JP4782480B2 - Flame retardant for polyester fiber - Google Patents
Flame retardant for polyester fiber Download PDFInfo
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- JP4782480B2 JP4782480B2 JP2005179673A JP2005179673A JP4782480B2 JP 4782480 B2 JP4782480 B2 JP 4782480B2 JP 2005179673 A JP2005179673 A JP 2005179673A JP 2005179673 A JP2005179673 A JP 2005179673A JP 4782480 B2 JP4782480 B2 JP 4782480B2
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- surfactant
- flame retardant
- polyester fiber
- flame
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- 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 title claims description 106
- 239000003063 flame retardant Substances 0.000 title claims description 106
- 239000000835 fiber Substances 0.000 title claims description 103
- 229920000728 polyester Polymers 0.000 title claims description 95
- 238000012545 processing Methods 0.000 claims description 72
- 239000003795 chemical substances by application Substances 0.000 claims description 60
- 239000004094 surface-active agent Substances 0.000 claims description 59
- -1 phosphate ester Chemical class 0.000 claims description 48
- 229910019142 PO4 Inorganic materials 0.000 claims description 44
- 239000010452 phosphate Substances 0.000 claims description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 150000003973 alkyl amines Chemical class 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 description 36
- 238000000034 method Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 13
- 238000004945 emulsification Methods 0.000 description 10
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000004043 dyeing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000001804 emulsifying effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 125000006267 biphenyl group Chemical group 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005108 dry cleaning Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- VSXGXPNADZQTGQ-UHFFFAOYSA-N oxirane;phenol Chemical class C1CO1.OC1=CC=CC=C1 VSXGXPNADZQTGQ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000003340 retarding agent Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 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 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000010021 flat screen printing Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000865 phosphorylative effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000010020 roller printing Methods 0.000 description 1
- 238000010022 rotary screen printing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000009976 warp beam dyeing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、耐久性に優れた難燃性をポリエステル繊維に付与し、安定な難燃加工を可能とする難燃加工剤に関する。 The present invention relates to a flame retardant processing agent that imparts flame resistance excellent in durability to polyester fibers and enables stable flame retardant processing.
従来、ポリエステル繊維の耐久難燃加工は、ヘキサブロモシクロドデカンに代表される脂環式ハロゲン化合物を染色浴中又はサーモゾル法にて繊維の内部に浸透させることにより行われていた。しかしながら、ハロゲン化合物により難燃加工されたポリエステル繊維は、燃焼時に人体に有害なガスを発生し、自然環境への有害性が危惧されるといった問題あったため、ハロゲン化合物に代わる難燃成分としてリン系化合物が用いられる様になってきた。例えば、特開平８−２６０３５１号公報（特許文献１）には、特定のリン系化合物と機能性薬剤が繊維表面に付与されている難燃性ポリエステル繊維が開示されており、特定のリン化合物として特定の縮合リン酸エステルが記載されている。しかしながら、特許文献１に記載の縮合リン酸エステルは、染色浴中で安定にエマルジョン化することが困難であるため、難燃性のばらつきが生じ、安定した難燃性が得られないといった問題があった。 Conventionally, durable flame retardant processing of polyester fibers has been performed by infiltrating the interior of the fibers with an alicyclic halogen compound typified by hexabromocyclododecane in a dyeing bath or by a thermosol method. However, the polyester fiber that has been flame-retardant processed with a halogen compound has a problem that it generates gases harmful to the human body during combustion, and there is a concern that it may be harmful to the natural environment. Has come to be used. For example, JP-A-8-260351 (Patent Document 1) discloses a flame retardant polyester fiber in which a specific phosphorus compound and a functional agent are imparted to the fiber surface. Specific condensed phosphate esters are described. However, since the condensed phosphate ester described in Patent Document 1 is difficult to be stably emulsified in a dyeing bath, there is a problem that variation in flame retardancy occurs and stable flame retardancy cannot be obtained. there were.
一方で、染色浴中で安定にエマルジョン化するために、例えば、特開２０００−３２８４４５号公報（特許文献２）には、レゾルシノールビス（ジフェニルホスフェート）を特定の界面活性剤の存在下で乳化分散させて乳化物を調製し、染色と同時に繊維に吸着させるポリエステル系繊維の難燃加工方法が開示されている。また、特開２００２−８８３６８号公報（特許文献３）には、レゾルシノールビス（ジフェニルホスフェート）を特定の非イオン界面活性剤及び／又はアニオン界面活性剤を用いて乳化分散させた難燃加工剤及び難燃加工方法が開示されている。 On the other hand, in order to stably emulsify in a dye bath, for example, JP-A-2000-328445 (Patent Document 2) emulsifies and disperses resorcinol bis (diphenyl phosphate) in the presence of a specific surfactant. A flame retardant processing method for polyester fiber is disclosed in which an emulsion is prepared and adsorbed onto the fiber simultaneously with dyeing. Japanese Patent Laid-Open No. 2002-88368 (Patent Document 3) discloses a flame retardant processing agent in which resorcinol bis (diphenyl phosphate) is emulsified and dispersed using a specific nonionic surfactant and / or anionic surfactant, and A flame retardant processing method is disclosed.
しかしながら、レゾルシノールビス（ジフェニルホスフェート）をこれらの公報に開示されている界面活性剤を用いて乳化分散させた難燃加工剤は、経時での乳化安定性が必ずしも十分とはいえなかった。また、これらの公報に開示されている難燃加工剤を用いて製造された従来の難燃性ポリエステル繊維は、特に洗濯後における難燃性が必ずしも十分といえるものではなかった。
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、経時の乳化安定性に優れ、且つ、ポリエステル繊維に耐久性に優れた難燃性を付与することを可能とするポリエステル繊維用難燃加工剤を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and is a polyester fiber that has excellent emulsification stability over time and can impart flame resistance with excellent durability to the polyester fiber. It aims at providing the flame retardant finishing agent.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、特定のリン酸エステルの乳化分散剤として特定の界面活性剤を用いて乳化分散させることによって、経時の乳化安定性に優れ、且つ、ポリエステル繊維に耐久性に優れた難燃性を付与することを可能とする難燃加工剤が得られるようになることを見出し、この知見に基づいて本発明を完成させた。 As a result of intensive research to solve the above-mentioned problems, the present inventors have improved emulsification stability over time by emulsifying and dispersing using a specific surfactant as an emulsifying dispersant for a specific phosphate ester. The present inventors have found that a flame retardant processing agent capable of imparting excellent flame resistance with excellent durability to a polyester fiber can be obtained, and the present invention has been completed based on this finding.
すなわち、本発明のポリエステル繊維用難燃加工剤は、下記一般式（１）： That is, the flame retardant agent for polyester fibers of the present invention has the following general formula (1):
〔式（１）中、ｐは１又は２を表す。〕
で表されるリン酸エステルが、下記界面活性剤（ｘ１）及び（ｘ３）からなる群より選択される少なくとも１種の界面活性剤を用いて、水中に乳化分散されてなることを特徴とするものである。
＜界面活性剤（ｘ１）＞
下記一般式（２）：
[In formula (1), p represents 1 or 2. ]
The phosphate ester represented by the formula ( 1 ) is characterized by being emulsified and dispersed in water using at least one surfactant selected from the group consisting of the following surfactants (x 1 ) and (x 3 ). It is what.
<Surfactant (x 1)>
The following general formula (2):
〔式（２）中、Ｒ１は炭素数２〜４のアルキレン基を表し、ａは１〜２００の整数を表し、ａが２以上の場合にはＲ１Ｏは同一でも異なっていてもよく、Ｒ１Ｏが２種以上の場合にはランダム付加でも、ブロック付加でもよく、ｍは１〜５の整数を表し、ｋは１又は２を表し、Ｍは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、炭素数１〜２０のアルキルアミン及び炭素数２〜１２のアルカノールアミンからなる群より選択される少なくとも１種を表す。〕
により表される化合物。
＜界面活性剤（ｘ ３ ）＞
下記一般式（４）：
A compound represented by
<Surfactant (x 3)>
The following general formula ( 4 ):
〔式（４）中、Ｒ３は炭素数２〜４のアルキレン基を表し、ｃは１〜２００の整数を表し、ｃが２以上の場合にはＲ３Ｏは同一でも異なっていてもよく、Ｒ３Ｏが２種以上の場合にはランダム付加でも、ブロック付加でもよく、ｓは１〜５の整数を表し、Ｙは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、炭素数１〜２０のアルキルアミン及び炭素数２〜１２のアルカノールアミンからなる群より選択される少なくとも１種を表す。〕
により表される化合物。
[In Formula (4), R 3 represents an alkylene group having 2 to 4 carbon atoms, c represents an integer of 1 to 200, and when c is 2 or more, R 3 O may be the same or different. , When R 3 O is 2 or more, it may be random addition or block addition, s represents an integer of 1 to 5, Y represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, 1 to C 1 It represents at least one selected from the group consisting of 20 alkylamines and alkanolamines having 2 to 12 carbon atoms. ]
A compound represented by
また、本発明のポリエステル繊維用難燃加工剤においては、前記界面活性剤として、界面活性剤（ｘ１）を用いることが好ましい。 In the polyester fibers for flame retarding agent of the present invention, as the surfactant, it is preferable to use a surfactant (x 1).
さらに、本発明のポリエステル繊維用難燃加工剤においては、前記界面活性剤として、界面活性剤（ｘ１）を用い、さらに下記界面活性剤（ｘ２）を用いることが好ましい。
＜界面活性剤（ｘ ２ ）＞
下記一般式（３）：
により表される化合物。
Furthermore, in the flame retardant processing agent for polyester fibers of the present invention, it is preferable to use a surfactant (x 1 ) as the surfactant and further use the following surfactant (x 2 ).
<Surfactant (x 2)>
The following general formula (3):
A compound represented by
また、本発明のポリエステル繊維用難燃加工剤においては、前記界面活性剤として、界面活性剤（ｘ１）及び界面活性剤（ｘ３）を用いることが好ましい。 In the polyester fibers for flame retarding agent of the present invention, as the surfactant, it is preferable to use a surfactant (x 1) and surfactant (x 3).
本発明によれば、経時の乳化安定性に優れ、且つ、ポリエステル繊維に耐久性に優れた難燃性を付与することを可能とするポリエステル繊維用難燃加工剤を提供することが可能となる。また、本発明のポリエステル繊維用難燃加工剤は、ハロゲン原子を含まないため、処理して得られたポリエステル繊維を廃棄焼却するときにも難燃加工剤からのダイオキシンの発生が少なく、環境保護、エコロジーの面からも好ましいものである。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the flame retardant processing agent for polyester fibers which is excellent in the emulsification stability with time, and can provide the flame retardancy excellent in durability to the polyester fiber. . In addition, since the flame retardant processing agent for polyester fibers of the present invention does not contain a halogen atom, the generation of dioxins from the flame retardant processing agent is small even when the polyester fiber obtained by treatment is discarded and incinerated, thereby protecting the environment. It is also preferable from the viewpoint of ecology.
以下、本発明のポリエステル繊維用難燃加工剤をその好適な実施形態に即して詳細に説明する。 Hereinafter, the flame retardant processing agent for polyester fibers of the present invention will be described in detail in line with preferred embodiments thereof.
本発明のポリエステル繊維用難燃加工剤は、後述する一般式（１）で表されるリン酸エステルが、後述する界面活性剤（ｘ１）〜（ｘ３）からなる群より選択される少なくとも１種の界面活性剤を用いて、水中に乳化分散されてなることを特徴とするものである。 The flame retardant processing agent for polyester fiber of the present invention is at least selected from the group consisting of surfactants (x 1 ) to (x 3 ) described later, wherein the phosphate ester represented by the general formula (1) described later. It is characterized by being emulsified and dispersed in water using one kind of surfactant.
本発明に用いられるリン酸エステルは、下記一般式（１）： The phosphate ester used in the present invention has the following general formula (1):
により表される化合物である。 It is a compound represented by these.
一般式（１）において、ｐは１又は２を表す。このようなリン酸エステルとしては、ジフェニルモノオルソキセニルホスフェート、フェニルジオルソキセニルホスフェートが挙げられる。 In general formula (1), p represents 1 or 2. Examples of such phosphoric acid esters include diphenyl monoorthoxenyl phosphate and phenyl diorthoxenyl phosphate.
また、本発明のポリエステル繊維用難燃加工剤においては、難燃加工剤中の固形分の総量に対して、このようなリン酸エステルの含有量が２０〜９０質量％であることが好ましく、３０〜７０質量％であることがより好ましい。このようなリン酸エステルの含有量が前記下限未満では、難燃加工剤の処理量を多くしないと耐久性を満足する良好な難燃性が得られない傾向にあり、他方、前記上限を超えると、難燃加工剤を液状として得ることが困難になり、取扱いが難しくなる傾向にある。さらに、本発明のポリエステル繊維用難燃加工剤中における前記リン酸エステルの乳化分散物の平均粒径としては、ポリエステル繊維への吸着・吸収のし易さの観点から２μｍ以下であることが好ましく、０．５μｍ以下であることがより好ましい。 Moreover, in the flame retardant processing agent for polyester fibers of the present invention, the content of such phosphate ester is preferably 20 to 90% by mass with respect to the total amount of solids in the flame retardant processing agent, It is more preferable that it is 30-70 mass%. If the content of such a phosphate ester is less than the lower limit, good flame retardancy that satisfies the durability tends to be obtained unless the amount of the flame retardant treatment is increased. On the other hand, the content exceeds the upper limit. In such a case, it becomes difficult to obtain the flame retardant finish as a liquid, and the handling tends to be difficult. Furthermore, the average particle diameter of the phosphoric acid ester emulsified dispersion in the flame retardant processing agent for polyester fibers of the present invention is preferably 2 μm or less from the viewpoint of easy adsorption and absorption to the polyester fibers. More preferably, it is 0.5 μm or less.
本発明に用いられる前記界面活性剤は、以下説明する界面活性剤（ｘ１）〜（ｘ３）からなる群より選択される少なくとも１種のものである。 The surfactant used in the present invention is at least one selected from the group consisting of surfactants (x 1 ) to (x 3 ) described below.
界面活性剤（ｘ１）は、下記一般式（２）により表される化合物である。 The surfactant (x 1 ) is a compound represented by the following general formula (2).
一般式（２）において、Ｒ１は炭素数２〜４のアルキレン基を表す。そして、Ｒ１の炭素数が２〜４のアルキレン基としては、例えば、エチレン基、プロピレン基、ブチレン基が挙げられるが、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化分散性）の観点から、エチレン基及びプロピレン基が好ましく、エチレン基が特に好ましい。また、ａは１〜２００の整数を表すが、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化分散性）の観点から５〜３０の整数であることがより好ましい。ａの値が０であっても、２００を超えても、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化安定性）が不良になる。さらに、ａが２以上の場合にはＲ１Ｏは同一でも異なっていてもよく、Ｒ１Ｏが２種以上の場合にはランダム付加でも、ブロック付加でもよい。また、ｍは１〜５の整数を表し、ｋは１又は２を表す。 In the general formula (2), R 1 represents an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms of R 1 include an ethylene group, a propylene group, and a butylene group, and the stability of the emulsion of the phosphate ester represented by the general formula (1). From the viewpoint of (emulsion dispersibility of flame retardant processing agent), ethylene group and propylene group are preferable, and ethylene group is particularly preferable. Moreover, although a represents the integer of 1-200, it is an integer of 5-30 from a viewpoint of the stability (emulsification dispersibility of a flame-retardant processing agent) of the phosphate ester emulsion represented by the said General formula (1). More preferably. Even if the value of a is 0 or exceeds 200, the stability of the emulsion of phosphate ester represented by the general formula (1) (emulsification stability of the flame retardant processing agent) becomes poor. Further, when a is 2 or more, R 1 O may be the same or different, and when R 1 O is 2 or more, random addition or block addition may be used. M represents an integer of 1 to 5, and k represents 1 or 2.
さらに、Ｍは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、炭素数１〜２０のアルキルアミン及び炭素数２〜１２のアルカノールアミンからなる群より選択される少なくとも１種を表す。そして、このようなアルカリ金属としては、リチウム、カリウム、ナトリウム等が挙げられる。また、このようなアルカリ土類金属としては、カルシウム、マグネシウム、バリウム等が挙げられる。さらに、このような炭素数１〜２０のアルキルアミンとしては、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、オクチルアミン、ドデシルアミン、ヘキサデシルアミン、オクタデシルアミン、ジメチルアミン、ジエチルアミン、トリエチルアミン等が挙げられる。また、このような炭素数２〜１２のアルカノールアミンとしては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等が挙げられる。これらの中でも、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化安定性）や難燃性の観点から、Ｍがアンモニウム、炭素数１〜６のアルキルアミン又は炭素数２〜６のアルカノールアミンであることが好ましい。 Further, M represents at least one selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkylamine having 1 to 20 carbon atoms, and an alkanolamine having 2 to 12 carbon atoms. And as such an alkali metal, lithium, potassium, sodium, etc. are mentioned. Examples of such alkaline earth metals include calcium, magnesium, barium and the like. Furthermore, examples of the alkylamine having 1 to 20 carbon atoms include methylamine, ethylamine, propylamine, butylamine, octylamine, dodecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine, and triethylamine. Examples of the alkanolamine having 2 to 12 carbon atoms include monoethanolamine, diethanolamine, and triethanolamine. Among these, M is ammonium and has 1 to 6 carbon atoms from the viewpoint of the stability of the emulsion of the phosphate ester represented by the general formula (1) (emulsion stability of the flame retardant processing agent) and flame retardancy. An alkylamine or an alkanolamine having 2 to 6 carbon atoms is preferable.
このような界面活性剤としては、例えば、スチレン１〜５モルをフェノール１モルに付加させたスチレン化フェノールにアルキレンオキサイドを付加させた化合物と、無水リン酸やオキシ塩化リン等のリン酸化剤とを反応させて得られるリン酸モノエステル又はリン酸ジエステルの塩が挙げられる。これらは、モノエステル単独の塩、ジエステル単独の塩、或いは両者の混合物の塩であるが、一般的にはモノエステルとジエステルの混合物の塩である。 As such a surfactant, for example, a compound obtained by adding alkylene oxide to styrenated phenol obtained by adding 1 to 5 mol of styrene to 1 mol of phenol, and a phosphorylating agent such as phosphoric anhydride or phosphorus oxychloride And salts of phosphoric acid monoesters or phosphoric acid diesters obtained by reacting. These are salts of a monoester alone, a salt of a diester alone, or a salt of a mixture of both, but generally a salt of a mixture of a monoester and a diester.
界面活性剤（ｘ２）は、下記一般式（３）により表される化合物である。 Surfactant (x 2) is a compound represented by the following general formula (3).
一般式（３）において、Ｒ２は炭素数２〜４のアルキレン基を表す。そして、Ｒ２の炭素数が２〜４のアルキレン基としては、例えば、エチレン基、プロピレン基、ブチレン基が挙げられるが、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化分散性）の観点からエチレン基及びプロピレン基が好ましく、エチレン基が特に好ましい。また、ｂは１〜２００の整数を表すが、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化分散性）の観点から５〜３０の整数であることがより好ましい。ｂの値が０であっても、２００を超えても、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化安定性）が不良になる。さらに、ｂが２以上の場合にはＲ２Ｏは同一でも異なっていてもよく、Ｒ２Ｏが２種以上の場合にはランダム付加でも、ブロック付加でもよい。また、ｎは１〜５の整数を表す。 In general formula (3), R 2 represents an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms of R 2 include an ethylene group, a propylene group, and a butylene group. The stability of the phosphate ester emulsion represented by the general formula (1) is described below. From the viewpoint of (emulsion dispersibility of flame retardant processing agent), ethylene group and propylene group are preferable, and ethylene group is particularly preferable. In addition, b represents an integer of 1 to 200, but an integer of 5 to 30 from the viewpoint of the stability of the emulsion of the phosphate ester represented by the general formula (1) (emulsion dispersibility of the flame retardant processing agent). More preferably. Even if the value of b is 0 or exceeds 200, the stability of the emulsion of the phosphate ester represented by the general formula (1) (emulsification stability of the flame retardant processing agent) becomes poor. Furthermore, when b is 2 or more, R 2 O may be the same or different, and when R 2 O is 2 or more, random addition or block addition may be used. N represents an integer of 1 to 5.
このような界面活性剤としては、例えば、スチレン１〜５モルをフェノール１モルに付加させたスチレン化フェノールにアルキレンオキサイドを付加させた化合物が挙げられる。 Examples of such a surfactant include a compound obtained by adding alkylene oxide to styrenated phenol obtained by adding 1 to 5 mol of styrene to 1 mol of phenol.
界面活性剤（ｘ３）は、下記一般式（４）により表される化合物である。 The surfactant (x 3 ) is a compound represented by the following general formula (4).
一般式（４）において、Ｒ３は炭素数２〜４のアルキレン基を表す。そして、Ｒ３の炭素数が２〜４のアルキレン基としては、例えば、エチレン基、プロピレン基、ブチレン基が挙げられるが、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化分散性）の観点からエチレン基及びプロピレン基が好ましく、エチレン基が特に好ましい。また、ｃは１〜２００の整数を表すが、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化分散性）の観点から５〜３０の整数であることがより好ましい。ｃの値が０であっても、２００を超えても、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化安定性）が不良になる。さらに、ａが２以上の場合にはＲ３Ｏは同一でも異なっていてもよく、Ｒ３Ｏが２種以上の場合にはランダム付加でも、ブロック付加でもよい。また、ｍは１〜５の整数を表し、ｋは１又は２を表す。 In the general formula (4), R 3 represents an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms of R 3 include an ethylene group, a propylene group, and a butylene group. The stability of the phosphate ester emulsion represented by the general formula (1) is described below. From the viewpoint of (emulsion dispersibility of flame retardant processing agent), ethylene group and propylene group are preferable, and ethylene group is particularly preferable. Moreover, c represents an integer of 1 to 200, and is an integer of 5 to 30 from the viewpoint of the stability of the emulsion of the phosphate ester represented by the general formula (1) (emulsion dispersibility of the flame retardant processing agent). More preferably. Even if the value of c is 0 or exceeds 200, the stability of the emulsion of phosphate ester represented by the general formula (1) (emulsification stability of the flame retardant processing agent) becomes poor. Furthermore, when a is 2 or more, R 3 O may be the same or different, and when R 3 O is 2 or more, random addition or block addition may be used. M represents an integer of 1 to 5, and k represents 1 or 2.
さらに、Ｙは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、炭素数１〜２０のアルキルアミン及び炭素数２〜１２のアルカノールアミンからなる群より選択される少なくとも１種を表す。そして、このようなアルカリ金属、アルカリ土類金属、アンモニウム、炭素数１〜２０のアルキルアミン及び炭素数２〜１２のアルカノールアミンとしては、一般式（２）中のＭとしてのアルカリ金属、アルカリ土類金属、アンモニウム、炭素数１〜２０のアルキルアミン及び炭素数２〜１２のアルカノールアミンと同様のものが挙げられる。これらの中でも、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化安定性）や難燃性の観点から、Ｙがアンモニウム、炭素数１〜６のアルキルアミン又は炭素数２〜６のアルカノールアミンであることが好ましい。 Y represents at least one selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkylamine having 1 to 20 carbon atoms, and an alkanolamine having 2 to 12 carbon atoms. And as such an alkali metal, alkaline-earth metal, ammonium, a C1-C20 alkylamine, and a C2-C12 alkanolamine, the alkali metal as M in general formula (2), alkaline-earth Examples thereof include the same metals, ammonium, alkylamines having 1 to 20 carbon atoms, and alkanolamines having 2 to 12 carbon atoms. Among these, from the viewpoints of the stability of the emulsion of the phosphate ester represented by the general formula (1) (emulsion stability of the flame retardant processing agent) and flame retardancy, Y is ammonium, and has 1 to 6 carbon atoms. An alkylamine or an alkanolamine having 2 to 6 carbon atoms is preferable.
このような界面活性剤としては、例えば、スチレン１〜５モルをフェノール１モルに付加させたスチレン化フェノールにアルキレンオキサイドを付加させた化合物と、クロルスルホン酸やスルファミン酸等の硫酸化剤とを反応させて得られる硫酸エステルの塩が挙げられる。 As such a surfactant, for example, a compound obtained by adding alkylene oxide to styrenated phenol obtained by adding 1 to 5 mol of styrene to 1 mol of phenol, and a sulfating agent such as chlorosulfonic acid or sulfamic acid are used. Examples thereof include a sulfate ester salt obtained by the reaction.
本発明のポリエステル繊維用難燃加工剤においては、前記界面活性剤（ｘ１）〜（ｘ３）のうち１種のものを単独で用いても２種以上のものを組み合わせて用いてもよく、特に制限されないが、前記一般式（１）で表されるリン酸エステルのエマルジョンの安定性（難燃加工剤の乳化安定性）や難燃性の観点から、前記界面活性剤（ｘ１）を単独で、又は、前記界面活性剤（ｘ１）と前記界面活性剤（ｘ２）との組み合わせ若しくは前記界面活性剤（ｘ１）と前記界面活性剤（ｘ３）との組み合わせで用いることが好ましい。 In the flame-retardant processing agent for polyester fibers of the present invention, one of the surfactants (x 1 ) to (x 3 ) may be used alone, or two or more may be used in combination. The surfactant (x 1 ) is not particularly limited, but from the viewpoint of stability of the phosphate ester emulsion represented by the general formula (1) (emulsion stability of the flame retardant processing agent) and flame retardancy. Is used alone or in combination of the surfactant (x 1 ) and the surfactant (x 2 ) or in combination of the surfactant (x 1 ) and the surfactant (x 3 ). Is preferred.
また、本発明のポリエステル繊維用難燃加工剤においては、前記界面活性剤の使用量は特に制限されないが、前記一般式（１）で表されるリン酸エステル１００質量部に対して１〜５０質量部であることが好ましく、１〜３０質量部であることがより好ましい。前記界面活性剤の使用量が前記下限未満であると、難燃加工剤のエマルジョンの安定性が不良になる傾向にあり、他方、前記上限を超えると、前記一般式（１）で表されるリン酸エステルのポリエステル繊維への吸着率の低下を招き難燃性が低下する傾向にある。 Moreover, in the flame-retardant processing agent for polyester fibers of this invention, the usage-amount of the said surfactant is not restrict | limited in particular, However, 1-50 with respect to 100 mass parts of phosphate ester represented with the said General formula (1). It is preferable that it is a mass part, and it is more preferable that it is 1-30 mass parts. When the amount of the surfactant used is less than the lower limit, the stability of the flame retardant emulsion tends to be poor. On the other hand, when the amount exceeds the upper limit, it is represented by the general formula (1). There exists a tendency for the flame retardant property to fall because the adsorption rate of the phosphate ester to the polyester fiber is lowered.
さらに、前記界面活性剤（ｘ１）は、使用量が多い程前記一般式（１）で表されるリン酸エステルの乳化分散性、染料の分散性に対して有効であるが、一般に泡立ちが大きくなり、泡立ちによりポリエステル繊維への処理の際に弊害もでてくるため、使用する場合には、前記界面活性剤（ｘ１）の使用量が前記一般式（１）で表されるリン酸エステル１００質量部に対して１〜５０質量部であることが好ましい。また、前記界面活性剤（ｘ２）は、使用量が多い程前記一般式（１）で表される縮合リン酸エステルの乳化分散性に対して有効であるが、緩染効果が大きく、染色への弊害も出てくる傾向にあるため、使用する場合には、前記界面活性剤（ｘ２）の使用量が前記一般式（１）で表されるリン酸エステル１００質量部に対して１〜５０質量部であることが好ましい。さらに、前記界面活性剤（ｘ３）は、使用量が多い程前記一般式（１）で表される縮合リン酸エステルの乳化分散性に対して有効であるが、一般に泡立ちが大きくなり、泡立ちによりポリエステル繊維への処理の際に弊害もでてくるため、使用する場合には、前記界面活性剤（ｘ３）の使用量が前記一般式（１）で表されるリン酸エステル１００質量部に対して１〜５０質量部であることが好ましい。 Furthermore, the surfactant (x 1 ) is more effective for the emulsifying dispersibility of the phosphate ester represented by the general formula (1) and the dispersibility of the dye as the amount used is larger. become large, to come out even negative effects during processing to polyester fibers by foaming, if used, phosphoric acid usage is represented by the general formula (1) of the surfactant (x 1) It is preferable that it is 1-50 mass parts with respect to 100 mass parts of ester. The surfactant (x 2 ) is more effective for the emulsifying dispersibility of the condensed phosphate ester represented by the general formula (1) as the amount used is larger, but the effect of slow dyeing is large, and the dyeing is performed. When used, the amount of the surfactant (x 2 ) used is 1 with respect to 100 parts by mass of the phosphate ester represented by the general formula (1). It is preferable that it is -50 mass parts. Furthermore, the surfactant (x 3 ) is more effective for the emulsifying dispersibility of the condensed phosphate ester represented by the general formula (1) as the amount used is larger. Therefore, when used, the amount of the surfactant (x 3 ) used is 100 parts by mass of the phosphate ester represented by the general formula (1). It is preferable that it is 1-50 mass parts with respect to.
本発明において、前記一般式（１）で表されるリン酸エステルを乳化分散させる方法としては、特に限定されないが、例えば、（i）前記一般式（１）で表されるリン酸エステル及び前記界面活性剤（ｘ１）、さらに場合により前記界面活性剤（ｘ２）及び／又は前記界面活性剤（ｘ３）を加えた混合物を撹拌しながら、そこに徐々に水を加えて行くことにより、前記一般式（１）で表されるリン酸エステルを乳化分散させる方法、（ii）前記一般式（１）で表されるリン酸エステル及び前記界面活性剤（ｘ１）、さらに場合により前記界面活性剤（ｘ２）及び／又は前記界面活性剤（ｘ３）を加えた水との混合物を、ホモジナイザー等の乳化分散機を用いて乳化分散して、前記一般式（１）で表されるリン酸エステルを乳化分散させる方法が挙げられる。 In the present invention, the method for emulsifying and dispersing the phosphate ester represented by the general formula (1) is not particularly limited. For example, (i) the phosphate ester represented by the general formula (1) and the above-mentioned By gradually adding water thereto while stirring the surfactant (x 1 ), and optionally the surfactant (x 2 ) and / or the mixture containing the surfactant (x 3 ). , A method of emulsifying and dispersing the phosphate ester represented by the general formula (1), (ii) the phosphate ester represented by the general formula (1) and the surfactant (x 1 ), and optionally A mixture of the surfactant (x 2 ) and / or the surfactant (x 3 ) with water is emulsified and dispersed using an emulsifier / disperser such as a homogenizer, and is represented by the general formula (1). Emulsify and disperse the phosphate ester The method and the like.
本発明のポリエステル繊維用難燃加工剤を用いて難燃性を付与することができるポリエステル繊維としては、特に限定されず、例えば、レギュラーポリエステル繊維、カチオン可染ポリエステル繊維、再生ポリエステル繊維、又はこれら２種以上からなるポリエステル繊維との糸、トウ、トップ、カセ、織物、編み物、不織布、ロープが挙げられる。さらに、これらポリエステル繊維と、綿、麻、絹、羊毛等の天然繊維；レーヨン、アセテート等の半合成繊維；ナイロン、アクリル、ポリアミド等の合成繊維；炭素繊維、ガラス繊維、セラミックス繊維、アスベスト繊維、金属繊維等の無機繊維；又はこれら２種以上からなる繊維との混紡により得られる糸、トウ、トップ、カセ、織物、編み物、不織布、ロープが挙げられる。 The polyester fiber that can impart flame retardancy using the flame retardant for polyester fiber of the present invention is not particularly limited. For example, regular polyester fiber, cationic dyeable polyester fiber, regenerated polyester fiber, or these Examples include yarns with two or more kinds of polyester fibers, tows, tops, casks, woven fabrics, knitted fabrics, non-woven fabrics, and ropes. Furthermore, these polyester fibers and natural fibers such as cotton, hemp, silk and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as nylon, acrylic and polyamide; carbon fibers, glass fibers, ceramic fibers, asbestos fibers, Examples thereof include inorganic fibers such as metal fibers; or yarns, tows, tops, casks, woven fabrics, knitted fabrics, non-woven fabrics, and ropes obtained by blending with fibers composed of two or more of these.
本発明のポリエステル繊維用難燃加工剤を用いてポリエステル繊維に難燃性を付与する場合、ポリエステル繊維に付与される前記一般式（１）で表されるリン酸エステルの量としては、特に制限されないが、通常はポリエステル繊維に対するリン酸エステルの吸着率が０．１〜３０％ｏ．ｗ．ｆ．であることが好ましく、０．３〜２５％ｏ．ｗ．ｆ．であることがより好ましい。リン酸エステルの吸着率が０．１％ｏ．ｗ．ｆ．未満であると、十分な難燃性の安定化効果が発揮されない傾向にある。一方、リン酸エステルの吸着率が高いほど、難燃性安定化の効果は大きくなるが、リン酸エステルの吸着率が３０％ｏ．ｗ．ｆ．を超えると、風合の著しい変化や、発粉を引き起こし易くなる傾向にある。 When imparting flame retardancy to the polyester fiber using the flame retardant for polyester fiber of the present invention, the amount of the phosphate ester represented by the general formula (1) imparted to the polyester fiber is particularly limited. In general, the adsorption rate of the phosphate ester to the polyester fiber is 0.1 to 30% o.d. w. f. Is preferably 0.3 to 25% o. w. f. It is more preferable that Phosphate ester adsorption rate of 0.1% o.d. w. f. If it is less than the range, sufficient flame retardancy stabilizing effect tends not to be exhibited. On the other hand, the higher the phosphate ester adsorption rate, the greater the effect of stabilizing the flame retardancy, but the phosphate ester adsorption rate is 30% o. w. f. Exceeding the value tends to cause a significant change in texture and to cause powdering.
本発明のポリエステル繊維用難燃加工剤を用いてポリエステル繊維に難燃性を付与する方法としては、特に限定されないが、例えば、ディッピング、パディング、スプレー、コーティング、プリント等の方法によりポリエステル繊維に難燃性を付与する方法を挙げることができる。 The method for imparting flame retardancy to the polyester fiber using the flame retardant for polyester fiber of the present invention is not particularly limited. For example, it is difficult for the polyester fiber by dipping, padding, spraying, coating, printing or the like. A method of imparting flammability can be mentioned.
また、例えば、ディッピングによって難燃加工をする場合には、ポリエステル繊維用難燃加工剤にポリエステル繊維を９０℃〜１５０℃、好ましくは１１０℃〜１４０℃の範囲の温度で１０〜６０分程度浸漬して、難燃加工剤を吸着、吸収させればよい。熱処理温度が前記下限未満では難燃加工剤が十分に吸収されず、難燃性が不十分となる傾向にあり、他方、前記上限を越えるとポリエステル繊維の変化や脆化が起こる傾向にある。このとき、難燃加工剤と同時に分散染料や蛍光染料を用いて染色を難燃加工と同時に行うこともできる。 For example, when flame-retardant processing is performed by dipping, the polyester fiber is immersed in the flame-retardant processing agent for polyester fiber at a temperature in the range of 90 ° C. to 150 ° C., preferably 110 ° C. to 140 ° C. for about 10 to 60 minutes. Then, the flame retardant processing agent may be adsorbed and absorbed. If the heat treatment temperature is less than the lower limit, the flame retardant processing agent is not sufficiently absorbed and the flame retardancy tends to be insufficient. On the other hand, if the upper limit is exceeded, the polyester fiber tends to change or become brittle. At this time, dyeing can be performed simultaneously with the flame retardant processing using a disperse dye or a fluorescent dye simultaneously with the flame retardant processing agent.
さらに、パディング、スプレー、コーティングやプリントによって難燃加工をする場合には、ポリエステル繊維にパディング、スプレー、コーティングやプリントによってポリエステル繊維用難燃加工剤を付着させた後、乾熱処理、飽和常圧スチーム処理、加熱スチーム処理、高圧スチーム処理等の蒸熱処理によって熱処理することができる。乾熱処理、蒸熱処理のいずれにおいても、熱処理温度は、通常、１１０℃〜２１０℃の範囲であり、好ましくは１６０℃〜２１０℃の範囲である。熱処理温度が前記下限未満では難燃加工剤が十分に吸収されず、難燃性が不十分となる傾向にあり、他方、前記上限を超えるときは、ポリエステル繊維の変色や脆化が起こる傾向にある。 Furthermore, when flame retardant processing is performed by padding, spraying, coating or printing, a polyester fiber flame retardant is attached to the polyester fiber, followed by dry heat treatment and saturated atmospheric steam. It can heat-process by steaming heat processing, such as a process, a heating steam process, and a high pressure steam process. In both the dry heat treatment and the steam heat treatment, the heat treatment temperature is usually in the range of 110 ° C to 210 ° C, preferably in the range of 160 ° C to 210 ° C. When the heat treatment temperature is less than the lower limit, the flame retardant processing agent is not sufficiently absorbed, and the flame retardancy tends to be insufficient, whereas when the upper limit is exceeded, discoloration and embrittlement of the polyester fibers tend to occur. is there.
なお、コーティングによって難燃加工をする場合には、ポリエステル繊維用難燃加工剤を加工に適した粘度に調整したものを難燃加工をする液として用いてもよく、また、難燃加工をする液を泡状にしてポリエステル繊維に付着させる泡加工コーティングによって難燃加工をしてもよい。泡加工コーティングによれば、起泡した難燃加工する液を必要量ポリエステル繊維に付与することができ、従って乾燥に要するエネルギー及び時間を大幅に短縮する事ができ、且つ難燃加工する液を全量無駄なく使用することができる。さらに、加工に適した粘度に調整するのに用いられる粘度調整剤としては、特に限定されないが、例えば、ポリビニルアルコール、メチルセルロース、プロピルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ザンタンガム、デンプン糊を挙げることができる。また、ディッピングによって難燃加工をする場合には、例えば、液流染色機、ビーム染色機、チーズ染色機を使用することができる。さらに、スプレーによって難燃加工をする場合には、例えば、圧搾空気により難燃加工する液を霧状にして吹き付けるエアースプレー、液圧霧化方式のエアースプレーを使用することができる。また、コーティングによって難燃加工をする場合には、例えば、エアードクターコーター、ブレードコーター、ロッドコーター、ナイフコーター、スクイズコーター、リバースコーター、トランスファーコーター、グラビアコーター、キスロールコーター、キャストコーター、カーテンコーター、カレンダーコーター等を用いるコーティングを使用することができる。さらに、プリントによって難燃加工をする場合には、例えば、ローラー捺染機、フラットスクリーン捺染機、ロータリースクリーン捺染機を用いるプリントを使用することができる。 In addition, when flame-retardant processing is performed by coating, a polyester fiber flame-retardant processing agent adjusted to a viscosity suitable for processing may be used as a liquid for flame-retardant processing, or flame-retardant processing is performed. Flame retardant processing may be performed by foam processing coating in which the liquid is foamed and adhered to the polyester fiber. According to the foam processing coating, it is possible to apply a necessary amount of foamed flame retardant processing liquid to the polyester fiber, so that the energy and time required for drying can be greatly reduced, and the liquid for flame retardant processing can be used. The entire amount can be used without waste. Furthermore, the viscosity modifier used for adjusting the viscosity suitable for processing is not particularly limited, and examples thereof include polyvinyl alcohol, methyl cellulose, propyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, xanthan gum, and starch paste. . Moreover, when performing a flame-retardant process by dipping, a liquid dyeing machine, a beam dyeing machine, and a cheese dyeing machine can be used, for example. Furthermore, when flame-retardant processing is performed by spraying, for example, an air spray that sprays a liquid that is flame-retardant processed with compressed air in a mist form, or a hydraulic atomization type air spray can be used. In the case of flame retardant processing by coating, for example, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse coater, transfer coater, gravure coater, kiss roll coater, cast coater, curtain coater, A coating using a calendar coater or the like can be used. Furthermore, when flame-retardant processing is performed by printing, for example, printing using a roller printing machine, a flat screen printing machine, or a rotary screen printing machine can be used.
さらに、前述のポリエステル繊維に難燃性を付与する方法においては、熱処理工程を実施した後に、通常の公知の方法によってポリエステル繊維のソーピング処理を行い、ポリエステル繊維に強固に固着せず、繊維内部に浸透せず表面に付着しているだけのリン酸エステルを除去することが好ましい。このようなソーピング処理に用いられる洗浄剤としては、通常のアニオン系、非イオン系、両性系の界面活性剤及びこれらが配合された洗剤を挙げることができる。 Furthermore, in the method of imparting flame retardancy to the polyester fiber described above, after performing the heat treatment step, the polyester fiber is soaped by an ordinary known method, and does not firmly adhere to the polyester fiber, It is preferable to remove the phosphate ester that does not penetrate and is only attached to the surface. Examples of the cleaning agent used in such a soaping process include ordinary anionic, nonionic, and amphoteric surfactants and detergents containing these.
また、難燃加工剤の他に従来から用いられている他の繊維用加工剤を、難燃性を損なわない程度に難燃加工剤と併用することもできる。このような繊維用加工剤としては、例えば、帯電防止剤、撥水撥油剤、防汚剤、硬仕上剤、風合調整剤、柔軟剤、抗菌剤、吸水剤、スリップ防止剤、耐光堅牢度向上剤が挙げられる。 In addition to the flame retardant processing agent, other conventionally used fiber processing agents can be used in combination with the flame retardant processing agent to the extent that flame retardancy is not impaired. Examples of such fiber processing agents include antistatic agents, water and oil repellents, antifouling agents, hard finishes, texture modifiers, softeners, antibacterial agents, water absorbing agents, antislip agents, and light fastness. An improver is mentioned.
以下に、実施例及び比較例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。なお、ポリエステル繊維用難燃加工剤の乳化安定性及びポリエステル繊維の難燃性はそれぞれ以下の方法により評価した。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the emulsion stability of the flame retardant processing agent for polyester fibers and the flame retardance of polyester fibers were evaluated by the following methods, respectively.
（１）ポリエステル繊維用難燃加工剤の乳化安定性の評価
得られた難燃加工剤３００ｍＬをガラス瓶に入れて密栓し、４５℃で３０日間保管した。３０日後の難燃加工剤の状態を観察し、乳化安定性を評価した。そして、分離が全くない場合を「安定」、極少量の分離がある場合を「分離（少）」、明らかに分離（全量の１０％以上分離）がある場合を「分離（大）」と判定した。
(1) Evaluation of Emulsification Stability of Flame Retardant for Polyester Fiber 300 mL of the obtained flame retardant was put in a glass bottle, sealed, and stored at 45 ° C. for 30 days. The state of the flame retardant after 30 days was observed to evaluate the emulsion stability. When there is no separation, it is judged as “stable”, when there is a very small amount of separation as “separation (low)”, and when there is clear separation (separation of 10% or more of the total amount), it is judged as “separation (large)” did.
（２）ポリエステル繊維の難燃性
水洗い洗濯なしの試料として、得られた難燃性ポリエステル繊維を用いた。また、水洗い洗濯した後の試料として、ＪＩＳ Ｌ １０９１に準じて難燃性ポリエステル繊維を水洗い洗濯したものを用いた。さらに、ドライクリーニング後の試料として、ＪＩＳ Ｌ １０１８に準じて難燃性ポリエステル繊維をドライクリーニングしたものを用いた。これらの試料を用いて、以下の方法によりポリエステル繊維の難燃性を評価した。
(2) Flame retardancy of polyester fiber The flame retardant polyester fiber obtained was used as a sample without washing and washing. Further, as a sample after washing and washing with water, a sample obtained by washing and washing flame-retardant polyester fiber according to JIS L 1091 was used. Furthermore, as a sample after dry cleaning, a flame-retardant polyester fiber dry-cleaned according to JIS L 1018 was used. Using these samples, the flame retardancy of the polyester fibers was evaluated by the following method.
（i）４５゜ミクロバーナー法
ＪＩＳ Ｌ １０９１に記載されているＡ−１法に準じて難燃性を評価した。なお、残炎時間３秒以内である場合を合格（○）と判定し、それ以外の場合を不合格（×）と判定した。
(I) 45 ° Micro Burner Method Flame retardancy was evaluated according to the A-1 method described in JIS L 1091. In addition, the case where it was within 3 seconds of afterflame time was determined as the pass ((circle)), and the case other than that was determined as the disqualification (x).
（ii）コイル法（接炎試験）
ＪＩＳ Ｌ １０９１に記載されているＤ法に準じて難燃性を評価した。なお、接炎回数３回以上である場合を合格（○）と判定し、それ以外の場合を不合格（×）と判定した。
(Ii) Coil method (flame contact test)
Flame retardancy was evaluated according to the D method described in JIS L 1091. In addition, the case where the number of times of flame contact was 3 times or more was determined to be acceptable (◯), and the other cases were determined to be unacceptable (x).
（実施例１）
先ず、ジフェニルモノオルソキセニルホスフェート４０ｇと、トリスチレン化フェノールのエチレンオキサイド１５モル付加物のリン酸エステルアンモニウム塩（モノエステル：ジエステル＝１：１）の５０質量％水溶液２０ｇとの混合物に、撹拌しながら水４０ｇを徐々に添加して乳化分散し、ポリエステル繊維用難燃加工剤を得た。得られたポリエステル繊維用難燃加工剤について、レーザー回折式粒度分布測定装置［ＬＡ−９２０：（株）堀場製作所製］を用いて乳化物の平均粒径を測定した結果、０．２μｍであった。また、得られたポリエステル繊維用難燃加工剤の乳化安定性は「安定」であった。
Example 1
First, a mixture of 40 g of diphenyl monoorthoxenyl phosphate and 20 g of a 50 mass% aqueous solution of a phosphoric ester ammonium salt of a 15 mol adduct of tristyrenated phenol with ethylene oxide (monoester: diester = 1: 1) was stirred. While gradually adding 40 g of water, the mixture was emulsified and dispersed to obtain a flame retardant finish for polyester fibers. About the obtained flame retardant processing agent for polyester fibers, the average particle size of the emulsion was measured using a laser diffraction particle size distribution analyzer [LA-920: manufactured by Horiba, Ltd.]. It was. Moreover, the emulsion stability of the obtained flame retardant for polyester fiber was “stable”.
次に、目付２２０ｇ／ｍ2の横糸原着レギュラーポリエステル１００質量％未染色布を、ミニカラー染色機［テクサム社製］を使用し、分散染料［Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ
Ｂｌｕｅ ５６］１％ｏ．ｗ．ｆ．、分散均染剤［ニッカサンソルトＲＭ−３４０Ｅ：日華化学(株)製］０.５ｇ／Ｌ、８０質量％酢酸０.３ｍＬ／Ｌ及びポリエステル繊維用難燃加工剤１５％ｏ．ｗ．ｆ．を含む染色浴で、浴比１：１５、温度１３０℃の条件で、３０分処理した。次いで、ソーピング剤［エスクードＦＲＮ：日華化学(株)製］２ｇ／Ｌ、苛性ソーダ１ｇ／Ｌを含む水溶液を用いて、８０℃で２０分ソーピングを行い、１７０℃で１分乾燥し、難燃性ポリエステル繊維を得た。
Next, a weft original regular polyester 100% by mass undyed cloth with a basis weight of 220 g / m 2 was used with a disperse dye [C.I. I. Disperse
Blue 56] 1% o. w. f. Dispersion leveling agent [Nikka Sun Salt RM-340E: manufactured by Nikka Chemical Co., Ltd.] 0.5 g / L, 80% by mass acetic acid 0.3 mL / L and polyester fiber flame retardant 15% o. w. f. In the dye bath containing No. 1, the mixture was treated for 30 minutes under the conditions of a bath ratio of 1:15 and a temperature of 130 ° C. Next, using an aqueous solution containing 2 g / L of a soaping agent [Escudo FRN: manufactured by Nikka Chemical Co., Ltd.] and 1 g / L of caustic soda, it is soaped at 80 ° C. for 20 minutes, dried at 170 ° C. for 1 minute, and flame retardant -Resistant polyester fibers were obtained.
（実施例２）
ジフェニルモノオルソキセニルホスフェート４０ｇと、トリスチレン化フェノールのエチレンオキサイド１０モル付加物４ｇと、トリスチレン化フェノールのエチレンオキサイド１５モル付加物のリン酸エステルアンモニウム塩の５０質量％水溶液１０ｇとの混合物に、撹拌しながら水３６ｇを徐々に添加して乳化分散し、ポリエステル繊維用難燃加工剤を得た以外は実施例１と同様にして難燃性ポリエステル繊維を得た。なお、得られたポリエステル繊維用難燃加工剤の乳化物の平均粒径は０．２μｍであった。また、得られたポリエステル繊維用難燃加工剤の乳化安定性は「安定」であった。
(Example 2)
In a mixture of 40 g of diphenyl monoorthoxenyl phosphate, 4 g of an ethylene oxide 10 mol adduct of tristyrenated phenol, and 10 g of a 50 mass% aqueous solution of a phosphoric ester ammonium salt of an ethylene oxide 15 mol adduct of tristyrenated phenol While stirring, 36 g of water was gradually added and emulsified and dispersed to obtain a flame retardant polyester fiber in the same manner as in Example 1, except that a flame retardant finish for polyester fiber was obtained. In addition, the average particle diameter of the emulsion of the flame retardant processing agent for polyester fibers obtained was 0.2 μm. Moreover, the emulsion stability of the obtained flame retardant for polyester fiber was “stable”.
（実施例３）
ジフェニルモノオルソキセニルホスフェート４０ｇと、トリスチレン化フェノールのエチレンオキサイド１５モル付加物の硫酸エステルアンモニウム塩の５０質量％水溶液８ｇと、トリスチレン化フェノールのエチレンオキサイド１５モル付加物のリン酸エステルアンモニウム塩の５０質量％水溶液１０ｇとの混合物に、撹拌しながら水３２ｇを徐々に添加して乳化分散し、ポリエステル繊維用難燃加工剤を得た以外は実施例１と同様にして難燃性ポリエステル繊維を得た。なお、得られたポリエステル繊維用難燃加工剤の乳化物の平均粒径は０．２μｍであった。また、得られたポリエステル繊維用難燃加工剤の乳化安定性は「安定」であった。
(Example 3)
40 g of diphenyl monoorthoxenyl phosphate, 8 g of a 50% by weight aqueous solution of ammonium sulfate ester of tristyrenated phenol ethylene oxide 15 mol adduct, and ammonium phosphate ester of tristyrenated phenol ethylene oxide 15 mol adduct Flame retardant polyester fiber in the same manner as in Example 1 except that 32 g of water was gradually added to a mixture with 10 g of a 50% by weight aqueous solution and emulsified and dispersed to obtain a flame retardant processing agent for polyester fiber. Got. In addition, the average particle diameter of the emulsion of the flame retardant processing agent for polyester fibers obtained was 0.2 μm. Moreover, the emulsion stability of the obtained flame retardant for polyester fiber was “stable”.
（実施例４）
フェニルジオルソキセニルホスフェート４０ｇと、トリスチレン化フェノールのエチレンオキサイド１０モル付加物の硫酸エステルアンモニウム塩の５０質量％水溶液２０ｇとの混合物に、撹拌しながら水４０ｇを徐々に添加して乳化分散し、ポリエステル繊維用難燃加工剤を得た以外は実施例１と同様にして難燃性ポリエステル繊維を得た。なお、得られたポリエステル繊維用難燃加工剤の乳化物の平均粒径は０．３μｍであった。また、得られたポリエステル繊維用難燃加工剤の乳化安定性は「安定」であった。
Example 4
40 g of water is gradually added with stirring to a mixture of 40 g of phenyl diorxoxenyl phosphate and 20 g of a 50% by weight aqueous solution of ammonium sulfate of 10 mol adduct of tristyrenated phenol, and the mixture is emulsified and dispersed. A flame retardant polyester fiber was obtained in the same manner as in Example 1 except that the flame retardant finish for polyester fiber was obtained. In addition, the average particle diameter of the emulsion of the obtained flame retardant processing agent for polyester fibers was 0.3 μm. Moreover, the emulsion stability of the obtained flame retardant for polyester fiber was “stable”.
（比較例１）
レゾルシノールビス（ジフェニルホスフェート）４０ｇと、トリスチレン化フェノールのエチレンオキサイド１５モル付加物の硫酸エステルアンモニウム塩の５０質量％水溶液２０ｇとの混合物に、撹拌しながら水４０ｇを徐々に添加して乳化分散し、比較用ポリエステル繊維用難燃加工剤を得た以外は実施例１と同様にして比較用難燃性ポリエステル繊維を得た。なお、得られた比較用ポリエステル繊維用難燃加工剤の乳化物の平均粒径は０．６μｍであった。また、得られた比較用ポリエステル繊維用難燃加工剤の乳化安定性は「分離（少）」であった。
(Comparative Example 1)
40 g of water was gradually added to a mixture of 40 g of resorcinol bis (diphenyl phosphate) and 20 g of a 50 mass% aqueous solution of ammonium sulfate 15 mol adduct of tristyrenated phenol with stirring, and the mixture was emulsified and dispersed. A comparative flame-retardant polyester fiber was obtained in the same manner as in Example 1 except that a flame-retardant processing agent for comparative polyester fiber was obtained. In addition, the average particle diameter of the emulsion of the flame retardant processing agent for comparative polyester fibers obtained was 0.6 μm. Moreover, the emulsification stability of the obtained flame retardant processing agent for a polyester fiber for comparison was “separation (low)”.
実施例１〜４及び比較例１で得られた各難燃性ポリエステル繊維について、難燃性を評価した。得られた結果を表１に示す。 About each flame-retardant polyester fiber obtained in Examples 1-4 and Comparative Example 1, the flame retardance was evaluated. The obtained results are shown in Table 1.
表１に記載した結果からも明らかなように、本発明のポリエステル繊維用難燃加工剤を用いてレギュラーポリエステル１００質量％未染色布を処理せしめた実施例１〜４で得られた難燃性ポリエステル繊維は、優れた難燃性を備えており、特に水洗なしの試料と水洗い洗濯後の試料及びドライクリーニング後の試料についても優れた難燃性を備えていることから、本発明のポリエステル繊維用難燃加工剤により、ポリエステル繊維に耐久性に優れた難燃性が付与されていることが確認できた。また、前述の通り本発明のポリエステル繊維用難燃加工剤は、乳化物の平均粒子径が小さく、３０日後も分離することなく、難燃加工剤の経時の乳化安定性に優れていることが確認できた。 As is apparent from the results shown in Table 1, flame retardancy obtained in Examples 1 to 4 in which 100% by mass of a regular polyester undyed fabric was treated with the flame retardant for polyester fiber of the present invention. The polyester fiber has excellent flame retardancy. In particular, the polyester fiber of the present invention also has excellent flame retardancy for a sample without water washing, a sample after washing with water, and a sample after dry cleaning. It was confirmed that the flame retardant having excellent durability was imparted to the polyester fiber by the flame retardant finishing agent. In addition, as described above, the flame retardant processing agent for polyester fibers of the present invention has a small average particle size of the emulsion, and is excellent in the emulsion stability over time of the flame retardant without separation after 30 days. It could be confirmed.
以上説明したように、本発明によれば、経時の乳化安定性に優れ、且つ、ポリエステル繊維に耐久性に優れた難燃性を付与することを可能とする難燃加工剤を提供することが可能となる。
As described above, according to the present invention, it is possible to provide a flame retardant processing agent that has excellent emulsification stability over time and can impart flame resistance with excellent durability to polyester fibers. It becomes possible.
Claims (4)
で表されるリン酸エステルが、下記界面活性剤（ｘ１）及び（ｘ３）からなる群より選択される少なくとも１種の界面活性剤を用いて、水中に乳化分散されてなることを特徴とするポリエステル繊維用難燃加工剤。
＜界面活性剤（ｘ１）＞
下記一般式（２）：
により表される化合物。
＜界面活性剤（ｘ３）＞
下記一般式（４）：
により表される化合物。 The following general formula (1):
The phosphate ester represented by the formula ( 1 ) is characterized by being emulsified and dispersed in water using at least one surfactant selected from the group consisting of the following surfactants (x 1 ) and (x 3 ). A flame retardant for polyester fiber.
<Surfactant (x 1)>
The following general formula (2):
Compounds represented by.
<Surfactant (x 3)>
The following general formula (4):
A compound represented by
＜界面活性剤（ｘ ２ ）＞
下記一般式（３）：
により表される化合物。 The flame retardant processing agent for polyester fiber according to claim 1, wherein the surfactant (x 1 ) is used as the surfactant , and the following surfactant (x 2 ) is further used.
<Surfactant (x 2)>
The following general formula (3):
A compound represented by
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| US9091019B2 (en) | 2008-11-14 | 2015-07-28 | Peach State Labs, Inc. | Compositions for treating textiles and carpet and applications thereof |
| CN102827201A (en) * | 2012-08-28 | 2012-12-19 | 江苏雅克科技股份有限公司 | Method for preparing diphenyl (2-biphenyl) phosphate fire retardant |
| CN105862411A (en) * | 2016-04-18 | 2016-08-17 | 河南工程学院 | Method for achieving dye-free coloring and flame retardancy of acrylic fibers |
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