure woven knit of the present invention is a three-layer structure woven knit composed of a front and back ground structure portion and a connecting portion connecting the front and back ground structure portions, and includes a total aromatic polyamide fiber.
Here, in order to obtain excellent flame retardancy, the three-layer structure woven knit may contain 40% by weight or more (more preferably 70 to 100% by weight) of all aromatic polyamide fibers with respect to the weight of the three-layer structure woven knit. preferable.
全芳香族ポリアミド繊維以外の繊維としては、全芳香族ポリエステル繊維、ポリベンズオキサゾール(PBO)繊維、ポリベンズイミダゾール(PBI)繊維、ポリベンズチアゾール(PBTZ)繊維、ポリイミド(PI)繊維、ポリスルホンアミド(PSA)繊維、ポリエーテルエーテルケトン(PEEK)繊維、ポリエーテルイミド(PEI)繊維、ポリアリレート(PAr)繊維、メラミン繊維、フェノール繊維、フッ素系繊維、およびポリフェニレンスルフィド(PPS)繊維などの難燃繊維が好ましい。かかる難燃性繊維において、限界酸素指数LOI値が20以上であることが好ましい。 Fibers other than total aromatic polyamide fibers include total aromatic polyester fibers, polybenzoxazole (PBO) fibers, polybenzimidazole (PBI) fibers, polybenzthiazole (PBTZ) fibers, polyimide (PI) fibers, and polysulfone amides ( Flame-retardant fibers such as PSA) fibers, polyether ether ketone (PEEK) fibers, polyetherimide (PEI) fibers, polyarylate (PAr) fibers, melamine fibers, phenol fibers, fluorofibers, and polyphenylene sulfide (PPS) fibers. Is preferable. In such flame-retardant fibers, the critical oxygen index LOI value is preferably 20 or more.
また、セルロース繊維、ポリオレフィン繊維、アクリル繊維、レーヨン繊維、コットン繊維、獣毛繊維、ポリウレタン繊維、ポリ塩化ビニル繊維、ポリ塩化ビニリデン繊維、アセテート繊維およびポリカーボネート繊維からなる群より選択されるいずれか1種以上がさらに含まれていてもよい。 Further, any one selected from the group consisting of cellulose fiber, polyolefin fiber, acrylic fiber, rayon fiber, cotton fiber, animal hair fiber, polyurethane fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, acetate fiber and polycarbonate fiber. The above may be further included.
本発明の三層構造織編物において、前記連結部に、見掛けヤング率5000kg/mm2以上(より好ましくは5000〜15000kg/mm2)の長繊維が配されていると、三層構造織編物の厚み保持率が大きくなり(すなわち、つぶれにくい。)、好ましい。
その際、該長繊維としては、パラ型全芳香族ポリアミド繊維からなる長繊維が好ましい。特に、厚み保持率を大きくすることにより遮熱性を向上させ、同時に難燃性を向上させる上で、表裏の地組織部にメタ型全芳香族ポリアミド繊維が配され、かつ連結部にパラ型全芳香族ポリアミド繊維が配されていることが好ましい。
In the three-layer structure woven knit of the present invention, when long fibers having an apparent Young's modulus of 5000 kg / mm 2 or more (more preferably 5000 to 15,000 kg / mm 2 ) are arranged at the connecting portion, the three-layer structure woven knit The thickness retention rate is large (that is, it is hard to be crushed), which is preferable.
At that time, as the long fibers, long fibers made of para-type total aromatic polyamide fibers are preferable. In particular, in order to improve heat insulation by increasing the thickness retention rate and at the same time improve flame retardancy, meta-type all-aromatic polyamide fibers are arranged on the front and back ground texture parts, and para-type all on the connecting part. It is preferable that aromatic polyamide fibers are arranged.
本発明の三層構造織編物は、地組織部用糸条と連結部用糸条を用いて、公知の方法により製造することができる。その際、編織組織に制限はなく、編物、織物いずれでもよい。編物であれば、経編、丸編、横編などが例示される。特に機械上で厚みを任意に設定できるダブルラッシェルが好ましい。例えば、ダンボールニットと称される、特開2002−235264号公報の図2に記載された表面層と裏面層とを結接糸(連結部用糸条)でタックしてなる三層構造編物や特開2004−183128号公報の図1に記載されたようなダンボール状立体織物などが好ましい。 The three-layer structure woven and knitted fabric of the present invention can be produced by a known method using a yarn for a ground structure portion and a yarn for a connecting portion. At that time, the knitting structure is not limited, and either knitting or woven fabric may be used. In the case of knitting, warp knitting, round knitting, horizontal knitting and the like are exemplified. In particular, a double raschel whose thickness can be arbitrarily set on the machine is preferable. For example, a three-layer structure knitted fabric called cardboard knit, which is formed by tacking the front surface layer and the back surface layer described in FIG. 2 of JP-A-2002-235264 with a binding yarn (thread for connecting portion). A cardboard-shaped three-dimensional woven fabric as shown in FIG. 1 of JP-A-2004-183128 is preferable.
かかる三層構造織編物には、精錬、リラックス、染色処理、セットなどの熱処理を施すことが好ましく、吸水加工、撥水加工、起毛加工、難燃加工、紫外線遮蔽あるいは抗菌剤、消臭剤、防虫剤、蓄光剤、再帰反射剤、マイナスイオン発生剤等の機能を付与する各種加工を付加適用してもよい。
かくして得られた三層構造織編物において、織編物の厚さが3〜10mmの範囲内であることが好ましい。かかる厚さが3mmよりも小さいと、遮熱性が低下するおそれがある。逆に、該厚さが10mmよりも大きいと、三層構造織編物を用いて衣料などを得た場合、着用快適性が損なわれるおそれがある。
Such a three-layer structure woven or knitted fabric is preferably subjected to heat treatment such as refining, relaxing, dyeing, and setting, and is preferably water-absorbent, water-repellent, brushed, flame-retardant, UV-shielding or antibacterial, deodorant, Various processings that impart functions such as insect repellents, phosphorescent agents, retroreflectors, and negative ion generators may be additionally applied.
In the three-layer structure woven or knitted fabric thus obtained, the thickness of the woven or knitted fabric is preferably in the range of 3 to 10 mm. If the thickness is less than 3 mm, the heat shield may be lowered. On the contrary, if the thickness is larger than 10 mm, the wearing comfort may be impaired when clothing or the like is obtained by using the three-layer structure woven or knitted fabric.
また、目付けとしては、軽量性と遮熱性とを両立させる上で50〜500g/m2(より好ましくは100〜300g/m2)の範囲内であることが好ましい。
また、厚み保持率が40%以上(より好ましくは40〜99%)であることが好ましい。該厚み保持率が40%では、織編物がつぶれやすく(十分なデッドエアを形成できず)遮熱性が低下するおそれがある。
The basis weight is preferably in the range of 50 to 500 g / m 2 (more preferably 100 to 300 g / m 2 ) in order to achieve both light weight and heat shielding properties.
Further, the thickness retention rate is preferably 40% or more (more preferably 40 to 99%). If the thickness retention rate is 40%, the woven or knitted fabric is easily crushed (sufficient dead air cannot be formed), and the heat shielding property may be lowered.
本発明の三層構造織編物は前記の構成を有するので難燃性および遮熱性に優れる。その際、その際、JIS L1091−1992 A−4法に規定される燃焼性測定において残炎時間が2.0秒以下であることが好ましい。また、炭化長が100mm以下(より好ましくは10〜80mm)であることが好ましい。 Since the three-layer structure woven or knitted fabric of the present invention has the above-mentioned structure, it is excellent in flame retardancy and heat shielding property. At that time, it is preferable that the residual flame time is 2.0 seconds or less in the combustibility measurement defined by the JIS L1091-1992 A-4 method. Further, the carbonization length is preferably 100 mm or less (more preferably 10 to 80 mm).
次に、本発明の繊維製品は前記の三層構造織編物を用いてなり、防護服、消防防火服、消防活動服、救助服、ワークウェア、警察制服、自衛隊衣服、および軍服からなる群より選択されるいずれかの繊維製品である。
かかる繊維製品は前記の三層構造織編物を用いているので、難燃性および遮熱性に優れる。
Next, the textile product of the present invention uses the above-mentioned three-layer structure woven and knitted fabric, and consists of a group consisting of protective clothing, fire-fighting fire-retardant clothing, fire-fighting activity clothing, rescue clothing, workwear, police uniforms, self-defense force clothing, and military uniform. Any textile product of choice.
Since such a textile product uses the above-mentioned three-layer structure woven knit, it is excellent in flame retardancy and heat shielding property.
以下、実施例をあげて本発明を詳細に説明するが、本発明はこれらによって何ら限定されるものではない。なお、実施例中の各物性は下記の方法により測定したものである。
(1)厚さ
JIS L 1018に準拠し、普通編物用の条件である0.7kPaの荷重をかけ測定を行なった。
(2)厚み保持率
JIS L 1018に準拠し、普通編物用の荷重条件0.7kPa及び織物用の荷重条件23.5kPaにて測定を行ない、下記式にて厚み保持率を算出した。
厚み保持率(%)=織物用条件による厚さ/普通編物用条件による厚さ×100
(3)布帛の難燃性(垂直燃焼試験)
JIS L1091−1992 A−4法により残炎時間、炭化長を測定した。
(4)見掛けヤング率
JIS L1013−2110 8.10で測定し、下記式により算出した。
見かけヤング率(kg/mm2)=繊維密度×初期引張抵抗度×1000
(5)限界酸素指数LOI値
JIS L1091−1999 E法で限界酸素指数LOI値を測定した。
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In addition, each physical property in an Example was measured by the following method.
(1) Thickness According to JIS L 1018, the measurement was carried out by applying a load of 0.7 kPa, which is a condition for ordinary knitting.
(2) Thickness retention rate In accordance with JIS L 1018, measurements were performed under a load condition of 0.7 kPa for ordinary knitting and a load condition of 23.5 kPa for woven fabrics, and the thickness retention rate was calculated by the following formula.
Thickness retention rate (%) = Thickness under woven conditions / Thickness under ordinary knitting conditions x 100
(3) Flame retardancy of fabric (vertical combustion test)
The residual flame time and carbonization length were measured by the JIS L1091-1992 A-4 method.
(4) Apparent Young's modulus Measured by JIS L1013-110 8.10 and calculated by the following formula.
Apparent Young's modulus (kg / mm 2 ) = fiber density x initial tensile resistance x 1000
(5) Limit oxygen index LOI value The limit oxygen index LOI value was measured by the JIS L1091-1999 E method.
[実施例1]
6枚筬を装備し、釜間5mmの22ゲージのダブルラッシェル機を使用して表面層および裏面層を構成する筬(L1、L2、L5、L6)に単繊維繊度1.9dtex、カット長(繊維長)51mm、LOI値が33であるポリメタフェニレンイソフタルアミド繊維(帝人株式会社製「コーネックス」(商標名))からなる短繊維からなる撚数20.87T/2.54cm(撚係数=3.3)、英式綿番手で60番単糸を配置し、表裏層を連結する連結糸を構成するL4筬に見かけヤング率7500kg/mm2を示すLOI値が25であるコパラフェニレン・3、4’オキシジフェニレンテレフタルアミド繊維(帝人株式会社製「テクノーラ」(商標名))からなる210dtex/65フィラメントの長繊維を配置し、編機上の密度を26コース/2.54cmにて製編し、全芳香族ポリアミド繊維の混率が100%の生機を得た。該生機を常法の加工条件で毛焼、精錬を実施した後、190℃でヒートセットを実施し、厚さ4.6mm、厚み保持率48%、目付けが238g/m2の、図1に示すような立体編物(三層構造織編物)を得た。得られた立体編物は、JIS L1091 A−4法に規定する残炎時間が0.0秒であり、良好な厚み有し、耐熱性にも大変優れるものであった。
[Example 1]
Equipped with 6 reeds, using a 22 gauge double raschel machine with a gap of 5 mm, the reeds (L1, L2, L5, L6) that make up the front and back layers have a single fiber fineness of 1.9 dtex and a cut length (L1, L2, L5, L6). The number of twists is 20.87T / 2.54cm (twist coefficient =) consisting of short fibers made of polymetaphenylene isophthalamide fiber (“Conex” (trade name) manufactured by Teijin Co., Ltd.) having a fiber length of 51 mm and an LOI value of 33. 3.3) Coparaphenylene with an LOI value of 25, which shows an apparent young rate of 7500 kg / mm 2 on the L4 reed that constitutes the connecting yarn that connects the front and back layers by arranging the 60th single yarn with an English cotton count. 210dtex / 65 filament long fibers made of 3,4'oxydiphenylene terephthalamide fibers ("Technora" (trade name) manufactured by Teijin Co., Ltd.) are arranged, and the density on the knitting machine is 26 courses / 2.54 cm. Knitting was performed to obtain a raw machine having a total aromatic polyamide fiber mixing ratio of 100%. The raw machine was hair-baked and refined under conventional processing conditions, and then heat-set at 190 ° C. to obtain a thickness of 4.6 mm, a thickness retention rate of 48%, and a basis weight of 238 g / m 2 , as shown in FIG. A three-dimensional knitted fabric (three-layered woven knitted fabric) as shown was obtained. The obtained three-dimensional knitted fabric had a residual flame time of 0.0 seconds specified in the JIS L1091 A-4 method, had a good thickness, and was extremely excellent in heat resistance.
[実施例2]
実施例1において、L4筬を見かけヤング率1300kg/mm2を示すポリエステルモノフィラメント220dtexに置き換えた以外は同様に製編、加工を実施した。得られた立体編物(三層構造織編物)は、全芳香族ポリアミド繊維の混率が65.6%、厚さが4.4mm、厚み圧縮率51%、重量が252g/m2、JIS L1091 A−4法に規定する残炎時間は全焼となり、良好な厚みは有するが、耐熱性に劣るものであった。
[Example 2]
In Example 1, knitting and processing were carried out in the same manner except that the L4 reed was replaced with a polyester monofilament 220dtex showing an apparent Young's modulus of 1300 kg / mm 2. The obtained three-dimensional knit (three-layer structure woven knit) has a total aromatic polyamide fiber mixing ratio of 65.6%, a thickness of 4.4 mm, a thickness compression ratio of 51%, a weight of 252 g / m 2 , and JIS L1091 A. -4 The residual flame time specified in the method was burnt down, and although it had a good thickness, it was inferior in heat resistance.
[実施例3]
実施例1において、L4筬に見かけヤング率700kg/mm2、単繊維繊度2.2dtex、カット長(繊維長)51mm、LOI値が33であるポリメタフェニレンイソフタルアミド繊維(帝人株式会社製「コーネックス」(商標名))からなる短繊維からなる撚数15.34T/2.54cm、を英式綿番手で20番単糸に置き換えた以外は同様に製編、加工を実施した。得られた立体編物(三層構造織編物)は、全芳香族ポリアミド繊維の混率が100%、厚さが2.4mm、厚み保持率49%、重量が244g/m2、JIS L1091 A−4法に規定する残炎時間は0.0秒となり、耐熱性は優れるものであったが、厚みが不足するものであった。
[Example 3]
In Example 1, a polymetaphenylene isophthalamide fiber having an apparent Young's modulus of 700 kg / mm 2 , a single fiber fineness of 2.2 dtex, a cut length (fiber length) of 51 mm, and a LOI value of 33 (Cau) manufactured by Teijin Limited. Knitting and processing were carried out in the same manner except that the twist number 15.34T / 2.54cm made of short fibers made of "Nex" (trade name) was replaced with 20th single yarn with an English cotton count. The obtained three-dimensional knit (three-layer structure woven knit) has a total aromatic polyamide fiber mixing ratio of 100%, a thickness of 2.4 mm, a thickness retention rate of 49%, a weight of 244 g / m 2 , and JIS L1091 A-4. The residual flame time stipulated by the law was 0.0 seconds, and the heat resistance was excellent, but the thickness was insufficient.
[比較例1]
単繊維繊度2.2dtex、カット長(繊維長)51mm、LOI値が33であるポリメタフェニレンイソフタルアミド繊維(帝人株式会社製「コーネックス」(商標名))からなる短繊維からなる撚数15.34T/2.54cm、を英式綿番手で40番単糸をワッフル組織として製織、加工を実施した。得られた織物は全芳香族ポリアミド繊維の混率が100%、厚さが1.4mm、厚み保持率34%、目付けが150g/m2、JIS L1091 A−4法に規定する残炎時間は0.2秒となり、耐熱性は優れるものであったが、厚み及び厚み保持率が不足するものであった。
[Comparative Example 1]
Single fiber fineness 2.2 dtex, cut length (fiber length) 51 mm, LOI value 33 polymetaphenylene isophthalamide fiber (Teijin Co., Ltd. "Cornex" (trade name)) twist number 15 Weaving and processing of .34T / 2.54cm with English cotton count and No. 40 single yarn as a waffle structure was carried out. The obtained woven fabric has a total aromatic polyamide fiber mixing ratio of 100%, a thickness of 1.4 mm, a thickness retention rate of 34%, a texture of 150 g / m 2 , and a residual flame time of 0 as stipulated by the JIS L1091 A-4 method. It took .2 seconds, and the heat resistance was excellent, but the thickness and the thickness retention rate were insufficient.
本発明によれば、難燃性および遮熱性に優れる三層構造織編物および繊維製品が提供され、その工業的価値は極めて大である。 According to the present invention, a three-layer structure woven knitted fabric and a textile product having excellent flame retardancy and heat shielding properties are provided, and their industrial value is extremely large.
1:地組織部
2:連結部
3:地組織部
1: Ground organization department 2: Connection part 3: Ground organization department
Claims (5)
前記連結部に、見掛けヤング率5000kg/mm 2 以上のパラ型全芳香族ポリアミド繊維からなる長繊維が配され、
表裏の地組織部にメタ型全芳香族ポリアミド繊維が配され、
織編物が編物であり、
織編物の厚さが3〜10mmの範囲内であり、
織編物の厚み保持率が40%以上であり、
かつJIS L1091−1992 A−4法により測定した残炎時間が2秒以下であることを特徴とする三層構造織編物。 It is a three-layer structure woven knit that is composed of a front and back ground structure part and a connecting part that connects the front and back ground structure parts.
Long fibers made of para-type total aromatic polyamide fibers having an apparent Young's modulus of 5000 kg / mm 2 or more are arranged at the connecting portion.
Meta-type total aromatic polyamide fibers are arranged on the front and back of the ground structure,
The woven knit is a knit,
The thickness of the woven or knitted fabric is in the range of 3 to 10 mm.
The thickness retention rate of woven and knitted fabrics is 40% or more.
Moreover, a three-layer structure woven knitted fabric characterized in that the residual flame time measured by the JIS L1091-1992 A-4 method is 2 seconds or less.
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