WO2015159749A1 - Colored organic fiber, fabric and clothing and method for manufacturing fabric - Google Patents
Colored organic fiber, fabric and clothing and method for manufacturing fabric Download PDFInfo
- Publication number
- WO2015159749A1 WO2015159749A1 PCT/JP2015/060712 JP2015060712W WO2015159749A1 WO 2015159749 A1 WO2015159749 A1 WO 2015159749A1 JP 2015060712 W JP2015060712 W JP 2015060712W WO 2015159749 A1 WO2015159749 A1 WO 2015159749A1
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- WO
- WIPO (PCT)
- Prior art keywords
- fiber
- fabric
- alcohol
- mass
- organic fiber
- Prior art date
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- 239000000835 fiber Substances 0.000 title claims abstract description 194
- 239000004744 fabric Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000004760 aramid Substances 0.000 claims description 46
- 229920003235 aromatic polyamide Polymers 0.000 claims description 44
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 239000013557 residual solvent Substances 0.000 claims description 14
- -1 aromatic dicarboxylic acid halide Chemical class 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- LEBQTCCCNMTXSF-UHFFFAOYSA-N (2,5-dimethylphenyl)methanol Chemical compound CC1=CC=C(C)C(CO)=C1 LEBQTCCCNMTXSF-UHFFFAOYSA-N 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 6
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 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
- 150000004984 aromatic diamines Chemical class 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003063 flame retardant Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 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
- 229920002530 polyetherether ketone 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
- 229920000742 Cotton Polymers 0.000 claims description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 5
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- ICJVQAHPHKYCNU-UHFFFAOYSA-N (2-ethoxyphenyl)methanol Chemical compound CCOC1=CC=CC=C1CO ICJVQAHPHKYCNU-UHFFFAOYSA-N 0.000 claims description 3
- WYLYBQSHRJMURN-UHFFFAOYSA-N (2-methoxyphenyl)methanol Chemical compound COC1=CC=CC=C1CO WYLYBQSHRJMURN-UHFFFAOYSA-N 0.000 claims description 3
- BWRBVBFLFQKBPT-UHFFFAOYSA-N (2-nitrophenyl)methanol Chemical compound OCC1=CC=CC=C1[N+]([O-])=O BWRBVBFLFQKBPT-UHFFFAOYSA-N 0.000 claims description 3
- ZSRDNPVYGSFUMD-UHFFFAOYSA-N (3-chlorophenyl)methanol Chemical compound OCC1=CC=CC(Cl)=C1 ZSRDNPVYGSFUMD-UHFFFAOYSA-N 0.000 claims description 3
- KWHVBVJDKLSOTB-UHFFFAOYSA-N 2-(3-methylphenyl)ethanol Chemical compound CC1=CC=CC(CCO)=C1 KWHVBVJDKLSOTB-UHFFFAOYSA-N 0.000 claims description 3
- DAVFJRVIVZOKKS-UHFFFAOYSA-N 2-(4-methylphenyl)ethanol Chemical compound CC1=CC=C(CCO)C=C1 DAVFJRVIVZOKKS-UHFFFAOYSA-N 0.000 claims description 3
- QGCCNWSXJHGUNL-UHFFFAOYSA-N 3-iodo-benzyl alcohol Chemical compound OCC1=CC=CC(I)=C1 QGCCNWSXJHGUNL-UHFFFAOYSA-N 0.000 claims description 3
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 claims description 3
- 229920002972 Acrylic fiber Polymers 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 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
- 229920000297 Rayon Polymers 0.000 claims description 3
- 229920006221 acetate fiber Polymers 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000005647 linker group Chemical group 0.000 claims description 3
- 229920006277 melamine fiber Polymers 0.000 claims description 3
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 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
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 3
- 239000002964 rayon Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 241000723347 Cinnamomum Species 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- OORRQYZWSVJKSO-UHFFFAOYSA-N bicyclo[4.4.1]undeca-1,3,5,7,9-pentaene Chemical compound C1=CC=C(C2)C=CC=CC2=C1 OORRQYZWSVJKSO-UHFFFAOYSA-N 0.000 claims description 2
- 235000017803 cinnamon Nutrition 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 15
- 238000009987 spinning Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 150000001408 amides Chemical class 0.000 description 9
- 238000005345 coagulation Methods 0.000 description 8
- 230000015271 coagulation Effects 0.000 description 8
- 229920006231 aramid fiber Polymers 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 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 4
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 4
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000009940 knitting Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- KTUVYMAZYSSBKC-UHFFFAOYSA-N hexyl benzenesulfonate Chemical compound CCCCCCOS(=O)(=O)C1=CC=CC=C1 KTUVYMAZYSSBKC-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical class CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 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
- 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
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 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
- IKNWWJMESJSJDP-UHFFFAOYSA-N benzyl(tributyl)phosphanium Chemical class CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 IKNWWJMESJSJDP-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000691 measurement method Methods 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
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 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
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical class C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- 238000009941 weaving Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/613—Polyethers without nitrogen
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/06—Dyes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
- D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
Definitions
- the present invention relates to a colored organic fiber that is dark and excellent in flame retardancy, and a fabric, a garment, and a method for manufacturing the fabric using the organic fiber.
- Patent Documents 1 to 3 propose the use of a core-sheath structured yarn.
- the core-sheath structure yarn is used, there is a problem that it takes a lot of time and cost, and a problem that the flame retardant property is not sufficient because it is necessary to use a normal synthetic fiber inferior in flame retardancy for the sheath yarn.
- Patent Document 4 proposes that a fabric is dyed with a carrier agent and then washed, but it has not been sufficient in terms of flame retardancy.
- the present invention has been made in view of the above-described background, and an object thereof is a colored organic fiber that is dark and excellent in flame retardancy, a fabric and a garment using the organic fiber, and a fabric. It is in providing the manufacturing method of.
- the inventor of the present invention has a dark color and flame retardancy by reducing the amount of the carrier agent remaining in the organic fiber in the organic fiber dyed with the carrier agent.
- the inventors have found that an excellent organic fiber can be obtained, and have further studied earnestly to complete the present invention.
- colored organic fiber characterized in that the content of the carrier agent is 1.8% by mass or less with respect to the mass of the fiber”.
- the content of the carrier agent is preferably in the range of 0.1 to 1.8% by mass relative to the fiber mass.
- the carrier agent may be DL- ⁇ -ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methyl.
- the organic fiber may be a meta-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber, polybenzoxazole (PBO) fiber, polybenzimidazole (PBI) fiber, polybenzthiazole (PBTZ) fiber, polyimide (PI).
- Fiber polysulfonamide (PSA), polyether ether ketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, polyphenylene sulfide (PPS) fiber It is preferably any one selected from the group consisting of
- the organic fiber is preferably a meta-type wholly aromatic polyamide fiber having a crystallinity of 15 to 25%. Moreover, it is preferable that the said organic fiber is a meta-type wholly aromatic polyamide fiber whose residual solvent amount is 1.0 mass% or less. Moreover, it is preferable that the said organic fiber is a meta type wholly aromatic polyamide fiber whose residual solvent amount is 0.1 mass% or less.
- the residual solvent is preferably any one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide.
- the organic fiber is a meta-type wholly aromatic polyamide fiber
- the meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber includes a repeating structural unit represented by the following formula (1).
- an aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main structural unit of the repeating structure is 1 to 10 mol% based on the total amount of the repeating structural unit of the aromatic polyamide as the third component.
- An aromatic polyamide copolymerized as described above is preferable.
- Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
- the aromatic diamine as the third component is the formula (2), (3), or the aromatic dicarboxylic acid halide is the formula (4), (5).
- Ar2 is a divalent aromatic group different from Ar1
- Ar3 is a divalent aromatic group different from Ar1
- Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
- the fabric containing the said colored organic fiber is provided.
- the fabric is polyester fiber, cellulose fiber, polyamide 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. It is preferable to include any one or more selected from the group consisting of: Moreover, it is preferable that any fiber which comprises a fabric contains a flame retardant. Moreover, it is preferable that any fiber which comprises a fabric contains a ultraviolet absorber or a ultraviolet reflector. Moreover, it is preferable that the fabric weight is 300 g / m 2 or less.
- LOI is 26 or more.
- the afterflame time is preferably 1 second or less in the vertical combustion test (JIS L1091A-4 method 3s flame contact).
- the lightness index L value is 80 or less.
- a method for producing a fabric containing the above-described colored organic fiber wherein the fabric containing the organic fiber is dyed with a carrier agent, and then the fabric is heated at a temperature of 90 to 140 ° C.
- a method for producing a fabric in which the content of the carrier agent contained in the organic fiber is 1.8% by mass or less with respect to the mass of the fiber is provided.
- a colored organic fiber that is dark and excellent in flame retardancy, a fabric and clothing using the organic fiber, and a method for producing the fabric are obtained.
- the present invention is directed to colored organic fibers.
- the content of the carrier agent is 1.8% by mass or less with respect to the mass of the fiber.
- the carrier agent is a dyeing assistant and is also called a swelling agent.
- the kind of carrier agent is not particularly limited. Specifically, L- ⁇ -ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methylphenethyl alcohol , 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamon alcohol, p-anisyl alcohol, benzhydrol, benzyl alcohol, propylene glycol phenyl ether, ethylene glycol phenyl Examples include ether and N-methylformanilide.
- the type of the organic fiber is not particularly limited.
- meta-type wholly aromatic polyamide fibers are preferable.
- the meta-type wholly aromatic polyamide fiber is a fiber made of a polymer in which 85 mol% or more of the repeating units is m-phenylene isophthalamide.
- Such a meta-type wholly aromatic polyamide may be a copolymer containing a third component within a range of less than 15 mol%.
- Such a meta-type wholly aromatic polyamide can be produced by a conventionally known interfacial polymerization method.
- the degree of polymerization of the polymer is such that the intrinsic viscosity (IV) measured with an N-methyl-2-pyrrolidone solution having a concentration of 0.5 g / 100 ml is in the range of 1.3 to 1.9 dl / g. Preferably used.
- the meta-type wholly aromatic polyamide may contain an alkylbenzene sulfonic acid onium salt.
- alkylbenzene sulfonic acid onium salt examples include tetrabutyl phosphonium salt of hexyl benzene sulfonate, tributyl benzyl phosphonium salt of hexyl benzene sulfonate, tetraphenyl phosphonium salt of dodecyl benzene sulfonate, tributyl tetradecyl phosphonate of dodecyl benzene sulfonate.
- Preferred examples include compounds such as a nium salt, tetrabutylphosphonium salt of dodecylbenzenesulfonate, and tributylbenzylammonium salt of dodecylbenzenesulfonate.
- dodecylbenzenesulfonic acid tetrabutylphosphonium salt or dodecylbenzenesulfonic acid tributylbenzylammonium salt is particularly easy to obtain and has good thermal stability and high solubility in N-methyl-2-pyrrolidone.
- tributylbenzylammonium salt is particularly easy to obtain and has good thermal stability and high solubility in N-methyl-2-pyrrolidone.
- the content ratio of the alkylbenzenesulfonic acid onium salt is 2.5 mol% or more, preferably 3.0 to 7.0 mol, relative to poly-m-phenyleneisophthalamide in order to obtain a sufficient dyeing effect. Those in the range of% are preferred.
- poly-m-phenylene isophthalamide As a method of mixing poly-m-phenylene isophthalamide and alkylbenzene sulfonic acid onium salt, poly-m-phenylene isophthalamide is mixed and dissolved in a solvent, and alkylbenzene sulfonic acid onium salt is dissolved in the solvent. Any of these may be used.
- the dope thus obtained is formed into fibers by a conventionally known method.
- the polymer used for the meta-type wholly aromatic polyamide fiber has a repeating structure in an aromatic polyamide skeleton containing a repeating structural unit represented by the following formula (2) for the purpose of improving dyeability and resistance to discoloration. It is also possible to copolymerize an aromatic diamine component or aromatic dicarboxylic acid halide component different from the main structural unit of 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide as the third component. It is.
- Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
- aromatic diamine represented by the formulas (2) and (3) include, for example, p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, Examples include acetylphenylenediamine, aminoanisidine, benzidine, bis (aminophenyl) ether, bis (aminophenyl) sulfone, diaminobenzanilide, diaminoazobenzene, and the like.
- aromatic dicarboxylic acid dichloride represented by the formulas (4) and (5) include, for example, terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4 Examples include '-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis (chlorocarbonylphenyl) ether, and the like.
- Ar2 is a divalent aromatic group different from Ar1
- Ar3 is a divalent aromatic group different from Ar1
- Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
- the crystallinity of the meta-type wholly aromatic polyamide fiber is 5 to 35% in terms of good exhaustibility of the dye and easy adjustment to the target color even with less dye or weak dyeing conditions. Preferably there is. Further, it is more preferably 15 to 25% from the viewpoint that the surface uneven distribution of the dye hardly occurs, the discoloration resistance is high, and the dimensional stability necessary for practical use can be secured.
- the residual solvent amount of the meta-type wholly aromatic polyamide fiber is 1.
- It is preferably 0% by mass or less (more preferably 0.1% by mass or less, and still more preferably 0.01 to 0.09% by mass).
- the meta-type wholly aromatic polyamide fiber can be produced by the following method, and in particular, the crystallinity and the residual solvent amount can be within the above ranges by the method described later.
- the polymerization method of the meta-type wholly aromatic polyamide polymer is not particularly limited.
- the solution polymerization method and the interfacial polymerization method described in Japanese Patent Publication No. 35-14399, US Pat. No. 3,360,595, Japanese Patent Publication No. 47-10863 may be used.
- the spinning solution is not particularly limited.
- An amide solvent solution containing an aromatic copolyamide polymer obtained by the solution polymerization or interfacial polymerization may be used, or the polymer is isolated from the polymerization solution and dissolved in an amide solvent. It may be used.
- examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like, and in particular, N, N-dimethylacetamide. Is preferred.
- the obtained copolymer aromatic polyamide polymer solution is further stabilized by containing an alkali metal salt or an alkaline earth metal salt, and can be used at a higher concentration and lower temperature, which is preferable.
- the alkali metal salt and alkaline earth metal salt are 1% by weight or less, more preferably 0.1% by weight or less, based on the total weight of the polymer solution.
- the spinning solution metal-type wholly aromatic polyamide polymer solution obtained above is spun into a coagulating solution and coagulated.
- the spinning apparatus is not particularly limited, and a conventionally known wet spinning apparatus can be used. Further, the number of spinning holes, the arrangement state, the hole shape and the like of the spinneret are not particularly limited. For example, a multi-hole spinneret for sufu having 1000 to 30000 holes and a spinning hole diameter of 0.05 to 0.2 mm may be used.
- the temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) when spinning from the spinneret is preferably in the range of 20 to 90 ° C.
- an aqueous solution containing 45 to 60% by mass of an amide solvent (preferably NMP) substantially free of inorganic salt is used, and the temperature of the bath solution is in the range of 10 to 50 ° C. It is preferable to use in. If the concentration of the amide solvent (preferably NMP) is less than 45% by mass, the skin has a thick structure, and the cleaning efficiency in the cleaning process may be reduced, making it difficult to reduce the amount of residual solvent in the fiber. . 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 residual solvent amount of the fiber can be reduced. May become difficult.
- the fiber immersion time in the coagulation bath is preferably in the range of 0.1 to 30 seconds.
- an amide solvent preferably an aqueous solution having a concentration of NMP of 45 to 60% by mass, and a draw ratio of 3 to 4 times in a plastic drawing bath in which the temperature of the bath liquid is in the range of 10 to 50 ° C. It is preferable to perform stretching. After stretching, it is preferable to perform sufficient washing through an aqueous solution having an NMP concentration of 10 to 30 ° C. of 20 to 40% by mass, followed by a hot water bath of 50 to 70 ° C.
- the washed fiber is subjected to a dry heat treatment at a temperature of 270 to 290 ° C. to obtain a meta-type wholly aromatic aramid fiber satisfying the above-mentioned range of crystallinity and residual solvent amount.
- the fiber may be a long fiber (multifilament) or a short fiber.
- short fibers having a fiber length of 25 to 200 mm are preferable in blending with other fibers.
- the single fiber fineness of the organic fiber is preferably in the range of 1 to 5 dtex.
- a dyeing method using a carrier agent is preferable as a coloring method.
- a method of dyeing with a cationic dye is preferred for obtaining excellent darkness.
- the conditions for the dyeing process are not particularly limited.
- the content of the carrier agent is not more than 1.8% by mass relative to the mass of the fiber (preferably 0.1 to 1.8% by mass, more preferably 0.1 to 1.0% by mass, still more preferably Is 0.3 to 0.9% by mass). If the content is greater than 1.8% by mass, flame retardancy may be impaired. On the other hand, if the content is less than 0.1% by weight, excellent darkness may not be obtained, and the hot water washing process described later may be complicated.
- a dyed fabric is reduced and washed as necessary, and then heated with hot water at a temperature of 90 to 140 ° C. (more preferably 110 to 140 ° C.) for 10 to 30 A method of washing with hot water for a minute is exemplified.
- the fabric of the present invention is a fabric containing the above-mentioned colored organic fibers.
- a fabric may be composed of only the above-mentioned colored organic fibers, and further, polyester fiber, cellulose fiber, polyamide fiber, polyolefin fiber, acrylic fiber, rayon fiber, cotton fiber, animal hair fiber, polyurethane fiber, poly Other fibers such as vinyl chloride fiber, polyvinylidene chloride fiber, acetate fiber, and polycarbonate fiber may be included.
- the meta-type wholly aromatic polyamide fiber contained in the fabric is 50% by mass or more based on the mass of the fabric because excellent flame retardancy is obtained.
- the flame retardant fiber, synthetic fiber, regenerated fiber, and natural fiber can be arbitrarily mixed according to the application and use needs.
- the meta-type wholly aromatic polyamide fiber is 50 to 98% by mass
- the polyester fiber is 2 to 50% by mass
- the cellulosic mass fiber is 0 to 50%, which has both dyeability and comfort. It can also be done.
- the ratio may be adjusted according to the performance to be emphasized.
- the solubility to water is 0.04 mg / L or less. If the solubility in water is greater than 0.04 mg / L, the ultraviolet absorber may be eluted when dyeing with a carrier agent, which may reduce the light resistance after dyeing.
- the method for producing the fabric is not particularly limited. For example, after obtaining a spun yarn using the organic fiber (or the organic fiber and other fibers), weaving or knitting with a single yarn or twin yarn, dyed with a carrier agent, It is good to wash with hot water by the method.
- the fabric structure is preferably a woven fabric such as plain weave, twill weave, satin or double weave, but may be knitted fabric or non-woven fabric.
- the method for producing the fabric is not particularly limited.
- known knitting and knitting machines such as rapier looms and gripper looms can be used.
- the obtained fabric is excellent in dark color and flame retardancy because it uses the organic fiber.
- the darkness is preferably 80 or less (more preferably 52.5 or less, and further preferably 10 to 52.3) in terms of lightness index L value.
- the LOI is preferably 26 or more (more preferably 26 to 40).
- the afterflame time is preferably 25 seconds or less (more preferably 1 second or less).
- the basis weight is preferably 300 g / m 2 or less (preferably 50 to 250 g / m 2 ). If the weight per unit area is larger than 300 g / m 2 , the lightness of the fabric may be impaired.
- the apparel of the present invention is apparel using the above-mentioned fabric.
- Such clothing includes protective clothing, fire fighting clothing, fire protection clothing, rescue clothing, activity clothing, office work clothing, motor sports racing suits, work clothing, gloves, hats, vests, and the like.
- the work clothes include work clothes worn when working in steelworks or steel factories, work clothes for welding work, work clothes in an explosion-proof area, and the like.
- the gloves include working gloves used in the aircraft industry, the information equipment industry, the precision equipment industry, etc. that handle precision parts.
- the fabric may be used for textile products such as curtains, car seats, bags and the like.
- each physical property in an Example is measured with the following method.
- the measurement conditions were a Cu-K ⁇ radiation source (50 kV, 300 mA), a scanning angle range of 10 to 35 °, a continuous measurement of 0.1 ° width measurement, and a scan of 1 ° / min. From the measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to obtain a total scattering profile. Next, a crystal scattering profile was obtained by subtracting the amorphous scattering profile from the total scattering profile. The degree of crystallinity was determined by the following equation from the area intensity of the crystal scattering profile (crystal scattering intensity) and the area intensity of the total scattering profile (total scattering intensity).
- Crystallinity (%) [crystal scattering intensity / total scattering intensity] ⁇ 100 (4) Amount of residual carrier agent Measurement method: A GC / MS sample comprising a fiber sample was packed in a sample tube and measured by ATD. After confirming the carrier agent by qualitative analysis, quantitative analysis was performed under the following conditions.
- polymetaphenylene isophthalamide powder produced by an interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863 and having an intrinsic viscosity (IV) of 1.9 is placed at ⁇ 10 ° C. It was suspended in 80.0 parts by mass of cooled N-methyl-2-pyrrolidone (NMP) to form a slurry. Subsequently, the suspension was heated to 60 ° C. and dissolved to obtain a transparent polymer solution.
- NMP N-methyl-2-pyrrolidone
- Spinning was performed by discharging into a coagulation bath at a yarn speed of 7 m / min.
- the washed fiber was subjected to a dry heat treatment with a heat roller having a surface temperature of 280 ° C. to obtain a meta-type wholly aromatic aramid fiber.
- the meta-type wholly aromatic aramid fiber was used for crimping and cutting to obtain a staple fiber (raw cotton) having a length of 51 mm.
- the physical properties of the obtained meta-type wholly aromatic aramid fiber were as follows: the single fiber fineness was 1.7 dtex, the residual solvent amount was 0.08% by mass, and the crystallinity was 19%.
- each staple fiber of meta type fully aromatic aramid fiber (MA) (length 51 mm), para type fully aromatic polyamide (PA) (length 50 mm), nylon conductive yarn (AS) (length 51 mm), MA / PA / AS 93/5/2 blended spun yarn 40 count / twist yarn, weaved at warp density of 65 / 25.4mm, weft 55 / 25.4mm, with a basis weight of 170g / m Two plain texture fabrics were obtained.
- MA meta type fully aromatic aramid fiber
- PA para type fully aromatic polyamide
- AS nylon conductive yarn
- Example 2 The same operation as in Example 1 was performed except that 130 ° C. ⁇ 20 minutes once in the hot water cleaning prescription was changed to 130 ° C. ⁇ 20 minutes twice. The evaluation results are shown in Table 1.
- Example 3 The same operation as in Example 1 was performed except that 130 ° C. ⁇ 20 minutes once in the hot water washing prescription was changed to 120 ° C. ⁇ 20 minutes twice. The evaluation results are shown in Table 1.
- Example 4 The same operation as in Example 1 was performed except that Dawanol PPH 40 g / L in the above dyeing prescription was changed to benzyl alcohol 60 g / L. The evaluation results are shown in Table 1.
- Example 5 Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. ⁇ 20 minutes of the hot water washing prescription is changed to 120 ° C. ⁇ 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.
- Example 6 Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. ⁇ 20 minutes of the hot water washing prescription is changed to 120 ° C. ⁇ 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.
- Example 7 Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. ⁇ 20 minutes of the hot water washing prescription is changed to 120 ° C. ⁇ 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.
- Example 1 The same operation as in Example 1 was performed except that 130 ° C. ⁇ 20 minutes of the hot water washing prescription was changed to 90 ° C. ⁇ 20 minutes once. The evaluation results are shown in Table 1.
- Example 8 The same operation as in Example 1 was performed except that 130 ° C. ⁇ 20 minutes of the hot water washing prescription was changed from 90 ° C. ⁇ 20 minutes to 5 times. The evaluation results are shown in Table 1.
- Example 9 The same operation as in Example 1 was performed except that 130 ° C. ⁇ 20 minutes of the hot water washing prescription was changed from 90 ° C. ⁇ 20 minutes to 10 times. The results are shown in Table 1.
- Example 10 The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 30 g / L. The evaluation results are shown in Table 1.
- Example 11 The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 20 g / L. The evaluation results are shown in Table 1.
- Example 12 The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 10 g / L. The evaluation results are shown in Table 1.
- the organic fiber which was the colored organic fiber and was dark and excellent in the flame retardance, the fabric and clothing using this organic fiber, and the manufacturing method of a fabric are provided,
- the industrial value is the It is extremely large.
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Abstract
The present invention addresses the problem of providing a colored organic fiber that has a deep color and excellent flame retardancy, a fabric and clothing using the organic fiber, and a method for manufacturing a fabric. To solve this problem, provided is a colored organic fiber wherein the content of a carrier agent is controlled to 1.8 mass% or lower relative to the fiber mass. If required, a fabric or clothing can be obtained using the colored organic fiber.
Description
本発明は、着色した有機繊維であって濃色かつ難燃性に優れた有機繊維、および該有機繊維を用いてなる布帛および衣料および布帛の製造方法に関する。
The present invention relates to a colored organic fiber that is dark and excellent in flame retardancy, and a fabric, a garment, and a method for manufacturing the fabric using the organic fiber.
従来、メタ型芳香族ポリアミド繊維などの有機繊維を含む難燃性布帛を着色する方法として、有機繊維に顔料を含有させる方法やキャリア剤を用いて布帛を染色する方法が知られている。
Conventionally, as a method of coloring a flame retardant fabric containing organic fibers such as meta-type aromatic polyamide fibers, a method of adding a pigment to organic fibers or a method of dyeing a fabric using a carrier agent is known.
しかしながら、有機繊維に顔料を含有させる方法では、濃色性に優れたものを得ることが困難であった。一方、キャリア剤を用いて染色する方法では、難燃性の点で十分とはいえなかった。
However, it has been difficult to obtain a product having excellent darkness by the method of adding a pigment to the organic fiber. On the other hand, the method of dyeing using a carrier agent is not sufficient in terms of flame retardancy.
このような問題を解決するため、例えば特許文献１～３では、芯鞘構造糸を用いることが提案されている。しかしながら、芯鞘構造糸を用いると、時間やコストを多く費やすという問題や、難燃性に劣る通常の合成繊維を鞘糸に用いる必要があるため難燃性の点で十分ではないという問題があった。また、例えば特許文献４では、キャリア剤を用いて布帛を染色した後、洗浄することが提案されているが、難燃性の点でまだ十分とはいえなかった。
In order to solve such problems, for example, Patent Documents 1 to 3 propose the use of a core-sheath structured yarn. However, when the core-sheath structure yarn is used, there is a problem that it takes a lot of time and cost, and a problem that the flame retardant property is not sufficient because it is necessary to use a normal synthetic fiber inferior in flame retardancy for the sheath yarn. there were. Further, for example, Patent Document 4 proposes that a fabric is dyed with a carrier agent and then washed, but it has not been sufficient in terms of flame retardancy.
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、着色した有機繊維であって濃色かつ難燃性に優れた有機繊維および該有機繊維を用いてなる布帛および衣料、および布帛の製造方法を提供することにある。
The present invention has been made in view of the above-described background, and an object thereof is a colored organic fiber that is dark and excellent in flame retardancy, a fabric and a garment using the organic fiber, and a fabric. It is in providing the manufacturing method of.
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、キャリア剤を用いて染色した有機繊維において、有機繊維に残留するキャリア剤の量を低減することにより濃色でありかつ難燃性に優れた有機繊維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 intensive studies to achieve the above-mentioned problems, the inventor of the present invention has a dark color and flame retardancy by reducing the amount of the carrier agent remaining in the organic fiber in the organic fiber dyed with the carrier agent. The inventors have found that an excellent organic fiber can be obtained, and have further studied earnestly to complete the present invention.
かくして、本発明によれば「着色した有機繊維であって、キャリア剤の含有率が繊維質量対比１．８質量％以下であることを特徴とする着色した有機繊維。」が提供される。
Thus, according to the present invention, there is provided “colored organic fiber characterized in that the content of the carrier agent is 1.8% by mass or less with respect to the mass of the fiber”.
その際、前記キャリア剤の含有率が繊維質量対比０．１～１．８質量％の範囲内であることが好ましい。また、前記キャリア剤が、ＤＬ－β－エチルフェネチルアルコール、２－エトキシベンジルアルコール、３－クロロベンジルアルコール、２，５－ジメチルベンジルアルコール、２－ニトロベンジルアルコール、ｐ－イソプロピルベンジルアルコール、２－メチルフェネチルアルコール、３－メチルフェネチルアルコール、４－メチルフェネチルアルコール、２－メトキシベンジルアルコール、３－ヨードベンジルアルコール、ケイ皮アルコール、ｐ－アニシルアルコール、ベンズヒドロール、ベンジルアルコール、プロピレングリコールフェニルエーテル、エチレングリコールフェニルエーテル、およびＮ－メチルホルムアニリドからなる群より選択されるいずれか１種以上であることが好ましい。また、前記有機繊維が、メタ型全芳香族ポリアミド繊維、パラ型全芳香族ポリアミド繊維、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）、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、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種であることが好ましい。
At that time, the content of the carrier agent is preferably in the range of 0.1 to 1.8% by mass relative to the fiber mass. The carrier agent may be DL-β-ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methyl. Phenethyl alcohol, 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamic alcohol, p-anisyl alcohol, benzhydrol, benzyl alcohol, propylene glycol phenyl ether, ethylene It is preferably at least one selected from the group consisting of glycol phenyl ether and N-methylformanilide. The organic fiber may be a meta-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber, polybenzoxazole (PBO) fiber, polybenzimidazole (PBI) fiber, polybenzthiazole (PBTZ) fiber, polyimide (PI). ) Fiber, polysulfonamide (PSA), polyether ether ketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, polyphenylene sulfide (PPS) fiber It is preferably any one selected from the group consisting of
また、前記有機繊維が、結晶化度が１５～２５％のメタ型全芳香族ポリアミド繊維であることが好ましい。また、前記有機繊維が、残存溶媒量が１．０質量％以下のメタ型全芳香族ポリアミド繊維であることが好ましい。また、前記有機繊維が、残存溶媒量が０．１質量％以下のメタ型全芳香族ポリアミド繊維であることが好ましい。その際、前記残存溶媒が、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からなる群より選択されるいずれかであることが好ましい。
The organic fiber is preferably a meta-type wholly aromatic polyamide fiber having a crystallinity of 15 to 25%. Moreover, it is preferable that the said organic fiber is a meta-type wholly aromatic polyamide fiber whose residual solvent amount is 1.0 mass% or less. Moreover, it is preferable that the said organic fiber is a meta type wholly aromatic polyamide fiber whose residual solvent amount is 0.1 mass% or less. In this case, the residual solvent is preferably any one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide.
また、前記有機繊維がメタ型全芳香族ポリアミド繊維であり、かつ該メタ型全芳香族ポリアミド繊維を形成するメタ型全芳香族ポリアミドが、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た芳香族ポリアミドであることが好ましい。
The organic fiber is a meta-type wholly aromatic polyamide fiber, and the meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber includes a repeating structural unit represented by the following formula (1). In the aromatic polyamide skeleton, an aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main structural unit of the repeating structure is 1 to 10 mol% based on the total amount of the repeating structural unit of the aromatic polyamide as the third component. An aromatic polyamide copolymerized as described above is preferable.
－（ＮＨ－Ａｒ１－ＮＨ－ＣＯ－Ａｒ１－ＣＯ）－ ・・・式（１）
ここで、Ａｒ１はメタ配位又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。 — (NH—Ar 1 —NH—CO—Ar 1 —CO) — (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
ここで、Ａｒ１はメタ配位又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。 — (NH—Ar 1 —NH—CO—Ar 1 —CO) — (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
その際、第３成分となる芳香族ジアミンが式（２）、（３）、または芳香族ジカルボン酸ハライドが、式（４）、（５）であることが好ましい。
In that case, it is preferable that the aromatic diamine as the third component is the formula (2), (3), or the aromatic dicarboxylic acid halide is the formula (4), (5).
Ｈ２Ｎ－Ａｒ２－ＮＨ２ ・・・式（２）
Ｈ２Ｎ－Ａｒ２－Ｙ－Ａｒ２－ＮＨ２ ・・・式（３）
ＸＯＣ－Ａｒ３－ＣＯＸ ・・・式（４）
ＸＯＣ－Ａｒ３－Ｙ－Ａｒ３－ＣＯＸ ・・・式（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。 H 2 N—Ar 2 —NH 2 Formula (2)
H 2 N—Ar 2 —Y—Ar 2 —NH 2 Formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
Ｈ２Ｎ－Ａｒ２－Ｙ－Ａｒ２－ＮＨ２ ・・・式（３）
ＸＯＣ－Ａｒ３－ＣＯＸ ・・・式（４）
ＸＯＣ－Ａｒ３－Ｙ－Ａｒ３－ＣＯＸ ・・・式（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。 H 2 N—Ar 2 —NH 2 Formula (2)
H 2 N—Ar 2 —Y—Ar 2 —NH 2 Formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
また、本発明によれば、前記の着色した有機繊維を含む布帛が提供される。その際、布帛が、ポリエステル繊維、セルロース繊維、ポリアミド繊維、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。また、布帛を構成するいずれかの繊維が難燃剤を含むことが好ましい。また、布帛を構成するいずれかの繊維が紫外線吸収剤または紫外線反射剤を含むことが好ましい。また、布帛の目付けが３００ｇ／ｍ２以下であることが好ましい。また、ＬＯＩが２６以上であることが好ましい。また、垂直燃焼試験（ＪＩＳ Ｌ１０９１Ａ－４法３ｓ接炎）で残炎時間１秒以下であることが好ましい。また、明度指数Ｌ値が８０以下であることが好ましい。
Moreover, according to this invention, the fabric containing the said colored organic fiber is provided. At that time, the fabric is polyester fiber, cellulose fiber, polyamide 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. It is preferable to include any one or more selected from the group consisting of: Moreover, it is preferable that any fiber which comprises a fabric contains a flame retardant. Moreover, it is preferable that any fiber which comprises a fabric contains a ultraviolet absorber or a ultraviolet reflector. Moreover, it is preferable that the fabric weight is 300 g / m 2 or less. Moreover, it is preferable that LOI is 26 or more. Further, the afterflame time is preferably 1 second or less in the vertical combustion test (JIS L1091A-4 method 3s flame contact). Moreover, it is preferable that the lightness index L value is 80 or less.
また、本発明によれば、前記の布帛を用いてなる衣料が提供される。
Further, according to the present invention, there is provided a clothing made using the above-mentioned fabric.
また、本発明によれば、前記の着色した有機繊維を含む布帛の製造方法であって、有機繊維を含む布帛を、キャリア剤を用いて染色した後、該布帛を温度９０～１４０℃の熱水で１０～３０分間洗浄することにより前記有機繊維に含まれるキャリア剤の含有率を繊維質量対比１．８質量％以下とする布帛の製造方法が提供される。
Further, according to the present invention, there is provided a method for producing a fabric containing the above-described colored organic fiber, wherein the fabric containing the organic fiber is dyed with a carrier agent, and then the fabric is heated at a temperature of 90 to 140 ° C. By washing with water for 10 to 30 minutes, a method for producing a fabric in which the content of the carrier agent contained in the organic fiber is 1.8% by mass or less with respect to the mass of the fiber is provided.
本発明によれば、着色した有機繊維であって濃色かつ難燃性に優れた有機繊維および該有機繊維を用いてなる布帛および衣料、および布帛の製造方法が得られる。
According to the present invention, a colored organic fiber that is dark and excellent in flame retardancy, a fabric and clothing using the organic fiber, and a method for producing the fabric are 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、本発明は着色した有機繊維を対象とする。かかる有機繊維において、キャリア剤の含有率が繊維質量対比１．８質量％以下である。
Hereinafter, embodiments of the present invention will be described in detail. First, the present invention is directed to colored organic fibers. In such an organic fiber, the content of the carrier agent is 1.8% by mass or less with respect to the mass of the fiber.
ここで、前記キャリア剤は染色助剤であり、膨潤剤とも称される。かかるキャリア剤の種類は特に限定されない。具体的には、Ｌ－β－エチルフェネチルアルコール、２－エトキシベンジルアルコール、３－クロロベンジルアルコール、２，５－ジメチルベンジルアルコール、２－ニトロベンジルアルコール、ｐ－イソプロピルベンジルアルコール、２－メチルフェネチルアルコール、３－メチルフェネチルアルコール、４－メチルフェネチルアルコール、２－メトキシベンジルアルコール、３－ヨードベンジルアルコール、ケイ皮アルコール、ｐ－アニシルアルコール、ベンズヒドロール、ベンジルアルコール、プロピレングリコールフェニルエーテル、エチレングリコールフェニルエーテル、Ｎ－メチルホルムアニリドなどが例示される。
Here, the carrier agent is a dyeing assistant and is also called a swelling agent. The kind of carrier agent is not particularly limited. Specifically, L-β-ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methylphenethyl alcohol , 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamon alcohol, p-anisyl alcohol, benzhydrol, benzyl alcohol, propylene glycol phenyl ether, ethylene glycol phenyl Examples include ether and N-methylformanilide.
本発明の着色した有機繊維において、有機繊維の種類は特に限定されないが、優れた難燃性を得る上で、メタ型全芳香族ポリアミド繊維、パラ型全芳香族ポリアミド繊維、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）、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、ポリフェニレンスルフィド（ＰＰＳ）繊維などが好ましい。
In the colored organic fiber of the present invention, the type of the organic fiber is not particularly limited. However, in order to obtain excellent flame retardancy, meta-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber, polybenzoxazole (PBO) ) Fiber, polybenzimidazole (PBI) fiber, polybenzthiazole (PBTZ) fiber, polyimide (PI) fiber, polysulfonamide (PSA), polyetheretherketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, polyphenylene sulfide (PPS) fiber and the like are preferable.
なかでも、メタ型全芳香族ポリアミド繊維が好ましい。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差しつかえない。
Of these, meta-type wholly aromatic polyamide fibers are preferable. The meta-type wholly aromatic polyamide fiber is a fiber made of a polymer in which 85 mol% or more of the repeating units is m-phenylene isophthalamide. Such a meta-type wholly aromatic polyamide may be a copolymer containing a third component within a range of less than 15 mol%.
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る。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。
Such a meta-type wholly aromatic polyamide can be produced by a conventionally known interfacial polymerization method. The degree of polymerization of the polymer is such that the intrinsic viscosity (IV) measured with an N-methyl-2-pyrrolidone solution having a concentration of 0.5 g / 100 ml is in the range of 1.3 to 1.9 dl / g. 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 wholly aromatic polyamide may contain an alkylbenzene sulfonic acid onium salt. Examples of the onium salt of alkylbenzene sulfonate include tetrabutyl phosphonium salt of hexyl benzene sulfonate, tributyl benzyl phosphonium salt of hexyl benzene sulfonate, tetraphenyl phosphonium salt of dodecyl benzene sulfonate, tributyl tetradecyl phosphonate of dodecyl benzene sulfonate. Preferred examples include compounds such as a nium salt, tetrabutylphosphonium salt of dodecylbenzenesulfonate, and tributylbenzylammonium salt of dodecylbenzenesulfonate. Among them, dodecylbenzenesulfonic acid tetrabutylphosphonium salt or dodecylbenzenesulfonic acid tributylbenzylammonium salt is particularly easy to obtain and has good thermal stability and 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。
The content ratio of the alkylbenzenesulfonic acid onium salt is 2.5 mol% or more, preferably 3.0 to 7.0 mol, relative to poly-m-phenyleneisophthalamide in order to obtain a sufficient dyeing effect. Those in the range of% are preferred.
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。
As a method of mixing poly-m-phenylene isophthalamide and alkylbenzene sulfonic acid onium salt, poly-m-phenylene isophthalamide is mixed and dissolved in a solvent, and alkylbenzene sulfonic acid onium salt is dissolved in the solvent. Any of these 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（２）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。
The polymer used for the meta-type wholly aromatic polyamide fiber has a repeating structure in an aromatic polyamide skeleton containing a repeating structural unit represented by the following formula (2) for the purpose of improving dyeability and resistance to discoloration. It is also possible to copolymerize an aromatic diamine component or aromatic dicarboxylic acid halide component different from the main structural unit of 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide as the third component. It is.
－（ＮＨ－Ａｒ１－ＮＨ－ＣＯ－Ａｒ１－ＣＯ）－ ・・・式（１）
ここで、Ａｒ１はメタ配位又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。 — (NH—Ar 1 —NH—CO—Ar 1 —CO) — (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
ここで、Ａｒ１はメタ配位又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。 — (NH—Ar 1 —NH—CO—Ar 1 —CO) — (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or 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。
Further, it is possible to copolymerize as the third component. Specific examples of the aromatic diamine represented by the formulas (2) and (3) include, for example, p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, Examples include acetylphenylenediamine, aminoanisidine, benzidine, bis (aminophenyl) ether, bis (aminophenyl) sulfone, diaminobenzanilide, diaminoazobenzene, and the like. Specific examples of the aromatic dicarboxylic acid dichloride represented by the formulas (4) and (5) include, for example, terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4 Examples include '-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis (chlorocarbonylphenyl) ether, and the like.
Ｈ２Ｎ－Ａｒ２－ＮＨ２ ・・・式（２）
Ｈ２Ｎ－Ａｒ２－Ｙ－Ａｒ２－ＮＨ２ ・・・式（３）
ＸＯＣ－Ａｒ３－ＣＯＸ ・・・式（４）
ＸＯＣ－Ａｒ３－Ｙ－Ａｒ３－ＣＯＸ ・・・式（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。 H 2 N—Ar 2 —NH 2 Formula (2)
H 2 N—Ar 2 —Y—Ar 2 —NH 2 Formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
Ｈ２Ｎ－Ａｒ２－Ｙ－Ａｒ２－ＮＨ２ ・・・式（３）
ＸＯＣ－Ａｒ３－ＣＯＸ ・・・式（４）
ＸＯＣ－Ａｒ３－Ｙ－Ａｒ３－ＣＯＸ ・・・式（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。 H 2 N—Ar 2 —NH 2 Formula (2)
H 2 N—Ar 2 —Y—Ar 2 —NH 2 Formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
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。更には、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。
The crystallinity of the meta-type wholly aromatic polyamide fiber is 5 to 35% in terms of good exhaustibility of the dye and easy adjustment to the target color even with less dye or weak dyeing conditions. Preferably there is. Further, it is more preferably 15 to 25% from the viewpoint that the surface uneven distribution of the dye hardly occurs, the discoloration resistance is high, and the dimensional stability necessary for practical use can be secured.
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および染料の表面偏在が起こり難く耐変褪色性も高い点で１．０質量％以下（より好ましくは０．１質量％以下、さらに好ましくは０．０１～０．０９質量％）であることが好ましい。
Further, the residual solvent amount of the meta-type wholly aromatic polyamide fiber is 1. The point that the excellent flame retardancy performance of the meta-type wholly aromatic polyamide fiber is not impaired and the surface uneven distribution of the dye hardly occurs and the discoloration resistance is high. It is preferably 0% by mass or less (more preferably 0.1% by mass or less, and still more preferably 0.01 to 0.09% by mass).
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。
The meta-type wholly aromatic polyamide fiber can be produced by the following method, and in particular, the crystallinity and the residual solvent amount can be within the above ranges by the method described later.
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、特に限定されない。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 polymerization method of the meta-type wholly aromatic polyamide polymer is not particularly limited. For example, the solution polymerization method and the interfacial polymerization method described in Japanese Patent Publication No. 35-14399, US Pat. No. 3,360,595, Japanese Patent Publication No. 47-10863 may be used.
紡糸溶液としては、とくに限定されない。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。
The spinning solution is not particularly limited. An amide solvent solution containing an aromatic copolyamide polymer obtained by the solution polymerization or interfacial polymerization may be used, or the polymer is isolated from the polymerization solution and dissolved in an amide solvent. It may be used.
ここで、前記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。
Here, examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like, and in particular, N, N-dimethylacetamide. Is preferred.
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また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およ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。
The obtained copolymer aromatic polyamide polymer solution is further stabilized by containing an alkali metal salt or an alkaline earth metal salt, and can be used at a higher concentration and lower temperature, which is preferable. Preferably, the alkali metal salt and alkaline earth metal salt are 1% by weight or less, more preferably 0.1% by weight or less, based on the total weight of the polymer solution.
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。
In the spinning / coagulation step, the spinning solution (meta-type wholly aromatic polyamide polymer solution) obtained above is spun into a 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、紡糸口金の紡糸孔数、配列状態、孔形状等は特に限定されない。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。
The spinning apparatus is not particularly limited, and a conventionally known wet spinning apparatus can be used. Further, the number of spinning holes, the arrangement state, the hole shape and the like of the spinneret are not particularly limited. For example, a multi-hole spinneret for sufu having 1000 to 30000 holes and a spinning hole diameter of 0.05 to 0.2 mm may be used.
また、紡糸口金から紡出する際の紡糸液（メタ型全芳香族ポリアミド重合体溶液）の温度は、２０～９０℃の範囲が好ましい。
The temperature of the spinning solution (meta-type wholly 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℃の範囲で用いることが好ましい。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おそれがある。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おそれがある。なお、凝固浴中への繊維の浸漬時間は、０．１～３０秒の範囲が好ましい。
As a coagulation bath used to obtain fibers, an aqueous solution containing 45 to 60% by mass of an amide solvent (preferably NMP) substantially free of inorganic salt is used, and the temperature of the bath solution is in the range of 10 to 50 ° C. It is preferable to use in. If the concentration of the amide solvent (preferably NMP) is less than 45% by mass, the skin has a thick structure, and the cleaning efficiency in the cleaning process may be reduced, making it difficult to reduce the amount of residual solvent in the fiber. . 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 residual solvent amount of the fiber can be reduced. May become difficult. The fiber immersion time in the coagulation bath is preferably in the range of 0.1 to 30 seconds.
次いで、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ことが好ましい。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ことが好ましい。
Next, an amide solvent, preferably an aqueous solution having a concentration of NMP of 45 to 60% by mass, and a draw ratio of 3 to 4 times in a plastic drawing bath in which the temperature of the bath liquid is in the range of 10 to 50 ° C. It is preferable to perform stretching. After stretching, it is preferable to perform sufficient washing through an aqueous solution having an NMP concentration of 10 to 30 ° C. of 20 to 40% by mass, followed by a hot water bath of 50 to 70 ° C.
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。
The washed fiber is subjected to a dry heat treatment at a temperature of 270 to 290 ° C. to obtain a meta-type wholly aromatic aramid fiber satisfying the above-mentioned range of crystallinity and residual solvent amount.
本発明の着色した有機繊維において、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、有機繊維の単繊維繊度としては１～５ｄｔｅｘの範囲が好ましい。
In the colored organic fiber of the present invention, 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 in blending with other fibers. The single fiber fineness of the organic fiber is preferably in the range of 1 to 5 dtex.
本発明の着色した有機繊維において、着色方法としてはキャリア剤を用いた染色方法が好ましい。特に、優れた濃色性を得る上でカチオン染料を用いて染色する方法が好ましい。染色工程の条件は特に限定されない。
In the colored organic fiber of the present invention, a dyeing method using a carrier agent is preferable as a coloring method. In particular, a method of dyeing with a cationic dye is preferred for obtaining excellent darkness. The conditions for the dyeing process are not particularly limited.
かかる着色した有機繊維において、キャリア剤の含有率が繊維質量対比１．８質量％以下(好ましくは０．１～１．８質量％、より好ましくは０．１～１．０質量％、さらに好ましくは０．３～０．９質量％)であることが肝要である。該含有率が１．８質量％よりも大きいと難燃性が損なわれるおそれがある。逆に、該含有率が０．１重量％よりも小さいと、優れた濃色性が得られなくなったり、後記の熱水洗浄工程が複雑になるおそれがある。
In such a colored organic fiber, the content of the carrier agent is not more than 1.8% by mass relative to the mass of the fiber (preferably 0.1 to 1.8% by mass, more preferably 0.1 to 1.0% by mass, still more preferably Is 0.3 to 0.9% by mass). If the content is greater than 1.8% by mass, flame retardancy may be impaired. On the other hand, if the content is less than 0.1% by weight, excellent darkness may not be obtained, and the hot water washing process described later may be complicated.
キャリア剤の含有率を低くする方法としては、例えば、染色した布帛を、必要に応じて還元洗浄した後、温度９０～１４０℃（より好ましくは１１０～１４０℃）の熱水で、１０～３０分間、熱水洗浄する方法が例示される。
As a method for reducing the content of the carrier agent, for example, a dyed fabric is reduced and washed as necessary, and then heated with hot water at a temperature of 90 to 140 ° C. (more preferably 110 to 140 ° C.) for 10 to 30 A method of washing with hot water for a minute is exemplified.
次に、本発明の布帛は前記の着色した有機繊維を含む布帛である。かかる布帛は前記の着色した有機繊維だけで構成されていてもよいが、さらに、ポリエステル繊維、セルロース繊維、ポリアミド繊維、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、ポリカーボネート繊維などの他の繊維が含まれていてもよい。
Next, the fabric of the present invention is a fabric containing the above-mentioned colored organic fibers. Such a fabric may be composed of only the above-mentioned colored organic fibers, and further, polyester fiber, cellulose fiber, polyamide fiber, polyolefin fiber, acrylic fiber, rayon fiber, cotton fiber, animal hair fiber, polyurethane fiber, poly Other fibers such as vinyl chloride fiber, polyvinylidene chloride fiber, acetate fiber, and polycarbonate fiber may be included.
その際、布帛に含まれるメタ型全芳香族ポリアミド繊維が布帛質量に対して５０質量％以上であると優れた難燃性が得られ好ましい。用途や使用のニーズに応じて、上記の難燃繊維、合成繊維、再生繊維、天然繊維を任意に混合できる。より具体的な例としては、メタ型全芳香族ポリアミド繊維が５０～９８質量％、ポリエステル繊維が２～５０質量％、セルロース系質量繊維が０～５０％の混率として染色性と快適性を併せ持つようにすることもできる。重視する性能に応じて比率を調整してもよい。
At that time, it is preferable that the meta-type wholly aromatic polyamide fiber contained in the fabric is 50% by mass or more based on the mass of the fabric because excellent flame retardancy is obtained. The flame retardant fiber, synthetic fiber, regenerated fiber, and natural fiber can be arbitrarily mixed according to the application and use needs. As a more specific example, the meta-type wholly aromatic polyamide fiber is 50 to 98% by mass, the polyester fiber is 2 to 50% by mass, and the cellulosic mass fiber is 0 to 50%, which has both dyeability and comfort. It can also be done. The ratio may be adjusted according to the performance to be emphasized.
また、布帛を構成するいずれかの繊維に難燃剤を含ませたり、紫外線吸収剤や紫外線反射剤を含ませることも好ましい。その際、前記紫外線吸収剤において、水への溶解度が０．０４ｍｇ／Ｌ以下であることが好ましい。水への溶解度が０．０４ｍｇ／Ｌよりも大きいとキャリア剤を用いて染色する際に紫外線吸収剤が溶出してしまい、染色後の耐光性が低下するおそれがある。
Moreover, it is also preferable to include a flame retardant, an ultraviolet absorber or an ultraviolet reflector in any of the fibers constituting the fabric. In that case, in the said ultraviolet absorber, it is preferable that the solubility to water is 0.04 mg / L or less. If the solubility in water is greater than 0.04 mg / L, the ultraviolet absorber may be eluted when dyeing with a carrier agent, which may reduce the light resistance after dyeing.
前記の布帛を製造する方法は、特に限定されない。例えば、前記の有機繊維（または前記の有機繊維と他の繊維）を用いて紡績糸を得た後、単糸または双糸にて製織または製編した後、キャリア剤を用いて染色し、前記の方法で熱水洗浄するとよい。
The method for producing the fabric is not particularly limited. For example, after obtaining a spun yarn using the organic fiber (or the organic fiber and other fibers), weaving or knitting with a single yarn or twin yarn, dyed with a carrier agent, It is good to wash with hot water by the method.
その際、布帛の組織としては、平織、綾織、サテン、二重織などの織物が好ましいが、編物や不織布でもよい。布帛の製造方法は特に限定されない。例えば、レピア織機やグリッパー織機など公知の織編機を用いることができる。
In this case, the fabric structure is preferably a woven fabric such as plain weave, twill weave, satin or double weave, but may be knitted fabric or non-woven fabric. The method for producing the fabric is not particularly limited. For example, known knitting and knitting machines such as rapier looms and gripper looms can be used.
得られた布帛は、前記の有機繊維を用いているので濃色性と難燃性とに優れる。その際、濃色性としては明度指数Ｌ値で８０以下（より好ましくは５２．５以下、さらに好ましくは１０～５２．３）であることが好ましい。また、難燃性としてはＬＯＩが２６以上（より好ましくは２６～４０）であることが好ましい。また、垂直燃焼試験（ＪＩＳ Ｌ１０９１ Ａ－４法 ３秒接炎）で、残炎時間が２５秒以下（より好ましくは１秒以下）であることが好ましい。
The obtained fabric is excellent in dark color and flame retardancy because it uses the organic fiber. At that time, the darkness is preferably 80 or less (more preferably 52.5 or less, and further preferably 10 to 52.3) in terms of lightness index L value. As the flame retardancy, the LOI is preferably 26 or more (more preferably 26 to 40). Further, in the vertical combustion test (JIS L1091 A-4 method, 3 seconds flame contact), the afterflame time is preferably 25 seconds or less (more preferably 1 second or less).
また、前記の布帛において、目付けが３００ｇ／ｍ２以下（好ましくは５０～２５０ｇ／ｍ２）であることが好ましい。かかる目付けが３００ｇ／ｍ２よりも大きいと布帛の軽量性が損なわれるおそれがある。
In the fabric, the basis weight is preferably 300 g / m 2 or less (preferably 50 to 250 g / m 2 ). If the weight per unit area is larger than 300 g / m 2 , the lightness of the fabric may be impaired.
次に、本発明の衣料は前記の布帛を用いてなる衣料である。かかる衣料には、防護服、消防服、防火服、救助服、活動服、執務服、モータースポーツ用レーシングスーツ、作業服、手袋、帽子、ベストなどが含まれる。また、前記作業服には、製鉄所や鉄鋼工場で作業する際に着用される作業服、溶接作業用作業服、防爆エリアにおける作業服などが含まれる。また、前記手袋には、精密部品を取り扱う航空機産業、情報機器産業、精密機器産業などで使用される作業手袋などが含まれる。
Next, the apparel of the present invention is apparel using the above-mentioned fabric. Such clothing includes protective clothing, fire fighting clothing, fire protection clothing, rescue clothing, activity clothing, office work clothing, motor sports racing suits, work clothing, gloves, hats, vests, and the like. In addition, the work clothes include work clothes worn when working in steelworks or steel factories, work clothes for welding work, work clothes in an explosion-proof area, and the like. The gloves include working gloves used in the aircraft industry, the information equipment industry, the precision equipment industry, etc. that handle precision parts.
また、前記の布帛は、カーテン、カーシート、かばんなどの繊維製品に用いてもよい。
Further, the fabric may be used for textile products such as curtains, car seats, bags and the like.
以下、実施例をあげて本発明を詳細に説明する。本発明はこれらによって何ら限定されるものではない。また、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）布帛の難燃性（垂直燃焼試験）
ＪＩＳ Ｌ１０９１ Ａ－４法（３秒接炎）に基づき、残炎時間（秒）を評価した。
（２）残存溶媒量
繊維を約８．０ｇ採取し、１０５℃で１２０分間乾燥させた後にデシケーター内で放冷し、繊維質量（Ｍ１）を秤量した。続いて、この繊維について、メタノール中で１．５時間、ソックスレー抽出器を用いて還流抽出を行い、繊維中に含まれるアミド系溶媒の抽出を行った。抽出を終えた繊維を取り出して、１５０℃で６０分間真空乾燥させた後にデシケーター内で放冷し、繊維質量（Ｍ２）を秤量した。繊維中に残存する溶媒量（アミド系溶媒質量）は、得られるＭ１およびＭ２を用いて、下記式により算出した。
残存溶媒量（％）＝［（Ｍ１－Ｍ２）／Ｍ１］×１００
（３）結晶化度
Ｘ線回折測定装置（リガク社製 ＲＩＮＴ ＴＴＲIII）を用い、原繊維を約1ｍｍ径の繊維束に引きそろえて繊維試料台に装着して回折プロファイルを測定した。測定条件は、Ｃｕ－Ｋα線源（５０ｋＶ、３００ｍＡ）、走査角度範囲１０～３５°、連続測定０．１°幅計測、１°/分走査でおこなった。実測した回折プロファイルから空気散乱、非干渉性散乱を直線近似で補正して全散乱プロファイルを得た。次に、全散乱プロファイルから非晶質散乱プロファイルを差し引いて結晶散乱プロファイルを得た。結晶化度は、結晶散乱プロファイルの面積強度（結晶散乱強度）と全散乱プロファイルの面積強度（全散乱強度）から、次式により求めた。
結晶化度（％）＝［結晶散乱強度／全散乱強度］×１００
（４）残存キャリア剤量
測定法：繊維試料からなるGC/MSサンプルをサンプルチューブに詰めATDで測定した。定性分析でキャリア剤を確認した後、以下の条件で定量分析した。
検量線 タ゛ワノールPPH 10.180mg/ml(n-ヘキサン) 0.50・0.75・1.00μl
Column:DB-5ms 0.25mm×28m
Carrier:He
Inject:ATD 350℃×20min(試料加熱) 300℃×10min(追い出し)
ColdTrap:10℃
インターフェース・ハ゛ルフ゛・トランスファー:250℃ Mass Range 94 108 152
Detecter:GCMS-QP2010
イオン源:200℃
電圧:1.35KV(-0.48KV)
Oven:110℃×2min 110～190℃(10℃/min)
カ゛ス流量1次=10:90 2次=1:4 2.0%
（５）濃色性（Ｌ値）
マクベス分光光度計Ｃｏｌｏｒ－Ｅｙｅ３１００にて測色した。
（６）目付け
ＪＩＳ Ｌ１０９６により目付け（ｇ／ｍ２）を測定した。 Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited by these. Moreover, each physical property in an Example is measured with the following method.
(1) Flame retardancy of fabric (vertical combustion test)
The afterflame time (seconds) was evaluated based on JIS L1091 A-4 method (3 second flame contact).
(2) Amount of residual solvent About 8.0 g of fiber was collected, dried at 105 ° C. for 120 minutes, allowed to cool in a desiccator, and the fiber mass (M1) was weighed. Subsequently, the fiber was subjected to reflux extraction using a Soxhlet extractor in methanol for 1.5 hours to extract an amide solvent contained in the fiber. The fiber after extraction was taken out, vacuum-dried at 150 ° C. for 60 minutes, allowed to cool in a desiccator, and the fiber mass (M2) was weighed. The amount of solvent remaining in the fiber (amide solvent mass) was calculated by the following formula using the obtained M1 and M2.
Residual solvent amount (%) = [(M1-M2) / M1] × 100
(3) Crystallinity Using an X-ray diffractometer (RINT TTRIII, manufactured by Rigaku Corporation), the fibrils were aligned on a fiber bundle having a diameter of about 1 mm and mounted on a fiber sample table to measure a diffraction profile. The measurement conditions were a Cu-Kα radiation source (50 kV, 300 mA), a scanning angle range of 10 to 35 °, a continuous measurement of 0.1 ° width measurement, and a scan of 1 ° / min. From the measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to obtain a total scattering profile. Next, a crystal scattering profile was obtained by subtracting the amorphous scattering profile from the total scattering profile. The degree of crystallinity was determined by the following equation from the area intensity of the crystal scattering profile (crystal scattering intensity) and the area intensity of the total scattering profile (total scattering intensity).
Crystallinity (%) = [crystal scattering intensity / total scattering intensity] × 100
(4) Amount of residual carrier agent Measurement method: A GC / MS sample comprising a fiber sample was packed in a sample tube and measured by ATD. After confirming the carrier agent by qualitative analysis, quantitative analysis was performed under the following conditions.
Calibration curve Dawanol PPH 10.180mg / ml (n-hexane) 0.50 ・ 0.75 ・ 1.00μl
Column: DB-5ms 0.25mm × 28m
Carrier: He
Inject: ATD 350 ℃ × 20min (sample heating) 300 ℃ × 10min (purge)
ColdTrap: 10 ℃
Interface valve transfer: 250 ° C Mass Range 94 108 152
Detecter: GCMS-QP2010
Ion source: 200 ℃
Voltage: 1.35KV (-0.48KV)
Oven: 110 ℃ × 2min 110 ～ 190 ℃ (10 ℃ / min)
Gas flow primary = 10: 90 Secondary = 1: 4 2.0%
(5) Dark color (L value)
The color was measured with a Macbeth spectrophotometer Color-Eye 3100.
(6) Fabric weight A fabric weight (g / m 2 ) was measured according to JIS L1096.
（１）布帛の難燃性（垂直燃焼試験）
ＪＩＳ Ｌ１０９１ Ａ－４法（３秒接炎）に基づき、残炎時間（秒）を評価した。
（２）残存溶媒量
繊維を約８．０ｇ採取し、１０５℃で１２０分間乾燥させた後にデシケーター内で放冷し、繊維質量（Ｍ１）を秤量した。続いて、この繊維について、メタノール中で１．５時間、ソックスレー抽出器を用いて還流抽出を行い、繊維中に含まれるアミド系溶媒の抽出を行った。抽出を終えた繊維を取り出して、１５０℃で６０分間真空乾燥させた後にデシケーター内で放冷し、繊維質量（Ｍ２）を秤量した。繊維中に残存する溶媒量（アミド系溶媒質量）は、得られるＭ１およびＭ２を用いて、下記式により算出した。
残存溶媒量（％）＝［（Ｍ１－Ｍ２）／Ｍ１］×１００
（３）結晶化度
Ｘ線回折測定装置（リガク社製 ＲＩＮＴ ＴＴＲIII）を用い、原繊維を約1ｍｍ径の繊維束に引きそろえて繊維試料台に装着して回折プロファイルを測定した。測定条件は、Ｃｕ－Ｋα線源（５０ｋＶ、３００ｍＡ）、走査角度範囲１０～３５°、連続測定０．１°幅計測、１°/分走査でおこなった。実測した回折プロファイルから空気散乱、非干渉性散乱を直線近似で補正して全散乱プロファイルを得た。次に、全散乱プロファイルから非晶質散乱プロファイルを差し引いて結晶散乱プロファイルを得た。結晶化度は、結晶散乱プロファイルの面積強度（結晶散乱強度）と全散乱プロファイルの面積強度（全散乱強度）から、次式により求めた。
結晶化度（％）＝［結晶散乱強度／全散乱強度］×１００
（４）残存キャリア剤量
測定法：繊維試料からなるGC/MSサンプルをサンプルチューブに詰めATDで測定した。定性分析でキャリア剤を確認した後、以下の条件で定量分析した。
検量線 タ゛ワノールPPH 10.180mg/ml(n-ヘキサン) 0.50・0.75・1.00μl
Column:DB-5ms 0.25mm×28m
Carrier:He
Inject:ATD 350℃×20min(試料加熱) 300℃×10min(追い出し)
ColdTrap:10℃
インターフェース・ハ゛ルフ゛・トランスファー:250℃ Mass Range 94 108 152
Detecter:GCMS-QP2010
イオン源:200℃
電圧:1.35KV(-0.48KV)
Oven:110℃×2min 110～190℃(10℃/min)
カ゛ス流量1次=10:90 2次=1:4 2.0%
（５）濃色性（Ｌ値）
マクベス分光光度計Ｃｏｌｏｒ－Ｅｙｅ３１００にて測色した。
（６）目付け
ＪＩＳ Ｌ１０９６により目付け（ｇ／ｍ２）を測定した。 Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited by these. Moreover, each physical property in an Example is measured with the following method.
(1) Flame retardancy of fabric (vertical combustion test)
The afterflame time (seconds) was evaluated based on JIS L1091 A-4 method (3 second flame contact).
(2) Amount of residual solvent About 8.0 g of fiber was collected, dried at 105 ° C. for 120 minutes, allowed to cool in a desiccator, and the fiber mass (M1) was weighed. Subsequently, the fiber was subjected to reflux extraction using a Soxhlet extractor in methanol for 1.5 hours to extract an amide solvent contained in the fiber. The fiber after extraction was taken out, vacuum-dried at 150 ° C. for 60 minutes, allowed to cool in a desiccator, and the fiber mass (M2) was weighed. The amount of solvent remaining in the fiber (amide solvent mass) was calculated by the following formula using the obtained M1 and M2.
Residual solvent amount (%) = [(M1-M2) / M1] × 100
(3) Crystallinity Using an X-ray diffractometer (RINT TTRIII, manufactured by Rigaku Corporation), the fibrils were aligned on a fiber bundle having a diameter of about 1 mm and mounted on a fiber sample table to measure a diffraction profile. The measurement conditions were a Cu-Kα radiation source (50 kV, 300 mA), a scanning angle range of 10 to 35 °, a continuous measurement of 0.1 ° width measurement, and a scan of 1 ° / min. From the measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to obtain a total scattering profile. Next, a crystal scattering profile was obtained by subtracting the amorphous scattering profile from the total scattering profile. The degree of crystallinity was determined by the following equation from the area intensity of the crystal scattering profile (crystal scattering intensity) and the area intensity of the total scattering profile (total scattering intensity).
Crystallinity (%) = [crystal scattering intensity / total scattering intensity] × 100
(4) Amount of residual carrier agent Measurement method: A GC / MS sample comprising a fiber sample was packed in a sample tube and measured by ATD. After confirming the carrier agent by qualitative analysis, quantitative analysis was performed under the following conditions.
Calibration curve Dawanol PPH 10.180mg / ml (n-hexane) 0.50 ・ 0.75 ・ 1.00μl
Column: DB-5ms 0.25mm × 28m
Carrier: He
Inject: ATD 350 ℃ × 20min (sample heating) 300 ℃ × 10min (purge)
ColdTrap: 10 ℃
Interface valve transfer: 250 ° C Mass Range 94 108 152
Detecter: GCMS-QP2010
Ion source: 200 ℃
Voltage: 1.35KV (-0.48KV)
Oven: 110 ℃ × 2min 110 ～ 190 ℃ (10 ℃ / min)
Gas flow primary = 10: 90 Secondary = 1: 4 2.0%
(5) Dark color (L value)
The color was measured with a Macbeth spectrophotometer Color-Eye 3100.
(6) Fabric weight A fabric weight (g / m 2 ) was measured according to JIS L1096.
［実施例１］
以下の方法でメタ型全芳香族アラミド繊維を作製した。 [Example 1]
Meta-type wholly aromatic aramid fibers were produced by the following method.
以下の方法でメタ型全芳香族アラミド繊維を作製した。 [Example 1]
Meta-type wholly aromatic aramid fibers were produced by the following method.
特公昭４７－１０８６３号公報記載の方法に準じた界面重合法により製造した、固有粘度（Ｉ．Ｖ．）が１．９のポリメタフェニレンイソフタルアミド粉末２０．０質量部を、－１０℃に冷却したＮ－メチル－２－ピロリドン（ＮＭＰ）８０．０質量部中に懸濁させ、スラリー状にした。引き続き、懸濁液を６０℃まで昇温して溶解させ、透明なポリマー溶液を得た。該ポリマー溶液に、ポリマー対比３．０質量％の２－［２Ｈ－ベンゾトリアゾール－２－イル］－４－６－ビス（１－メチル－１－フェニルエチル）フェノール粉末（水への溶解度：０．０１ｍｇ／Ｌ）からなる紫外線吸収剤を混合溶解させ、減圧脱法して紡糸液（紡糸ドープ）とした。
［紡糸・凝固工程］
上記紡糸ドープを、孔径０．０７ｍｍ、孔数５００の紡糸口金から、浴温度３０℃の凝固浴中に吐出して紡糸した。凝固液の組成は、水／ＮＭＰ＝４５／５５（質量部）である。凝固浴中に糸速７ｍ／分で吐出して紡糸した。
［可塑延伸浴延伸工程］
引き続き、温度４０℃の水／ＮＭＰ＝４５／５５の組成の可塑延伸浴中にて、３．７倍の延伸倍率で延伸した。
［洗浄工程］
延伸後、２０℃の水／ＮＭＰ＝７０／３０の浴（浸漬長１．８ｍ）、続いて２０℃の水浴（浸漬長３．６ｍ）で洗浄し、さらに６０℃の温水浴（浸漬長５．４ｍ）に通して十分に洗浄を行った。
［乾熱処理工程］
洗浄後の繊維について、表面温度２８０℃の熱ローラーにて乾熱処理を施し、メタ型全芳香族アラミド繊維を得た。
［カット工程］
該メタ型全芳香族アラミド繊維を用いて、捲縮加工、カットを行い、長さ５１ｍｍのステープルファイバー（原綿）を得た。
［原綿の物性］
得られたメタ型全芳香族アラミド繊維の物性は、単繊維繊度１．７ｄｔｅｘ、残存溶媒量０．０８質量％、結晶化度は１９％であった。 20.0 parts by mass of polymetaphenylene isophthalamide powder produced by an interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863 and having an intrinsic viscosity (IV) of 1.9 is placed at −10 ° C. It was suspended in 80.0 parts by mass of cooled N-methyl-2-pyrrolidone (NMP) to form a slurry. Subsequently, the suspension was heated to 60 ° C. and dissolved to obtain a transparent polymer solution. To the polymer solution, 3.0% by mass of 2- [2H-benzotriazol-2-yl] -4-6-bis (1-methyl-1-phenylethyl) phenol powder (solubility in water: 0) .01 mg / L) was mixed and dissolved, and depressurized to obtain a spinning solution (spinning dope).
[Spinning and coagulation process]
The spinning dope was spun from a spinning nozzle having a hole diameter of 0.07 mm and a hole number of 500 into a coagulation bath having a bath temperature of 30 ° C. The composition of the coagulation liquid is water / NMP = 45/55 (parts by mass). Spinning was performed by discharging into a coagulation bath at a yarn speed of 7 m / min.
[Plastic stretching bath stretching process]
Subsequently, the film was stretched at a stretching ratio of 3.7 times in a plastic stretching bath having a composition of water / NMP = 45/55 at a temperature of 40 ° C.
[Washing process]
After stretching, the film was washed with a 20 ° C. water / NMP = 70/30 bath (immersion length 1.8 m), followed by a 20 ° C. water bath (immersion length 3.6 m), and then a 60 ° C. hot water bath (immersion length 5). 4m) and thoroughly washed.
[Dry heat treatment process]
The washed fiber was subjected to a dry heat treatment with a heat roller having a surface temperature of 280 ° C. to obtain a meta-type wholly aromatic aramid fiber.
[Cut process]
The meta-type wholly aromatic aramid fiber was used for crimping and cutting to obtain a staple fiber (raw cotton) having a length of 51 mm.
[Physical properties of raw cotton]
The physical properties of the obtained meta-type wholly aromatic aramid fiber were as follows: the single fiber fineness was 1.7 dtex, the residual solvent amount was 0.08% by mass, and the crystallinity was 19%.
［紡糸・凝固工程］
上記紡糸ドープを、孔径０．０７ｍｍ、孔数５００の紡糸口金から、浴温度３０℃の凝固浴中に吐出して紡糸した。凝固液の組成は、水／ＮＭＰ＝４５／５５（質量部）である。凝固浴中に糸速７ｍ／分で吐出して紡糸した。
［可塑延伸浴延伸工程］
引き続き、温度４０℃の水／ＮＭＰ＝４５／５５の組成の可塑延伸浴中にて、３．７倍の延伸倍率で延伸した。
［洗浄工程］
延伸後、２０℃の水／ＮＭＰ＝７０／３０の浴（浸漬長１．８ｍ）、続いて２０℃の水浴（浸漬長３．６ｍ）で洗浄し、さらに６０℃の温水浴（浸漬長５．４ｍ）に通して十分に洗浄を行った。
［乾熱処理工程］
洗浄後の繊維について、表面温度２８０℃の熱ローラーにて乾熱処理を施し、メタ型全芳香族アラミド繊維を得た。
［カット工程］
該メタ型全芳香族アラミド繊維を用いて、捲縮加工、カットを行い、長さ５１ｍｍのステープルファイバー（原綿）を得た。
［原綿の物性］
得られたメタ型全芳香族アラミド繊維の物性は、単繊維繊度１．７ｄｔｅｘ、残存溶媒量０．０８質量％、結晶化度は１９％であった。 20.0 parts by mass of polymetaphenylene isophthalamide powder produced by an interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863 and having an intrinsic viscosity (IV) of 1.9 is placed at −10 ° C. It was suspended in 80.0 parts by mass of cooled N-methyl-2-pyrrolidone (NMP) to form a slurry. Subsequently, the suspension was heated to 60 ° C. and dissolved to obtain a transparent polymer solution. To the polymer solution, 3.0% by mass of 2- [2H-benzotriazol-2-yl] -4-6-bis (1-methyl-1-phenylethyl) phenol powder (solubility in water: 0) .01 mg / L) was mixed and dissolved, and depressurized to obtain a spinning solution (spinning dope).
[Spinning and coagulation process]
The spinning dope was spun from a spinning nozzle having a hole diameter of 0.07 mm and a hole number of 500 into a coagulation bath having a bath temperature of 30 ° C. The composition of the coagulation liquid is water / NMP = 45/55 (parts by mass). Spinning was performed by discharging into a coagulation bath at a yarn speed of 7 m / min.
[Plastic stretching bath stretching process]
Subsequently, the film was stretched at a stretching ratio of 3.7 times in a plastic stretching bath having a composition of water / NMP = 45/55 at a temperature of 40 ° C.
[Washing process]
After stretching, the film was washed with a 20 ° C. water / NMP = 70/30 bath (immersion length 1.8 m), followed by a 20 ° C. water bath (immersion length 3.6 m), and then a 60 ° C. hot water bath (immersion length 5). 4m) and thoroughly washed.
[Dry heat treatment process]
The washed fiber was subjected to a dry heat treatment with a heat roller having a surface temperature of 280 ° C. to obtain a meta-type wholly aromatic aramid fiber.
[Cut process]
The meta-type wholly aromatic aramid fiber was used for crimping and cutting to obtain a staple fiber (raw cotton) having a length of 51 mm.
[Physical properties of raw cotton]
The physical properties of the obtained meta-type wholly aromatic aramid fiber were as follows: the single fiber fineness was 1.7 dtex, the residual solvent amount was 0.08% by mass, and the crystallinity was 19%.
一方、他の繊維原綿として、パラ型アラミド繊維；テイジンアラミド社製「トワロン（登録商標）」と導電糸（ナイロン）：ソルシア社製「ＮＯ ＳＨＯＣＫ（登録商標）」（導電性カーボン微粒子を練り込みナイロン導電糸）を用意した。
On the other hand, as other fiber raw materials, para-type aramid fibers; Teijin Aramid's "Twaron (registered trademark)" and conductive yarn (nylon): Solcia's "NO SHOCK (registered trademark)" (conducting conductive carbon fine particles Nylon conductive yarn) was prepared.
次いで、メタ型全芳香族アラミド繊維（ＭＡ）（長さ５１ｍｍ）、パラ型全芳香族ポリアミド（ＰＡ）（長さ５０ｍｍ）、ナイロン導電糸（ＡＳ）（長さ５１ｍｍ）の各ステープルファイバーを、ＭＡ／ＰＡ／ＡＳ＝９３／５／２の比率で混紡した紡績糸４０番手／双糸とし、織密度 経６５本／２５．４ｍｍ、緯５５本／２５．４ｍｍで製織し、目付け１７０ｇ／ｍ２の平組織織物を得た。
Next, each staple fiber of meta type fully aromatic aramid fiber (MA) (length 51 mm), para type fully aromatic polyamide (PA) (length 50 mm), nylon conductive yarn (AS) (length 51 mm), MA / PA / AS = 93/5/2 blended spun yarn 40 count / twist yarn, weaved at warp density of 65 / 25.4mm, weft 55 / 25.4mm, with a basis weight of 170g / m Two plain texture fabrics were obtained.
次いで、下記の染色処方および熱水洗浄処方で布帛を処理した。
（染色処方）
まず、以下の処方で染色した。
・カチオン染料：日本化薬社製、商品名：Kayacryl Red GL-ED ６．０％ｏｗｆ
・キャリア剤：プロピレングリコールフェニルエーテル（ダウケミカル製ダワノールＰＰＨ）４０ｇ／Ｌ
なお「４０ｇ／Ｌ」とは「水１リットルに対して４０グラム含まれる。」という意味である。
・酢酸０．３ｃｃ/Ｌ
・分散剤０．５ｃｃ/Ｌ
・硝酸ナトリウム２５ｇ/Ｌ
・浴比；１：２０
・温度×時間；１３５℃×６０分間
次いで、得られた着色した布帛を下記の還元浴中で洗浄した。
・浴比；１：２０
・温度×時間；９０℃×２０分間
・還元浴；ハイドロサルファイト １ｇ/Ｌ、ソーダ灰１ｇ/Ｌ
(熱水洗浄処方)
次いで、該布帛を温度１３０℃の熱水で２０分間、熱水洗浄した。次いで、該布帛に温度１８０℃、２分間の乾熱セットを施した。 The fabric was then treated with the following dyeing recipe and hot water washing recipe.
(Dyeing prescription)
First, it dye | stained with the following prescription.
Cationic dye: Nippon Kayaku Co., Ltd., trade name: Kayacryl Red GL-ED 6.0% owf
Carrier agent: Propylene glycol phenyl ether (Dow Chemical Pdanol PPH) 40 g / L
“40 g / L” means “40 grams per liter of water”.
・ Acetic acid 0.3cc / L
・ Dispersant 0.5cc / L
・ Sodium nitrate 25g / L
・ Bath ratio; 1:20
-Temperature * time; 135 degreeC * 60 minutes Then, the obtained colored fabric was wash | cleaned in the following reduction bath.
・ Bath ratio; 1:20
・ Temperature x time: 90 ° C. × 20 minutes ・ Reduction bath; Hydrosulfite 1 g / L, Soda ash 1 g / L
(Hot water cleaning prescription)
Subsequently, the fabric was washed with hot water at a temperature of 130 ° C. for 20 minutes. Subsequently, the fabric was subjected to a dry heat setting at a temperature of 180 ° C. for 2 minutes.
（染色処方）
まず、以下の処方で染色した。
・カチオン染料：日本化薬社製、商品名：Kayacryl Red GL-ED ６．０％ｏｗｆ
・キャリア剤：プロピレングリコールフェニルエーテル（ダウケミカル製ダワノールＰＰＨ）４０ｇ／Ｌ
なお「４０ｇ／Ｌ」とは「水１リットルに対して４０グラム含まれる。」という意味である。
・酢酸０．３ｃｃ/Ｌ
・分散剤０．５ｃｃ/Ｌ
・硝酸ナトリウム２５ｇ/Ｌ
・浴比；１：２０
・温度×時間；１３５℃×６０分間
次いで、得られた着色した布帛を下記の還元浴中で洗浄した。
・浴比；１：２０
・温度×時間；９０℃×２０分間
・還元浴；ハイドロサルファイト １ｇ/Ｌ、ソーダ灰１ｇ/Ｌ
(熱水洗浄処方)
次いで、該布帛を温度１３０℃の熱水で２０分間、熱水洗浄した。次いで、該布帛に温度１８０℃、２分間の乾熱セットを施した。 The fabric was then treated with the following dyeing recipe and hot water washing recipe.
(Dyeing prescription)
First, it dye | stained with the following prescription.
Cationic dye: Nippon Kayaku Co., Ltd., trade name: Kayacryl Red GL-ED 6.0% owf
Carrier agent: Propylene glycol phenyl ether (Dow Chemical Pdanol PPH) 40 g / L
“40 g / L” means “40 grams per liter of water”.
・ Acetic acid 0.3cc / L
・ Dispersant 0.5cc / L
・ Sodium nitrate 25g / L
・ Bath ratio; 1:20
-Temperature * time; 135 degreeC * 60 minutes Then, the obtained colored fabric was wash | cleaned in the following reduction bath.
・ Bath ratio; 1:20
・ Temperature x time: 90 ° C. × 20 minutes ・ Reduction bath; Hydrosulfite 1 g / L, Soda ash 1 g / L
(Hot water cleaning prescription)
Subsequently, the fabric was washed with hot water at a temperature of 130 ° C. for 20 minutes. Subsequently, the fabric was subjected to a dry heat setting at a temperature of 180 ° C. for 2 minutes.
得られた布帛の評価結果を表１に示す。
The evaluation results of the obtained fabric are shown in Table 1.
［実施例２］
上記熱水洗浄処方の１３０℃×２０分 １回を１３０℃×２０分を２回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 2]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes once in the hot water cleaning prescription was changed to 130 ° C. × 20 minutes twice. The evaluation results are shown in Table 1.
上記熱水洗浄処方の１３０℃×２０分 １回を１３０℃×２０分を２回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 2]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes once in the hot water cleaning prescription was changed to 130 ° C. × 20 minutes twice. The evaluation results are shown in Table 1.
［実施例３］
上記熱水洗浄処方の１３０℃×２０分 １回を１２０℃×２０分を２回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 3]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes once in the hot water washing prescription was changed to 120 ° C. × 20 minutes twice. The evaluation results are shown in Table 1.
上記熱水洗浄処方の１３０℃×２０分 １回を１２０℃×２０分を２回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 3]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes once in the hot water washing prescription was changed to 120 ° C. × 20 minutes twice. The evaluation results are shown in Table 1.
［実施例４］
上記染色処方のダワノールＰＰＨ４０ｇ/Ｌをベンジルアルコール６０ｇ/Ｌに変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 4]
The same operation as in Example 1 was performed except that Dawanol PPH 40 g / L in the above dyeing prescription was changed to benzyl alcohol 60 g / L. The evaluation results are shown in Table 1.
上記染色処方のダワノールＰＰＨ４０ｇ/Ｌをベンジルアルコール６０ｇ/Ｌに変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 4]
The same operation as in Example 1 was performed except that Dawanol PPH 40 g / L in the above dyeing prescription was changed to benzyl alcohol 60 g / L. The evaluation results are shown in Table 1.
［実施例５］
上記染色処方のダワノールＰＰＨ４０ｇ/Ｌをベンジルアルコール６０ｇ/Ｌに変更し、上記熱水洗浄処方の１３０℃×２０分を１２０℃×２０分を２回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 5]
Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. × 20 minutes of the hot water washing prescription is changed to 120 ° C. × 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.
上記染色処方のダワノールＰＰＨ４０ｇ/Ｌをベンジルアルコール６０ｇ/Ｌに変更し、上記熱水洗浄処方の１３０℃×２０分を１２０℃×２０分を２回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 5]
Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. × 20 minutes of the hot water washing prescription is changed to 120 ° C. × 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.
［実施例６］
上記染色処方のダワノールＰＰＨ４０ｇ/Ｌをベンジルアルコール６０ｇ/Ｌに変更し、上記熱水洗浄処方の１３０℃×２０分を１２０℃×２０分を２回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 6]
Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. × 20 minutes of the hot water washing prescription is changed to 120 ° C. × 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.
上記染色処方のダワノールＰＰＨ４０ｇ/Ｌをベンジルアルコール６０ｇ/Ｌに変更し、上記熱水洗浄処方の１３０℃×２０分を１２０℃×２０分を２回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 6]
Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. × 20 minutes of the hot water washing prescription is changed to 120 ° C. × 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.
［実施例７］
上記染色処方のダワノールＰＰＨ４０ｇ/Ｌをベンジルアルコール６０ｇ/Ｌに変更し、上記熱水洗浄処方の１３０℃×２０分を１２０℃×２０分を２回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 7]
Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. × 20 minutes of the hot water washing prescription is changed to 120 ° C. × 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.
上記染色処方のダワノールＰＰＨ４０ｇ/Ｌをベンジルアルコール６０ｇ/Ｌに変更し、上記熱水洗浄処方の１３０℃×２０分を１２０℃×２０分を２回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 7]
Same as Example 1 except that Dawanol PPH 40 g / L of the dyeing prescription is changed to benzyl alcohol 60 g / L, and 130 ° C. × 20 minutes of the hot water washing prescription is changed to 120 ° C. × 20 minutes twice. The operation was performed. The evaluation results are shown in Table 1.
［比較例１］
上記熱水洗浄処方の１３０℃×２０分を９０℃×２０分を１回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Comparative Example 1]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes of the hot water washing prescription was changed to 90 ° C. × 20 minutes once. The evaluation results are shown in Table 1.
上記熱水洗浄処方の１３０℃×２０分を９０℃×２０分を１回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Comparative Example 1]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes of the hot water washing prescription was changed to 90 ° C. × 20 minutes once. The evaluation results are shown in Table 1.
［実施例８］
上記熱水洗浄処方の１３０℃×２０分を９０℃×２０分を５回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 8]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes of the hot water washing prescription was changed from 90 ° C. × 20 minutes to 5 times. The evaluation results are shown in Table 1.
上記熱水洗浄処方の１３０℃×２０分を９０℃×２０分を５回に変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 8]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes of the hot water washing prescription was changed from 90 ° C. × 20 minutes to 5 times. The evaluation results are shown in Table 1.
［実施例９］
上記熱水洗浄処方の１３０℃×２０分を９０℃×２０分を１０回に変更した以外は、実施例１と同様の操作を行った。結果を表１に示す。 [Example 9]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes of the hot water washing prescription was changed from 90 ° C. × 20 minutes to 10 times. The results are shown in Table 1.
上記熱水洗浄処方の１３０℃×２０分を９０℃×２０分を１０回に変更した以外は、実施例１と同様の操作を行った。結果を表１に示す。 [Example 9]
The same operation as in Example 1 was performed except that 130 ° C. × 20 minutes of the hot water washing prescription was changed from 90 ° C. × 20 minutes to 10 times. The results are shown in Table 1.
［実施例１０］
上記染色処方のダワノールＰＰＨを３０ｇ/Ｌに変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 10]
The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 30 g / L. The evaluation results are shown in Table 1.
上記染色処方のダワノールＰＰＨを３０ｇ/Ｌに変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 10]
The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 30 g / L. The evaluation results are shown in Table 1.
［実施例１１］
上記染色処方のダワノールＰＰＨを２０ｇ/Ｌに変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 11]
The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 20 g / L. The evaluation results are shown in Table 1.
上記染色処方のダワノールＰＰＨを２０ｇ/Ｌに変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 11]
The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 20 g / L. The evaluation results are shown in Table 1.
［実施例１２］
上記染色処方のダワノールＰＰＨを１０ｇ/Ｌに変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 12]
The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 10 g / L. The evaluation results are shown in Table 1.
上記染色処方のダワノールＰＰＨを１０ｇ/Ｌに変更した以外は、実施例１と同様の操作を行った。評価結果を表１に示す。 [Example 12]
The same operation as in Example 1 was performed except that Dawanol PPH of the dyeing prescription was changed to 10 g / L. The evaluation results are shown in Table 1.
本発明によれば、着色した有機繊維であって濃色かつ難燃性に優れた有機繊維および該有機繊維を用いてなる布帛および衣料、および布帛の製造方法が提供され、その工業的価値は極めて大である。
ADVANTAGE OF THE INVENTION According to this invention, the organic fiber which was the colored organic fiber and was dark and excellent in the flame retardance, the fabric and clothing using this organic fiber, and the manufacturing method of a fabric are provided, The industrial value is the It is extremely large.
Claims (20)
- 着色した有機繊維であって、キャリア剤の含有率が繊維質量対比１．８質量％以下であることを特徴とする着色した有機繊維。 Colored organic fiber, characterized in that the content of the carrier agent is 1.8% by mass or less relative to the mass of the fiber.
- 前記キャリア剤の含有率が繊維質量対比０．１～１．８質量％の範囲内である、請求項１に記載の着色した有機繊維。 The colored organic fiber according to claim 1, wherein the content of the carrier agent is in the range of 0.1 to 1.8% by mass relative to the mass of the fiber.
- 前記キャリア剤が、ＤＬ－β－エチルフェネチルアルコール、２－エトキシベンジルアルコール、３－クロロベンジルアルコール、２，５－ジメチルベンジルアルコール、２－ニトロベンジルアルコール、ｐ－イソプロピルベンジルアルコール、２－メチルフェネチルアルコール、３－メチルフェネチルアルコール、４－メチルフェネチルアルコール、２－メトキシベンジルアルコール、３－ヨードベンジルアルコール、ケイ皮アルコール、ｐ－アニシルアルコール、ベンズヒドロール、ベンジルアルコール、プロピレングリコールフェニルエーテル、エチレングリコールフェニルエーテル、およびＮ－メチルホルムアニリドからなる群より選択されるいずれか１種以上である、請求項１に記載の着色した有機繊維。 The carrier agent is DL-β-ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methylphenethyl alcohol. , 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamon alcohol, p-anisyl alcohol, benzhydrol, benzyl alcohol, propylene glycol phenyl ether, ethylene glycol phenyl The colored organic fiber according to claim 1, which is at least one selected from the group consisting of ether and N-methylformanilide.
- 前記有機繊維が、メタ型全芳香族ポリアミド繊維、パラ型全芳香族ポリアミド繊維、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）、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、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種である、請求項１に記載の着色した有機繊維。 The organic fiber is a meta-type wholly aromatic polyamide fiber, para-type wholly aromatic polyamide fiber, polybenzoxazole (PBO) fiber, polybenzimidazole (PBI) fiber, polybenzthiazole (PBTZ) fiber, polyimide (PI) fiber. , Polysulfonamide (PSA), polyether ether ketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, polyphenylene sulfide (PPS) fiber The colored organic fiber according to claim 1, wherein the organic fiber is any one selected from the above.
- 前記有機繊維が、結晶化度が１５～２５％のメタ型全芳香族ポリアミド繊維である、請求項１に記載の着色した有機繊維。 The colored organic fiber according to claim 1, wherein the organic fiber is a meta-type wholly aromatic polyamide fiber having a crystallinity of 15 to 25%.
- 前記有機繊維が、残存溶媒量が１．０質量％以下のメタ型全芳香族ポリアミド繊維である、請求項１に記載の着色した有機繊維。 The colored organic fiber according to claim 1, wherein the organic fiber is a meta-type wholly aromatic polyamide fiber having a residual solvent amount of 1.0% by mass or less.
- 前記有機繊維が、残存溶媒量が０．１質量％以下のメタ型全芳香族ポリアミド繊維である、請求項１に記載の着色した有機繊維。 The colored organic fiber according to claim 1, wherein the organic fiber is a meta-type wholly aromatic polyamide fiber having a residual solvent amount of 0.1% by mass or less.
- 前記残存溶媒が、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からなる群より選択されるいずれかである、請求項６または請求項７に記載の有機繊維。 The residual solvent is any one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Organic fiber.
- 前記有機繊維がメタ型全芳香族ポリアミド繊維であり、かつ該メタ型全芳香族ポリアミド繊維を形成するメタ型全芳香族ポリアミドが、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た芳香族ポリアミドである、請求項１に記載の着色した有機繊維。
－（ＮＨ－Ａｒ１－ＮＨ－ＣＯ－Ａｒ１－ＣＯ）－ ・・・式（１）
ここで、Ａｒ１はメタ配位又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 organic fiber is a meta-type wholly aromatic polyamide fiber, and the meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber is an aromatic containing a repeating structural unit represented by the following formula (1) In the polyamide skeleton, an aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main structural unit of the repeating structure is used as the third component so as to be 1 to 10 mol% based on the total amount of the repeating structural unit of the aromatic polyamide. The colored organic fiber according to claim 1, wherein the colored organic fiber is an aromatic polyamide copolymerized.
— (NH—Ar 1 —NH—CO—Ar 1 —CO) — (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction. - 第３成分となる芳香族ジアミンが式（２）、（３）、または芳香族ジカルボン酸ハライドが、式（４）、（５）である、請求項９に記載の着色した有機繊維。
Ｈ２Ｎ－Ａｒ２－ＮＨ２ ・・・式（２）
Ｈ２Ｎ－Ａｒ２－Ｙ－Ａｒ２－ＮＨ２ ・・・式（３）
ＸＯＣ－Ａｒ３－ＣＯＸ ・・・式（４）
ＸＯＣ－Ａｒ３－Ｙ－Ａｒ３－ＣＯＸ ・・・式（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。 The colored organic fiber according to claim 9, wherein the aromatic diamine as the third component is represented by formulas (2) and (3), or the aromatic dicarboxylic acid halide is represented by formulas (4) and (5).
H 2 N—Ar 2 —NH 2 Formula (2)
H 2 N—Ar 2 —Y—Ar 2 —NH 2 Formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom. - 請求項１に記載の着色した有機繊維を含む布帛。 A fabric comprising the colored organic fiber according to claim 1.
- 布帛が、ポリエステル繊維、セルロース繊維、ポリアミド繊維、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、請求項１１に記載の布帛。 The fabric is made of polyester fiber, cellulose fiber, polyamide 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 fabric according to claim 11, comprising any one or more selected from the above.
- 布帛を構成するいずれかの繊維が難燃剤を含む、請求項１１に記載の布帛。 The fabric according to claim 11, wherein any of the fibers constituting the fabric contains a flame retardant.
- 布帛を構成するいずれかの繊維が紫外線吸収剤または紫外線反射剤を含む、請求項１１に記載の布帛。 The fabric according to claim 11, wherein any of the fibers constituting the fabric contains an ultraviolet absorber or an ultraviolet reflector.
- 布帛の目付けが３００ｇ／ｍ２以下である、請求項１１に記載の布帛。 The fabric according to claim 11, wherein the fabric weight is 300 g / m 2 or less.
- ＬＯＩが２６以上である、請求項１１に記載の布帛。 The fabric according to claim 11, wherein the LOI is 26 or more.
- 垂直燃焼試験（ＪＩＳ Ｌ１０９１ Ａ－４法 ３ｓ接炎）で残炎時間１秒以下である、請求項１１に記載の布帛。 The fabric according to claim 11, wherein the afterflame time is 1 second or less in a vertical combustion test (JIS L1091, A-4 method, 3s flame contact).
- 明度指数Ｌ値が８０以下である、請求項１１に記載の布帛。 The fabric according to claim 11, wherein the lightness index L value is 80 or less.
- 請求項１１に記載の布帛を用いてなる衣料。 Clothing comprising the fabric according to claim 11.
- 請求項１１に記載の着色した有機繊維を含む布帛の製造方法であって、
有機繊維を含む布帛を、キャリア剤を用いて染色した後、該布帛を温度９０～１４０℃の熱水で１０～３０分間洗浄することにより前記有機繊維に含まれるキャリア剤の含有率を繊維質量対比１．８質量％以下とする布帛の製造方法。 A method for producing a fabric comprising colored organic fibers according to claim 11,
After a fabric containing organic fibers is dyed with a carrier agent, the fabric is washed with hot water at a temperature of 90 to 140 ° C. for 10 to 30 minutes to determine the content of the carrier agent contained in the organic fibers as the fiber mass. The manufacturing method of the fabric made into 1.8 mass% or less of contrast.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
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| EP15779705.1A EP3133204B1 (en) | 2014-04-14 | 2015-04-06 | Colored organic fiber, fabric and clothing and method for manufacturing fabric |
| KR1020167031358A KR20160140951A (en) | 2014-04-14 | 2015-04-06 | Colored organic fiber, fabric and clothing and method for manufacturing fabric |
| JP2016513722A JP6355720B2 (en) | 2014-04-14 | 2015-04-06 | COLORED ORGANIC FIBER AND FABRIC, AND METHOD FOR PRODUCING APPAREL AND FABRIC |
| BR112016023687A BR112016023687A2 (en) | 2014-04-14 | 2015-04-06 | colored organic fiber, cloth, garments, and, method for producing a cloth |
| MX2016013384A MX2016013384A (en) | 2014-04-14 | 2015-04-06 | Colored organic fiber, fabric and clothing and method for manufacturing fabric. |
| US15/303,824 US20170037543A1 (en) | 2014-04-14 | 2015-04-06 | Colored organic fiber, cloth, and garments, and method for producing cloth |
| RU2016144442A RU2658246C2 (en) | 2014-04-14 | 2015-04-06 | Color organic fiber, fabric and sewn products and also method of fabrics obtaining |
| CN201580019932.3A CN106232898B (en) | 2014-04-14 | 2015-04-06 | Organic fiber, cloth and silk and the dress material of coloring and the manufacturing method of cloth and silk |
| AU2015247107A AU2015247107B2 (en) | 2014-04-14 | 2015-04-06 | Colored organic fiber, fabric and clothing and method for manufacturing fabric |
| CA2945737A CA2945737A1 (en) | 2014-04-14 | 2015-04-06 | Colored organic fiber, cloth, and garments,and method for producing cloth |
| US16/373,948 US20190226122A1 (en) | 2014-04-14 | 2019-04-03 | Colored organic fiber, cloth, and garments, and method for producing cloth |
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| JP2014-082799 | 2014-04-14 |
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| US15/303,824 A-371-Of-International US20170037543A1 (en) | 2014-04-14 | 2015-04-06 | Colored organic fiber, cloth, and garments, and method for producing cloth |
| US16/373,948 Division US20190226122A1 (en) | 2014-04-14 | 2019-04-03 | Colored organic fiber, cloth, and garments, and method for producing cloth |
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| PCT/JP2015/060712 WO2015159749A1 (en) | 2014-04-14 | 2015-04-06 | Colored organic fiber, fabric and clothing and method for manufacturing fabric |
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| US (2) | US20170037543A1 (en) |
| EP (1) | EP3133204B1 (en) |
| JP (2) | JP6355720B2 (en) |
| KR (1) | KR20160140951A (en) |
| CN (1) | CN106232898B (en) |
| AU (1) | AU2015247107B2 (en) |
| BR (1) | BR112016023687A2 (en) |
| CA (1) | CA2945737A1 (en) |
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| JP2017115265A (en) * | 2015-12-24 | 2017-06-29 | 帝人株式会社 | Flame-retardant antibacterial fabric, method for producing the same and fiber product |
| JP2018040068A (en) * | 2016-09-05 | 2018-03-15 | 帝人株式会社 | Fabric and fiber product |
| CN109778342A (en) * | 2017-11-14 | 2019-05-21 | 中蓝晨光化工有限公司 | A kind of native staining method of polyparaphenylene's benzo dioxazole fiber |
| CN109778338A (en) * | 2017-11-14 | 2019-05-21 | 中蓝晨光化工有限公司 | A kind of production technology of polyparaphenylene's benzo dioxazole fiber continuous polymerization spinning |
| US11078608B2 (en) | 2016-11-01 | 2021-08-03 | Teijin Limited | Fabric, method for manufacturing same, and fiber product |
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| CN107447553B (en) * | 2017-08-15 | 2020-01-17 | 江南大学 | Ketone ester carrier dyeing method for polyimide fiber and fabric |
| CN109774282B (en) * | 2019-03-15 | 2021-03-05 | 杭州友普装饰材料有限公司 | Fire-resistant antibacterial curtain fabric and preparation method thereof |
| CN112376300B (en) * | 2020-10-27 | 2022-07-05 | 武汉纺织大学 | Post-dyeing method of polypropylene fabric |
| CN115821417A (en) * | 2021-09-17 | 2023-03-21 | 中国石油化工股份有限公司 | Preparation method of copolymerized self-coloring aramid fiber and copolymerized self-coloring aramid fiber |
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| Publication number | Publication date |
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| MX2016013384A (en) | 2017-02-15 |
| CN106232898A (en) | 2016-12-14 |
| BR112016023687A2 (en) | 2017-08-15 |
| JP6570703B2 (en) | 2019-09-04 |
| EP3133204B1 (en) | 2018-07-11 |
| CN106232898B (en) | 2019-05-10 |
| RU2658246C2 (en) | 2018-06-19 |
| EP3133204A1 (en) | 2017-02-22 |
| RU2016144442A (en) | 2018-05-15 |
| KR20160140951A (en) | 2016-12-07 |
| AU2015247107A1 (en) | 2016-11-24 |
| EP3133204A4 (en) | 2017-05-03 |
| JPWO2015159749A1 (en) | 2017-04-13 |
| JP6355720B2 (en) | 2018-07-11 |
| JP2018138713A (en) | 2018-09-06 |
| US20170037543A1 (en) | 2017-02-09 |
| CA2945737A1 (en) | 2015-10-22 |
| TW201606150A (en) | 2016-02-16 |
| RU2016144442A3 (en) | 2018-05-15 |
| US20190226122A1 (en) | 2019-07-25 |
| AU2015247107B2 (en) | 2018-08-30 |
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