CN101981157A - Aqueous dispersion of organic phosphorus compound and flameproofing method using the same - Google Patents
Aqueous dispersion of organic phosphorus compound and flameproofing method using the same Download PDFInfo
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- CN101981157A CN101981157A CN2009801113714A CN200980111371A CN101981157A CN 101981157 A CN101981157 A CN 101981157A CN 2009801113714 A CN2009801113714 A CN 2009801113714A CN 200980111371 A CN200980111371 A CN 200980111371A CN 101981157 A CN101981157 A CN 101981157A
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- phenyl
- alkyl
- formula
- compound
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- 239000006185 dispersion Substances 0.000 title claims abstract description 54
- 150000002903 organophosphorus compounds Chemical class 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 237
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 181
- -1 phosphinic acid ester compound Chemical class 0.000 claims abstract description 114
- 239000000835 fiber Substances 0.000 claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 73
- 125000003545 alkoxy group Chemical group 0.000 claims description 73
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 64
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 63
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 52
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 51
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 48
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 47
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 37
- 125000003118 aryl group Chemical group 0.000 claims description 36
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims description 35
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 32
- 125000000217 alkyl group Chemical class 0.000 claims description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 24
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 claims description 23
- 238000012545 processing Methods 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 18
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical group O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 18
- 125000001624 naphthyl group Chemical group 0.000 claims description 17
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 16
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 16
- 230000002265 prevention Effects 0.000 claims description 16
- 238000004079 fireproofing Methods 0.000 claims description 14
- 229920004935 Trevira® Polymers 0.000 claims description 13
- 239000006096 absorbing agent Substances 0.000 claims description 12
- 239000013543 active substance Substances 0.000 claims description 12
- 125000004104 aryloxy group Chemical group 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000003944 tolyl group Chemical group 0.000 claims description 10
- 125000003282 alkyl amino group Chemical group 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000006502 nitrobenzyl group Chemical group 0.000 claims description 7
- 125000006501 nitrophenyl group Chemical group 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 196
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 139
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 60
- 238000006243 chemical reaction Methods 0.000 description 55
- 239000000463 material Substances 0.000 description 52
- 239000013530 defoamer Substances 0.000 description 51
- 239000003112 inhibitor Substances 0.000 description 51
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 51
- 230000008719 thickening Effects 0.000 description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 46
- 235000010290 biphenyl Nutrition 0.000 description 32
- 239000004305 biphenyl Substances 0.000 description 32
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 32
- 125000006267 biphenyl group Chemical group 0.000 description 31
- 238000004519 manufacturing process Methods 0.000 description 31
- 125000005499 phosphonyl group Chemical group 0.000 description 31
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 27
- 238000012360 testing method Methods 0.000 description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 20
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 18
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 16
- 235000002639 sodium chloride Nutrition 0.000 description 15
- 238000012797 qualification Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 10
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 10
- 239000000975 dye Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 238000003287 bathing Methods 0.000 description 7
- 229960004217 benzyl alcohol Drugs 0.000 description 6
- 235000019445 benzyl alcohol Nutrition 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 150000002366 halogen compounds Chemical class 0.000 description 5
- 238000009980 pad dyeing Methods 0.000 description 5
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 229940100630 metacresol Drugs 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Chemical group 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 3
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 230000000176 photostabilization Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- 229940061334 2-phenylphenol Drugs 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 description 2
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- CJAAPVQEZPAQNI-UHFFFAOYSA-N (2-methylphenyl)methanamine Chemical compound CC1=CC=CC=C1CN CJAAPVQEZPAQNI-UHFFFAOYSA-N 0.000 description 1
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- 125000006526 (C1-C2) alkyl group Chemical group 0.000 description 1
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- UZGKAASZIMOAMU-UHFFFAOYSA-N 124177-85-1 Chemical class NP(=O)=O UZGKAASZIMOAMU-UHFFFAOYSA-N 0.000 description 1
- 125000006179 2-methyl benzyl group Chemical group [H]C1=C([H])C(=C(C([H])=C1[H])C([H])([H])*)C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 1
- SJPJHLBDGCNLAL-UHFFFAOYSA-N 3-(dimethylamino)-1-(4-nitrophenyl)propan-1-one Chemical compound CN(C)CCC(=O)C1=CC=C([N+]([O-])=O)C=C1 SJPJHLBDGCNLAL-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102100024974 Caspase recruitment domain-containing protein 8 Human genes 0.000 description 1
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- 101000761247 Homo sapiens Caspase recruitment domain-containing protein 8 Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
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- 239000000084 colloidal system Substances 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- 125000006317 cyclopropyl amino group Chemical group 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
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- 229920000591 gum Polymers 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000002514 liquid chromatography mass spectrum Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 239000003961 penetration enhancing agent Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3229—Esters of aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/36—Amides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/44—Amides thereof
- C07F9/4403—Amides thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4419—Amides of aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
- D06M13/447—Phosphonates or phosphinates containing nitrogen atoms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Fireproofing Substances (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Disclosed is an aqueous dispersion that provides excellent and durable flameproof performance to fibers, in particular, to CDP and polyester fibers, and includes a surfactant and at least one of the following organic phosphorus compounds or salts thereof: a phosphinic acid ester compound represented by formula (1), a phosphinic acid ester compound represented by formula (2), a phosphinic acid amide compound represented by formula (3), a phosphinic acid amide compound represented by formula (4), a phosphinic diamide compound represented by formula (5). In the formulas, R11, R12, R13, R21, R22, R23, R31, R32, R33, R34, R41, R42, R43, R44, R51, R52, R53, R54, and R55 represent phenyl groups and the like.
Description
Technical field
The fire prevention working method that the present invention relates to the aqueous liquid dispersion of organo phosphorous compounds and use this dispersion liquid.More specifically, relate to the fire prevention processing use dispersion liquid that can utilize organo phosphorous compounds to give the good fire resistance of weather resistance and carried out the fiber and the novel organo phosphorous compounds of fire prevention processing with the fire prevention working method and by it to synthetic fiber structure.
Background technology
In the past, give the method for fiber with fire resistance as handling by post-treatment, known had: halogen compounds is distributed to the machining agent and use it to the fiber method for processing of preventing fires of obtaining in the water preventing fires.As the typical example of above-mentioned halogen compounds, can enumerate 1,2,5,6,9, the brominated alkane that the 10-hexabromocyclododecane is such.The fire resistance of known halogen compounds is generally than higher, but the fiber after the fire prevention processing produces deleterious halogenation gas when burning, and exists it that human body and physical environment are produced problems such as harmful effect.Therefore, in recent years, use halogen compounds to be restricted as fireproofing agent.
Therefore, instead the fireproofing agent of halogen compounds has proposed (patent documentations 1～4) such as fiber fire prevention working methods that use the fireproofing agent of the such phosphorus compound of organophosphate and use this fireproofing agent.
But, when using these phosphorus compounds, can not or give various functional fibers such as antibiotic processing, deodorizing processing, surface working and give sufficient fire resistance the mixed fibre of fiber, particularly CDP (cation-dyeable type polyester) fiber and trevira.
In addition, put down in writing phosphonic acids naphthalene ester cpds in the patent documentation 5 as the fire prevention phosphorus compound, but had problems such as photostabilization is low.
In addition, put down in writing phosphinic acid compounds in the non-patent literature 1 and 2, still, do not put down in writing fire resistance.
Patent documentation 1: TOHKEMY 2001-254268 communique
Patent documentation 2: TOHKEMY 2000-328445 communique
Patent documentation 3: TOHKEMY 2004-225176 communique
Patent documentation 4: TOHKEMY 2006-70417 communique
Patent documentation 5: TOHKEMY 2007-239108 communique
Non-patent literature 1:Phosphorus and Sulfur and the RelatedElements, 29 (2-4), 169-178 (1987)
Non-patent literature 2:J.Org.Chem., 23,1889-1893 (1958)
Summary of the invention
Problem of the present invention is to provide can be to the mixed fibre of fiber, particularly CDP fiber and trevira or given fire prevention processing use dispersion liquid that functional fiber gives the good fire resistance of weather resistance and fire prevention working method and by fiber and novel organo phosphorous compounds after its processing of preventing fires.
The inventor has carried out extensive and deep research in order to address the above problem, and found that, by using specific organo phosphorous compounds, can give weather resistance good fire resistance to fiber, thereby finish the present invention.
That is, the present invention relates to following [1]～[15].
[1] a kind of aqueous liquid dispersion, it contains the Phosphoramido compounds of inferior Phosphoramido compounds, following formula (4) expression of phosphonate compound, following formula (3) expression of the phosphinate compounds that is selected from following formula (1) expression, following formula (2) expression and at least a organo phosphorous compounds or their salt and the tensio-active agent in the phosphine diamide that following formula (5) is represented
In the formula (1), R
11, R
12And R
13Respectively the expression aryl that can replace by substituting group group A or (C1-C10) alkyl independently; at this; substituting group group A represents hydroxyl, amino, nitro, cyano group, formyl radical, carboxyl, urea groups, (C1-C10) alkyl, (C1-C10) alkylamino, two (C1-C10) alkylamino, phenyl, phenoxy group and (C1-C10) alkoxyl group
In the formula (2), R
21The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
22The phenyl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
23The phenyl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl, wherein, this alkyl can be replaced by following groups: the aryloxy that can be replaced by substituting group group A, (C7-C15) aralkoxy that can be replaced by substituting group group A or (C1-C10) alkoxyl group, at this, substituting group group A is identical with above-mentioned definition
In the formula (3), R
31, R
32And R
33Respectively the expression aryl that can replace by substituting group group A or (C1-C10) alkyl independently; R
34Be hydrogen atom, the aryl that can be replaced by substituting group group A or (C1-C10) alkyl, at this, substituting group group A is identical with above-mentioned definition,
In the formula (4), R
41The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
42The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl, wherein, this alkyl can be replaced by following groups: the aryloxy that can be replaced by substituting group group A, (C7-C15) aralkoxy that can be replaced by substituting group group A or (C1-C10) alkoxyl group; R
43The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
44Expression hydrogen atom, the aryl that can replace by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl that can replace by substituting group group A, at this, substituting group group A is identical with above-mentioned definition,
In the formula (5), R
51, R
52And R
53Respectively the expression aryl that can replace by substituting group group A or (C1-C10) alkyl independently; R
54And R
55Represent hydrogen atom, the aryl that can be replaced by substituting group group A or (C1-C10) alkyl respectively independently, at this, substituting group group A is identical with above-mentioned definition.
[2] as above-mentioned [1] described aqueous liquid dispersion, wherein, the aryl that can be replaced by substituting group group A be (C1-C10) alkyl phenyl, xenyl or (C1-C10) alkoxyl phenyl.
[3], wherein, in aqueous liquid dispersion, contain the organo phosphorous compounds of the formula (1) of 1～90 weight % to formula (5) expression in total amount as above-mentioned [1] or [2] described aqueous liquid dispersion.
[4] as each described aqueous liquid dispersion in above-mentioned [1] to [3], wherein, tensio-active agent is nonionic surface active agent or aniorfic surfactant or the two.
[5] as each described aqueous liquid dispersion in above-mentioned [1] to [4], wherein, also contain UV light absorber.
[6] as each described aqueous liquid dispersion in above-mentioned [1] to [5], its fireproofing agent of using as fiber uses.
[7] as above-mentioned [6] described aqueous liquid dispersion, wherein, fiber is a trevira.
[8] as above-mentioned [7] described aqueous liquid dispersion, wherein, trevira is cation-dyeable type trevira or the mixed fibre that contains cation-dyeable type trevira.
[9] a kind of fire prevention working method of fiber is characterized in that, uses each described aqueous liquid dispersion in above-mentioned [1] to [8].
[10] by the method for above-mentioned [9] prevent fires processing after fiber.
[11] phosphonate compound of following formula (2) expression or the Phosphoramido compounds of following formula (4) expression or their salt,
In the formula (2), R
21The aryl that expression can be replaced by substituting group group A or (C7-C15) aralkyl that can replace by substituting group group A; R
22The phenyl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
23The phenyl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl, wherein, this alkyl can be replaced by following groups: the aryloxy that can be replaced by substituting group group A, (C7-C15) aralkoxy that can be replaced by substituting group group A or (C1-C10) alkoxyl group, at this, substituting group group A is identical with above-mentioned definition
In the formula (4), R
41The aryl that expression can be replaced by substituting group group A or (C7-C15) aralkyl that can replace by substituting group group A; R
42The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl, wherein, this alkyl can be replaced by following groups: the aryloxy that can be replaced by substituting group group A, (C7-C15) aralkoxy that can be replaced by substituting group group A or (C1-C10) alkoxyl group; R
43The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
44Expression hydrogen atom, (C7-C15) aralkyl that can be replaced by substituting group group A or (C1-C10) alkyl that can be replaced by substituting group group A, at this, substituting group group A is identical with above-mentioned definition.
[12] as above-mentioned [11] described phosphonate compound or its salt, wherein, R
21For can by hydroxyl, nitro, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) phenyl that replaces of alkoxyl group, can be by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) naphthyl that replaces of alkoxyl group or can be by hydroxyl, nitro, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R
22For can be by nitro, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl or (C1-C6) phenyl that replaces of alkoxyl group or can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R23 is can be by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) (C7-C12) aralkoxy of replacing of alkoxyl group, (C1-C6) alkyl that can be replaced by (C1-C6) alkoxyl group, hydroxyl, amino, (C1-C6) alkylamino, carboxyl or urea groups or can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group.
[13] as above-mentioned [11] or [12] described phosphonate compound or its salt, wherein, R
21Be phenyl, tolyl, nitrophenyl, nitrobenzyl or xenyl R
22Be the phenyl that can replace by (C1-C6) alkyl, nitro or phenyl; R
23Be (C1-C6) alkyl, benzyl or the styroyl that can replace by phenoxy group.
[14] as above-mentioned [11] described Phosphoramido compounds or its salt, wherein, R
41For can by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) phenyl that replaces of alkoxyl group, can be by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) naphthyl that replaces of alkoxyl group or can be by hydroxyl, nitro, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R
42For can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group, (C7-C12) aralkyl or (C1-C6) phenyl of alkoxyl group replacement, can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group, (C7-C12) aralkyl or (C1-C6) naphthyl of alkoxyl group replacement, can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group, perhaps can be by (C1-C6) alkyl of phenoxy group replacement; R
43For can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group or (C1-C6) phenyl that replaces of alkoxyl group, can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group or (C1-C6) naphthyl that replaces of alkoxyl group, perhaps can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R44 is (C1-C6) alkyl or hydrogen atom.
[15] as above-mentioned [11] or [14] described Phosphoramido compounds or its salt, wherein, R
41Be phenyl, p-methoxyphenyl or benzyl; R
42Be phenyl, the naphthyl that can replace by (C1-C6) alkyl, phenyl, benzyl, styroyl or hydrocinnamyl; Can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl or the 2-phenoxy group ethyl that replace of alkoxyl group; R
43Be phenyl, benzyl or styroyl; R
44Be methyl, ethyl or hydrogen atom.
The organo phosphorous compounds of above-mentioned formula (1)～(5) expression and the aqueous liquid dispersion of tensio-active agent of containing provided by the invention, it is good fireproofing agent, by using it that fiber is implemented fire prevention processing, can give good fire resistance with photostabilization, weather resistance.In addition, most of phosphonate compound and the Phosphoramido compounds in the organo phosphorous compounds of above-mentioned (2) and (4) expression is novel cpd.
Embodiment
Below, to the detailed description of the invention.
Conduct (C1-C10) alkyl among the present invention, can enumerate straight chain, side chain or the cyclic alkyl of carbonatoms 1～10, for example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-octyl, positive decyl, cyclopropyl, cyclopentyl, cyclohexyl etc.As (C1-C6) alkyl, can enumerate straight chain, side chain or the cyclic alkyl of carbonatoms 1～6, for example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, cyclopropyl, cyclopentyl, cyclohexyl etc.
(C1-C10) alkoxyl group is meant the group that above-mentioned (C1-C10) alkyl and Sauerstoffatom bonding form among the present invention, for example can enumerate: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy, n-octyloxy, n-decyloxy, cyclopentyloxy, cyclohexyloxy etc.(C1-C6) alkoxyl group is meant the group that above-mentioned (C1-C6) alkyl and Sauerstoffatom bonding form, and for example can enumerate: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy, cyclopentyloxy, cyclohexyloxy etc.
(C1-C10) alkylamino is meant the group that above-mentioned (C1-C10) alkyl and nitrogen atom bonding form among the present invention, for example can enumerate: methylamino, ethylamino, n-propyl amino, sec.-propyl amino, normal-butyl amino, tertiary butyl amino, n-pentyl amino, n-hexyl amino, n-octyl amino, positive decyl amino, cyclopropyl amino, cyclopentyl amino, cyclohexyl amino etc.(C1-C6) alkylamino is meant the group that above-mentioned (C1-C6) alkyl and nitrogen atom bonding form, and for example can enumerate: methylamino, ethylamino, n-propyl amino, sec.-propyl amino, normal-butyl amino, tertiary butyl amino, n-pentyl amino, n-hexyl amino, cyclopentyl amino, cyclohexyl amino etc.
Two (C1-C10) alkylamino is meant the group that two above-mentioned (C1-C10) alkyl and nitrogen atom bonding form among the present invention, for example can enumerate: dimethylamino, diethylamino, two (n-propyl) amino, diisopropylaminoethyl, two (normal-butyl) amino, two (tertiary butyls) amino, two (n-pentyls) amino, two (n-hexyls) amino, two (n-octyls) amino, two (just decyl) amino, two cyclopropyl amino, two cyclopentyl amino, dicyclohexyl amino etc.Two (C1-C6) alkylamino is meant the group that two above-mentioned (C1-C6) alkyl and nitrogen atom bonding form, and for example can enumerate: dimethylamino, diethylamino, two (n-propyl) amino, diisopropylaminoethyl, two (normal-butyl) amino, two (tertiary butyls) amino, two (n-pentyls) amino, two (n-hexyls) amino, two cyclopentyl amino, dicyclohexyl amino etc.
As aryl, can enumerate phenyl, naphthyl etc. among the present invention.
(C7-C15) aralkyl is the group that the bonding alkyl forms on phenyl, naphthyl etc. among the present invention, for example can enumerate: benzyl, styroyl, hydrocinnamyl, benzene butyl, benzene amyl group, benzene hexyl, benzene octyl group, menaphthyl, naphthalene ethyl, naphthalene propyl group etc.(C7-C12) aralkyl for example can be enumerated: benzyl, styroyl, hydrocinnamyl, benzene butyl, benzene amyl group, menaphthyl, naphthalene ethyl etc.
As aryloxy, can enumerate phenoxy group or naphthyloxy etc. among the present invention.
(C7-C15) aralkoxy is the group that Sauerstoffatom and above-mentioned (C7-C15) aralkyl bonding form among the present invention, for example can enumerate: benzyloxy, benzene oxyethyl group, benzene propoxy-, benzene butoxy, benzene pentyloxy, benzene hexyloxy, benzene octyloxy, naphthalene methoxyl group, naphthalene oxyethyl group, naphthalene propoxy-etc.(C7-C12) aralkoxy is the group that Sauerstoffatom and above-mentioned (C7-C12) aralkyl bonding form, and for example can enumerate: benzyloxy, benzene oxyethyl group, benzene propoxy-, benzene butoxy, benzene pentyloxy, naphthalene methoxyl group, naphthalene oxyethyl group etc.
Substituting group group A is meant hydroxyl, nitro, amino, cyano group, formyl radical, carboxyl, urea groups, (C1-C10) alkyl, (C1-C10) alkylamino, two (C1-C10) alkylamino, phenyl, phenoxy group and (C1-C10) alkoxyl group among the present invention.These are selected from the substituting group of substituting group group A, replace 1 to 3 usually in each functional group.
Particularly in the present invention, as the aryl that can replace by substituting group group A, preferred (C1-C10) alkyl phenyl, xenyl or (C1-C10) alkoxyl phenyl, Phenoxyphenyl, nitrophenyl etc.
R in the organo phosphorous compounds of above-mentioned formula (1) to (5) expression that contains in the aqueous liquid dispersion that in fire prevention processing, uses of the present invention
11To R
13, R
31To R
33, R
41To R
43, R
51To R
53Preferred group, can enumerate: phenyl, tolyl, xenyl, p-methoxy-phenyl, Phenoxyphenyl, benzyl, wherein, preferred especially phenyl, xenyl, p-methoxy-phenyl.As R
34, R
44, R
54, R
55, preferred hydrogen atom.As R
21To R
23, can preferably enumerate phenyl, tolyl, p-methoxy-phenyl, nitrophenyl, Phenoxyphenyl, benzyl, xenyl, nitrobenzyl, preferred especially phenyl, xenyl, p-methoxy-phenyl.
Below, the new phosphide compound in the compound of the above-mentioned formula (2) that comprises among the present invention expression is described.
That is, in the formula (2), following phosphonate compound is a novel cpd, wherein, and R
21The aryl that expression can be replaced by substituting group group A or (C7-C15) aralkyl that can replace by substituting group group A; R
22The phenyl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
23The phenyl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl (this alkyl can be replaced by following groups: the aryloxy that can be replaced by substituting group group A, (C7-C15) aralkoxy that can be replaced by substituting group group A or (C1-C10) alkoxyl group).
At this, be preferably as follows phosphonate compound, wherein, R
21For can by hydroxyl, cyano group, nitro, (C1-C6) alkyl, phenyl or (C1-C6) phenyl that replaces of alkoxyl group, can be by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) naphthyl that replaces of alkoxyl group or can be by hydroxyl, nitro, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R
22For can be by nitro, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl or (C1-C6) phenyl that replaces of alkoxyl group or can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R
23For can be by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) (C7-C12) aralkoxy of replacing of alkoxyl group, (C1-C6) alkyl that can replace by (C1-C6) alkoxyl group, hydroxyl, amino, (C1-C6) alkylamino, carboxyl or urea groups or can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group.Be preferably as follows phosphonate compound especially, wherein, R
21Be phenyl, tolyl, nitrophenyl, nitrobenzyl or xenyl; R
22Be the phenyl that can replace by nitro, (C1-C6) alkyl or phenyl; R
23Be (C1-C6) alkyl, benzyl or the styroyl that replaces by phenyl, phenoxy group.
Wherein, particularly as the R in the formula (2)
21, preferred phenyl, tolyl, xenyl, p-methoxy-phenyl, nitrophenyl, benzyl, nitrobenzyl, styroyl, wherein, preferred especially phenyl, p-methoxy-phenyl, benzyl, further preferred especially phenyl.As R
22, preferred especially phenyl, tolyl, xenyl, p-methoxy-phenyl, benzyl, styroyl, wherein, further preferred especially phenyl, p-methoxy-phenyl, benzyl.As R
23, preferred phenyl, benzyl, styroyl, phenoxy group ethyl.
New phosphide compound in the compound of the above-mentioned formula (4) that comprises among the present invention expression is described.
That is, in the formula (4), following Phosphoramido compounds is a novel cpd, wherein, and R
41The aryl that expression can be replaced by substituting group group A or (C7-C15) aralkyl that can replace by substituting group group A; R
42The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl (this alkyl can be replaced by following groups: the aryloxy that can be replaced by substituting group group A, (C7-C15) aralkoxy that can be replaced by substituting group group A or (C1-C10) alkoxyl group); R
43The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
44Expression hydrogen atom, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl that can replace by substituting group group A.
At this, be preferably as follows Phosphoramido compounds, wherein, R
41For can by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) phenyl that replaces of alkoxyl group, can be by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) naphthyl that replaces of alkoxyl group or can be by hydroxyl, nitro, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R
42For can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group, (C7-C12) aralkyl or (C1-C6) phenyl of alkoxyl group replacement, can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group, (C7-C12) aralkyl or (C1-C6) naphthyl of alkoxyl group replacement, can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group, perhaps can be by (C1-C6) alkyl of phenoxy group replacement; R
43For can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group or (C1-C6) phenyl that replaces of alkoxyl group, can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group or (C1-C6) naphthyl that replaces of alkoxyl group, perhaps can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R
44Be (C1-C6) alkyl or hydrogen atom.
Be preferably as follows Phosphoramido compounds especially, wherein, R
41Be phenyl, p-methoxyphenyl or benzyl; R
42For the phenyl that can replace by (C1-C6) alkyl, phenyl, benzyl, styroyl or hydrocinnamyl, naphthyl, can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl or the 2-phenoxy group ethyl that replace of alkoxyl group; R
43Be phenyl, benzyl or styroyl; R
44Be methyl, ethyl or hydrogen atom.
Wherein, particularly as the R in the formula (4)
41, be preferably phenyl, tolyl, xenyl, p-methoxy-phenyl, benzyl, styroyl, wherein preferred especially phenyl, p-methoxy-phenyl, benzyl, further preferred especially phenyl.As R
42, especially preferably enumerate phenyl, benzyl, styroyl, phenoxy group ethyl etc.As R
43, preferred especially phenyl, tolyl, xenyl, p-methoxy-phenyl, benzyl, styroyl, wherein, further preferred phenyl, p-methoxy-phenyl, benzyl, styroyl, further preferred especially phenyl, benzyl or styroyl.As R
44, special preferable methyl, ethyl, hydrogen atom.
Formula (1) to the organo phosphorous compounds of formula (5) can be their salt.As salt, for example can enumerate salt, particular certain cancers and ammonium salt with lithium, sodium, potassium, ammonium etc.
The organo phosphorous compounds of formula (1), formula (3) and formula (5) can be made by the method for known method or application of known.In addition, a part of known compound of the organo phosphorous compounds of formula (2) and formula (4) can be by the known method manufacturing.Above-mentioned novel cpd in the organo phosphorous compounds of formula (2) and formula (4), method that can application of known is made.Particularly, for example, can make with reference to the manufacture method of the similar compound of putting down in writing in non-patent literature 2 documents such as grade.For example, Phosphorates phosphorus Halides compound that can be by will be corresponding and alcohols, phenols or amine with target compound under condition of no solvent or the method for in the presence of alkali, reacting as required in the organic solvent make.For the compound that uses among the embodiment, its manufacture method as described later, still, the manufacture method of the novel Phosphoramido compounds of the novel phosphonate compound of formula of the present invention (2) and formula (4) is not limited to these.
Aqueous liquid dispersion of the present invention is characterized in that, uses to be selected from least a compound or their salt and the tensio-active agent of formula (1) to the organo phosphorous compounds of formula (5).In addition, in order further to improve fast light fastness, can contain UV light absorber.
Tensio-active agent is known cationic, non-ionic type and anionic, as the tensio-active agent that contains in the aqueous liquid dispersion of the present invention, can use any one type.When preparing aqueous liquid dispersion of the present invention, can use non-ionic type or anionic or non-ionic type is mixed use with anionic.
As this anion surfactant, can enumerate: alkylphosphonic such as the oxirane affixture of alkylsulfonate such as alkyl sulfuric ester salt such as higher alcohol sulfate salt, senior alkyl ether sulfuric acid, sulfated fatty acid ester or alkylbenzene sulfonate, sulfonated alkyl naphathalene and high alcohol phosphate salt, higher alcohols, phosphate ester salt.In addition, can enumerate: alkylaryl sulphonate, polyoxyalkylene alkyl ether vitriol, polyoxy alkylidene alkyl ester phosphate ester salt, polyoxyalkylene alkyl ether carboxylate salt, polycarboxylate, turkey red oil (ロ one ト oil), petroleum sulfonate, alkyl diphenyl ether sulphonate salt.Preferred polyoxyethylene toluylene phenyl ether sulfuric acid or polyoxyethylene triphenylethylene phenyl ether sulfuric acid.
Particularly preferred anion surfactant in above-mentioned can be enumerated the phosphoric acid ester of the polyoxyethylene alkyl aryl ether of the sulfuric ester of polyoxyethylene phenyl ether of following formula (107) expression or following formula (31) expression,
In the formula (107), R represents hydrogen atom, (C1-C18) alkyl, styryl or benzyl, and n represents 1～15 integer,
In the formula (31), R ' expression (C8-C30) alkyl or (C8-C30) alkylaryl, n represents 1～30 integer, R " expression hydrogen atom or R ' O (CH
2CH
2O)
nBase.
As the compound of formula (31) expression, for example can enumerate プ ラ イ サ one Off AL (trade(brand)name, Di-ichi Kogyo Seiyaku Co., Ltd.'s system) etc.
Represent with the form of free acid for convenience in formula (107) and the formula (31), but, also can use to have the salt as counter cation such as basic metal, ammonium, as this counter cation, for example lithium, sodium, potassium, ammonium etc. be can enumerate, sodium salt and ammonium salt preferably used.
As the compound of preferred formula (107), can enumerate R is that (C6-C12) straight chained alkyl, n are 4～12 compound, and preferred especially R is that nonyl, n are 7 compound.
As nonionic surface active agent, can for example preferably use: polyoxyethylene vinylbenzene phenyl ether, polyoxyethylene toluylene phenyl ether or polyoxyethylene triphenylethylene phenyl ether etc.
As polyoxyethylene vinylbenzene phenyl ether, can enumerate the compound of for example following formula (108) expression or the mixture of the compound that formula (108) is represented.In the formula (108), preferred m ' is 1～3, and n ' is 8～30 compound.
As the mixture of the compound of formula (108) expression, for example can enumerate: the trade(brand)name ノ イ ゲ Application EA-87 that Di-ichi Kogyo Seiyaku Co., Ltd. makes etc.
Tensio-active agent can use or mix use separately.That is, anionic or the multiple separately mixing of non-ionic type can be used, also multiple separately anionic and non-ionic type can be mixed.
As the UV light absorber that can contain in the aqueous liquid dispersion of the present invention, then can use so long as absorb ultraviolet compound with being not particularly limited.In addition, this UV light absorber is used for further improving fast light fastness.
As UV light absorber, for example can use: salicylic acid compounds, benzophenone compound, benzotriazole compound, hindered amine compound, compound in triazine class, cinnamic acid compound, stilbene compound; Perhaps with benzo
Azole compounds is the compound (so-called white dyes) that fluorescence is sent in the absorption ultraviolet ray of representative.
The structural formula of preferred UV light absorber is as follows.
In the formula of benzotriazole category UV light absorber (106), as R
15Can enumerate (C1-C12) straight or branched alkyl or cumyl, more preferably enumerate (C3-C6) straight or branched alkyl, further preferably enumerate (C3-C5) branched-chain alkyl, for example can enumerate: sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl propyl etc.
In the following formula (106), as R
16Can enumerate hydroxyl, (C1-C12) straight or branched alkyl, (C1-C12) straight or branched alkoxyl group or benzyloxy, preferred (C1-C12) straight or branched alkyl.More preferably (C1-C6) straight or branched alkyl, further preferred (C1-C3) straight or branched alkyl for example can be enumerated methyl, ethyl, n-propyl, sec.-propyl.
In the formula (106), as R
17Can enumerate hydrogen atom, hydroxyl, (C1-C12) straight or branched alkyl or (C1-C12) straight or branched alkoxyl group, preferred hydrogen atom, methyl, ethyl, n-propyl or sec.-propyl, more preferably hydrogen atom.
In the formula (106), as R
18Can enumerate hydrogen atom or hydroxyl, preferred hydroxyl can be enumerated hydrogen atom or chlorine atom as X, preferred chlorine atom.
As particularly preferred R
15～R
18And the combination of X, be R
15Be the tertiary butyl, R
16Be methyl, R
17Be hydrogen atom, R
18For hydroxyl, X are the chlorine atom.
In addition, as the preferred compound of UV light absorber beyond the benzotriazole compound of formula (106) expression, can enumerate: the compound in triazine class of the benzophenone compound that formula (101), formula (102) and formula (103) are represented, formula (104) expression (in the formula, R
9And R
10Represent hydrogen atom, hydroxyl or (C1-C5) alkyl respectively independently), the complex chemical compound of the benzotriazole category of formula (105) expression and benzophenone (in the formula, R
1Expression (C1-C2) alkyl or cumyl, R
2Expression hydroxyl, (C1-C2) alkoxyl group or benzyloxy, R
3Expression hydrogen atom, hydroxyl or (C1-C2) alkoxyl group, R
4Expression hydrogen atom or hydroxyl, X represents hydrogen atom or chlorine atom).
In the above-mentioned UV light absorber, particularly preferred compound is the benzotriazole compound of formula (106) expression.
The optimal way of the aqueous dispersant of fireproofing agent of the present invention is listed below.
That is, the total amount with these compounds is 1-90 weight %, preferred 5-50 weight % to the compound of formula (1), formula (2), formula (3), formula (4) or formula (5) usually in aqueous liquid dispersion, especially preferably the scope of 5-30 weight % contains.
When containing UV light absorber, its content is generally the scope of 0.1-10 weight %, preferred 0.5-10 weight %, preferred especially 1-5 weight % in aqueous liquid dispersion.
With respect to organo phosphorous compounds with as any total amount of the UV light absorber of composition, the content of tensio-active agent is generally the scope of 5-80 weight %, preferred 10-50 weight %, preferred especially 15-35 weight %.
In the scope of not damaging effect of the present invention, as required, in aqueous liquid dispersion of the present invention, can contain additives such as tensio-active agent beyond above-mentioned or dispersion agent.In addition, as required,, can contain fire proofing additive that protective colloid agent, phosphoric acid ester or phosphoamides etc. such as polyvinyl alcohol, methylcellulose gum, carboxymethyl cellulose, starch paste are used to improve flameproof effect, antioxidant etc. in order to improve stability in storage.In addition, as required, can add alkaline agent, acids, grease, higher alcohols, higher fatty acid, lower alcohols, organic solvent, penetration enhancer, polyvalent alcohol, sanitas, sequestrant, pH regulator agent, pigment and pigment etc.
By above-mentioned each composition is added in the water, prepare aqueous liquid dispersion of the present invention.
Fiber as the enough dispersion liquids of the present invention of energy are prevented fires and processed is not particularly limited, and can enumerate the mixed fibre of trevira, particularly CDP fiber and CDP fiber and trevira.
As CDP fiber or trevira, for example can enumerate: the fiber of polyester such as polyethylene terephthalate, polybutylene terephthalate, polyoxy ethoxy benzonitrile acid esters (Port リ オ キ シ エ ト キ シ ベ Application ゾ エ one ト), PEN, poly terephthalic acid cyclohexanedimethanoester ester; And make the such glycol component of the such di-carboxylic acid composition of m-phthalic acid, hexanodioic acid, sulfoisophthalic acid as supplementary component or propylene glycol, butyleneglycol, cyclohexanedimethanol, Diethylene Glycol and above-mentioned polyethylene terephthalate copolymer and the fiber of the material that obtains etc., but be not limited to these.
In addition, as fiber structure, can be any one forms such as fabric, yarn fabric, non-woven fabrics.
, can use the fiber processing of preventing fires by aqueous liquid dispersion of the present invention with bathing known method such as dip method or pad dyeing method.
Use when bathing dip method, dispersed dye that fiber is used or disperse type cationic dye etc. are used in combination with aqueous liquid dispersion, the about 60 minutes processing treatment of about 10-under 110-150 ℃, the temperature of preferred 120-140 ℃ of scope.As required, can further add dyestuffs such as fluorescence dye.
When using the pad dyeing method, after fiber structure pad dyeing, heat-treat by steaming processing such as dry heat treatment or the processing of saturated atmospheric steam, superheated vapour processing or autoclaved.During any one that handle in dry heat treatment, steaming handled, thermal treatment temp was usually 110-210 ℃ scope, preferred 170-210 ℃ scope.When thermal treatment temp surpasses 210 ℃, the xanthochromia or the embrittlement that might produce polyethylene terephthalate.
As required, can will be used in combination with bathing dip method and pad dyeing method.At this moment, can reprocess by the pad dyeing method by fiber being prevented fires after the processing with bathing dip method.By this method, can give higher fire resistance.
Embodiment
Below, be described more specifically the present invention by embodiment, still, the invention is not restricted to these embodiment.Occur among the embodiment if not otherwise specified, being meant " weight part " and " weight % " respectively under the situation of " part " and " % ".
The structural formula of the organo phosphorous compounds that uses among following embodiment 1-12 and the comparative example 1-3 gathers as follows.Me represents methyl, and Ph represents phenyl.Each compound can or be used this manufacture method and make by the known manufacture method of document.
The compound of formula (201) is R
11To R
13It all is the compound of the above-mentioned formula (1) of phenyl.This compound can come synthetic in 1 hour by making diphenyl phosphonyl chloride and phenol and triethylamine reacting by heating in tetrahydrofuran (THF).
The compound of formula (202) is R
21, R
22And R
23Compound for the above-mentioned formula (2) of phenyl.This compound can come synthetic in 1 hour by making Phenylphosphine diacid chloride and phenol and triethylamine reacting by heating in tetrahydrofuran (THF).
The compound of formula (203) is R
31, R
32, R
33Be phenyl, R
34Compound for the above-mentioned formula (3) of hydrogen atom.This compound can come synthetic in 1 hour by making diphenyl phosphonyl chloride and aniline and triethylamine reacting by heating in tetrahydrofuran (THF).
The compound of formula (204) is R
41, R
42, R
43Be phenyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.This compound can synthesize with the aniline reacting by heating then by making phenyl time phosphine diacid chloride and phenol and triethylamine reacting by heating 1 hour in tetrahydrofuran (THF) in 1 hour.
The compound of formula (205) is R
51, R
52, R
53Be phenyl, R
54, R
55Compound for the above-mentioned formula (5) of hydrogen atom.This compound can come synthetic in 1 hour by making phenyl time phosphine diacid chloride and aniline and triethylamine reacting by heating in tetrahydrofuran (THF).
The compound of formula (206) is R
11, R
12Be phenyl, R
13Compound for the above-mentioned formula (1) of 3-aminomethyl phenyl.This compound can come synthetic in 1 hour by making diphenyl phosphonyl chloride and meta-cresol and triethylamine reacting by heating in tetrahydrofuran (THF).
The compound of formula (207) is R
21Be phenyl, R
22, R
23Compound for the above-mentioned formula (2) of 3-aminomethyl phenyl.This compound can come synthetic in 1 hour by making phenyl time phosphine diacid chloride and meta-cresol and triethylamine reacting by heating in tetrahydrofuran (THF).
The compound of formula (208) is R
11, R
12Be phenyl, R
13Compound for the above-mentioned formula (1) of 4-aminomethyl phenyl.This compound can come synthetic in 1 hour by making diphenyl phosphonyl chloride and p-cresol and triethylamine reacting by heating in tetrahydrofuran (THF).
The compound of formula (209) is R
21Be phenyl, R
22, R
23Compound for the above-mentioned formula (2) of 4-aminomethyl phenyl.This compound can come synthetic in 1 hour by making phenyl time phosphine diacid chloride and p-cresol and triethylamine reacting by heating in tetrahydrofuran (THF).
The compound of formula (210) is R
11, R
12Be phenyl, R
13Compound for the above-mentioned formula (1) of 4-p-methoxy-phenyl.This compound can come synthetic in 1 hour by making diphenyl phosphonyl chloride and p methoxy phenol and triethylamine reacting by heating in tetrahydrofuran (THF).
The compound of formula (211) is R
21Be phenyl, R
22, R
23Compound for the above-mentioned formula (2) of 4-p-methoxy-phenyl.This compound can come synthetic in 1 hour by making phenyl time phosphine diacid chloride and p methoxy phenol and triethylamine reacting by heating in tetrahydrofuran (THF).
The compound of formula (212) is R
41, R
43Be phenyl, R
42Be p-methoxyphenyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.This compound can synthesize with the aniline reacting by heating then by making phenyl time phosphine diacid chloride and p methoxy phenol and triethylamine reacting by heating 1 hour in tetrahydrofuran (THF) in 1 hour.
The compound of formula (301) is made by big eight KCCs, and NDPP sells on market with trade(brand)name.
The compound of formula (302) is learned Co., Ltd. by northern Xinghua and is made, and TPPO sells on market with trade(brand)name.
The compound of formula (303) is made by big eight KCCs, and TPP sells on market with trade(brand)name.
In following embodiment 1-12 and comparative example 1-3, each organo phosphorous compounds shown in the table 1-15 is pulverized with sand mill as required, each composition is added in the water, obtain aqueous liquid dispersion.
Embodiment 1
Table 1
Water 63.0%
The compound of formula (201) (compound of above-mentioned formula (1)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 2
Table 2
Water 63.0%
The compound of formula (202) (compound of above-mentioned formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 3
Table 3
Water 63.0%
The compound of formula (203) (compound of above-mentioned formula (3)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 4
Table 4
Water 63.0%
The compound of formula (204) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 5
Table 5
Water 63.0%
The compound of formula (205) (compound of above-mentioned formula (5)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 6
Table 6
Water 63.0%
The compound of formula (206) (compound of above-mentioned formula (1)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 7
Table 7
Water 63.0%
The compound of formula (207) (compound of above-mentioned formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 8
Table 8
Water 63.0%
The compound of formula (208) (compound of above-mentioned formula (1)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 9
Table 9
Water 63.0%
The compound of formula (209) (compound of above-mentioned formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 10
Table 10
Water 63.0%
The compound of formula (210) (compound of above-mentioned formula (1)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 11
Table 11
Water 63.0%
The compound of formula (211) (compound of above-mentioned formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 12
Table 12
Water 63.0%
The compound of formula (212) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Comparative example 1
Table 13
Water 63.0%
The compound 30.0% of formula (301)
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Comparative example 2
Table 14
Water 63.0%
The compound 30.0% of formula (302)
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Comparative example 3
Table 15
Water 63.0%
The compound 30.0% of formula (303)
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Test example 1
Use the aqueous liquid dispersion of the fireproofing agent for preparing among the above embodiments 1-12 or the comparative example 1-3, carry out the painted processing of preventing fires simultaneously respectively utilizing with bathing the cloth of dip method to 40 centimeter square of the mixed fibre that contains 30% polyester and 70%CDP.
That is,, the fire prevention machining agent for preparing among dispersed dye 0.72%o.w.f. (based on the weight of fiber) and cationic dyestuff 0.92%o.w.f. and embodiment 1-12 or the comparative example 1-3 is carried out handling in 130 ℃ * 60 minutes with bath raio respectively at 1: 20 as dye bath.
The dyestuff that uses, be カ ヤ ロ Application マ イ Network ロ エ ス テ Le イ エ ロ one AQ-LE0.24%, カ ヤ ロ Application マ イ Network ロ エ ス テ Le レ Star De AQ-LE0.24%, カ ヤ ロ Application マ イ Network ロ エ ス テ Le Block Le one AQ-LE0.24%, as カ ヤ Network リ Le イ エ ロ one 3RL-ED0.46% (being Nippon Kayaku K. K makes), カ ヤ Network リ Le レ Star De GL-ED0.24%, カ ヤ Network リ Le Block Le one GSL-ED0.22% (being Nippon Kayaku K. K makes) of cationic dyestuff as dispersed dye.
Afterwards, each cloth is carried out reduction clearing, carry out thermal treatment in 60 seconds at 170 ℃ then.In addition, according to JIS K3371, use weakly alkaline first kind of lotion with the ratio of 1g/L, with 1: 40,60 ℃ ± 2 ℃, 15 minutes condition of bath raio each cloth is washed, under 40 ℃ ± 2 ℃, carry out three times 5 minutes washing then, and carry out 2 minutes centrifuge dehydration, under 60 ℃ ± 5 ℃, carry out warm air drying then, above operation as a circulation, is carried out 5 circulations altogether.
15 kinds of mixed fibre cloth that will be obtained by aforesaid operations carry out flammability test as test film to them.
In addition, above-mentioned reduction clearing is meant following operation.That is, preparation contains the aqueous solution of tensio-active agent of sodium hydroxide, the 1g/L of sulfoxylate, the 2g/L of 2g/L, be heated 80 ℃ after, add above-mentioned cloth after the fire prevention processing and carry out the operation handled in 20 minutes.
The test method of flammability test
Test according to fire service law JIS L1091A-1 method (45 degree microburner method), carry out following evaluation.Its result is as shown in table 16 below.
Estimate A: qualification rate
With the residual flame time be situation below 3 seconds as qualified, with the qualified number of times in this mensuration divided by measuring numerical value that number of times obtains as qualification rate.Radix point rounds up later on, and unit is %.Qualification rate is high more, and fire resistance is high more.
The bracket of qualification rate back for calculating qualified number of times and the mensuration number of times that qualification rate is used, is represented with " (qualified number of times/mensuration number of times) ".
Estimate B: the average residual flame time
The summation of the residual flame time that test is measured among the A is calculated the average residual flame time thus divided by measuring number of times.Unit is second.The average residual flame time is short more, and fire resistance is high more.
Estimate C: average burning area
The burning area of determination test sheet divided by measuring number of times, calculates average burning area with its summation thus.Unit is cm
2Average burning area is more little, and fire resistance is high more.
Table 16
From the result of table 16 as can be seen, the qualification rate of estimating A is 95% to 100% in embodiments of the invention 1-12, and relative therewith, each comparative example is 57% to 65%, and the qualification rate of embodiments of the invention is higher.In addition, about estimating the average residual flame time of B, among the embodiment 1-12 be 0.5-0.9, relative therewith, each comparative example is 2.5-3.8, and the latter is about 3 to about 7 times, and the average residual flame time is longer.In addition, about estimating the average burning area of C, among the embodiment 1-12 be 3.6-4.1, relative therewith, each comparative example is 5.6-7.1, and the latter is 1.4-2.0 times, and average burning area is bigger.
As mentioned above, use the test film of aqueous liquid dispersion of the present invention, show good fire resistance.In addition, although use the test film of aqueous liquid dispersion of the present invention to repeat five circulations such as water washing, still keep above-mentioned performance, therefore as can be seen, weather resistance is also extremely good.
Embodiment 13
As novel cpd, make the compound of following formula (213) to (238) expression by above-mentioned formula provided by the invention (2) and formula (4) expression.In addition, compound as a comparison uses the compound of following formula (304) and (305).
1. the compound of formula (213) is R
21, R
22Be phenyl, R
23Compound for the above-mentioned formula (2) of benzyl.
In 200 parts of tetrahydrofuran (THF)s, make 57 parts of 50 parts of diphenyl phosphonyl chlorides, 24 parts of phenol and triethylamines reaction below 10 ℃ 1 hour, at room temperature reacted 1 hour with benzylalcohol then.Add 100 parts in water, be adjusted to below the pH7 with dilute hydrochloric acid again, leave standstill.The upper strata is told,, lower floor is told discarded, distill from upper layer part with vaporizer and to remove tetrahydrofuran (THF) etc., obtain phosphinic acid compounds with after the saturated common salt water washing.The gained compound is flaxen liquid, is measured the compound that is accredited as formula (213) by LC-MS (high performance liquid chromatography-mass spectrum).
MS:324.09 (theoretical value 324.09)
2. the compound of formula (214) is R
41, R
42Be phenyl, R
43Be benzyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), made diphenyl phosphonyl chloride, phenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the benzylamine reaction then.
MS:323.11 (theoretical value 323.11)
3. the compound of formula (215) is R
21Be phenyl, R
22Be 4-aminomethyl phenyl, R
23Compound for the above-mentioned formula (2) of benzyl.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and p-cresol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the benzylalcohol reaction then.
MS:338.11 (theoretical value 338.11)
4. the compound of formula (216) is R
41Be phenyl, R
42Be 3-aminomethyl phenyl, R
43Be benzyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and meta-cresol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the benzylamine reaction then.
MS:337.12 (theoretical value 337.12)
5. the compound of formula (217) is R
41, R
43Be phenyl, R
42Be 3-aminomethyl phenyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and meta-cresol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with aniline reaction then.
MS:323.11 (theoretical value 323.11)
6. the compound of formula (218) is R
21Be phenyl, R
22Be 4-phenyl, R
23Compound for the above-mentioned formula (2) of benzyl.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and p-phenyl phenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the benzylalcohol reaction then.
MS:400.12 (theoretical value 400.12)
7. the compound of formula (219) is R
41Be phenyl, R
42Be 4-aminomethyl phenyl, R
43Be benzyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and p-cresol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the benzylamine reaction then.
MS:337.12 (theoretical value 337.12)
8. the compound of formula (220) is R
41, R
43Be phenyl, R
42Be 4-aminomethyl phenyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), made diphenyl phosphonyl chloride, p-cresol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with aniline reaction then.
MS:323.11 (theoretical value 323.11)
9. the compound of formula (221) is R
21Be phenyl, R
22Be 4-tert-butyl-phenyl, R
23Compound for the above-mentioned formula (2) of benzyl.
Similarly in tetrahydrofuran (THF), made diphenyl phosphonyl chloride and 4-tert.-butyl phenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the benzylalcohol reaction then.
MS:380.15 (theoretical value 380.15)
10. the compound of formula (222) is R
41Be phenyl, R
42Be 4-tert-butyl-phenyl, R
43Be benzyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), made diphenyl phosphonyl chloride, 4-tert.-butyl phenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the benzylamine reaction then.
MS:379.17 (theoretical value 379.17)
11. the compound of formula (223) is R
41Be phenyl, R
42Be 4-phenyl, R
43Be benzyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and p-phenyl phenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the benzylamine reaction then.
MS:399.14 (theoretical value 399.14)
12. the compound of formula (224) is R
41Be phenyl, R
42For to cumyl phenyl, R
43Be benzyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
With the manufacture method of the compound of formula (213) similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride with to cumyl phenol and triethylamine reaction 1 hour, came synthetic in 1 hour with the benzylamine reaction then.
MS:441.19 (theoretical value 441.19)
13. the compound of formula (225) is R
41Be phenyl, R
42Be 2-naphthyl, R
43Be benzyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and beta naphthal and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the benzylamine reaction then.
MS:373.12 (theoretical value 373.12)
14. the compound of formula (226) is R
41, R
43Be phenyl, R
42Be 2-naphthyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and beta naphthal and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with aniline reaction then.
MS:359.11 (theoretical value 359.11)
15. the compound of formula (227) is R
41, R
42Be phenyl, R
43Be 2-methyl-benzyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and phenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the reaction of 2-methylbenzylamine then.
MS:337.12 (theoretical value 337.12)
16. the compound of formula (228) is R
41, R
42Be phenyl, R
43Be benzyl, R
44Compound for the above-mentioned formula (4) of methyl.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and phenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the reaction of N-methylbenzylamine then.
MS:337.12 (theoretical value 337.12)
17. the compound of formula (229) is R
41Be phenyl, R
42Be 4-tert-butyl-phenyl, R
43Be phenyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), made diphenyl phosphonyl chloride and 4-tert.-butyl phenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with aniline reaction then.
MS:365.15 (theoretical value 365.15)
18. the compound of formula (230) is R
41, R
42, R
43Be phenyl, R
44Compound for the above-mentioned formula (4) of N-aminomethyl phenyl.
The manufacture method of the compound of formula (213) similarly makes diphenyl phosphonyl chloride and phenol and triethylamine reaction 1 hour in tetrahydrofuran (THF), came synthetic in 1 hour with the methylphenylamine reaction then.
MS:323.11 (theoretical value 323.11)
19. the compound of formula (231) is R
41Be phenyl, R
42Be 2-phenyl, R
43Be benzyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), made diphenyl phosphonyl chloride and 2-phenylphenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the benzylamine reaction then.
MS:399.14 (theoretical value 399.14)
20. the compound of formula (232) is R
41Be phenyl, R
42Be 2-phenyl, R
43Be phenyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), made diphenyl phosphonyl chloride and 2-phenylphenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with aniline reaction then.
MS:385.12 (theoretical value 385.12)
21. the compound of formula (233) is R
21, R
23Be phenyl, R
22Compound for the above-mentioned formula (2) of 2-phenoxy group ethyl.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and phenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the reaction of 2-phenoxyethyl alcohol then.
MS:354.10 (theoretical value 354.10)
22. the compound of formula (234) is R
41, R
43Be phenyl, R
42Be 2-phenoxy group ethyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), made diphenyl phosphonyl chloride and 2-phenoxyethyl alcohol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with aniline reaction then.
MS:353.12 (theoretical value 353.12)
23. the compound of formula (235) is R
41, R
43Be phenyl, R
42For to cumyl phenyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
With the manufacture method of the compound of formula (213) similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride with to cumyl phenol and triethylamine reaction 1 hour, came synthetic in 1 hour with aniline reaction then.
MS:427.17 (theoretical value 427.17)
24. the compound of formula (236) is R
41Be phenyl, R
42, R
43Be benzyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and benzylalcohol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the benzylamine reaction then.
MS:337.12 (theoretical value 337.12)
25. the compound of formula (237) is R
41, R
43Be phenyl, R
42Be benzyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and benzylalcohol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with aniline reaction then.
MS:323.11 (theoretical value 323.11)
26. the compound of formula (238) is R
41, R
42Be phenyl, R
43Be cyclohexyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.
Similarly in tetrahydrofuran (THF), make diphenyl phosphonyl chloride and phenol and triethylamine reaction 1 hour with the manufacture method of the compound of formula (213), came synthetic in 1 hour with the hexahydroaniline reaction then.
MS:315.14 (theoretical value 315.14)
The compound of formula (304) by make diphenyl phosphinyl chloride and phenol and triethylamine reaction 1 hour in tetrahydrofuran (THF), came synthetic in 1 hour with aniline reaction then.
The compound of formula (305) is R
21, R
23Be phenyl, R
22Phosphonate compound for patent documentation 5 record of 2-naphthyl.
In tetrahydrofuran (THF), make diphenyl phosphonyl chloride and phenol and triethylamine reaction 1 hour, came synthetic in 1 hour with the beta naphthal reaction then.
Among following the embodiment 14-39 and comparative example 4-5, each organo phosphorous compounds shown in the table 17-44 is pulverized with sand mill as required, each composition is added to obtaining aqueous liquid dispersion in the water.
Embodiment 14
Table 17
Water 63.0%
The compound of formula (213) (compound of above-mentioned formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 15
Table 18
Water 63.0%
The compound of formula (214) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 16
Table 19
Water 63.0%
The compound of formula (215) (compound of above-mentioned formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 17
Table 20
Water 63.0%
The compound of formula (216) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 18
Table 21
Water 63.0%
The compound of formula (217) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 19
Table 22
Water 63.0%
The compound of formula (218) (compound of above-mentioned formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 20
Table 23
Water 63.0%
The compound of formula (219) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 21
Table 24
Water 63.0%
The compound of formula (220) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 22
Table 25
Water 63.0%
The compound of formula (221) (compound of above-mentioned formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 23
Table 26
Water 63.0%
The compound of formula (222) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 24
Table 27
Water 63.0%
The compound of formula (223) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 25
Table 28
Water 63.0%
The compound of formula (224) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 26
Table 29
Water 63.0%
The compound of formula (225) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 27
Table 30
Water 63.0%
The compound of formula (226) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 28
Table 31
Water 63.0%
The compound of formula (227) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 29
Table 32
Water 63.0%
The compound of formula (228) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 30
Table 33
Water 63.0%
The compound of formula (229) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 31
Table 34
Water 63.0%
The compound of formula (230) (compound of above-mentioned formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 32
Table 35
Water 63.0%
The compound of formula (231) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 33
Table 36
Water 63.0%
The compound of formula (232) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 34
Table 37
Water 63.0%
The compound of formula (233) (compound of above-mentioned formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 35
Table 38
Water 63.0%
The compound of formula (234) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 36
Table 39
Water 63.0%
The compound of formula (235) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 37
Table 40
Water 63.0%
The compound of formula (236) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 38
Table 41
Water 63.0%
The compound of formula (237) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 39
Table 42
Water 63.0%
The compound of formula (238) (compound of above-mentioned formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Comparative example 4
Table 43
Water 63.0%
The compound 30.0% of formula (304)
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Comparative example 5
Table 44
Water 63.0%
The compound 30.0% of formula (305)
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 01%
100.0％
Test example 2
Use the aqueous liquid dispersion of the fireproofing agent for preparing among the foregoing description 14-39 or the comparative example 4-5, similarly carry out the painted processing of preventing fires simultaneously respectively utilizing with bathing the cloth of dip method to 20 centimeter square of the mixed fibre that contains 30% polyester and 70%CDP with test example 1.
Afterwards, similarly carry out combustion test (estimate A, estimate B) with test example 1.In addition, carry out the evaluation C (average burning area) of the test replacement test example 1 of following evaluation D (fast light fastness).The result is shown in following table 45.
Estimate D: fast light fastness
Fast light fastness is with 1～5 grade of expression.
Table 45
From the result of table 45 as can be seen, the qualification rate of estimating A is 86% to 100% in embodiments of the invention 14-39, and relative therewith, comparative example 4 is 57%, and the qualification rate of embodiments of the invention is higher.Under the situation of comparative example 5, the qualification rate of estimating A is up to 86%, but fast light fastness is low, and photostabilization is poor.In addition, about estimating the average residual flame time of B, among the embodiment 14-39 be 0.5-4.5, relative therewith, comparative example 4-5 is 4.9-7.8, and the latter's the average residual flame time is longer.
That is, fireproofing agent of the present invention can be used as fireproofing agent and uses showing the isostatic performance aspect evaluation A, evaluation B and the evaluation D.
Embodiment 40
As novel cpd, make the compound of following formula (239) to (246) expression by above-mentioned formula provided by the invention (2) and formula (4) expression.
1. the compound of formula (239) is R
21Be benzyl, R
22, R
23Compound for the above-mentioned formula (2) of phenyl.This compound can come synthetic in 1 hour by making benzyl time phosphine diacid chloride and phenol reacting by heating in tetrahydrofuran (THF).
MS:324.09 (theoretical value 324.09)
2. the compound of formula (240) is R
21Be phenyl, R
22Be p-nitrophenyl, R
23Compound for the above-mentioned formula (2) of phenyl.This compound can synthesize with the phenol reacting by heating then by making phenyl time phosphine diacid chloride and p-NP and triethylamine reacting by heating 1 hour in tetrahydrofuran (THF) in 1 hour.
MS:355.06 (theoretical value 355.06)
3. the compound of formula (241) is R
21Be p-methylphenyl, R
22, R
23Compound for the above-mentioned formula (2) of phenyl.This compound can come synthetic in 1 hour by making tolyl time phosphine diacid chloride and phenol and triethylamine reacting by heating in tetrahydrofuran (THF).
MS:324.09 (theoretical value 324.09)
4. the compound of formula (242) is R
21Be m-nitro base, R
22, R
23Compound for the above-mentioned formula (2) of phenyl.This compound can come synthetic in 1 hour by making m-nitro base time phosphine diacid chloride and phenol and triethylamine reacting by heating in tetrahydrofuran (THF).
MS:355.06 (theoretical value 355.06)
5. the compound of formula (243) is R
21For to nitrobenzyl, R
22, R
23Compound for the above-mentioned formula (2) of phenyl.This compound can synthesize nitrobenzyl time phosphine diacid chloride and phenol and triethylamine reacting by heating in tetrahydrofuran (THF) by making in 1 hour.
MS:369.08 (theoretical value 369.08)
6. the compound of formula (244) is R
21Be 4-phenyl, R
22, R
23Compound for the above-mentioned formula (2) of phenyl.This compound can come synthetic in 1 hour by making 4-phenyl time phosphine diacid chloride and phenol and triethylamine reacting by heating in tetrahydrofuran (THF).
MS:386.11 (theoretical value 386.11)
7. the compound of formula (245) is R
41Be benzyl, R
42, R
43Be phenyl, R
44Compound for the above-mentioned formula (4) of hydrogen atom.This compound can synthesize with the aniline reacting by heating then by making benzyl time phosphine diacid chloride and phenol and triethylamine reacting by heating 1 hour in tetrahydrofuran (THF) in 1 hour.
MS:323.11 (theoretical value 323.11)
8. the compound of formula (246) is R
41Be p-methoxy-phenyl, R
42, R
43For phenyl, R44 is the compound of the above-mentioned formula (4) of hydrogen atom.This compound can synthesize with the aniline reacting by heating then by making p-methoxy-phenyl time phosphine diacid chloride and phenol and triethylamine reacting by heating 1 hour in tetrahydrofuran (THF) in 1 hour.
MS:323.11 (theoretical value 339.10)
Among the following embodiment 41-48, each organo phosphorous compounds shown in the table 46-53 is pulverized with sand mill as required, each composition is added to obtaining aqueous liquid dispersion in the water.
Embodiment 41
Table 46
Water 63.0%
Formula (239) (compound of general formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 42
Table 47
Water 63.0%
Formula (240) (compound of general formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 43
Table 48
Water 63.0%
Formula (241) (compound of general formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 44
Table 49
Water 63.0%
Formula (242) (compound of general formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 45
Table 50
Water 63.0%
Formula (243) (compound of general formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 46
Table 51
Water 63.0%
Formula (244) (compound of general formula (2)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 47
Table 52
Water 63.0%
Formula (245) (compound of general formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Embodiment 48
Table 53
Water 63.0%
Formula (246) (compound of general formula (4)) 30.0%
プ ラ イ サ one Off AL Na salt 6.3%
Thickening material 0.5%
Defoamer 0.1%
Mould inhibitor 0.1%
100.0％
Test example 3
Use the aqueous liquid dispersion of the fireproofing agent for preparing among the foregoing description 41-48, similarly carry out the painted processing of preventing fires simultaneously respectively utilizing with bathing the cloth of dip method to 20 centimeter square of the mixed fibre that contains 30% polyester and 70%CDP with test example 1.
Afterwards, similarly carry out combustion test (estimate A, estimate B) and average burning area (estimating C) with test example 1.The result is shown in following table 54.
Table 54
From the result of table 54 as can be seen, the qualification rate of estimating A all is 100% in embodiments of the invention 41-48, the average residual flame time of estimating B is 0.5-0.8, the average burning area of estimating C is 3.1-3.9, uses the test film of aqueous liquid dispersion of the present invention to show good fire resistance as can be seen.
As above as can be known, use the test film of aqueous liquid dispersion of the present invention to show good fire resistance.In addition we know, though use the test film of aqueous liquid dispersion of the present invention to repeat five circulations such as water washing, but still keep above-mentioned performance, so weather resistance is also extremely good.
Industrial applicability
By the present invention, can provide the aqueous liquid dispersion that to give the organic phosphorus compound of the good fire protecting performance with durability to the blend fibre of fiber, particularly CDP and polyester fiber.
Claims (15)
1. aqueous liquid dispersion, it contains the Phosphoramido compounds of inferior Phosphoramido compounds, following formula (4) expression of phosphonate compound, following formula (3) expression of the phosphinate compounds that is selected from following formula (1) expression, following formula (2) expression and at least a organo phosphorous compounds or their salt and the tensio-active agent in the phosphine diamide that following formula (5) is represented
In the formula (1), R
11, R
12And R
13Respectively the expression aryl that can replace by substituting group group A or (C1-C10) alkyl independently; at this; substituting group group A represents hydroxyl, nitro, amino, cyano group, formyl radical, carboxyl, urea groups, (C1-C10) alkyl, (C1-C10) alkylamino, two (C1-C10) alkylamino, phenyl, phenoxy group and (C1-C10) alkoxyl group
In the formula (2), R
21The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
22The phenyl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
23The phenyl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl, wherein, this alkyl can be replaced by following groups: the aryloxy that can be replaced by substituting group group A, (C7-C15) aralkoxy that can be replaced by substituting group group A or (C1-C10) alkoxyl group, at this, substituting group group A is identical with above-mentioned definition
In the formula (3), R
31, R
32And R
33Respectively the expression aryl that can replace by substituting group group A or (C1-C10) alkyl independently; R
34Be hydrogen atom, the aryl that can be replaced by substituting group group A or (C1-C10) alkyl, at this, substituting group group A is identical with above-mentioned definition,
In the formula (4), R
41The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
42The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl, wherein, this alkyl can be replaced by following groups: the aryloxy that can be replaced by substituting group group A, (C7-C15) aralkoxy that can be replaced by substituting group group A or (C1-C10) alkoxyl group; R
43The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
44Expression hydrogen atom, the aryl that can replace by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl that can replace by substituting group group A, at this, substituting group group A is identical with above-mentioned definition,
In the formula (5), R
51, R
52And R
53Respectively the expression aryl that can replace by substituting group group A or (C1-C10) alkyl independently; R
54And R
55Represent hydrogen atom, the aryl that can be replaced by substituting group group A or (C1-C10) alkyl respectively independently, at this, substituting group group A is identical with above-mentioned definition.
2. aqueous liquid dispersion as claimed in claim 1, wherein, the aryl that can be replaced by substituting group group A be (C1-C10) alkyl phenyl, xenyl or (C1-C10) alkoxyl phenyl.
3. aqueous liquid dispersion as claimed in claim 1 or 2 wherein, contains the organo phosphorous compounds of the formula (1) of 1～90 weight % to formula (5) expression in total amount in aqueous liquid dispersion.
4. as each described aqueous liquid dispersion in the claim 1 to 3, wherein, tensio-active agent is nonionic surface active agent or aniorfic surfactant or the two.
5. as each described aqueous liquid dispersion in the claim 1 to 4, wherein, also contain UV light absorber.
6. as each described aqueous liquid dispersion in the claim 1 to 5, its fireproofing agent of using as fiber uses.
7. aqueous liquid dispersion as claimed in claim 6, wherein, fiber is a trevira.
8. aqueous liquid dispersion as claimed in claim 7, wherein, trevira is cation-dyeable type trevira or the mixed fibre that contains cation-dyeable type trevira.
9. the fire prevention working method of a fiber is characterized in that, uses each described aqueous liquid dispersion in the claim 1 to 8.
By the described method of claim 9 prevent fires processing after fiber.
11. the Phosphoramido compounds of the phosphonate compound of following formula (2) expression or following formula (4) expression or their salt,
In the formula (2), R
21The aryl that expression can be replaced by substituting group group A or (C7-C15) aralkyl that can replace by substituting group group A; R
22The phenyl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
23The phenyl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl, wherein, this alkyl can be replaced by following groups: the aryloxy that can be replaced by substituting group group A, (C7-C15) aralkoxy that can be replaced by substituting group group A or (C1-C10) alkoxyl group, at this, substituting group group A is identical with above-mentioned definition
In the formula (4), R
41The aryl that expression can be replaced by substituting group group A or (C7-C15) aralkyl that can replace by substituting group group A; R
42The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl, wherein, this alkyl can be replaced by following groups: the aryloxy that can be replaced by substituting group group A, (C7-C15) aralkoxy that can be replaced by substituting group group A or (C1-C10) alkoxyl group; R
43The aryl that expression can be replaced by substituting group group A, (C7-C15) aralkyl that can replace by substituting group group A or (C1-C10) alkyl; R
44Expression hydrogen atom, (C7-C15) aralkyl that can be replaced by substituting group group A or (C1-C10) alkyl that can be replaced by substituting group group A, at this, substituting group group A is identical with above-mentioned definition.
12. phosphonate compound as claimed in claim 11 or its salt, wherein, R
21For can by hydroxyl, nitro, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) phenyl that replaces of alkoxyl group, can be by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) naphthyl that replaces of alkoxyl group or can be by hydroxyl, nitro, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R
22For can be by nitro, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl or (C1-C6) phenyl that replaces of alkoxyl group or can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R
23For can be by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) (C7-C12) aralkoxy of replacing of alkoxyl group, (C1-C6) alkyl that can replace by (C1-C6) alkoxyl group, hydroxyl, amino, (C1-C6) alkylamino, carboxyl or urea groups or can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group.
13. as claim 11 or 12 described phosphonate compounds or its salt, wherein, R
21Be phenyl, tolyl, nitrophenyl, nitrobenzyl or xenyl; R
22Be the phenyl that can replace by (C1-C6) alkyl, nitro or phenyl; R
23Be (C1-C6) alkyl, benzyl or the styroyl that replaces by phenoxy group.
14. Phosphoramido compounds as claimed in claim 11 or its salt, wherein, R
41For can by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) phenyl that replaces of alkoxyl group, can be by hydroxyl, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) naphthyl that replaces of alkoxyl group or can be by hydroxyl, nitro, cyano group, (C1-C6) alkyl, phenyl or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R
42For can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group, (C7-C12) aralkyl or (C1-C6) phenyl of alkoxyl group replacement, can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group, (C7-C12) aralkyl or (C1-C6) naphthyl of alkoxyl group replacement, can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group, perhaps can be by (C1-C6) alkyl of phenoxy group replacement; R
43For can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group or (C1-C6) phenyl that replaces of alkoxyl group, can be by hydroxyl, amino, cyano group, (C1-C6) alkyl, (C1-C6) alkylamino, two (C1-C6) alkylamino, phenyl, phenoxy group or (C1-C6) naphthyl that replaces of alkoxyl group, perhaps can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl of replacing of alkoxyl group; R
44Be (C1-C6) alkyl or hydrogen atom.
15. as claim 11 or 14 described Phosphoramido compounds or its salt, wherein, R
41Be phenyl, p-methoxyphenyl or benzyl; R
42For the phenyl that can replace by (C1-C6) alkyl, phenyl, benzyl, styroyl or hydrocinnamyl, naphthyl, can be by hydroxyl, cyano group, formyl radical, carboxyl, urea groups, (C1-C6) alkyl, phenyl, phenoxy group or (C1-C6) (C7-C12) aralkyl or the 2-phenoxy group ethyl that replace of alkoxyl group; R
43Be phenyl, benzyl or styroyl; R
44Be methyl, ethyl or hydrogen atom.
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| PCT/JP2009/056231 WO2009119789A1 (en) | 2008-03-28 | 2009-03-27 | Aqueous dispersion of organic phosphorus compound and flameproofing method using the same |
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| CN102782093B (en) * | 2010-02-02 | 2014-12-31 | 日本化药株式会社 | Aqueous dispersion for fireproofing, fireproofing method, and fireproofed fiber |
| CN101792463B (en) * | 2010-03-02 | 2012-07-11 | 苏州科技学院 | Nitrogen-containing aryl hypophosphorous acid metal salt and preparation method thereof |
| JP5739693B2 (en) * | 2011-03-10 | 2015-06-24 | 松本油脂製薬株式会社 | Synthetic fiber production method, fiber treatment agent, and synthetic fiber fusion prevention method |
| TWI475100B (en) * | 2013-05-29 | 2015-03-01 | Sino Japan Chemical Co Ltd | Water-soluble flame retardant composition and application thereof |
| JP6439345B2 (en) * | 2014-09-22 | 2018-12-19 | 富士ゼロックス株式会社 | Flame retardant emulsion, resin emulsion, resin composition and molded product |
| WO2016121750A1 (en) * | 2015-01-29 | 2016-08-04 | 株式会社Adeka | Flame-retardant epoxy resin composition, prepreg formed using this, and laminate plate |
| KR101965572B1 (en) * | 2018-09-20 | 2019-04-04 | 한국화학연구원 | Synthesis method of flame retarding diol, flame retarding diol for the production of thermoplastic polyurethane, and thermoplastic polyurethane having the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101981157B (en) | 2013-08-21 |
| WO2009119789A1 (en) | 2009-10-01 |
| TW201002729A (en) | 2010-01-16 |
| JPWO2009119789A1 (en) | 2011-07-28 |
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