JP2012167411A - Frame retardant agent and frame retardant method for polyester fiber product - Google Patents
Frame retardant agent and frame retardant method for polyester fiber product Download PDFInfo
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- JP2012167411A JP2012167411A JP2011030593A JP2011030593A JP2012167411A JP 2012167411 A JP2012167411 A JP 2012167411A JP 2011030593 A JP2011030593 A JP 2011030593A JP 2011030593 A JP2011030593 A JP 2011030593A JP 2012167411 A JP2012167411 A JP 2012167411A
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- Prior art keywords
- flame retardant
- polyester fiber
- flame
- fiber product
- retardant processing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000728 polyester Polymers 0.000 title claims abstract description 270
- 239000000835 fiber Substances 0.000 title claims abstract description 242
- 239000003795 chemical substances by application Substances 0.000 title claims description 116
- 238000000034 method Methods 0.000 title claims description 50
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- OUPCDFWTGHUQRO-UHFFFAOYSA-N 5,5-dimethyl-2-(2-phenylphenoxy)-1,3,2$l^{5}-dioxaphosphinane 2-oxide Chemical compound O1CC(C)(C)COP1(=O)OC1=CC=CC=C1C1=CC=CC=C1 OUPCDFWTGHUQRO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003063 flame retardant Substances 0.000 claims description 341
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$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 331
- 238000012545 processing Methods 0.000 claims description 151
- 239000004744 fabric Substances 0.000 claims description 90
- 125000002091 cationic group Chemical group 0.000 claims description 37
- 238000003672 processing method Methods 0.000 claims description 15
- 239000002736 nonionic surfactant Substances 0.000 claims description 12
- 239000000975 dye Substances 0.000 claims description 11
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- 239000000986 disperse dye Substances 0.000 claims description 9
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 abstract description 21
- 239000004094 surface-active agent Substances 0.000 abstract description 9
- 239000012757 flame retardant agent Substances 0.000 abstract description 8
- 230000001804 emulsifying effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- 125000000129 anionic group Chemical group 0.000 abstract 1
- -1 isocyanurate bromine compound Chemical class 0.000 description 66
- 230000000052 comparative effect Effects 0.000 description 46
- 229910019142 PO4 Inorganic materials 0.000 description 31
- 239000010452 phosphate Substances 0.000 description 31
- 239000006185 dispersion Substances 0.000 description 25
- 238000002156 mixing Methods 0.000 description 19
- 238000004043 dyeing Methods 0.000 description 18
- 238000002485 combustion reaction Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 7
- 229910052794 bromium Inorganic materials 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 239000004645 polyester resin Substances 0.000 description 6
- 239000002759 woven fabric Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- VSXGXPNADZQTGQ-UHFFFAOYSA-N oxirane;phenol Chemical class C1CO1.OC1=CC=CC=C1 VSXGXPNADZQTGQ-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000005108 dry cleaning Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229930182843 D-Lactic acid Natural products 0.000 description 3
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 229940022769 d- lactic acid Drugs 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 238000009991 scouring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- XMVBHZBLHNOQON-UHFFFAOYSA-N 2-butyl-1-octanol Chemical compound CCCCCCC(CO)CCCC XMVBHZBLHNOQON-UHFFFAOYSA-N 0.000 description 2
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 description 2
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HHAPGMVKBLELOE-UHFFFAOYSA-N 2-(2-methylpropoxy)ethanol Chemical compound CC(C)COCCO HHAPGMVKBLELOE-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- DPKBSJDAVQLNGF-UHFFFAOYSA-N 5,5-dimethyl-2-(2-phenylphenoxy)-1,3,2-dioxaphosphinane Chemical compound O1CC(C)(C)COP1OC1=CC=CC=C1C1=CC=CC=C1 DPKBSJDAVQLNGF-UHFFFAOYSA-N 0.000 description 1
- HDOWBRRHPRGVCZ-UHFFFAOYSA-N C1CO1.CCCCCCC(CO)CCCC Chemical compound C1CO1.CCCCCCC(CO)CCCC HDOWBRRHPRGVCZ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
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- 230000001133 acceleration Effects 0.000 description 1
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- 239000012190 activator Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
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- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 208000018747 cerebellar ataxia with neuropathy and bilateral vestibular areflexia syndrome Diseases 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- RZHBMYQXKIDANM-UHFFFAOYSA-N dioctyl butanedioate;sodium Chemical compound [Na].CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC RZHBMYQXKIDANM-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical class [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
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- 150000008282 halocarbons Chemical class 0.000 description 1
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- 239000012943 hotmelt Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
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- 235000010981 methylcellulose Nutrition 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HEOTUWROLIPMOE-UHFFFAOYSA-N nonoxybenzene;oxirane Chemical compound C1CO1.CCCCCCCCCOC1=CC=CC=C1 HEOTUWROLIPMOE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Fireproofing Substances (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は、ポリエステル系繊維品の難燃加工に関し、詳しくは、１，２，５，６，９，１０−ヘキサブロモシクロドデカン（以下、ＨＢＣＤという。）を難燃剤として用いることなく、しかも、ＨＢＣＤを用いる場合に比較して、ポリエステル系繊維品にその種類を問わず、耐久性にすぐれる難燃性を付与することができる難燃加工剤と、そのような難燃加工剤を用いるポリエステル系繊維品の難燃加工方法と、そのような難燃加工剤を用いて得られる難燃加工ポリエステル系繊維品に関する。 The present invention relates to a flame retardant processing of a polyester-based fiber product. Specifically, 1,2,5,6,9,10-hexabromocyclododecane (hereinafter referred to as HBCD) is not used as a flame retardant, Compared to the case where HBCD is used, regardless of the type of the polyester fiber product, a flame retardant that can impart flame retardancy with excellent durability, and polyester using such a flame retardant The present invention relates to a flame-retardant processing method for a fiber-based fiber product and a flame-retardant processed polyester-based fiber product obtained using such a flame-retardant processing agent.
従来、ポリエステル系繊維品に後加工によって難燃性を付与する代表的な方法として、ＨＢＣＤを難燃剤として分散剤を用いて水に分散させてなる難燃加工剤をポリエステル系繊維品に付着させる方法がよく知られている（例えば、特許文献１参照）。 Conventionally, as a typical method for imparting flame retardancy to a polyester fiber product by post-processing, a flame retardant agent in which HBCD is dispersed in water using a dispersant as a flame retardant is attached to the polyester fiber product. The method is well known (for example, refer to Patent Document 1).
しかしながら、ＨＢＣＤを難燃剤としてポリエステル系繊維品に難燃性を付与する方法によれば、このＨＢＣＤが難分解性で高蓄積性であることから、環境や生物に有害な影響を及ぼす問題があり、かくして、現在では、繊維品の難燃加工において、ＨＢＣＤを用いることが規制されるに至っている。 However, according to the method for imparting flame retardancy to a polyester fiber product using HBCD as a flame retardant, since this HBCD is indegradable and highly accumulative, there is a problem of having a harmful effect on the environment and living organisms. Thus, at present, the use of HBCD is regulated in the flame-retardant processing of textiles.
そこで、ポリエステル系繊維品に難燃性を付与することができるＨＢＣＤ以外のハロゲン系難燃剤として、トリス（２，３−ジブロモプロピル）イソシアヌレートを代表例とするイソシアヌレート系臭素化合物が提案されている。ポリエステル系繊維品の燃焼時、上記イソシアヌレート化合物は、その熱分解過程において、臭素ガスを発生して難燃性に寄与するが、同時に残渣も生じ、この残渣がポリエステル系繊維品の燃焼時、炭化物を生じて、ポリエステル系繊維品の溶融滴下を阻害するので、添加量が少量の場合には、却って燃焼を助長させることがある。そこで、ポリエステル系繊維品に十分な難燃性を付与するには、多量のイソシアヌレート系臭素化合物を使用せざるを得ず、かくして、難燃加工後のポリエステル系繊維品の風合いを硬化させるという望ましくない問題がある。また、そのように多量のイソシアヌレート系臭素化合物を使用する難燃加工は、経済性の面でも不利である。 Therefore, an isocyanurate bromine compound having tris (2,3-dibromopropyl) isocyanurate as a representative example has been proposed as a halogen flame retardant other than HBCD that can impart flame retardancy to polyester fiber products. Yes. When the polyester fiber product is burned, the isocyanurate compound generates bromine gas in the thermal decomposition process and contributes to flame retardancy. Since a carbide is generated and melt dripping of the polyester fiber product is inhibited, combustion may be promoted when the addition amount is small. Therefore, in order to impart sufficient flame retardancy to the polyester fiber product, a large amount of isocyanurate bromine compound must be used, and thus the texture of the polyester fiber product after flame retardant processing is cured. There is an undesirable problem. In addition, such a flame-retardant processing using a large amount of isocyanurate bromine compound is disadvantageous in terms of economy.
そこで、上記イソシアヌレート系臭素化合物に液状のハロゲン化アルキルリン酸エステル、従来、例えば、トリス（ジクロロプロピル）ホスフェートを併用することによって、ポリエステル系繊維品の有する風合いを維持しつつ、難燃加工する方法が提案されている（特許文献２参照）。しかし、この方法において、上記ハロゲン化アルキルリン酸エステルと共に分散染料を用いて、ポリエステル系繊維品を難燃加工すると同時に染色する場合には、得られた難燃加工ポリエステル系繊維品は、染料のブリードアウトが生じやすく、摩擦堅牢度が低い問題がある。 Accordingly, by using a liquid halogenated alkyl phosphate ester, for example, tris (dichloropropyl) phosphate, in combination with the above isocyanurate bromine compound, flame retardant processing is performed while maintaining the texture of the polyester fiber product. A method has been proposed (see Patent Document 2). However, in this method, when using a disperse dye together with the above-mentioned halogenated alkyl phosphate ester and simultaneously dyeing a polyester fiber product, the resulting flame-retardant polyester fiber product is obtained from the dye. There is a problem that bleeding out easily occurs and friction fastness is low.
また、上記イソシアヌレート系臭素化合物と固体のハロゲン化アルキルリン酸エステル、例えば、トリス（トリブロモネオペンチル）ホスフェートを併用する方法も、従来から、提案されているが（特許文献３参照）、上記トリス（トリブロモネオペンチル）ホスフェートは、浴中処理による難燃加工において、ポリエステル系繊維品への吸尽率が非常に低く、実用上、浴中処理に用いることができない。 Further, a method of using the isocyanurate bromine compound and a solid halogenated alkyl phosphate ester, for example, tris (tribromoneopentyl) phosphate in combination has been proposed (see Patent Document 3). Tris (tribromoneopentyl) phosphate has a very low exhaustion rate to polyester fiber products in the flame-retardant processing by treatment in bath, and cannot be practically used for treatment in bath.
一方、ＨＢＣＤをはじめとするハロゲン系難燃剤を用いずに、ポリエステル系繊維品に耐久性にすぐれた難燃性を付与することができる方法として、ある種の芳香族リン酸エステルアミドを難燃剤として水に分散させてなる難燃加工剤を用いる方法が提案されている（特許文献４参照）。この方法によれば、レギュラーポリエステルのほか、カチオン可染ポリエステルの一部については、すぐれた難燃性を付与することができるが、しかし、その種類を問わず、広い範囲にわたるポリエステル系繊維品に十分な難燃性を付与することは困難であり、汎用性において十分とはいえない問題が残されている。 On the other hand, as a method that can impart flame resistance with excellent durability to a polyester fiber product without using a halogen flame retardant such as HBCD, a certain kind of aromatic phosphate ester amide is used as a flame retardant. A method using a flame retardant agent dispersed in water has been proposed (see Patent Document 4). According to this method, in addition to regular polyester, a part of cationic dyeable polyester can provide excellent flame retardancy, but it can be applied to a wide range of polyester fiber products regardless of the type. It is difficult to impart sufficient flame retardancy, and there remains a problem that is not sufficient in general versatility.
本発明は、従来のポリエステル系繊維品の難燃加工における上述した問題、特に、ＨＢＣＤを難燃剤として用いることなく、しかも、ＨＢＣＤを用いる場合に比較して、ポリエステル系繊維品にその種類を問わず、耐久性にすぐれる難燃性を付与することができる難燃加工剤を提供することを目的とする。 The present invention is not limited to the above-mentioned problems in the flame retardant processing of conventional polyester fiber products, in particular, without using HBCD as a flame retardant, and the type of polyester fiber product is compared to when using HBCD. It aims at providing the flame retardant processing agent which can provide the flame retardance which is excellent in durability.
更に、本発明は、上記難燃加工剤を用いるポリエステル系繊維品の難燃加工方法と、そのような難燃加工剤を用いて、又は難燃加工方法によって得られる難燃加工ポリエステル系繊維品を提供することを目的とする。 Furthermore, the present invention provides a flame retardant processing method for a polyester fiber product using the above flame retardant processing agent, and a flame retardant processing polyester fiber product obtained using or using such a flame retardant processing method. The purpose is to provide.
本発明によれば、トリス（２，３−ジブロモプロピル）イソシアヌレート１００重量部に対して、５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシド３０〜３００重量部をノニオン系界面活性剤とアニオン系界面活性剤の存在下に水に分散させ、又は乳化させてなることを特徴とするポリエステル系繊維品の難燃加工剤が提供される。 According to the present invention, 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane per 100 parts by weight of tris (2,3-dibromopropyl) isocyanurate A flame retardant processing agent for a polyester fiber product, characterized in that 30 to 300 parts by weight of 2-oxide is dispersed or emulsified in water in the presence of a nonionic surfactant and an anionic surfactant. Provided.
また、本発明によれば、上記難燃加工剤を用いてポリエステル系繊維品を難燃加工することを特徴とするポリエステル系繊維品の難燃加工方法が提供される。 Moreover, according to this invention, the flame-retardant processing method of the polyester-type fiber goods characterized by flame-retardant-processing a polyester-type fiber goods using the said flame-retardant processing agent is provided.
更に、本発明によれば、上記ポリエステル系繊維品の難燃加工方法の好ましい態様として、上記難燃加工剤を用いて、ポリエステル系繊維品を６０〜１４０℃の温度で浴中処理する方法、上記難燃加工剤と共に染料として少なくとも分散染料を用いて、ポリエステル系繊維品を６０〜１４０℃の温度で浴中処理する方法、上記難燃加工剤をポリエステル系繊維品に付着させ、１００〜２００℃の温度範囲で熱処理する方法、及び上記難燃加工剤と共に硬仕上げ剤をポリエステル系繊維品に付着させ、１００〜２００℃の温度範囲で熱処理する方法が提供される。 Furthermore, according to the present invention, as a preferred embodiment of the flame retardant processing method for the polyester fiber product, a method for treating the polyester fiber product in a bath at a temperature of 60 to 140 ° C. using the flame retardant processing agent, A method of treating a polyester fiber product in a bath at a temperature of 60 to 140 ° C. using at least a disperse dye as a dye together with the flame retardant processing agent, adhering the flame retardant processing agent to a polyester fiber product, and 100 to 200 There are provided a method of heat treatment in a temperature range of ° C. and a method of heat-treating in a temperature range of 100 to 200 ° C. by attaching a hard finish together with the flame retardant processing agent to a polyester fiber product.
また、本発明によれば、上記難燃加工方法において、ポリエステル系繊維品がカチオン可染ポリエステル繊維を含む布帛である方法、ポリエステル系繊維品がポリエステル紡績糸を含む布帛である方法が提供される。 In addition, according to the present invention, in the flame retardant processing method, there is provided a method in which the polyester fiber product is a fabric containing a cationic dyeable polyester fiber, and a method in which the polyester fiber product is a fabric containing polyester spun yarn. .
上記に加えて、本発明によれば、上記ポリエステル系繊維品の難燃加工方法によって得られる難燃加工ポリエステル系繊維品と、前記難燃加工剤を用いてポリエステル系繊維品を難燃加工してなる難燃加工ポリエステル系繊維品が提供される。 In addition to the above, according to the present invention, a flame retardant polyester fiber product obtained by the flame retardant processing method for a polyester fiber product and a flame retardant treatment of the polyester fiber product using the flame retardant agent are provided. A flame retardant processed polyester fiber product is provided.
本発明に従って、トリス（２，３−ジブロモプロピル）イソシアヌレートに所定の割合で５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドを組み合わせてなる難燃剤を含む難燃加工剤は、従来のポリエステル系繊維品の難燃加工における上述した問題を解決して、ＨＢＣＤを難燃剤として用いることなく、しかも、ＨＢＣＤを用いる場合に比較して、ポリエステル系繊維品にその種類を問わず、耐久性にすぐれる難燃性を付与することができる。 According to the present invention, 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide in a predetermined ratio to tris (2,3-dibromopropyl) isocyanurate The flame retardant containing a flame retardant combined with the above solution solves the above-mentioned problems in the flame retardant processing of conventional polyester fiber products, and does not use HBCD as a flame retardant, and compared with the case where HBCD is used. And the flame retardance which is excellent in durability can be provided to the polyester fiber regardless of the kind.
本発明による難燃加工剤は、トリス（２，３−ジブロモプロピル）イソシアヌレートと５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドの組み合わせを含むことから、トリス（２，３−ジブロモプロピル）イソシアヌレートと前述したような従来のリン酸エステルとの組み合わせを含む難燃加工剤と相違して、ポリエステル系繊維品にその種類を問わず、耐久性にすぐれる高い難燃性を付与することができる。 The flame retardant finish according to the present invention comprises tris (2,3-dibromopropyl) isocyanurate and 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2- Unlike the flame retardant processing agent containing a combination of tris (2,3-dibromopropyl) isocyanurate and a conventional phosphate ester as described above, it contains a combination of oxides, and the type of polyester fiber product Regardless of, high flame retardance with excellent durability can be imparted.
また、従来、難燃性を付与することが困難であるカチオン可染ポリエステル系繊維品についても、本発明による難燃加工剤を用いて難燃加工することによって、上記ポリエステル系繊維品に高性能で耐久性のある難燃性を付与することができる。 Further, conventionally, it is also possible to perform high performance on the above-mentioned polyester fiber product by performing flame retardant processing using the flame retardant processing agent according to the present invention for cationic dyeable polyester fiber products that are difficult to impart flame retardancy. Can provide durable flame retardancy.
更に、カチオン可染ポリエステル繊維と共にポリエステル紡績糸を含み、従来、難燃性を付与することが極めて困難であったポリエステル系繊維品についても、本発明による難燃加工剤を用いて難燃加工することによって、そのようなポリエステル系繊維品に高性能で耐久性のある難燃性を付与することができる。 Furthermore, polyester fiber products that contain polyester spun yarn together with cationic dyeable polyester fibers and have been conventionally difficult to impart flame retardancy are also flame-retardant processed using the flame retardant processing agent according to the present invention. As a result, high-performance and durable flame retardancy can be imparted to such a polyester fiber product.
本発明において、ポリエステル系繊維品とは、芳香族及び脂肪族を問わず、少なくともポリエステル繊維を含む繊維と、そのような繊維を含む糸、綿、編織布や不織布の布帛をいい、好ましくは、ポリエステル繊維、これよりなる糸、綿、編織布や不織布等の布帛をいう。 In the present invention, the polyester-based fiber product refers to a fiber including at least a polyester fiber, regardless of whether it is aromatic or aliphatic, and a yarn, cotton, a woven fabric, or a non-woven fabric including such a fiber. It refers to fabrics such as polyester fibers, yarns made of this, cotton, knitted fabrics and non-woven fabrics.
従って、上記ポリエステル系繊維として、例えば、ポリエチレンテレフタレート、ポリプロピレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリエチレンテレフタレート／イソフタレート、ポリエチレンテレフタレート／５−スルホイソフタレート、ポリエチレンテレフタレート／ポリオキシベンゾイル、ポリブチレンテレフタレート／イソフタレート等の芳香族ポリエステル系繊維、ポリ（Ｄ−乳酸）、ポリ（Ｌ−乳酸）、Ｄ−乳酸とＬ−乳酸の共重合体、Ｄ−乳酸と脂肪族ヒドロキシカルボン酸との共重合体、Ｌ−乳酸と脂肪族ヒドロキシカルボン酸との共重合体、Ｄ−乳酸とＬ−乳酸と脂肪族ヒドロキシカルボンとの共重合体、ポリ−ε−カプロラクトン（ＰＣＬ）等のポリカプロラクトン、ポリリンゴ酸、ポリヒドロキシカルボン酪酸、ポリヒドロキシ吉草酸、β−ヒドロキシ酪酸（３ＨＢ）−３−ヒドロキシ吉草酸（３ＨＶ）ランダム共重合体等のポリ脂肪族ヒドロキシカルボン酸、ポリエチレンサクシネート（ＰＥＳ）、ポリブチレンサクシネート（ＰＢＳ）、ポリブチレンアジペート、ポリブチレンサクシネート−アジペート共重合体等のグリコールと脂肪族ジカルボン酸とのポリエステル等の脂肪族ポリエステル系繊維を挙げることができる。 Accordingly, examples of the polyester fiber include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / 5-sulfoisophthalate, polyethylene terephthalate / polyoxybenzoyl , Aromatic polyester fiber such as polybutylene terephthalate / isophthalate, poly (D-lactic acid), poly (L-lactic acid), copolymer of D-lactic acid and L-lactic acid, D-lactic acid and aliphatic hydroxycarboxylic acid Copolymer, L-lactic acid and aliphatic hydroxycarboxylic acid copolymer, D-lactic acid, L-lactic acid and aliphatic hydroxycarboxylic acid copolymer, poly-ε-caprolactone (PCL), etc. Polyaliphatic hydroxycarboxylic acids such as licaprolactone, polymalic acid, polyhydroxycarboxylic butyric acid, polyhydroxyvaleric acid, β-hydroxybutyric acid (3HB) -3-hydroxyvaleric acid (3HV) random copolymer, polyethylene succinate (PES) ), Polybutylene succinate (PBS), polybutylene adipate, polybutylene succinate-adipate copolymer, etc., and aliphatic polyester fibers such as polyester of aliphatic dicarboxylic acid.
しかし、本発明において、ポリエステル系繊維は、上記例示したものに限定されることはなく、更に、難燃性化合物をポリエステルの製造時にポリエステル中に共重合させたもの、また、重合時又は製糸時に難燃性化合物をブレンドした難燃原糸であってもよい。 However, in the present invention, the polyester fibers are not limited to those exemplified above, and further, those obtained by copolymerizing a flame retardant compound in the polyester at the time of production of the polyester, and at the time of polymerization or yarn production It may be a flame retardant yarn blended with a flame retardant compound.
本発明に従って難燃加工されたポリエステル系繊維品は、例えば、座席シート、シートカバー、カーテン、ロールブラインド、プリーツブラインド、壁紙、天井クロス、カーペット、緞帳、建築養生シート、テント、帆布、ブラウス、ユニフォーム等の衣服、エプロン等に好適に用いられる。 Examples of the polyester-based fiber products that are flame-retardant processed according to the present invention include seat sheets, seat covers, curtains, roll blinds, pleated blinds, wallpaper, ceiling cloths, carpets, notebooks, architectural curing sheets, tents, canvases, blouses, uniforms It is suitably used for clothes such as clothes, apron and the like.
先ず、本発明によるポリエステル系繊維品のための難燃加工剤について説明する。
本発明によるポリエステル系繊維品の難燃加工剤は、次式（Ｉ）
First, the flame retardant processing agent for polyester fiber products according to the present invention will be described.
The flame-retardant finishing agent for polyester fiber products according to the present invention has the following formula (I):
で表されるトリス（２，３−ジブロモプロピル）イソシアヌレート１００重量部に対して、次式（II） And 100 parts by weight of tris (2,3-dibromopropyl) isocyanurate represented by the following formula (II)
で表される５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシド３０〜３００重量部をノニオン系界面活性剤とアニオン系界面活性剤の存在下に水に分散させ、又は乳化させてなるものである。 30-300 parts by weight of 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide represented by the formula: Nonionic surfactant and anionic surfactant Dispersed in water or emulsified in the presence of an agent.
本発明において難燃剤として用いる上記５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドは、１種の有機リン酸エステルであって、芳香族基と脂肪族基を併せ有するので、芳香脂肪族有機リン酸エステルということができる。そこで、以下においては、前述したような従来のリン酸エステルと区別するために、特に、断りのない限り、芳香脂肪族有機リン酸エステルは、５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドを意味するものとする。この芳香脂肪族有機リン酸エステルは、既に知られている化合物である（国際公開（ＷＯ）第２００７／０３２２７７号）。 The 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide used as a flame retardant in the present invention is an organic phosphate ester. Since it has both an aromatic group and an aliphatic group, it can be called an araliphatic organic phosphate ester. Therefore, in the following, in order to distinguish from the conventional phosphate ester as described above, unless otherwise specified, the araliphatic organic phosphate ester is 5,5-dimethyl-2- (2′-phenyl). Phenoxy) -1,3,2-dioxaphosphorinane-2-oxide. This araliphatic organophosphate is a known compound (International Publication (WO) No. 2007/032277).
本発明による難燃加工剤において、上記芳香脂肪族有機リン酸エステルとトリス（２，３−ジブロモプロピル）イソシアヌレートの配合割合は、トリス（２，３−ジブロモプロピル）イソシアヌレート１００重量部に対して、芳香脂肪族有機リン酸エステルが３０〜３００重量部の範囲であり、好ましくは、３５〜２００重量部の範囲であり、最も好ましくは４０〜１５０重量部の範囲である。トリス（２，３−ジブロモプロピル）イソシアヌレート１００重量部に対して、芳香脂肪族有機リン酸エステルの割合が３０重量部よりも少ないときは、ポリエステル系繊維品が燃焼する際に炭化傾向を示すため、十分な難燃性を得ることができず、他方、３００重量部を越えても、ポリエステル系繊維品への難燃剤の吸尽率が芳香脂肪族有機リン酸エステルの量に見合って上がらないので、徒に多量の芳香脂肪族有機リン酸エステルを用いることとなり、難燃加工の経済性の点でも不利である。 In the flame retardant processing agent according to the present invention, the blending ratio of the araliphatic organophosphate and tris (2,3-dibromopropyl) isocyanurate is 100 parts by weight of tris (2,3-dibromopropyl) isocyanurate. The araliphatic organophosphate is in the range of 30 to 300 parts by weight, preferably in the range of 35 to 200 parts by weight, and most preferably in the range of 40 to 150 parts by weight. When the proportion of the araliphatic organic phosphate is less than 30 parts by weight with respect to 100 parts by weight of tris (2,3-dibromopropyl) isocyanurate, the polyester fiber product shows a carbonization tendency when burned. Therefore, sufficient flame retardancy cannot be obtained. On the other hand, even if the amount exceeds 300 parts by weight, the exhaust rate of the flame retardant into the polyester fiber product is increased in accordance with the amount of the araliphatic organic phosphate ester. Therefore, a large amount of araliphatic organic phosphoric acid ester is used, which is disadvantageous in terms of economics of flame retardant processing.
ポリエステルは、本来、燃焼時は溶融型のポリマーであるところ、トリス（２，３−ジブロモプロピル）イソシアヌレートは、前述したように、ポリエステル系繊維品の燃焼時、その熱分解過程で残渣を生じ、炭化物を形成して、ポリエステル系繊維品の溶融滴下を妨げるので、添加量が少量の場合には、ポリエステル系繊維品の燃焼を却って助長させることがあるため、ポリエステル系繊維品に十分な難燃性を付与するには、多量の難燃剤を付与することを必要とする。一方、本発明において用いる前記芳香脂肪族有機リン酸エステルは、上記トリス（２，３−ジブロモプロピル）イソシアヌレートと相違して、ポリエステル系繊維品の燃焼時の熱分解過程において、実質的に残渣を生じず、本来、熱溶融型のポリエステル系繊維品の燃焼時の熱分解過程において、可塑剤として作用することによって、即ち、ポリエステル系繊維品の燃焼時の溶融滴下を促進することによって難燃性を付与する。 Polyester is originally a molten polymer at the time of combustion. As described above, tris (2,3-dibromopropyl) isocyanurate produces a residue during the pyrolysis process of polyester fiber products. Since it forms carbides and hinders melt dripping of polyester fiber products, if the addition amount is small, it may encourage combustion of polyester fiber products, which is not enough for polyester fiber products. In order to impart flammability, it is necessary to impart a large amount of flame retardant. On the other hand, unlike the tris (2,3-dibromopropyl) isocyanurate, the araliphatic organophosphate used in the present invention is substantially a residue in the thermal decomposition process during the burning of the polyester fiber product. Incombustible flame retardant by acting as a plasticizer in the thermal decomposition process during the combustion of the hot-melt type polyester fiber product, that is, by promoting the melt dripping during the combustion of the polyester fiber product. Gives sex.
そこで、本発明によれば、前記芳香脂肪族有機リン酸エステルの上記作用に基づく難燃化を阻害しない範囲において、これにポリエステル系繊維品の燃焼時、残渣を生じるトリス（２，３−ジブロモプロピル）イソシアヌレートを組み合わせて難燃剤とし、これをポリエステル系繊維品に付着させて、難燃性を付与するものである。 Therefore, according to the present invention, tris (2,3-dibromo) that produces a residue when a polyester fiber product is burned in a range in which flame retardancy based on the above-described action of the araliphatic organic phosphate ester is not inhibited. Propyl) isocyanurate is used as a flame retardant, and this is attached to a polyester fiber product to impart flame retardancy.
このような難燃剤によれば、ポリエステル系繊維品の燃焼に際して、臭素系難燃剤であるトリス（２，３−ジブロモプロピル）イソシアヌレートが前述したように臭素ガスを発生し、燃焼の連鎖を抑制する効果と、前記芳香脂肪族有機リン酸エステルの溶融促進効果との相乗効果によって、ＨＢＣＤと同等又はそれ以上のすぐれた難燃性をポリエステル系繊維品に付与することができる。また、トリス（２，３−ジブロモプロピル）イソシアヌレートと前述したような従来のリン酸エステルとの組み合わせと比較すれば、ポリエステル系繊維品にその種類を問わず、耐久性にすぐれる難燃性を付与することができる。 According to such a flame retardant, tris (2,3-dibromopropyl) isocyanurate, which is a brominated flame retardant, generates bromine gas and suppresses the combustion chain during the combustion of polyester fiber products. The flame retardant effect equivalent to or higher than that of HBCD can be imparted to the polyester fiber product by the synergistic effect of the effect of the above and the melting acceleration effect of the araliphatic organic phosphate ester. In addition, compared with the combination of tris (2,3-dibromopropyl) isocyanurate and the conventional phosphate ester as described above, regardless of the type of polyester fiber product, flame retardancy is excellent. Can be granted.
本発明による難燃加工剤は、その製造方法において、特に限定されるものではないが、好ましくは、例えば、前記芳香脂肪族有機リン酸エステルとトリス（２，３−ジブロモプロピル）イソシアヌレートと界面活性剤と水を混合し、湿式粉砕機を用いて、上記難燃剤を微粒子に粉砕し、水に分散させることによって、水分散体としての難燃加工剤を得ることができる。また、別の方法として、前記芳香脂肪族有機リン酸エステルとトリス（２，３−ジブロモプロピル）イソシアヌレートのそれぞれの単独の水分散体を同様にして製造し、得られたそれぞれの水分散体を混合することによっても、本発明の難燃加工剤を得ることもできる。 The flame retardant finish according to the present invention is not particularly limited in its production method, but preferably, for example, the araliphatic organophosphate, tris (2,3-dibromopropyl) isocyanurate and the interface. The flame retardant processing agent as an aqueous dispersion can be obtained by mixing the activator and water, pulverizing the flame retardant into fine particles using a wet pulverizer, and dispersing it in water. In addition, as another method, each of the above-mentioned aromatic aliphatic organophosphates and tris (2,3-dibromopropyl) isocyanurate was produced in the same manner, and each of the resulting water dispersions was produced. The flame retardant processing agent of the present invention can also be obtained by mixing.
本発明においては、トリス（２，３−ジブロモプロピル）イソシアヌレートと前記芳香脂肪族有機リン酸エステルを水中に分散させると共に、後述するように、得られる難燃加工剤が高温度での難燃加工の際にも安定性にすぐれるように、ノニオン界面活性剤とアニオン界面活性剤が併用される。 In the present invention, tris (2,3-dibromopropyl) isocyanurate and the araliphatic organophosphate are dispersed in water, and as described later, the obtained flame retardant is a flame retardant at a high temperature. A nonionic surfactant and an anionic surfactant are used in combination so as to have excellent stability during processing.
上記ノニオン界面活性剤としては、例えば、高級アルコールアルキレンオキサイド付加物、アルキルフェノールアルキレンオキサイド付加物、脂肪酸アルキレンオキサイド付加物、多価アルコール脂肪族エステルアルキレンオキサイド付加物、高級アルキルアミンアルキレンオキサイド付加物、脂肪酸アミドアルキレンオキサイド付加物、ポリオキシアルキレンスチレン化フェニルエーテル等のポリオキシアルキレン型非イオン系界面活性剤や、アルキルグリコキシド、ショ糖脂肪酸エステル等の多価アルコール型非イオン系界面活性剤を挙げることができる。 Examples of the nonionic surfactant include higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, fatty acid alkylene oxide adducts, polyhydric alcohol aliphatic ester alkylene oxide adducts, higher alkylamine alkylene oxide adducts, and fatty acid amides. Examples include polyoxyalkylene type nonionic surfactants such as alkylene oxide adducts, polyoxyalkylene styrenated phenyl ether, and polyhydric alcohol type nonionic surfactants such as alkylglycoxide and sucrose fatty acid ester. it can.
例えば、２−ブチルオクタノールの酸化エチレン１２モルと酸化プロピレン１２モル付加体は、本発明において、高級アルコールアルキレンオキサイド付加物として好ましく用いることができるノニオン界面活性剤の一例である。 For example, an adduct of 12 mol of ethylene oxide and 12 mol of propylene oxide of 2-butyloctanol is an example of a nonionic surfactant that can be preferably used as a higher alcohol alkylene oxide adduct in the present invention.
一方、上記アニオン界面活性剤としては、例えば、高級アルコール硫酸エステル塩、高級アルキルエーテル硫酸エステル塩、硫酸化脂肪酸エステル塩、スチレン化フェノールアルキレンオキサイド付加物の硫酸エステル塩等の硫酸エステル塩や、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、ビス（スチレン化フェニルエーテルアルキレンオキサイド付加物）コハク酸エステルスルホン化物の塩等のスルホン酸塩、トリスチレン化フェノール酸化エチレン付加物のスルホコハク酸エステルナトリウム塩、高級アルコールリン酸エステル塩、高級アルコールのアルキレンオキサイド付加物リン酸エステル塩等を挙げることができる。 On the other hand, examples of the anionic surfactant include sulfate esters such as higher alcohol sulfates, higher alkyl ether sulfates, sulfated fatty acid ester salts, sulfate esters of styrenated phenol alkylene oxide adducts, and alkylbenzenes. Sulfonates such as sulfonates, alkylnaphthalene sulfonates, salts of bis (styrenated phenyl ether alkylene oxide adducts) succinate esters, sulfosuccinate sodium salts of tristyrenated phenolic ethylene oxide adducts, higher grades Alcohol phosphate ester salts, higher alcohol alkylene oxide adduct phosphate ester salts, and the like can be mentioned.
例えば、トリスチレン化フェノール酸化エチレン１０モル付加物のスルホコハク酸エステルナトリウム塩は、本発明において好ましく用いることができるアニオン界面活性剤の一例である。 For example, sulfosuccinic acid ester sodium salt of tristyrenated phenol ethylene oxide 10 mol adduct is an example of an anionic surfactant that can be preferably used in the present invention.
また、本発明による難燃加工剤は、必要に応じて、乳化物として得ることもできる。好ましくは、例えば、前記芳香脂肪族有機リン酸エステルとトリス（２，３−ジブロモプロピル）イソシアヌレートを適宜の有機溶剤に溶解させ、これを適宜の界面活性剤を用いて水に乳化させることによって、本発明による難燃加工剤を乳化物として得ることができる。別の方法として、前記芳香脂肪族有機リン酸エステルとトリス（２，３−ジブロモプロピル）イソシアヌレートのそれぞれの単独の乳化物を同様にして製造し、得られたそれぞれの乳化物を混合することによっても、本発明の難燃加工剤を得ることもできる。 Moreover, the flame retardant processing agent by this invention can also be obtained as an emulsion as needed. Preferably, for example, the araliphatic organophosphate and tris (2,3-dibromopropyl) isocyanurate are dissolved in an appropriate organic solvent, and this is emulsified in water using an appropriate surfactant. The flame retardant processing agent according to the present invention can be obtained as an emulsion. As another method, each of the above-mentioned araliphatic organophosphates and tris (2,3-dibromopropyl) isocyanurate is produced in the same manner, and the resulting emulsions are mixed. Also, the flame retardant processing agent of the present invention can be obtained.
上記有機溶剤としては、例えば、トルエン、キシレン、アルキルナフタレン等の芳香族炭化水素、アセトン、メチルエチルケトン等のケトン類、メチルアルコール、エチルアルコール等のアルコール類、エチレングリコール、プロピレングリコール等のグリコール類、ジオキサン等のエーテル類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノイソブチルエーテル等のアルキレングリコールアルキルエーテル類、ジメチルホルムアミド等のアミド類、ジメチルスルホキシド等のスルホキシド類、メチレンクロライド、クロロホルム等のハロゲン化炭化水素類を挙げることができる。これらの有機溶剤は、単独で用いてもよく、また、必要に応じて、２種以上組み合わせて用いてもよい。このような有機溶剤を用いる場合は、その使用量は、通常、難燃剤に対して、１〜２０重量％の範囲である。 Examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene and alkylnaphthalene, ketones such as acetone and methyl ethyl ketone, alcohols such as methyl alcohol and ethyl alcohol, glycols such as ethylene glycol and propylene glycol, and dioxane. Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, alkylene glycol alkyl ethers such as ethylene glycol monoisobutyl ether, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylene chloride And halogenated hydrocarbons such as chloroform. These organic solvents may be used alone or in combination of two or more as required. When such an organic solvent is used, the amount used is usually in the range of 1 to 20% by weight with respect to the flame retardant.
このように、本発明に従って、前記芳香脂肪族有機リン酸エステルとトリス（２，３−ジブロモプロピル）イソシアヌレートを難燃剤として併用し、これらを水に分散させ、又は乳化させて、本発明による難燃加工剤を製造する際に、ポリエステル系繊維品に付与する難燃性に有害な影響を与えない範囲において、その他の難燃剤を含んでいてもよい。例えば、本発明による難燃加工剤は、前述したような従来から知られているリン酸エステル、ホスホン酸エステル、ホスフィン酸エステル、ホスファゼン系難燃剤等のリン系難燃剤、グアニジン等の窒素系難燃剤、臭素化ビスフェノールＡとその誘導体、臭素化ビスフェノールＳとその誘導体等の臭素系難燃剤等を含んでいてもよい。 Thus, according to the present invention, the araliphatic organophosphate and tris (2,3-dibromopropyl) isocyanurate are used in combination as a flame retardant, and these are dispersed or emulsified in water, according to the present invention. When the flame retardant finish is produced, other flame retardants may be included within a range that does not adversely affect the flame retardancy imparted to the polyester fiber product. For example, the flame retardants according to the present invention include the conventionally known phosphoric flame retardants such as phosphate esters, phosphonic acid esters, phosphinic acid esters and phosphazene flame retardants, and nitrogen-based flame retardants such as guanidine. It may contain a brominated flame retardant such as a flame retardant, brominated bisphenol A and derivatives thereof, brominated bisphenol S and derivatives thereof, and the like.
本発明による難燃加工剤は、前記芳香脂肪族有機リン酸エステル、即ち、５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドとトリス（２，３−ジブロモプロピル）イソシアヌレートを通常、合計にて２０〜６０重量％の割合で含んでいる。難燃加工剤における難燃剤の割合が余りに低いときは、難燃加工に際して、徒に多量の難燃加工剤を用いざるを得ず、難燃加工の効率が低下し、一方、難燃加工剤における難燃剤の割合が余りに高いときは、難燃加工剤が安定性に欠けるおそれがある。好ましくは、本発明による難燃加工剤は、上記難燃剤を合計にて３０〜５０重量％の割合で含んでいる。 The flame retardant processing agent according to the present invention comprises the above-described araliphatic organic phosphate ester, that is, 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide. And tris (2,3-dibromopropyl) isocyanurate are usually contained in a proportion of 20 to 60% by weight in total. When the ratio of the flame retardant in the flame retardant is too low, a large amount of flame retardant must be used in the flame retardant processing, and the efficiency of the flame retardant is reduced. When the ratio of the flame retardant in is too high, the flame retardant finish may lack stability. Preferably, the flame retardant processing agent according to the present invention contains the above flame retardant in a proportion of 30 to 50% by weight in total.
次に、本発明に従って、上述した難燃加工剤を用いるポリエステル系繊維品の難燃加工について説明する。 Next, according to the present invention, the flame retardant processing of a polyester fiber product using the above-described flame retardant processing agent will be described.
本発明による難燃加工剤を用いて、ポリエステル系繊維品を難燃加工し、ポリエステル系繊維品に難燃性を付与する方法としては、特に限定されるものではないが、例えば、パディング法、スプレー法、コーティング法、捺染法、スクリーン印刷法等によって、難燃加工剤をポリエステル系繊維品に付着させ、１００〜２００℃の温度で熱処理して、前記芳香脂肪族有機リン酸エステルとトリス（２，３−ジブロモプロピル）イソシアヌレートを繊維に固着させる方法を挙げることができる。 Using the flame retardant processing agent according to the present invention, the method of flame retardant processing the polyester fiber product and imparting flame resistance to the polyester fiber product is not particularly limited, for example, a padding method, The flame retardant is attached to the polyester fiber product by spraying, coating, printing, screen printing, etc., and heat-treated at a temperature of 100 to 200 ° C., and the araliphatic organic phosphate ester and tris ( A method of fixing 2,3-dibromopropyl) isocyanurate to the fiber can be mentioned.
より詳細には、例えば、パディング法によるときは、本発明による難燃加工剤にポリエステル系繊維品を浸漬して、所定の付着量になるようにマングル等で絞った後、例えば、１００〜２００℃、好ましくは１５０〜１９０℃の範囲の温度で数秒から数分間、乾熱処理を行う。 More specifically, for example, when the padding method is used, after immersing the polyester fiber product in the flame retardant processing agent according to the present invention and squeezing with a mangle or the like so as to obtain a predetermined adhesion amount, for example, 100 to 200 Dry heat treatment is performed at a temperature in the range of 150 ° C., preferably 150 to 190 ° C. for a few seconds to a few minutes.
また、本発明による難燃加工剤をポリエステル系繊維品に付与して、難燃加工する別の方法として、浴中処理によることができる。この方法によるときは、例えば、難燃加工剤を入れた処理浴にポリエステル系繊維品を浸漬し、処理浴中で６０〜１４０℃の温度、好ましくは、８０〜１３５℃の温度にて処理して、前記芳香脂肪族有機リン酸エステルとトリス（２，３−ジブロモプロピル）イソシアヌレートを繊維に固着させる。この方法によるときは、例えば、液流染色機、ビーム染色機、チーズ染色機等のパッケージ染色機を用いることができる。 Moreover, the flame retardant processing agent by this invention can be given to a polyester-type fiber article, and it can be based on a process in a bath as another method of performing a flame retardant processing. When using this method, for example, a polyester fiber product is immersed in a treatment bath containing a flame retardant and treated at a temperature of 60 to 140 ° C., preferably 80 to 135 ° C. in the treatment bath. Then, the araliphatic organophosphate and tris (2,3-dibromopropyl) isocyanurate are fixed to the fiber. When using this method, for example, a package dyeing machine such as a liquid dyeing machine, a beam dyeing machine, or a cheese dyeing machine can be used.
本発明によれば、上述した浴中処理を行う場合に、難燃加工剤と共に少なくとも分散染料を含む処理浴中にポリエステル系繊維品を浸漬して、難燃加工すると同時に染色することができる。染料としては、ポリエステル系繊維品がレギュラーポリエステル繊維糸を含むときは、分散染料が好ましく用いられるが、例えば、ポリエステル系繊維品がレギュラーポリエステル繊維糸とカチオン可染ポリエステル繊維糸との混織品であるときは、分散染料と共にカチオン染料が用いられる。このように、浴中処理によって、ポリエステル系繊維品の難燃加工と同時に染色を行う場合には、所要の染料と共に、必要に応じて、均染剤や緩染剤等を併用し、更に、ｐＨ調整剤やｐＨ緩衝剤を用いて、処理浴のｐＨを３〜６に調整することが望ましい。 According to the present invention, when the treatment in the bath described above is performed, the polyester fiber can be immersed in a treatment bath containing at least a disperse dye together with the flame retardant and dyed at the same time as the flame retardant treatment. As the dye, when the polyester fiber product includes a regular polyester fiber yarn, a disperse dye is preferably used. For example, the polyester fiber product is a mixed woven product of a regular polyester fiber yarn and a cationic dyeable polyester fiber yarn. Sometimes a cationic dye is used together with a disperse dye. Thus, when performing dyeing simultaneously with flame retardant processing of polyester fiber products by treatment in the bath, together with the required dye, if necessary, a leveling agent or a slow dyeing agent is used in combination, It is desirable to adjust the pH of the treatment bath to 3 to 6 using a pH adjuster or a pH buffer.
浴中処理においては、上述したように、通常、難燃加工剤は高圧下に高温に加熱されるので、浴中処理の間、難燃加工剤は前記界面活性剤の存在下に溶融状態、即ち、乳化状態にある。そこで、用いる難燃剤がそのような高温下において乳化安定性が悪いときは、難燃加工中に難燃剤である前記芳香脂肪族有機リン酸エステルやトリス（２，３−ジブロモプロピル）イソシアヌレートが乳化破壊を起こし、ポリエステル系繊維中のポリエステルオリゴマーを取り込んで、ポリエステル系繊維品に汚れ物質として付着する不都合を生じる。更に、そのようにポリエステル系繊維品に付着した汚れ物質が加工機内を汚染する不都合も起こる。 In the treatment in the bath, as described above, since the flame retardant processing agent is usually heated to a high temperature under high pressure, the flame retardant processing agent is in a molten state in the presence of the surfactant during the treatment in the bath. That is, it is in an emulsified state. Therefore, when the flame retardant used has poor emulsion stability at such high temperatures, the araliphatic organic phosphate ester or tris (2,3-dibromopropyl) isocyanurate, which is a flame retardant during the flame retardant processing, Emulsion breakage is caused, and the polyester oligomer in the polyester fiber is taken in, resulting in inconvenience of adhering to the polyester fiber product as a soiling substance. Furthermore, there is a disadvantage that the soiled material adhering to the polyester fiber product contaminates the processing machine.
ここに、難燃剤である前記芳香脂肪族有機リン酸エステルとトリス（２，３−ジブロモプロピル）イソシアヌレートを水に分散させ、又は乳化させるに際して、ノニオン界面活性剤のみを用いるときは、得られる難燃加工剤が高温下において乳化安定性が悪くなり、上述したような不都合が生じる。そこで、本発明に従って、ノニオン界面活性剤とアニオン界面活性剤を併用することによって、難燃加工剤に高温下において高い乳化安定性を有せしめることができる。 This is obtained when only the nonionic surfactant is used in dispersing or emulsifying the above-mentioned araliphatic organic phosphate ester and tris (2,3-dibromopropyl) isocyanurate, which are flame retardants, in water. The flame retardant processing agent has poor emulsification stability at high temperatures, causing the disadvantages described above. Therefore, according to the present invention, by using a nonionic surfactant and an anionic surfactant in combination, the flame retardant processing agent can have high emulsion stability at high temperatures.
このように、高温下において乳化安定性にすぐれる難燃加工剤を得るには、難燃剤である前記芳香脂肪族有機リン酸エステルとトリス（２，３−ジブロモプロピル）イソシアヌレートの合計量に対してノニオン界面活性剤を２〜２０重量％の範囲で用いると共に、アニオン界面活性剤を２〜１０重量％の範囲で用いることが好ましい。
本発明によれば、少量の難燃加工剤を用いる難燃加工によって、通常のポリエステル系繊維品、即ち、レギュラーポリエステル系繊維品に容易に十分な難燃性を付与することができる。
Thus, in order to obtain a flame retardant having excellent emulsion stability at high temperatures, the total amount of the araliphatic organic phosphate ester and tris (2,3-dibromopropyl) isocyanurate, which are flame retardants, is used. On the other hand, it is preferable to use a nonionic surfactant in the range of 2 to 20% by weight and an anionic surfactant in the range of 2 to 10% by weight.
According to the present invention, sufficient flame retardancy can be easily imparted to a normal polyester fiber product, that is, a regular polyester fiber product, by flame retardant processing using a small amount of flame retardant processing agent.
しかし、本発明によれば、従来のポリエステル系繊維品のための難燃加工剤にみられない重要な特徴として、通常は、難燃性を付与することが困難であるカチオン可染ポリエステル系繊維品についても、本発明による難燃加工剤を用いて難燃加工することによって、高性能で耐久性のある難燃性を付与することができる。
更に、本発明によれば、従来、難燃性を付与することが極めて困難であるポリエステル紡績糸を含むポリエステル系繊維品や、従ってまた、カチオン可染ポリエステル繊維と共にポリエステル紡績糸を含むポリエステル系繊維品についても、本発明による難燃加工剤を用いて難燃加工することによって、高性能で耐久性のある難燃性を付与することができる。
However, according to the present invention, as an important feature not found in the flame retardant for conventional polyester fiber products, it is usually a cationic dyeable polyester fiber that is difficult to impart flame retardancy. A product can be imparted with high-performance and durable flame retardancy by subjecting the product to flame-retardant processing using the flame retardant processing agent according to the present invention.
Furthermore, according to the present invention, a polyester fiber product including a polyester spun yarn, which has conventionally been extremely difficult to impart flame retardancy, and thus a polyester fiber including a polyester spun yarn together with a cationic dyeable polyester fiber. A product can be imparted with high-performance and durable flame retardancy by subjecting the product to flame-retardant processing using the flame retardant processing agent according to the present invention.
本発明において、カチオン可染ポリエステル繊維を含む布帛とは、カチオン可染ポリエステル繊維糸とレギュラーポリエステル繊維糸との混織による布帛を意味し、カチオン可染ポリエステル繊維糸のみからなる布帛をも含めることとする。ポリエステル紡績糸含む布帛とは、ポリエステル紡績糸とレギュラーポリエステル繊維糸との混織による布帛を意味し、ポリエステル紡績糸のみからなる布帛をも含めることとする。また、カチオン可染ポリエステル繊維と共にポリエステル紡績糸を含む布帛とは、カチオン可染ポリエステル繊維糸とポリエステル紡績糸（とレギュラーポリエステル繊維糸）との混織による布帛を意味する。 In the present invention, the cloth containing a cationic dyeable polyester fiber means a cloth made of a mixture of a cationic dyeable polyester fiber thread and a regular polyester fiber thread, and includes a cloth made only of a cationic dyeable polyester fiber thread. And The cloth containing the polyester spun yarn means a fabric by a mixed weave of the polyester spun yarn and the regular polyester fiber yarn, and includes a fabric composed only of the polyester spun yarn. Moreover, the cloth containing polyester spun yarn together with cationic dyeable polyester fiber means a cloth made of a mixture of cationic dyeable polyester fiber yarn and polyester spun yarn (and regular polyester fiber yarn).
ここに、カチオン可染ポリエステル繊維を含む布帛中に含まれるカチオン可染ポリエステル繊維糸の重量基準による割合（重量％）をカチオン可染ポリエステル繊維の混率といい、ポリエステル紡績糸を含む布帛におけるポリエステル紡績糸の重量基準による割合（重量％）をポリエステル紡績糸の混率という。 Here, the proportion (% by weight) of the cationic dyeable polyester fiber yarn contained in the cloth containing the cationic dyeable polyester fiber is called the mixing ratio of the cationic dyeable polyester fiber, and the polyester spinning in the cloth containing the polyester spun yarn The ratio (% by weight) based on the weight of the yarn is called the blend ratio of the polyester spun yarn.
本発明による難燃加工剤を用いて、ポリエステル系繊維品を難燃加工するに際して、難燃剤、即ち、トリス（２，３−ジブロモプロピル）イソシアヌレートと前記芳香脂肪族有機リン酸エステルの合計量のポリエステル系繊維品への付着量は、厳密には、そのポリエステル系繊維品の種類にもよるが、一般に、０．１〜１０重量％の範囲であり、好ましくは、本発明によれば、０．３〜６重量％の範囲の付着量でポリエステル系繊維品に十分な難燃性を付与することができる。 When a polyester fiber product is subjected to flame retardant processing using the flame retardant processing agent according to the present invention, the total amount of the flame retardant, that is, tris (2,3-dibromopropyl) isocyanurate and the araliphatic organic phosphate ester. The amount of adhesion to the polyester fiber product is strictly in the range of 0.1 to 10% by weight, although strictly depending on the type of the polyester fiber product, preferably according to the present invention. Sufficient flame retardancy can be imparted to the polyester fiber product with an adhesion amount in the range of 0.3 to 6% by weight.
ポリエステル系繊維品への難燃剤の付着量が０．１重量％よりも少ないときは、通常のポリエステル系繊維品であっても、これに十分な難燃性を付与することができず、他方、１０重量％を越えるときは、難燃加工後の繊維品の染色堅牢度が低下する等の不具合を生じる。 When the adhesion amount of the flame retardant to the polyester fiber product is less than 0.1% by weight, even if it is a normal polyester fiber product, sufficient flame retardancy cannot be imparted thereto, When it exceeds 10% by weight, problems such as a decrease in dyeing fastness of the fiber product after the flame-retardant processing occur.
難燃加工のほかに、ポリエステル系繊維品に無機化合物を触媒として用いる光触媒加工や、また、フッ素樹脂を撥水剤として用いる撥水加工のような付加的な機能を施す場合や、また、ポリエステル系繊維品に無機顔料を印刷して、意匠加工を施す場合には、このような種々の加工に用いられた上記無機物質や樹脂類が燃焼時の熱分解過程において残渣を生じ、ポリエステル系繊維品の燃焼時、その溶融滴下を阻害して、燃焼を助長させることがあり、一般に、難燃化を困難にするので、そのようなポリエステル系繊維品に十分な難燃性を付与するには、６重量％以上の付着量を必要とすることがある。 In addition to flame retardant processing, polyester fiber products may be subjected to additional functions such as photocatalytic processing using inorganic compounds as catalysts, and water repellent processing using fluororesins as water repellents. When an inorganic pigment is printed on a textile product and subjected to design processing, the above-mentioned inorganic substances and resins used in such various processing produce residues in the thermal decomposition process during combustion, and polyester fiber In order to give sufficient flame retardancy to such polyester-based fiber products, it may hinder the melting and dripping of the product when it is burned, and promote combustion. In some cases, an adhesion amount of 6% by weight or more is required.
カチオン可染ポリエステル混織布帛は、前述したように、カチオン可染ポリエステル繊維糸を含む布帛であり、そのポリエステル繊維を形成するポリエステルの分子中にカチオン染料による染色を容易にするために、例えば、５−スルホイソフタル酸のようなスルホン酸基を有するジカルボン酸モノマー成分がポリエステル分子中に組み込まれている。このようなスルホン酸基を有するモノマー成分を含まないポリエステルからなる繊維がレギュラーポリエステル繊維である。このようなカチオン可染ポリエステル混織布帛は、レギュラーポリエステル系繊維品に比較して、燃焼後に燃焼残渣を生じやすく、また、燃焼後に生じた燃焼残渣がいわば「蝋燭の芯」の役割をして、レギュラーポリエステルのドリップを阻害するので、その難燃化が困難であるとされている。 As described above, the cationic dyeable polyester mixed woven fabric is a cloth containing cationic dyeable polyester fiber yarns, and in order to facilitate dyeing with a cationic dye in the polyester molecules forming the polyester fiber, for example, A dicarboxylic acid monomer component having a sulfonic acid group such as 5-sulfoisophthalic acid is incorporated in the polyester molecule. The fiber which consists of polyester which does not contain the monomer component which has such a sulfonic acid group is a regular polyester fiber. Such a cationic dyeable polyester blend fabric is more likely to generate a combustion residue after combustion than a regular polyester fiber product, and the combustion residue generated after combustion functions as a “candle core”. In addition, since it inhibits the drip of regular polyester, it is said that its flame retardancy is difficult.
即ち、カチオン可染ポリエステル繊維糸は融点約２４６℃、５％分解温度約３７３℃であり、レギュラーポリエステル繊維糸は融点約２５６℃、５％分解温度約４００℃であるのでカチオン可染ポリエステル混織布帛が燃焼した場合、カチオン可染ポリエステル繊維糸の分解温度がレギュラーポリエステル繊維糸の分解温度よりも低く、燃焼残渣がレギュラーポリエステル繊維糸の分解前に形成され、その結果として、燃焼残渣が「蝋燭の芯」の役割をするとみられる。 That is, the cationic dyeable polyester fiber yarn has a melting point of about 246 ° C. and a 5% decomposition temperature of about 373 ° C., and the regular polyester fiber yarn has a melting point of about 256 ° C. and a 5% decomposition temperature of about 400 ° C. When the fabric burns, the decomposition temperature of the cationic dyeable polyester fiber yarn is lower than the decomposition temperature of the regular polyester fiber yarn, and a combustion residue is formed prior to the decomposition of the regular polyester fiber yarn. It seems to play the role of a “candle core”.
このようなカチオン可染ポリエステル混織布帛、特に、カチオン可染ポリエステルの混率が２５％以上のものは、レギュラーポリエステル系繊維品に比較して、従来、難燃化が困難であるといわれている。 Such a cationic dyeable polyester mixed woven fabric, in particular, a cationic dyeable polyester having a mixing ratio of 25% or more is conventionally said to be difficult to flame retardant compared to regular polyester fiber products. Yes.
しかしながら、本発明によれば、カチオン可染ポリエステル繊維を含む布帛を難燃加工するに際して、難燃剤のカチオン可染ポリエステル繊維を含む布帛への付着量は、通常、１〜１０重量％の範囲であり、好ましくは、１．５〜５重量％の範囲であり、難燃剤のこのような付着量によって、カチオン可染ポリエステル繊維を含む布帛に十分な難燃性を付与することができる。 However, according to the present invention, when a fabric containing a cationic dyeable polyester fiber is flame-retardant processed, the amount of the flame retardant attached to the fabric containing the cationic dyeable polyester fiber is usually in the range of 1 to 10% by weight. Yes, preferably in the range of 1.5 to 5% by weight, and the flame retarder can give sufficient flame retardancy to the fabric containing the cationic dyeable polyester fiber by such an amount of the flame retardant attached.
カチオン可染ポリエステル系繊維を含む布帛への難燃剤の付着量が１重量％よりも少ないときは、ポリエステル系繊維品に十分な難燃性を付与することができず、他方、１０重量％を超えるときは、難燃加工後の繊維品の染色堅牢度が低下する等の不具合を生じる。 When the amount of the flame retardant attached to the fabric containing the cationic dyeable polyester fiber is less than 1% by weight, sufficient flame retardancy cannot be imparted to the polyester fiber product. When exceeding, problems, such as the dyeing fastness of the textile after a flame-retardant process fall, will arise.
ポリエステル紡績糸は、短繊維をより合わせて製造されることから、繊維中に空気を抱え込み、燃焼を助長させる性質を有するので、このようなポリエステル紡績糸を含む布帛は、レギュラーポリエステル繊維品に比較して、難燃化が困難であるといわれている。 Polyester spun yarn is manufactured by combining short fibers, so it has the property of trapping air in the fiber and promoting combustion, so fabrics containing such polyester spun yarn are compared to regular polyester fiber products. Therefore, it is said that flame retardancy is difficult.
しかしながら、本発明によれば、ポリエステル紡績糸を含む布帛を難燃加工するに際して、難燃剤のポリエステル紡績糸を含む布帛への付着量は、通常、１〜１０重量％の範囲であり、好ましくは、１．５〜５重量％の範囲であり、難燃剤のこのような付着量によって、ポリエステル紡績糸を含む布帛に十分な難燃性を付与することができる。 However, according to the present invention, when a fabric containing polyester spun yarn is subjected to flame retardant processing, the amount of flame retardant attached to the fabric containing polyester spun yarn is usually in the range of 1 to 10% by weight, preferably The amount of the flame retardant attached can impart sufficient flame retardancy to the fabric containing the polyester spun yarn.
更には、ポリエステル紡績糸とカチオン可染ポリエステル繊維が混織された布帛の場合には、上述したことから明らかなように、カチオン可染ポリエステル繊維の混率が低いものでも、その難燃化は、一層、困難であり、トリス（２，３−ジブロモプロピル）イソシアヌレートや５，５−ジメチル−２−（２−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドを単独で用いて難燃加工しても、極めて不十分な難燃性を付与し得るにすぎない。 Furthermore, in the case of a fabric in which a polyester spun yarn and a cationic dyeable polyester fiber are woven together, as is apparent from the above, even if the mixing ratio of the cationic dyeable polyester fiber is low, its flame retardancy is More difficult, tris (2,3-dibromopropyl) isocyanurate and 5,5-dimethyl-2- (2-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide alone Even if it is used and flame-retarded, it can only give very poor flame retardancy.
しかし、本発明による難燃剤を用いることによって、このようなカチオン可染ポリエステル繊維と共にポリエステル紡績糸を含む布帛であっても、十分な難燃性を有しせしめることができる。 However, by using the flame retardant according to the present invention, even a fabric including a polyester spun yarn together with such a cationic dyeable polyester fiber can have sufficient flame retardancy.
本発明によれば、カチオン可染ポリエステル繊維と共にポリエステル紡績糸を含む布帛を難燃加工するに際して、難燃剤である前記芳香脂肪族有機リン酸エステルとトリス（２，３−ジブロモプロピル）イソシアヌレートのポリエステル繊維布帛への付着量は、通常、１．５〜１０重量％の範囲であり、好ましくは、２〜６重量％の範囲である。ポリエステル系繊維品への難燃剤の付着量が１．５重量％よりも少ないときは、ポリエステル系繊維品に十分な難燃性を付与することができず、他方、１０重量％を越えるときは、難燃加工後の繊維品の染色堅牢度が低下する等の不具合を生じる。 According to the present invention, when a fabric containing a polyester spun yarn together with a cationic dyeable polyester fiber is flame-retardant processed, the araliphatic organic phosphate ester and tris (2,3-dibromopropyl) isocyanurate, which are flame retardants, are used. The adhesion amount to the polyester fiber fabric is usually in the range of 1.5 to 10% by weight, and preferably in the range of 2 to 6% by weight. When the adhesion amount of the flame retardant to the polyester fiber product is less than 1.5% by weight, sufficient flame retardancy cannot be imparted to the polyester fiber product, and when it exceeds 10% by weight. , Problems such as a decrease in dyeing fastness of fiber products after flame-retardant processing occur.
本発明による難燃加工剤を前述したパディング法にてポリエステル系繊維品に付与する場合には、必要に応じて、硬仕上げ剤を併せて用いてもよい。本発明による難燃加工剤は、常温で可塑剤として寄与するものではないので、本発明による難燃加工剤を用いる難燃加工方法は、風合いを軟化させることなく、ポリエステル系繊維品を難燃硬仕上げ加工するために好適である。 When applying the flame retardant processing agent according to the present invention to a polyester fiber product by the padding method described above, a hard finish may be used as required. Since the flame retardant processing agent according to the present invention does not contribute as a plasticizer at room temperature, the flame retardant processing method using the flame retardant processing agent according to the present invention does not soften the texture and flame retardant polyester fiber products. Suitable for hard finishing.
上記硬仕上げ剤としては、例えば、硬度の高いポリエステル樹脂が好ましく用いられる。例えば、ガラス転移点５０〜７０℃、軟化点１３０〜１８０℃、重量平均分子量２００００〜４００００、被膜の鉛筆硬度４Ｈ〜５Ｈのポリエステル樹脂が好ましく用いられる。このようなポリエステル樹脂は、例えば、互応化学工業（株）製のポリエステル樹脂水分散体プラスコートＲＺ−１０５、Ｚ−５６５等として入手することができる。しかし、本発明において、硬仕上げ剤は、上記例示に限定されるものではない。 As the hard finish, for example, a polyester resin having high hardness is preferably used. For example, a polyester resin having a glass transition point of 50 to 70 ° C., a softening point of 130 to 180 ° C., a weight average molecular weight of 20,000 to 40,000, and a pencil hardness of 4H to 5H of the coating is preferably used. Such a polyester resin can be obtained, for example, as polyester resin water dispersion plus coat RZ-105, Z-565, etc. manufactured by Kyoyo Chemical Industry Co., Ltd. However, in the present invention, the hard finish is not limited to the above examples.
難燃加工剤と共に、このような硬仕上げ剤を用いて、ポリエステル系繊維品を難燃硬仕上げ加工するには、厳密には、用いるポリエステル樹脂の硬度や、加工後に布帛として要求される硬さにもよるが、通常、ポリエステル系繊維品に硬仕上げ剤を３〜３０重量％の範囲で付着させればよく、好ましくは、５〜２０重量％の範囲で付着させる。このように、難燃硬仕上げ加工されたポリエステル系繊維品は、ロールブラインドやプリーツブラインドの用途に好ましく供することができる。 Strictly speaking, using such a hard finish together with a flame retardant, a polyester fiber product is subjected to a fire retardant hard finish, strictly speaking, the hardness of the polyester resin used and the hardness required for the fabric after processing. However, usually, a hard finish may be attached to the polyester fiber product in the range of 3 to 30% by weight, and preferably 5 to 20% by weight. Thus, the flame-retardant and hard-finished polyester fiber product can be preferably used for roll blinds and pleated blinds.
本発明による難燃加工剤は、その性能が阻害されない範囲において、必要に応じて、ポリビニルアルコール、メチルセルロース、カルボキシメチルセルロース、デンプン糊等の分散安定剤、難燃加工剤の難燃性を高めるための難燃助剤、耐光堅牢度を高めるための紫外線吸収剤や酸化防止剤等を含んでいてもよい。更に、必要に応じて、従来から知られている難燃剤や界面活性剤を含んでいてもよい。 The flame retardant processing agent according to the present invention is a dispersion stabilizer such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, starch paste, and the like for enhancing the flame resistance of the flame retardant processing agent, as long as the performance is not hindered. It may contain a flame retardant aid, an ultraviolet absorber or an antioxidant for increasing light fastness. Furthermore, if necessary, a conventionally known flame retardant or surfactant may be included.
更に、本発明による難燃加工剤は、他の機能加工剤と併用することもできる。機能加工剤の例としては、上述した硬仕上げ剤のほか、柔軟剤、帯電防止剤、撥水撥油剤、風合い調整剤、ＳＲ剤等を挙げることできる。 Furthermore, the flame retardant processing agent according to the present invention can be used in combination with other functional processing agents. Examples of the functional processing agent include a softening agent, an antistatic agent, a water / oil repellent agent, a texture adjusting agent, an SR agent and the like in addition to the hard finish agent described above.
以下に本発明による難燃加工剤の製造と本発明による難燃加工の実施例を挙げて本発明を詳細に説明するが、本発明はこれら実施例によって何ら限定されるものではない。尚、以下において、不揮発分とは、難燃加工剤中の難燃剤と、難燃加工剤に含まれるときは、界面活性剤と消泡剤を合わせた成分をいう。 Hereinafter, the present invention will be described in detail with reference to examples of the production of the flame retardant processing agent according to the present invention and the flame retardant processing according to the present invention, but the present invention is not limited to these examples. In the following, the term “nonvolatile content” refers to a combination of a flame retardant in a flame retardant processing agent and, when included in the flame retardant processing agent, a surfactant and an antifoaming agent.
Ｉ．難燃加工剤の製造 I. Manufacture of flame retardants
実施例Ｉ−１
（５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドの水分散体の製造）
前記芳香脂肪族有機リン酸エステル、即ち、５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシド４０重量部と、界面活性剤として、２−ブチルオクタノールの酸化エチレン１２モルと酸化プロピレン１２モル付加体１．５重量部とトリスチレン化フェノール酸化エチレン１０モル付加物のスルホコハク酸エステルナトリウム塩１．５重量部と、シリコーン系消泡剤０．１重量部を水３０重量部と混合し、これを０．８ｍｍのガラスビーズを充填したミルに仕込み、上記難燃剤の平均粒子径がレーザー回折式粒度分布測定装置（（株）島津製作所製ＳＡＬＤ−２０００Ｊ、以下、同じ。）で測定して１．０μｍとなるまで粉砕し、１０５℃の温度で３０分乾燥させたときの不揮発分濃度が４０％（難燃剤濃度３７％）となるように水で希釈して、上記芳香脂肪族有機リン酸エステルの水分散体を得た。
Example I-1
(Production of aqueous dispersion of 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide)
40 parts by weight of the araliphatic organophosphate, that is, 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide, and a surfactant 12 parts of 2-butyloctanol ethylene oxide and 12 parts of propylene oxide 12 parts adduct, 1.5 parts by weight of sodium salt of sulfosuccinate ester of tristyrenated phenol ethylene oxide 10 moles, and silicone-based defoaming 0.1 part by weight of the agent is mixed with 30 parts by weight of water, and this is charged into a mill filled with 0.8 mm glass beads. The average particle diameter of the flame retardant is determined by a laser diffraction particle size distribution analyzer (Shimadzu Corporation). SALD-2000J (manufactured by Seisakusho, the same shall apply hereinafter)) is pulverized to 1.0 μm and dried at a temperature of 105 ° C. for 30 minutes. 0% was diluted with water so that the (flame retardant concentration 37%) to obtain an aqueous dispersion of the aromatic aliphatic organic phosphate.
この５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドの水分散体を難燃加工剤として用いるとき、この難燃加工剤を比較例による難燃加工剤１という。 When this aqueous dispersion of 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide is used as a flame retardant, this flame retardant is used. It is referred to as a flame retardant finishing agent 1 according to a comparative example.
（トリス（２，３−ジブロモプロピル）イソシアヌレートの水分散体の製造）
トリス（２，３−ジブロモプロピル）イソシアヌレート４０重量部と、界面活性剤として、２−ブチルオクタノールの酸化エチレン１２モルと酸化プロピレン１２モル付加体１．５重量部とトリスチレン化フェノール酸化エチレン１０モル付加物のスルホコハク酸エステルナトリウム塩１．５重量部と、シリコーン系消泡剤０．１重量部を水３０重量部と混合し、これを０．８ｍｍのガラスビーズを充填したミルに仕込み、上記難燃剤の平均粒子径がレーザー回折式粒度分布測定装置で測定して１．０μｍとなるまで粉砕し、１０５℃の温度で３０分乾燥させたときの不揮発分濃度が４０％（難燃剤濃度３７％）となるように水で希釈して、上記トリス（２，３−ジブロモプロピル）イソシアヌレートの水分散体を得た。
(Production of tris (2,3-dibromopropyl) isocyanurate aqueous dispersion)
40 parts by weight of tris (2,3-dibromopropyl) isocyanurate, 12 moles of ethylene oxide of 12-butyl octanol, 1.5 parts by weight of an adduct of 12 moles of propylene oxide and 10 parts of tristyrenated phenol ethylene oxide as a surfactant Mole adduct sodium sulfosuccinate ester (1.5 parts by weight) and silicone antifoam (0.1 part by weight) were mixed with 30 parts by weight of water and charged into a mill filled with 0.8 mm glass beads. When the average particle diameter of the flame retardant is measured with a laser diffraction particle size distribution measuring device to 1.0 μm and pulverized and dried at a temperature of 105 ° C. for 30 minutes, the nonvolatile content concentration is 40% (flame retardant concentration) 37%) to obtain an aqueous dispersion of the above tris (2,3-dibromopropyl) isocyanurate.
このトリス（２，３−ジブロモプロピル）イソシアヌレートの水分散体を難燃加工剤として用いるとき、この難燃加工剤を比較例による難燃加工剤２という。 When the aqueous dispersion of tris (2,3-dibromopropyl) isocyanurate is used as a flame retardant, this flame retardant is referred to as a flame retardant 2 according to a comparative example.
（難燃加工剤Ａの製造）
上記５，５−ジメチル−２−（２−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドの水分散体と上記トリス（２，３−ジブロモプロピル）イソシアヌレートの水分散体をトリス（２，３−ジブロモプロピル）イソシアヌレート１００重量部に対する上記芳香脂肪族有機リン酸エステルの割合が１００重量部となるように混合して、不揮発分４０％（難燃剤濃度３７％）の水分散型の難燃加工剤Ａを得た。
(Manufacture of flame retardant finishing agent A)
An aqueous dispersion of the 5,5-dimethyl-2- (2-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide and an aqueous dispersion of the tris (2,3-dibromopropyl) isocyanurate The body was mixed so that the ratio of the araliphatic organophosphate to 100 parts by weight of tris (2,3-dibromopropyl) isocyanurate was 100 parts by weight, and the nonvolatile content was 40% (flame retardant concentration 37%) Water-dispersible flame retardant finishing agent A was obtained.
実施例Ｉ−２
（難燃加工剤Ｂの製造）
実施例Ｉ−１においてそれぞれ製造した前記芳香脂肪族有機リン酸エステルの水分散体とトリス（２，３−ジブロモプロピル）イソシアヌレートの水分散体をトリス（２，３−ジブロモプロピル）イソシアヌレート１００重量部に対する前記芳香脂肪族有機リン酸エステルの割合が４０重量部となるように混合して、不揮発分４０％（難燃剤濃度３７％）の水分散型の難燃加工剤Ｂを得た。
Example I-2
(Manufacture of flame retardant finishing agent B)
Tris (2,3-dibromopropyl) isocyanurate was prepared by mixing an aqueous dispersion of the araliphatic organic phosphate ester prepared in Example I-1 and an aqueous dispersion of tris (2,3-dibromopropyl) isocyanurate, respectively. Mixing was performed so that the ratio of the araliphatic organophosphate to 40 parts by weight was 40 parts by weight to obtain a water-dispersed flame retardant B having a nonvolatile content of 40% (flame retardant concentration: 37%).
実施例Ｉ−３
（難燃加工剤Ｃの製造）
実施例Ｉ−１においてそれぞれ製造した前記芳香脂肪族有機リン酸エステルの水分散体とトリス（２，３−ジブロモプロピル）イソシアヌレートの水分散体をトリス（２，３−ジブロモプロピル）イソシアヌレート１００重量部に対する前記芳香脂肪族有機リン酸エステルの割合が７０重量部となるように混合して、不揮発分４０％（難燃剤濃度３７％）の水分散型の難燃加工剤Ｃを得た。
Example I-3
(Manufacture of flame retardant finishing agent C)
Tris (2,3-dibromopropyl) isocyanurate was prepared by mixing an aqueous dispersion of the araliphatic organic phosphate ester prepared in Example I-1 and an aqueous dispersion of tris (2,3-dibromopropyl) isocyanurate, respectively. Mixing was performed so that the ratio of the araliphatic organophosphate to 70 parts by weight was 70 parts by weight to obtain a water-dispersed flame retardant C having a nonvolatile content of 40% (flame retardant concentration: 37%).
実施例Ｉ−４
（難燃加工剤Ｄの製造）
実施例Ｉ−１においてそれぞれ製造した前記芳香脂肪族有機リン酸エステルの水分散体とトリス（２，３−ジブロモプロピル）イソシアヌレートの水分散体をトリス（２，３−ジブロモプロピル）イソシアヌレート１００重量部に対する前記芳香脂肪族有機リン酸エステルの割合が１４０重量部となるように混合して、不揮発分４０％（難燃剤濃度３７％）の水分散型の難燃加工剤Ｄを得た。
Example I-4
(Manufacture of flame retardant finishing agent D)
Tris (2,3-dibromopropyl) isocyanurate was prepared by mixing an aqueous dispersion of the araliphatic organic phosphate ester prepared in Example I-1 and an aqueous dispersion of tris (2,3-dibromopropyl) isocyanurate, respectively. Mixing was performed so that the ratio of the araliphatic organophosphate to 140 parts by weight was 140 parts by weight to obtain a water-dispersed flame-retardant processing agent D having a nonvolatile content of 40% (flame retardant concentration: 37%).
実施例Ｉ−５
（難燃加工剤Ｅの製造）
実施例Ｉ−１においてそれぞれ製造した前記芳香脂肪族有機リン酸エステルの水分散体とトリス（２，３−ジブロモプロピル）イソシアヌレートの水分散体をトリス（２，３−ジブロモプロピル）イソシアヌレート１００重量部に対する前記芳香脂肪族有機リン酸エステルの割合が２７０重量部となるように混合して、不揮発分４０％（難燃剤濃度３７％）の水分散型の難燃加工剤Ｅを得た。
Example I-5
(Manufacture of flame retardant finishing agent E)
Tris (2,3-dibromopropyl) isocyanurate was prepared by mixing an aqueous dispersion of the araliphatic organic phosphate ester prepared in Example I-1 and an aqueous dispersion of tris (2,3-dibromopropyl) isocyanurate, respectively. Mixing was performed so that the ratio of the araliphatic organophosphate to 270 parts by weight was 270 parts by weight to obtain a water-dispersed flame retardant E having a nonvolatile content of 40% (flame retardant concentration: 37%).
比較例Ｉ−１
（難燃加工剤ａの製造）
実施例Ｉ−１においてそれぞれ製造した前記芳香脂肪族有機リン酸エステルの水分散体とトリス（２，３−ジブロモプロピル）イソシアヌレートの水分散体をトリス（２，３−ジブロモプロピル）イソシアヌレート１００重量部に対する前記芳香脂肪族有機リン酸エステルの割合が２０重量部となるように混合して、不揮発分４０％（難燃剤濃度３７％）の水分散型の難燃加工剤ａを得た。
Comparative Example I-1
(Manufacture of flame retardant finishing agent a)
Tris (2,3-dibromopropyl) isocyanurate was prepared by mixing an aqueous dispersion of the araliphatic organic phosphate ester prepared in Example I-1 and an aqueous dispersion of tris (2,3-dibromopropyl) isocyanurate, respectively. Mixing was performed so that the ratio of the araliphatic organic phosphate to 20 parts by weight was 20 parts by weight to obtain a water-dispersed flame retardant processing agent a having a nonvolatile content of 40% (flame retardant concentration: 37%).
比較例Ｉ−２
（難燃加工剤ｂの製造）
実施例Ｉ−１においてそれぞれ製造した前記芳香脂肪族有機リン酸エステルの水分散体とトリス（２，３−ジブロモプロピル）イソシアヌレートの水分散体をトリス（２，３−ジブロモプロピル）イソシアヌレート１００重量部に対する前記芳香脂肪族有機リン酸エステルの割合が４００重量部となるように混合して、不揮発分４０％（難燃剤濃度３７％）の水分散型の難燃加工剤ｂを得た。
Comparative Example I-2
(Manufacture of flame retardant finishing agent b)
Tris (2,3-dibromopropyl) isocyanurate was prepared by mixing an aqueous dispersion of the araliphatic organic phosphate ester prepared in Example I-1 and an aqueous dispersion of tris (2,3-dibromopropyl) isocyanurate, respectively. Mixing was performed so that the ratio of the araliphatic organophosphate to 400 parts by weight was 400 parts by weight to obtain a water-dispersed flame retardant processing agent b having a nonvolatile content of 40% (flame retardant concentration: 37%).
比較例Ｉ−３
（難燃加工剤ｃの製造）
難燃剤として１，２，５，６，９，１０−ヘキサブロモシクロドデカン４０重量部、界面活性剤としてジスチレン化フェノールエチレンオキサイド１０モル付加物２重量部、トリスチレン化フェノールエチレンオキサイド１０モル付加物の硫酸エステルのアンモニウム塩１重量部とシリコーン系消泡剤０．１重量部を水３０重量部と混合し、これを０．８ｍｍのガラスビーズを充填したミルに仕込み、上記難燃剤の平均粒子径がレーザー回折式粒度分布測定装置で測定して１．０μｍとなるまで粉砕し、１０５℃の温度で３０分乾燥させたときの不揮発分が４０％（難燃剤濃度３７％）となるように水で希釈して、上記難燃剤を含む水分散型の難燃加工剤ｃを得た。
Comparative Example I-3
(Manufacture of flame retardant finishing agent c)
40 parts by weight of 1,2,5,6,9,10-hexabromocyclododecane as a flame retardant, 2 parts by weight of distyrenated phenol ethylene oxide 10 mol adduct as a surfactant, 10 mol of tristyrenated phenol ethylene oxide adduct 1 part by weight of an ammonium sulfate ester and 0.1 part by weight of a silicone-based antifoaming agent are mixed with 30 parts by weight of water and charged in a mill filled with 0.8 mm glass beads. Grinding until the diameter is 1.0 μm as measured with a laser diffraction particle size distribution analyzer and dried at a temperature of 105 ° C. for 30 minutes so that the non-volatile content is 40% (flame retardant concentration 37%). Dilution with water gave a water-dispersed flame retardant c containing the above flame retardant.
II．ポリエステル繊維系繊維品の難燃加工（その１−ポリエステル系繊維品がポリエステル紡績糸を含む布帛である場合） II. Flame-retardant processing of polyester fiber products (when the 1-polyester fiber product is a fabric containing polyester spun yarn)
実施例II−１
経糸としてフルダルポリエステル繊維からなる５６デシテックス１８フィラメントのポリエステル繊維を用い、緯糸としてフルダルポリエステル繊維からなるポリエステル紡績糸を用いて、密度縦１３０本／２．５４ｃｍ×横７０本／２．５４ｃｍ、平織りとした織物に通常の方法によって精練、プレセットを施して、ポリエステル系紡績糸の混率３３％の試料ポリエステル繊維布帛１とした。
Example II-1
Using warp yarns of 56 dtex 18 filaments made of full dull polyester fibers and polyester spun yarns made of full dull polyester fibers as weft yarns, density longitudinal 130 / 2.54 cm × width 70 / 2.54 cm, plain weave The woven fabric was scoured and pre-set by a conventional method to obtain a sample polyester fiber fabric 1 having a polyester spun yarn mixing ratio of 33%.
上記試料ポリエステル繊維布帛１を本発明による難燃加工剤Ａを用いて、以下に示すように、浴中処理によって染色と同時に難燃加工して、難燃加工ポリエステル繊維布帛を得た。 The sample polyester fiber fabric 1 was flame-retardant processed simultaneously with dyeing by a treatment in a bath using the flame-retardant processing agent A according to the present invention to obtain a flame-retardant processed polyester fiber fabric.
（難燃加工方法）
分散染料（Ｄｉａｎｉｘ Ｂｌａｃｋ ＣＣ−Ｒ）１．５％ｏｗｆと本発明による難燃加工剤を難燃剤に換算して３．０％ｏｗｆ用い、浴比１：１５にて試料ポリエステル繊維布帛ａを染浴に投入し、染浴を氷酢酸でｐＨ３．５〜５．０に調整した。
(Flame retardant processing method)
The sample polyester fiber fabric a is dyed at a bath ratio of 1:15 using a disperse dye (Dianix Black CC-R) of 1.5% owf and a flame retardant processing agent according to the present invention in terms of a flame retardant of 3.0% owf. The bath was poured and the dyeing bath was adjusted to pH 3.5-5.0 with glacial acetic acid.
染浴を６０℃から毎分２℃の昇温速度で１３０℃まで昇温し、その温度で６０分間保持した後、毎分３℃の降温速度で６０℃まで冷却した。この後、無水炭酸ナトリウム１ｇ／Ｌ、ノニオン系精練剤１ｇ／Ｌを溶解させた温湯を用いて、８０℃で１５分間ソーピングした。次いで、６０℃で１０分間湯洗いした後、５分間水洗し、乾燥後、１７０℃で１分間熱処理を行い、染色と同時に難燃加工して、難燃加工ポリエステル繊維布帛を得た。 The dye bath was heated from 60 ° C. to 130 ° C. at a rate of 2 ° C./min, held at that temperature for 60 minutes, and then cooled to 60 ° C. at a rate of 3 ° C./min. Thereafter, soaping was performed at 80 ° C. for 15 minutes using hot water in which 1 g / L of anhydrous sodium carbonate and 1 g / L of a nonionic scouring agent were dissolved. Next, after washing with hot water at 60 ° C. for 10 minutes, washing with water for 5 minutes, drying, heat treatment at 170 ° C. for 1 minute, and flame-retardant processing at the same time as dyeing, a flame-retardant polyester fiber fabric was obtained.
実施例II−２
実施例II−１において、本発明による難燃加工剤Ａに代えて、本発明による難燃加工剤Ｂを用いた以外は、同様にして、難燃加工ポリエステル繊維布帛を得た。
Example II-2
In Example II-1, a flame retardant polyester fiber fabric was obtained in the same manner except that the flame retardant processing agent B according to the present invention was used instead of the flame retardant processing agent A according to the present invention.
実施例II−３
実施例II−１において、本発明による難燃加工剤Ａに代えて、本発明による難燃加工剤Ｃを用いた以外は、同様にして、難燃加工ポリエステル繊維布帛を得た。
Example II-3
In Example II-1, a flame retardant polyester fiber fabric was obtained in the same manner except that the flame retardant processing agent C according to the present invention was used instead of the flame retardant processing agent A according to the present invention.
実施例II−４
実施例II−１において、本発明による難燃加工剤Ａに代えて、本発明による難燃加工剤Ｄを用いた以外は、同様にして、難燃加工ポリエステル繊維布帛を得た。
Example II-4
In Example II-1, a flame retardant polyester fiber fabric was obtained in the same manner except that the flame retardant processing agent D according to the present invention was used instead of the flame retardant processing agent A according to the present invention.
実施例II−５
実施例II−１において、本発明による難燃加工剤Ａに代えて、本発明による難燃加工剤Ｅを用いた以外は、同様にして、難燃加工ポリエステル繊維布帛を得た。
Example II-5
In Example II-1, a flame retardant polyester fiber fabric was obtained in the same manner except that the flame retardant processing agent E according to the present invention was used instead of the flame retardant processing agent A according to the present invention.
比較例II−１
実施例II−１において、本発明による難燃加工剤Ａに代えて、比較例による難燃加工剤ａを用いた以外は、同様にして、難燃加工ポリエステル繊維布帛を得た。
Comparative Example II-1
In Example II-1, a flame retardant polyester fiber fabric was obtained in the same manner except that the flame retardant agent a according to the comparative example was used in place of the flame retardant agent A according to the present invention.
比較例II−２
実施例II−１において、本発明による難燃加工剤Ａに代えて、比較例による難燃加工剤ｂを用いた以外は、同様にして、難燃加工ポリエステル繊維布帛を得た。
Comparative Example II-2
In Example II-1, a flame retardant polyester fiber fabric was obtained in the same manner except that the flame retardant processing agent b according to the comparative example was used instead of the flame retardant processing agent A according to the present invention.
比較例II−３
実施例II−１において、本発明による難燃加工剤Ａに代えて、比較例による難燃加工剤ｃを用いた以外は、同様にして、難燃加工ポリエステル繊維布帛を得た。
Comparative Example II-3
In Example II-1, a flame retardant polyester fiber fabric was obtained in the same manner except that the flame retardant processing agent c according to the comparative example was used in place of the flame retardant processing agent A according to the present invention.
比較例II−４
実施例II−１において、本発明による難燃加工剤Ａに代えて、比較例による難燃加工剤１を用いた以外は、同様にして、難燃加工ポリエステル繊維布帛を得た。
Comparative Example II-4
In Example II-1, a flame retardant polyester fiber fabric was obtained in the same manner except that the flame retardant processing agent 1 according to the comparative example was used in place of the flame retardant processing agent A according to the present invention.
比較例II−５
実施例II−１において、本発明による難燃加工剤Ａに代えて、比較例による難燃加工剤２を用いた以外は、同様にして、難燃加工ポリエステル繊維布帛を得た。
Comparative Example II-5
In Example II-1, a flame retardant polyester fiber fabric was obtained in the same manner except that the flame retardant processing agent 2 according to the comparative example was used instead of the flame retardant processing agent A according to the present invention.
上記実施例II−１〜II−５及び比較例II−１〜II−５において得た難燃加工ポリエステル繊維布帛のそれぞれについて、下記のようにして、難燃剤の付着量、初期（水洗濯及びドライクリーニングする前）の難燃性能、水洗濯及びドライクリーニング後の難燃性能を測定した。結果を表１に示す。 For each of the flame retardant processed polyester fiber fabrics obtained in Examples II-1 to II-5 and Comparative Examples II-1 to II-5, the amount of flame retardant adhered, and the initial (water washing and washing) The flame retardant performance before dry cleaning) and the flame retardant performance after water washing and dry cleaning were measured. The results are shown in Table 1.
（難燃剤の付着量）
上記実施例II−１〜II−５及び比較例II−１〜II−５の難燃加工における難燃剤の付着量は、次のようにして求めた。
(Amount of flame retardant attached)
The adhesion amount of the flame retardant in the flame retardant processing of Examples II-1 to II-5 and Comparative Examples II-1 to II-5 was determined as follows.
即ち、一般に、難燃加工において、染色を同時に行わないとき、難燃加工前の被処理布帛の重量をＷ０、難燃加工した処理布帛の重量をＷとすれば、難燃加工前後の布帛の重量変化率ΔＷが難燃剤の付着量Ｒである。従って、難燃剤の付着量Ｒは、式 That is, generally, in the flame retardant processing, when dyeing is not performed at the same time, if the weight of the treated fabric before the flame retardant processing is W 0 and the weight of the treated fabric subjected to the flame retardant processing is W, the fabric before and after the flame retardant processing The weight change rate ΔW of the flame retardant is R. Therefore, the adhesion amount R of the flame retardant is given by the formula
Ｒ＝ΔＷ＝［（Ｗ−Ｗ０）／Ｗ０］×１００ （％） R = ΔW = [(W−W 0 ) / W 0 ] × 100 (%)
から求められる。 It is requested from.
上記実施例II−１〜II−５及び比較例II−１〜II−５の難燃加工においては、難燃加工と同時に染色を行ったので、難燃剤の付着量Ｒは、染色処理のみによる重量変化率ｗ（％）を別に求めて、下記式 In the flame retardant processing of Examples II-1 to II-5 and Comparative Examples II-1 to II-5, since the dyeing was performed at the same time as the flame retardant processing, the adhesion amount R of the flame retardant is based only on the dyeing process. Calculate the weight change rate w (%) separately,
Ｒ＝ΔＷ−ｗ （％） R = ΔW−w (%)
から求めた。 I asked for it.
（難燃性能試験）
難燃性能は、ＪＩＳ Ｌ １０９１ Ａ−１法（ミクロバーナー法）とＪＩＳ Ｌ １０９１ Ｄ法（コイル法）にて評価した。ミクロバーナー法においては、１分間加熱試験、着炎３秒加熱試験共に残炎が３秒以内、残塵が５秒以内、炭化面積が３０ｃｍ２以内のときを○とし、これらの条件に満たないときを×とした。コイル法においては、接炎回数が３回以上であれば、難燃性能にすぐれるといえる。
(Flame retardant performance test)
The flame retardancy was evaluated by the JIS L 1091 A-1 method (micro burner method) and the JIS L 1091 D method (coil method). In the micro-burner method, both the 1-minute heating test and the flame-setting 3 second heating test indicate that the after flame is within 3 seconds, the residual dust is within 5 seconds, and the carbonized area is within 30 cm 2 , and these conditions are not satisfied. Time was marked with x. In the coil method, if the number of times of flame contact is 3 or more, it can be said that the flame retardancy is excellent.
（水洗濯）
ＪＩＳ Ｋ ３３７１に従って、弱アルカリ性第１種洗剤を１ｇ／Ｌの割合で用い、浴比１：４０として、６０±２℃で１５分間水洗濯した後、４０±２℃で５分間の濯ぎを３回行い、遠心脱水を２分間行い、その後、６０℃±５℃で熱風乾燥する処理を１サイクルとして、これを５サイクル行った。
(Water washing)
According to JIS K 3371, a weak alkaline first-class detergent was used at a rate of 1 g / L, and a bath ratio of 1:40 was washed with water at 60 ± 2 ° C. for 15 minutes, and then rinsed at 40 ± 2 ° C. for 5 minutes. This was repeated for 5 minutes, followed by centrifugal dehydration for 2 minutes, followed by hot air drying at 60 ° C. ± 5 ° C. for one cycle.
（ドライクリーニング（ＤＣ））
試料１ｇにつき、テトラクロロエチレン１２．６ｍＬ、チャージソープ０．２６５ｇ（チャージソープの重量組成はノニオン系界面活性剤（ノニルフェニルエーテルのエチレンオキサイド１０モル付加物）／アニオン系界面活性剤（ジオクチルコハク酸ナトリウム塩）／水＝１０／１０／１）を用いて、３０±２℃で１５分間クリーニングする処理を１サイクルとして、これを５サイクル行った。
(Dry cleaning (DC))
1 g of sample, 12.6 mL of tetrachloroethylene, 0.265 g of charge soap (weight composition of charge soap is nonionic surfactant (10 mol adduct of nonylphenyl ether ethylene oxide) / anionic surfactant (sodium dioctyl succinate) ) / Water = 10/10/1), and the process of cleaning at 30 ± 2 ° C. for 15 minutes was defined as one cycle, and this was performed for 5 cycles.
実施例II−１〜II−５に示すように、本発明による難燃加工剤を用いてポリエステル紡績糸を含むポリエステル繊維布帛を難燃加工することによって、そのポリエステル繊維布帛に耐久性のあるすぐれた難燃性を付与することができる。 As shown in Examples II-1 to II-5, a polyester fiber fabric containing polyester spun yarn is flame retardant processed using the flame retardant processing agent according to the present invention, whereby the polyester fiber fabric has excellent durability. Flame retardancy can be imparted.
しかし、比較例II−１とII−２に示すように、難燃剤である５，５−ジメチル−２−（２−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドを本発明で規定する範囲外の割合で含む難燃加工剤を用いても、ポリエステル繊維布帛に十分な難燃性を付与することはできない。また、比較例II−４と比較例II−５に示すように、５，５−ジメチル−２−（２−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドとトリス（２，３−ジブロモプロピル）イソシアヌレートのうちの一方のみを難燃剤として含む難燃加工剤を用いても、ポリエステル繊維布帛に十分な難燃性を付与することができない。 However, as shown in Comparative Examples II-1 and II-2, the flame retardant 5,5-dimethyl-2- (2-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide Even if the flame retardant processing agent contained at a ratio outside the range defined in the present invention is used, sufficient flame retardancy cannot be imparted to the polyester fiber fabric. Further, as shown in Comparative Example II-4 and Comparative Example II-5, 5,5-dimethyl-2- (2-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide and tris ( Even if a flame retardant processing agent containing only one of 2,3-dibromopropyl) isocyanurate as a flame retardant is used, sufficient flame retardancy cannot be imparted to the polyester fiber fabric.
比較例II−３は、難燃剤としてＨＢＣＤを含む難燃加工剤を用いて、ポリエステル繊維布帛を難燃加工したものである。比較例II−３の結果を実施例II−１〜II−５の難燃加工と比較すれば明らかなように、本発明の難燃加工によれば、ＨＢＣＤを用いる難燃加工よりも、すぐれた難燃性をポリエステル繊維布帛に付与することができる。 In Comparative Example II-3, a polyester fiber fabric is flame-retardant processed using a flame retardant processing agent containing HBCD as a flame retardant. As is clear when the results of Comparative Example II-3 are compared with the flame retardant processing of Examples II-1 to II-5, the flame retardant processing of the present invention is superior to the flame retardant processing using HBCD. Flame retardancy can be imparted to the polyester fiber fabric.
III．ポリエステル繊維系繊維品の難燃加工（その２−ポリエステル系繊維品がカチオン可染ポリエステル繊維を含む布帛である場合） III. Flame-retardant processing of polyester fiber products (when the 2-polyester fabric is a fabric containing cationic dyeable polyester fibers)
実施例III−１
経糸としてカチオン可染ポリエステル繊維からなる８４デシテックス３６フィラメントのポリエステル繊維を用い、緯糸として黒原着ポリエステル繊維からなる１６７デシテックス４８フィラメントのポリエステル繊維を用いて、密度縦３６０本／２．５４ｃｍ×横１００本／２．５４ｃｍ、両面朱子織とした織物に通常の方法によって精練、プレセットを施して、カチオン可染ポリエステル混織布帛の混率５７．６％の試料ポリエステル繊維布帛２とした。
Example III-1
Using warp yarn polyester fiber of 84 dtex 36 filament made of cationic dye polyester fiber and polyester fiber of 167 dtex 48 filament made of black original polyester fiber as weft yarn, density length 360 / 2.54 cm x width 100 A sample polyester fiber fabric 2 having a mixture ratio of 57.6% of the cationic dyeable polyester blend fabric was obtained by scouring and pre-setting the woven fabric made of /2.54 cm, double-sided satin weave by a usual method.
上記試料ポリエステル繊維布帛２を本発明による難燃加工剤Ａを用いて、以下に示すように、浴中処理によって染色と同時に難燃加工して、難燃加工ポリエステル繊維布帛を得た。 As shown below, the sample polyester fiber fabric 2 was flame-retardant processed simultaneously with dyeing by a treatment in a bath using the flame-retardant processing agent A according to the present invention to obtain a flame-retardant processed polyester fiber fabric.
（難燃加工方法）
分散染料（Ｄｉａｎｉｘ Ｂｌａｃｋ ＣＣ−Ｒ）１．５％ｏｗｆと本発明による難燃加工剤を難燃剤に換算して３．６％ｏｗｆ用い、浴比１：１５にて試料ポリエステル繊維布帛１を染浴に投入し、染浴を氷酢酸でｐＨ３．５〜５．０に調整した。
(Flame retardant processing method)
Sample polyester fiber fabric 1 is dyed at a bath ratio of 1:15 using a disperse dye (Dianix Black CC-R) of 1.5% owf and the flame retardant processing agent according to the present invention in terms of a flame retardant of 3.6% owf. The bath was poured and the dyeing bath was adjusted to pH 3.5-5.0 with glacial acetic acid.
染浴を６０℃から毎分２℃の昇温温度で１３０℃まで昇温し、その温度で６０分間保持した後、６０℃まで毎分３℃の降温速度で冷却した。この後、無水炭酸ナトリウム２ｇ／Ｌ、ノニオン系精練剤２ｇ／Ｌを溶解させた温湯を用いて、８０℃で１５分間ソーピングした。次いで、６０℃１０分間湯洗いした後、５分間水洗し、乾燥後、１７０℃で１分間熱処理を行い、染色と同時に難燃加工して、難燃加工ポリエステル繊維布帛を得た。 The dye bath was heated from 60 ° C. to 130 ° C. at a temperature rising temperature of 2 ° C. per minute, held at that temperature for 60 minutes, and then cooled to 60 ° C. at a temperature decreasing rate of 3 ° C. per minute. Thereafter, soaping was performed at 80 ° C. for 15 minutes using hot water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of a nonionic scouring agent were dissolved. Next, after washing with hot water at 60 ° C. for 10 minutes, washing with water for 5 minutes, drying, heat treatment at 170 ° C. for 1 minute, and flame-retardant processing at the same time as dyeing, a flame-retardant polyester fiber fabric was obtained.
実施例III−２
実施例III−１において、本発明による難燃加工剤Ａに代えて、本発明による難燃加工剤Ｂを用いた以外は、同様にして、本発明による難燃加工ポリエステル繊維布帛を得た。
Example III-2
In Example III-1, a flame retardant processed polyester fiber fabric according to the present invention was obtained in the same manner except that the flame retardant finish B according to the present invention was used instead of the flame retardant finish A according to the present invention.
実施例III−３
実施例III−１において、本発明による難燃加工剤Ａに代えて、本発明による難燃加工剤Ｅを用いた以外は、同様にして、本発明による難燃加工ポリエステル繊維布帛を得た。
Example III-3
In Example III-1, a flame retardant processed polyester fiber fabric according to the present invention was obtained in the same manner except that the flame retardant processing agent E according to the present invention was used instead of the flame retardant processing agent A according to the present invention.
比較例III−１
実施例III−１において、本発明による難燃加工剤Ａに代えて、比較例による難燃加工剤ａを用いた以外は、同様にして、比較例による難燃加工ポリエステル繊維布帛を得た。
Comparative Example III-1
In Example III-1, a flame retardant processed polyester fiber fabric according to a comparative example was obtained in the same manner except that the flame retardant processing agent a according to a comparative example was used instead of the flame retardant processing agent A according to the present invention.
比較例III−２
実施例III−１において、本発明による難燃加工剤Ａに代えて、比較例による難燃加工剤ｂを用いた以外は、同様にして、比較例による難燃加工ポリエステル繊維布帛を得た。
Comparative Example III-2
In Example III-1, a flame retardant processed polyester fiber fabric according to a comparative example was obtained in the same manner except that the flame retardant processing agent b according to the comparative example was used instead of the flame retardant processing agent A according to the present invention.
比較例III−３
実施例III−１において、本発明による難燃加工剤Ａに代えて、比較例による難燃加工剤ｃを用いた以外は、同様にして、比較例による難燃加工ポリエステル繊維布帛を得た。
Comparative Example III-3
In Example III-1, a flame-retardant processed polyester fiber fabric according to a comparative example was obtained in the same manner except that the flame-retardant processing agent c according to the comparative example was used instead of the flame-retardant processing agent A according to the present invention.
上記実施例II−１〜II−３及び比較例II−１〜３において得た難燃加工ポリエステル繊維布帛のそれぞれについて、前述したと同様にして、難燃剤の付着量、初期の難燃性能、水洗濯及びドライクリーニング後の難燃性能を測定した。結果を表２に示す。 For each of the flame retardant processed polyester fiber fabrics obtained in Examples II-1 to II-3 and Comparative Examples II-1 to III, as described above, the amount of flame retardant attached, the initial flame retardant performance, Flame retardant performance after water washing and dry cleaning was measured. The results are shown in Table 2.
実施例III−１〜III−３を比較例III−３と比較すれば明らかなように、本発明による難燃加工剤を用いて、カチオン可染ポリエステル繊維を含むポリエステル繊維布帛を難燃加工することによって、ＨＢＣＤを用いる難燃加工と同等か、又はよりすぐれた難燃性をポリエステル繊維布帛に付与することができる。 As is clear when Examples III-1 to III-3 are compared with Comparative Example III-3, a flame retardant processing of a polyester fiber fabric containing a cationic dyeable polyester fiber is performed using the flame retardant processing agent according to the present invention. By this, it is possible to impart a flame retardancy equal to or better than the flame retardant processing using HBCD to the polyester fiber fabric.
しかし、比較例III−１とIII−２に示すように、５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドとトリス（２，３−ジブロモプロピル）イソシアヌレートを本発明で規定する範囲外の割合で含む難燃加工剤を用いても、ポリエステル繊維布帛に十分な難燃性を付与することはできない。 However, as shown in Comparative Examples III-1 and III-2, 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide and tris (2 , 3-dibromopropyl) isocyanurate cannot be imparted to the polyester fiber fabric with sufficient flame retardancy even when a flame retardant containing a ratio outside the range specified in the present invention is used.
IV．ポリエステル繊維系繊維品の難燃加工（その３−難燃加工剤と共に硬仕上げ剤を併用してポリエステル系繊維品を難燃硬仕上げ加工する場合） IV. Flame Retardant Processing of Polyester Fiber-Based Fiber Products (Part 3-When Flame Retardant Hard Finishing of Polyester Fiber Products Using a Hard Finishing Agent Together with a Flame Retardant)
実施例IV−１
経糸としてレギュラーポリエステル繊維からなる１８０デシテックス８４フィラメントのポリエステル繊維を用い、緯糸としてレギュラーポリエステル繊維からなる３５５デシテックス１２０フィラメントのポリエステル繊維を用いて、密度縦１２０本／２．５４ｃｍ×横５１本／２．５４ｃｍ、平織とした織物に通常の方法によって精練、プレセットを施して、試料ポリエステル繊維布帛３とし、分散染料（Ｄｉａｎｉｘ Ｂｌａｃｋ ＣＣ−Ｒ）３．０％ｏｗｆを用いて染色して、被処理ポリエステル繊維布帛とした。これを以下に示すように難燃硬仕上げ加工して、本発明による難燃加工ポリエステル系繊維品を得た。
Example IV-1
A polyester fiber of 180 dtex 84 filament made of regular polyester fiber is used as the warp, and a polyester fiber of 355 dtex 120 filament made of regular polyester fiber is used as the weft, and the density is 120 in length / 2.54 cm × 51 in width / 2. 54cm, plain woven fabric is scoured and pre-set by the usual method to make a sample polyester fiber fabric 3, dyed with 3.0% owf of disperse dye (Dianix Black CC-R), treated polyester A fiber fabric was obtained. This was subjected to a flame retardant hard finish as shown below to obtain a flame retardant polyester fiber product according to the present invention.
（難燃硬仕上げ方法）
硬仕上げ剤としてポリエステル樹脂水分散体（互応化学工業（株）製プラスコートＲＺ−５７０、固形分２５％、樹脂被膜の鉛筆硬度４Ｈ）５０重量％と難燃加工剤Ａ５重量％と水４５重量％とからなる難燃硬仕上げ処理液をパディング法にて上記被処理ポリエステル繊維布帛にピックアップ８５％にて付着させた。引き続き、１３０℃で３分間乾燥した後、１７０℃で１分間熱処理を行って、難燃硬仕上げポリエステル繊維布帛を得た。
(Flame-retardant hard finishing method)
Polyester resin water dispersion (Plus Coat RZ-570, solid content 25%, resin film pencil hardness 4H) 50% by weight, flame retardant processing agent A 5% by weight and water 45% as a hard finish % Flame retardant hard finishing treatment liquid was adhered to the treated polyester fiber fabric by a padding method with a pickup of 85%. Subsequently, after drying at 130 ° C. for 3 minutes, heat treatment was performed at 170 ° C. for 1 minute to obtain a flame-retardant hard-finished polyester fiber fabric.
実施例IV−２
実施例IV−１において、本発明による難燃加工剤Ａに代えて、本発明による難燃加工剤Ｃを用いた以外は、同様にして、難燃硬仕上げポリエステル繊維布帛を得た。
Example IV-2
In Example IV-1, a flame-retardant hard-finished polyester fiber fabric was obtained in the same manner except that the flame-retardant processing agent C according to the present invention was used instead of the flame-retardant processing agent A according to the present invention.
実施例IV−３
実施例IV−１において、本発明による難燃加工剤Ａに代えて、本発明による難燃加工剤Ｄを用いた以外は、同様にして、難燃硬仕上げポリエステル繊維布帛を得た。
Example IV-3
In Example IV-1, a flame-retardant hard-finished polyester fiber fabric was obtained in the same manner except that the flame-retardant processing agent D according to the present invention was used instead of the flame-retardant processing agent A according to the present invention.
比較例IV−１
実施例IV−１において、本発明による難燃加工剤を含まない硬仕上げ処理液を用いた以外は、同様にして、硬仕上げポリエステル繊維布帛を得た。
Comparative Example IV-1
In Example IV-1, a hard-finished polyester fiber fabric was obtained in the same manner except that the hard-finishing liquid containing no flame retardant finish according to the present invention was used.
比較例IV−２
実施例IV−１において、本発明による難燃加工剤Ａに代えて、比較例による難燃加工剤２を含む難燃硬仕上げ処理液を用いた以外は、同様にして、難燃硬仕上げポリエステル繊維布帛を得た。
Comparative Example IV-2
In Example IV-1, the flame retardant hard finish polyester was used in the same manner except that the flame retardant finishing liquid containing the flame retardant finish 2 according to the comparative example was used instead of the flame retardant finish A according to the present invention. A fiber fabric was obtained.
比較例IV−３
実施例IV−１において、本発明による難燃加工剤Ａに代えて、比較例による難燃加工剤１を含む難燃硬仕上げ処理液を用いた以外は、同様にして、難燃硬仕上げポリエステル繊維布帛を得た。
Comparative Example IV-3
In Example IV-1, the flame retardant hard finish polyester was used in the same manner except that a flame retardant finishing liquid containing the flame retardant finish 1 according to the comparative example was used instead of the flame retardant finish A according to the present invention. A fiber fabric was obtained.
上記実施例IV−１〜IV−３及び比較例IV−１〜IV−３において得た硬仕上げ又は難燃硬仕上げポリエステル繊維布帛のそれぞれについて、下記のようにして、難燃剤の付着量を求めると共に、前述したと同様にして、初期の難燃性能を測定した。結果を表３に示す。 For each of the hard finish or flame retardant hard finish polyester fiber fabric obtained in Examples IV-1 to IV-3 and Comparative Examples IV-1 to IV-3, the adhesion amount of the flame retardant is determined as follows. In addition, the initial flame retardancy was measured in the same manner as described above. The results are shown in Table 3.
（難燃剤の付着量）
実施例IV−１〜IV−３と比較例IV−１〜IV−３において、被処理ポリエステル繊維布帛に染色処理をした後の重量変化率はいずれも、＋１．１％であった。その後、実施例IV−１〜IV−３及び比較例IV−１〜IV−３においては、上述したように染色処理したポリエステル繊維布帛に対して、硬仕上げ剤と難燃加工剤をパディング法にて同時に付与したので、パディング法による加工前後の布帛の重量変化率から、比較例IV−１におけるように、硬仕上げ剤のみを付与した場合の重量変化率＋１０．５％を減じたものを難燃剤の付着率とした。
(Amount of flame retardant attached)
In Examples IV-1 to IV-3 and Comparative Examples IV-1 to IV-3, the weight change rate after dyeing the treated polyester fiber fabric was + 1.1%. Thereafter, in Examples IV-1 to IV-3 and Comparative Examples IV-1 to IV-3, a hard finish and a flame retardant were used as a padding method for the polyester fiber fabric dyed as described above. Therefore, it is difficult to reduce the weight change rate of the fabric before and after processing by the padding method by subtracting the weight change rate + 0.5% when only the hard finish is applied, as in Comparative Example IV-1. It was set as the adhesion rate of the flame retardant.
実施例IV−１〜IV−３に示すように、本発明による難燃加工剤を用いることによって、ポリエステル繊維布帛にすぐれた難燃性を付与することができる。 As shown in Examples IV-1 to IV-3, excellent flame retardancy can be imparted to the polyester fiber fabric by using the flame retardant processing agent according to the present invention.
しかし、比較例IV−１に示すように、本発明による難燃加工を施さず、硬仕上げ剤を用いる硬仕上げ加工のみを行ったポリエステル繊維布帛は難燃性をもたない。比較例IV−２とIV−３に示すように、トリス（２，３−ジブロモプロピル）イソシアヌレートと５，５−ジメチル−２−（２’−フェニルフェノキシ）−１，３，２−ジオキサホスホリナン−２−オキシドのうちの一方のみを難燃剤として含む難燃加工剤を用いても、ポリエステル繊維布帛に十分な難燃性を付与することができない。 However, as shown in Comparative Example IV-1, a polyester fiber fabric that is not subjected to the flame retardant processing according to the present invention and is subjected only to a hard finishing process using a hard finish does not have flame resistance. As shown in Comparative Examples IV-2 and IV-3, tris (2,3-dibromopropyl) isocyanurate and 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxa Even if a flame retardant processing agent containing only one of phosphorinan-2-oxide as a flame retardant is used, sufficient flame retardancy cannot be imparted to the polyester fiber fabric.
Claims (10)
A flame retardant polyester fiber product obtained by flame retardant processing using the flame retardant processing agent according to claim 1.
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