CN107974826A - A kind of fabric floride-free water-proof finish lotion and its application - Google Patents
A kind of fabric floride-free water-proof finish lotion and its application Download PDFInfo
- Publication number
- CN107974826A CN107974826A CN201711292001.8A CN201711292001A CN107974826A CN 107974826 A CN107974826 A CN 107974826A CN 201711292001 A CN201711292001 A CN 201711292001A CN 107974826 A CN107974826 A CN 107974826A
- Authority
- CN
- China
- Prior art keywords
- carbon chain
- long carbon
- lotion
- fabric
- floride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004744 fabric Substances 0.000 title claims abstract description 43
- 239000006210 lotion Substances 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- -1 carbon chain carboxylic acids Chemical class 0.000 claims abstract description 41
- 238000004078 waterproofing Methods 0.000 claims abstract description 24
- 239000000839 emulsion Substances 0.000 claims abstract description 22
- 229920003180 amino resin Polymers 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 239000001993 wax Substances 0.000 claims abstract description 14
- 125000002091 cationic group Chemical group 0.000 claims abstract description 10
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 21
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 20
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 20
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 claims description 17
- 150000003512 tertiary amines Chemical class 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 8
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical group C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 7
- 239000012875 nonionic emulsifier Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 241000370738 Chlorion Species 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 238000005829 trimerization reaction Methods 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 150000002148 esters Chemical class 0.000 abstract description 6
- 229920000742 Cotton Polymers 0.000 abstract description 3
- 229920004933 Terylene® Polymers 0.000 abstract description 3
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 3
- 235000005985 organic acids Nutrition 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- 229920000877 Melamine resin Polymers 0.000 description 9
- 235000011167 hydrochloric acid Nutrition 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 125000004079 stearyl 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])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])[H] 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000289 melt material Substances 0.000 description 5
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 description 3
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- USZLCYNVCCDPLQ-UHFFFAOYSA-N hydron;n-methoxymethanamine;chloride Chemical class Cl.CNOC USZLCYNVCCDPLQ-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- VRQWWCJWSIOWHG-UHFFFAOYSA-J octadecanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O VRQWWCJWSIOWHG-UHFFFAOYSA-J 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
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- 238000007670 refining Methods 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
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- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CQXDDVVZHUFGSJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;zirconium Chemical compound [Zr].CCCCCCCC\C=C/CCCCCCCC(O)=O CQXDDVVZHUFGSJ-KVVVOXFISA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- QSSXAAUXGBMLNR-UHFFFAOYSA-N 1-chloropentadecylbenzene Chemical compound CCCCCCCCCCCCCCC(Cl)C1=CC=CC=C1 QSSXAAUXGBMLNR-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- UZZYXZWSOWQPIS-UHFFFAOYSA-N 3-fluoro-5-(trifluoromethyl)benzaldehyde Chemical compound FC1=CC(C=O)=CC(C(F)(F)F)=C1 UZZYXZWSOWQPIS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- RWWVEQKPFPXLGL-ONCXSQPRSA-N L-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC=C(C(C)C)C=C2CC1 RWWVEQKPFPXLGL-ONCXSQPRSA-N 0.000 description 1
- RWWVEQKPFPXLGL-UHFFFAOYSA-N Levopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CC=C(C(C)C)C=C1CC2 RWWVEQKPFPXLGL-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 1
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- ZFLJZKCETUJUJI-UHFFFAOYSA-N N-ethoxy-N-methyloctadecan-1-amine Chemical class CCCCCCCCCCCCCCCCCCN(C)OCC ZFLJZKCETUJUJI-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000017339 Pinus palustris Nutrition 0.000 description 1
- 241000204936 Pinus palustris Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
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- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
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- AXLHVTKGDPVANO-UHFFFAOYSA-N methyl 2-amino-3-[(2-methylpropan-2-yl)oxycarbonylamino]propanoate Chemical compound COC(=O)C(N)CNC(=O)OC(C)(C)C AXLHVTKGDPVANO-UHFFFAOYSA-N 0.000 description 1
- MAQCMFOLVVSLLK-UHFFFAOYSA-N methyl 4-(bromomethyl)pyridine-2-carboxylate Chemical compound COC(=O)C1=CC(CBr)=CC=N1 MAQCMFOLVVSLLK-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
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- 239000001923 methylcellulose Substances 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012165 plant wax Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012177 spermaceti Substances 0.000 description 1
- 229940084106 spermaceti Drugs 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
-
- 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
- D06M13/372—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 etherified or esterified hydroxy groups ; Polyethers of low molecular weight
-
- 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
- D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
-
- 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
- D06M13/10—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 oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
-
- 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
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
-
- 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
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The present invention relates to fabric waterproofing agent, specifically a kind of fabric floride-free water-proof finish lotion and its application.Floride-free water-proof finish emulsion components are counted (dry matter component) in parts by weight：A) 80 40 parts of Long carbon chains are modified amino resins, b) 18 parts of cation-modified Long carbon chain amino resins, c) metal complex of 1 10 parts of Long carbon chain carboxylic acids, d) 10 55 parts of waxes, e) 0.05 3 parts of cationic emulsifiers, f) 0.01 2 parts of nonionic emulsifiers and g) 0.001 1.5 parts of organic acids or inorganic acid.Waterproofing agent of the present invention is suitable for the water-proof finish of terylene, cotton, ester, artificial board or papermaking and various blended fabric, and water resistance is excellent.
Description
Invention field
The present invention relates to fabric waterproofing agent, specifically a kind of fabric floride-free water-proof finish lotion and its application.
Background technology
Fabric waterproofing agent is usually organic fluoride, organosilicon, melamine resin, wax, polyurethane, pyridiniujm etc..Wherein
Organofluorine compound effect is best, waterproof, grease proofing and antifouling.But due to perfluorooctane sulfonate PFOS and perfluoro caprylic acid PFOA
Property is highly stable, and degraded is difficult, bioaccumulation is high, harmful to biology.European Union, which has made laws, progressively disables PFOA and its esters,
And the material containing PFOA in the year two thousand twenty starts to completely forbid using PFOA and degradation product July.Other kinds of waterproofing agent waterproof
Performance not as good as organic fluoride, but they the advantages of be Safety and Environmental Protection height.Such as organic silicon waterproofing agent is usually right
The process condition for handling fabric requires harshness, is otherwise easy to cause fabric face and spot occurs.Polyurethane can fabric face into
Row covering, forms one layer of waterproof membrane, but hinders the gas permeability of fabric, and comfort is poor.And the hydrophobicity of polyurethane is not
Very high, water proofing property is poor.Other kinds of waterproofing agent is there is also similar problems, therefore people are constantly to the waterproofing agent of the above-mentioned type
It is modified, to improve the properties such as waterproof, ventilative, feel, washable, it is desirable to reach the waterproof water of organic fluoride as far as possible
It is flat, to reduce or substitute the use of organofluorine compound.
It is copolymerized for example, Japan Patent EP0632157A1 discloses a kind of acrylate and methacrylate with organosilicon
Copolymer, the feel of fabric waterproof and softness can be assigned for solvent, after use when which uses with ethanol etc..
United States Patent (USP) US3374100A discloses the composition emulsion of a kind of tertiary amine, wax and multivalent metal salt.Through the lotion
Fabric after processing has water proofing property.
United States Patent (USP) US3432319A discloses a kind of paraffin wax emulsions using methylcellulose as emulsifying agent, is mainly used for fibre
Tie up the waterproof and dampproof of plate.
United States Patent (USP) US7354458B2 discloses the composition emulsion of a kind of wax, polyurethane and emulsifying agent.The lotion can be assigned
Give textile water-proof performance.
United States Patent (USP) WO2013057303A discloses a kind of cross-linking agent resin prepared by melamine, formaldehyde and alkanol,
The resin can be reacted with thermal sensitivity ground so as to assign ground certain water proofing property.
Consider that fabric waterproofing agent is usually processed into aqueous emulsion for the convenience of environmental protection and operation, this is just needed anti-
Hydrophilic radical or use are introduced in the structure of aqua hydrophilic additional emulsifying agent, so as to cause the water proofing property of final products
Decline.As a result, it is often necessary to filter out the emulsifying agent of a variety of suitable main body water-repellent substances, reasonably combined, performance collaboration work is carried out
With ensureing water resistance while stability of emulsion is ensured.Present invention employs a kind of cation-modified Long carbon chain amino
Resin, the resin use the stabilization that can be significantly improved the present invention relates to lotion with other cations and nonionic emulsifier collocation
Property.
The content of the invention
Present invention aims at provide a kind of fabric floride-free water-proof finish lotion and its application.
To achieve the above object, the present invention use technical solution for：
A kind of fabric counts (dry matter group in parts by weight with floride-free water-proof finish lotion, floride-free water-proof finish emulsion components
Point)：A) 80-40 parts of Long carbon chains are modified amino resins, b) 1-8 parts of cation-modified Long carbon chain amino resins, c) 1-10 parts
The metal complex of Long carbon chain carboxylic acid, d) 10-55 parts of waxes, e) 0.05-3 parts of cationic emulsifiers, f) 0.01-2 parts of nonionic Emulsions
Agent and g) 0.001-1.5 part organic acid or inorganic acid.
Solid content is 20-40wt% in the free-floride water-proof finish lotion, is preferably 30-40%, more preferably 40%.
The amino resins that the component a) Long carbon chains are modified is hexamethylolmelamine or hexamethylolmelamine
Short carbon chain alcohol etherate is reacted with aliphatic Long carbon chain alcohol, aliphatic Long carbon chain carboxylic acid or aliphatic Long carbon chain N- methylol amides
Obtain.
It is further by 1mol hexamethylolmelamines or its short carbon chain alcohol etherate and 6mol Long carbon chain alcohol
Or the reaction of carboxylic acid, methylol amide obtains, obtained product can be Long carbon chain ether, ester or acid amides.This kind of material is due to structure
Periphery is dispersed with a large amount of hydrophobic groupings, so with good water proofing property.
Now by taking hexamethylolmelamine or its short carbon chain alcohol etherate prepare component a) with the reaction of Long carbon chain alcohol as an example,
Reaction equation is as follows：
Group R1For H or C1-C8 alkyl, preferably carbon number is C1-C4 alkyl, R2For C12-C40 alkyl, C12-C40 alkenyls or
C12-C40 alkynyls, preferably carbon number are C12-C22 alkyl, C12-C22 alkenyls or C12-C22 alkynyls.
The amino resins that component a Long carbon chains are modified by 1mol hexamethylolmelamines or its short carbon chain alcohol etherate with
6mol Long carbon chains alcohol or carboxylic acid, methylol amide reaction obtain, and obtained product can be Long carbon chain ether, ester or acid amides.It is above-mentioned short
Carbochain alcohol refers generally to the fatty alcohol that carbon number is less than 4, and most commonly used is methanol.Due on melamine>N(CH2OH)2Group
Activity is higher, is easily crosslinked between melamine methylol monomer, so the hydroxyl first of short carbon chain etherificate is preferred in the reaction
Base melamine.Preparation process is：By the melamine methylol and Long carbon chain ether or carboxylic acid, methylol amide of short carbon chain etherificate
Mixing, heating and melting, adds 0.1-0.5% hydrochloric acid or sulfuric acid etc. and makees catalyst, is warming up to 90 DEG C of reaction 1.5h, then be warming up to
When 140 DEG C of reactions 2 are small, add vacuum removal low-boiling-point substance all the time in reaction process.Products therefrom is component a.It is worth noting that,
When being reacted using methylol amide with the melamine methylol that short carbon chain is etherified, reaction is more violent, and since material glues
Thick, system easy slug in vacuum decompression, should carefully control vacuum.
Long carbon chain amino resins cation-modified the component b) is by hexamethylolmelamine or hexamethylol three
After poly cyanamid short carbon chain alcohol etherate and quaternary ammonium salt or reactive tertiary amine again with aliphatic Long carbon chain alcohol or aliphatic Long carbon chain carboxylic acid
Or the reaction of aliphatic Long carbon chain N- methylol amides is made.
Further, by 1mol hexamethylolmelamines or its short carbon chain alcohol etherate and 5mol Long carbon chain alcohol
The quaternary ammonium salt or reactive tertiary amine of (or carboxylic acid, methylol amide etc.) and one hydroxyl of 1mol bands are made.The compound is due to main body
Structure is similar to component a, its hydrophobic part can be embedded in component a well, and hydrophilic group then stretches into water phase, so that with certain
Surface-active action.
Now with the quaternary ammonium salt of hexamethylolmelamine or its short carbon chain alcohol etherate with Long carbon chain alcohol and with ethoxy
Exemplified by reaction prepares component b), reaction equation is as follows：
Preparation process is：The melamine methylol that 1mol short carbon chains are etherified and hydroxyl 1mol quaternary ammonium salt or tertiary amine
Mixing, heating and melting, adds 0.1-0.5% hydrochloric acid or sulfuric acid etc. and makees catalyst, is warming up to 90 DEG C of reaction 1.5h, adds 5mol
Long carbon chain ether or carboxylic acid, methylol amide, continue at 90 DEG C of reaction 2h, add vacuum removal low-boiling-point substance all the time in reaction process.Institute
It is component b to obtain product.
The anion of quaternary ammonium salt is Cl in above-mentioned reaction equation-, can also be outside the anion removing chloride of quaternary ammonium salt bromine from
Son, Methylsulfate base etc..
Exemplifications set out is hexamethylolmelamine or its short carbon chain alcohol etherate and long carbon in above-mentioned reaction equation
Chain alcohol and the quaternary ammonium reactant salt preparation component b with ethoxy, and use hexamethylolmelamine or its short carbon chain alcohol to be etherified
It is identical when the process and principle of reactive tertiary amine preparation component b of the thing with Long carbon chain alcohol and with ethoxy are with using quaternary ammonium salt, no longer
Repeated description.
The short carbon chain alcohol etherate of the hexamethylolmelamine is hexamethylolmelamine and the fatty alcohol of C1-C8
Reaction obtains；
The aliphatic Long carbon chain alcohol, aliphatic Long carbon chain carboxylic acid or carbon number contained by aliphatic Long carbon chain N- methylol amides
It is C12-C20, preferably C12-C18.Such as laruyl alcohol, octadecyl alcolol, palmitic acid, oleic acid, N- methylol stearamides.
Respectively containing a hydroxyl, a rosin group in the structure of the quaternary ammonium salt or tertiary amine；Or hydroxyl and
The aliphatic Long carbon chain of C12-C20.
Wherein, rosin group includes rosin acid groups and dehydrogenated rosin amine groups
Wherein, the typical structure of rosin acid groups is：
Since rosin is the mixture of various kinds of resin acid, said structure is the knot of the main component rosin acid in rosin
Structure, the Rosin Surfactants of actual use further include the other components in rosin resin, such as levopimaric acid, longleaf pine
Acid, the loose acid of dehydrogenation, neoabietic acid, dihydroabietic acid, tetrahydrochysene pine acid etc..
The typical structure of dehydroabietylamine is：
Equally, dehydroabietylamine also includes the dehydroabietylamine as made from other components in rosin resin.
The quaternary ammonium salt of the group containing rosin is quaternary ammonium salt shown in the quaternary ammonium salt shown in I or formula II
Formula I
In formula, R8,R9=C1-C20 alkyl, R6For rosin acid groups；
Formula II
In formula, R8,R9=C1-C20 alkyl, R7For dehydrogenated rosin amine groups；
The tertiary amine of the group containing rosin is tertiary amine shown in the tertiary amine shown in III or formula IV,
Formula III
In formula, R8=C1-C20 alkyl, R6For rosin acid groups；
Formula IV
In formula, R8=C1-C20 alkyl, R7For dehydrogenated rosin amine groups.
The straight chain aliphatic hydrocarbons based quaternary ammonium salt containing hydroxyl or the example of tertiary amine being adapted in above-mentioned reaction process have N, N-
Dimethyl-N-hydroxy-N- octadecyl sulfate methyl ammoniums, the double octadecyl Methylsulfates of N- methyl-N- ethoxys-N, N-
Ammonium, N- methyl-N- ethoxy-N- octadecylamines, N- methyl-N- ethoxy-N- tetradecylamines, the double octadecyls of N, N--
N- ethylol amines, the double dodecyl-N- ethylol amines of N, N-.
The example for the quaternary ammonium salt containing a hydroxyl and rosin group being adapted in above-mentioned reaction process has a N, and N- dimethyl-
N- ethoxy-N- rosin acid carboxylic methoxyl methyl ammonium chlorides, N, N- dimethyl-N-hydroxy-N- dehydrogenated rosin ammonium chlorides.It is adapted to
The example of the tertiary amine containing a hydroxyl and rosin group have N- methyl-N- ethoxy-N- rosin acid carboxylic methoxyl methyl amine, N-
Methyl-N- ethoxy-N- dehydrogenation rosin-base amine.
Component c) the Long carbon chains carboxylic acid metal complex is (RCOO)nM, wherein, R is C12-C20 straight-chain aliphatic carboxylics
The carboxylic acid containing 1-3 unsaturated double-bond or three keys of acid or C12-C20, n 1-4, M are metal ion.
Further, component c Long carbon chains carboxylic acid metal complex, for carbon number C12-C20 straight-chain aliphatics carboxylic acid or contains
The straight-chain aliphatic carboxylic acid or unsaturated containing 1-3 that the carboxylic acid of 1-3 unsaturated double-bond or three keys, preferably carbon number are C12-C18
The carboxylic acid of double or triple bonds, above-mentioned carboxylic acid and Ca2+、Mg2+、Al3+、Zr4+、Ba2+The network formed Deng the water soluble salt of metal ion
Compound, available metal salt have calcium chloride, magnesium chloride, aluminium chloride, barium chloride, acetic acid zirconium, magnesium sulfate, aluminum sulfate etc., preferably
Metal salt be calcium chloride, aluminum sulfate and acetic acid zirconium, more preferably aluminum sulfate and acetic acid zirconium.Workable carboxylic acid metal's complexing
The example of thing has calcium stearate, aluminum stearate, magnesium stearate, zirconium stearate, magnesium oleate, aluminum oleate, oleic acid zirconium etc., preferably stearic
Sour aluminium and zirconium stearate.
Wax in the component d) is one or more of mixing of the fusing point in 40-85 DEG C of wax.
Further, component d is wax of the fusing point at 40-85 DEG C, preferably 50-75 DEG C, more elects 50-65 DEG C as.It is optional
Natural animal-plant wax includes but not limited to candelila wax, Brazil wax, Chinese wax, spermaceti, beeswax etc..Paraffin is optional
With refining or semi-refined paraffin wax.Suitable wax component further includes the synthetic waxs such as microwax, Tissuemat E.Preferable wax is refining stone
Wax and microwax, more preferably fully refined paraffin wax.
The emulsifying agent used in emulsion preparation process has cationic emulsifier (e) and nonionic emulsifier (f), they same group
Dividing b to mix together can good stable emulsion.
Cationic emulsifier in the component e) is that the preferred carbon number of C8-C20 quaternary ammonium salt cationic emulsifying agents is C16-
The Long carbon chain of C18, wherein, the anion of quaternary ammonium salt is chlorion or Methylsulfate base；Nonionic emulsifier in component f) is
Polyoxyethylene ether, tween and the sapn of C8-C20.
The cationic emulsifier can be selected as cocotrimonium chloride, tetradecyl trimethyl ammonium chloride, 16
Alkyl trimethyl ammonium chloride, octadecyltrimethylammonium chloride, myristyl benzyl chloride, double hexadecyldimethylamines
Ammonium chloride, palm carboxyethylhydroxyethyl sulfate methyl ammonium, lauroyl oxypropyl trimethyl sulfate methyl ammonium, distearyl ethyl two
Ammonio methacrylate, trimethylene base-bis- (octadecyldimethyl) diammonium, three blubber methyl ammoniums, double octadecyl polyoxy second
Alkenyl bi-quaternary ammonium salt etc..
The nonionic emulsifier is polyoxyethylene ether, tween and sapn of Long carbon chain starting etc..The length of polyoxyethylene ether
Carbochain end carbon number is C8-C20, preferably C12-C18；The ethoxy radix of polymerization is 3-20, preferably 3-15, more preferably 5-12.Can
The example of the polyoxyethylene ether of selection has AEO-10, stearic acid polyoxyethylene (15) ether, castor oil acid polyoxyethylene (20) ether, different
Structure alcohol polyoxyethylene (10) ether etc..
Waterproof agent emulsion pH scopes prepared by this patent are in 4-6, usable inorganic acid or organic acid for adjusting pH.Inorganic acid can
Select hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid etc..Formic acid, acetic acid, citric acid etc. may be selected in organic acid.It is preferred that organic monoacid, such as second
Acid.
First all materials are mixed during emulsification, are heated to about 95 DEG C, 95 DEG C or so of water is then added, uses high speed dispersor
It is uniformly dispersed, particle diameter is less than 1 μ, then handled at 75-85 DEG C with high pressure homogenizer, obtain particle diameter about 400nm stablizes breast
Liquid.To make emulsion particle sufficiently small, peripheral velocity when high speed dispersor works is not less than 15m/s, high pressure homogenizer work
Pressure is not less than 800bar.
A kind of application of the floride-free water-proof finish lotion of fabric, it is characterised in that：The lotion is as blended fabric, people
Make the application of waterproofing agent in the preparation process of plate or papermaking.Suitable for terylene, cotton, ester and various blended fabric, artificial board
Or the water-proof finish of papermaking, water resistance are excellent.Advantage for present invention：
Lotion of the present invention introduces Long carbon chain hydrophobic group in melamine molecule, plays the role of waterproof.At the same time in trimerization
A small amount of cationic structural is introduced in cyanamide molecule, it is therefore an objective to while water proofing property is ensured ensure waterproofing agent can smoothly emulsify and
Lotion stable storage.
Free-floride water-proof emulsion of the invention, including the water repellent component based on wax and Long carbon chain modified aminoresin, with long carbon
Chain modified amino resins structure is similar and carries amino resins, quaternary ammonium salt and the non-ionic surface active of cationic hydrophilic group
Agent, and other auxiliary elements etc..The cationic amino resin being modified in water-proof emulsion of the present invention comprising a kind of Long carbon chain, the tree
Fat agent structure is similar to the Long carbon chain modified aminoresin with water resistance, and difference is to introduce the hydrophilic of cation
Base.The amino resins for introducing cationic hydrophilic base can mutually melt well with former amino resins, have to emulsion intercalation method very big
Help.The present invention uses cation-modified Long carbon chain amino resins, the resin and other cations and nonionic emulsifier
Using that can significantly improve, the present invention relates to emulsion intercalation method for collocation.And then the present composition is suitable for terylene, cotton, ester and each
Kind blended fabric, artificial board or the water-proof finish of papermaking, first water resistance are excellent.Lotion and polyurethane prepared by the present invention
Lotion, which is used cooperatively, can also provide repeatedly washing water proofing property.
Embodiment
The present invention is further explained with reference to embodiment.
Embodiment 1.
Synthesize component a1：Put into 39g in a 500mL four-hole boiling flasks, 0.1mol hexa methoxy methylene tri poly cyanamids and
162g, 0.6mol octadecyl alcolol, heating melt material, add 0.4g concentrated hydrochloric acids, continue to be warming up to 90 DEG C.When system is begun with
During reflux, vacuum is added to steam methanol.90 DEG C react be warming up to after 1.5h 140 DEG C of reactions 2 it is small when, product is viscous for water white transparency
Thick thing, is waxy solid after cooling.
Embodiment 2.
Synthesize component a2：Put into 39g in a 500mL four-hole boiling flasks, 0.1mol hexa methoxy methylene tri poly cyanamids and
170g, 0.6mol stearic acid, heating melt material, add 0.4g concentrated hydrochloric acids, continue to be warming up to 90 DEG C.When system is begun with
During reflux, vacuum is added to steam methanol.90 DEG C react be warming up to after 1.5h 140 DEG C of reactions 2 it is small when, product is viscous for water white transparency
Thick thing, is waxy solid after cooling.
Embodiment 3.
Synthesize component a3：Put into 39g in a 500mL four-hole boiling flasks, 0.1mol hexa methoxy methylene tri poly cyanamids and
188g, 0.6mol octadecyl alcolol, heating melt material, add 0.4g concentrated hydrochloric acids, continue to be warming up to 90 DEG C.When system is begun with
During reflux, add vacuum to steam methanol, pay attention to controlling vacuum to prevent slug.140 DEG C of reactions 2 are warming up to after reacting 1.5h at 90 DEG C
Hour, product is the transparent dope of faint yellow color, is waxy solid after cooling.
Embodiment 4.
Synthesize component b1：Put into 18g in a 250mL four-hole boiling flasks, 0.05mol hexa methoxy methylene tri poly cyanamids and
22.5g, 0.05molN, N- dimethyl-N-hydroxy-N- rosin acid carboxylic methoxyl methyl ammonium chlorides, heating melt material, then add
Enter 0.4g concentrated hydrochloric acids, continue to be warming up to 90 DEG C of reaction 1.5h, add 67.5g, 0.25mol octadecyl alcolols, continue at 90 DEG C of reactions
2h.Reaction adds vacuum removal low-boiling-point substance after reflux is begun with.Product is the dope of water white transparency, is wax-like solid after cooling
Body.
Embodiment 5.
Synthesize component b2：Put into 18g in a 250mL four-hole boiling flasks, 0.05mol hexa methoxy methylene tri poly cyanamids and
22.6g, 0.05mol N, N- dimethyl-N-hydroxy-N- octadecyl sulfate methyl ammoniums, heating are melted material, are added
0.4g concentrated hydrochloric acids, continue to be warming up to 90 DEG C of reaction 1.5h, add 67.5g, 0.25mol octadecyl alcolols, continue at 90 DEG C of reaction 2h.
Reaction adds vacuum removal low-boiling-point substance after reflux is begun with.Product is the dope of water white transparency, is waxy solid after cooling.
Embodiment 6.
Synthesize component b3：Put into 18g in a 250mL four-hole boiling flasks, 0.05mol hexa methoxy methylene tri poly cyanamids and
13.5g, 0.05mol N- methyl-N- ethoxy-N- tetradecylamines, heating melt material, add 0.4g concentrated hydrochloric acids, after
It is continuous to be warming up to 90 DEG C of reaction 1.5h, 67.5g is added, 0.25mol octadecyl alcolols, continue at 90 DEG C of reaction 2h.Reaction is being begun with
Add vacuum removal low-boiling-point substance after reflux.Product is the dope of water white transparency, is waxy solid after cooling.
Embodiment 7- examples 17.
The present invention provides a variety of lotion preparating examples, certain embodiments are listed in Table 1 below.
1. embodiment 7-17 of table
1631：Hexadecyltrimethylammonium chloride, D1821：Dioctadecyl dimethyl ammonium chloride, TC-90：Three blubber bases
Ammonio methacrylate, E1310：Isomerous tridecanol polyoxyethylene (10) ether
*：Lotion solid separation rate after 2300G centrifuges 15min
Fabric waterproof arranges process：Lotion is diluted to 1% concentration using deionized water, soaks the fabric into working solution
In, roll surplus liquid, upper liquid rate 60% or so.The cloth rolled dries 60-120s at 100-120 DEG C, then in 160 DEG C of bakings
60-120s.Got wet water resistance of the method evaluation fabric after water-proof emulsion is handled according to GB/T 4745-2012 (referring to table 2).
The first water proofing property of fabric after the processing of table 2.
As can be seen from the above experimental data, it with the addition of the lotion of cation-modified melamine than the lotion do not added more
Stablize, the solid separation rate that lotion centrifuges 15min in 2300G substantially reduces.And by reasonably combined between different material,
The water resistance of lotion does not influence.
Embodiment 18-19
Water-proof emulsion provided by the invention can provide good first water resistance for fabric, can meet to be not required to chemical cleaning
The waterproof applications of agent washing.But the washing water proofing property of the cloth after the water-proof emulsion processing prepared through the present invention is poor, to improve
Water proofing property is washed, lotion and cation or nonionic polyurethane latex composite compounding can be used, the washing of fabric can be significantly improved
Water proofing property.The dosage of usual polyaminoester emulsion accounts for the 5-20% of composite finishing agent.The polyaminoester emulsion used in following embodiments
The FP-BA provided for Yayun Texile Agents Co., Ltd., Shanghai, dosage 10%.Table 3. is fabric waterproof before and after addition polyurethane
Performance compares.
Textile water-proof performance compares before and after table 3. adds polyurethane
IN SR：First waterproof, 5HL IR SR：5 household washing ironings
It can be seen from the data in Table 3 that water-proof emulsion provided by the invention and polyurethane latex composite compounding are using can significantly carry
The washing water proofing property of high fabric, becomes apparent from particularly with polyesters fabric effects.
Claims (10)
- A kind of 1. floride-free water-proof finish lotion of fabric, it is characterised in that：Floride-free water-proof finish emulsion components are counted in parts by weight (dry matter component)：Amino resins that a) 80-40 parts of Long carbon chains are modified, b) 1-8 parts of cation-modified Long carbon chain amino resins, C) metal complex of 1-10 parts of Long carbon chain carboxylic acids, d) 10-55 parts of waxes, e) 0.05-3 parts of cationic emulsifiers, f) 0.01-2 parts Nonionic emulsifier and g) 0.001-1.5 part organic acid or inorganic acid.
- 2. the fabric free-floride water-proof finish lotion as described in claim 1, it is characterised in that：The free-floride water-proof finish lotion Middle solid content is 20-40wt%.
- 3. the fabric free-floride water-proof finish lotion as described in claim 1, it is characterised in that：Component a) the Long carbon chains are modified Amino resins for hexamethylolmelamine or hexamethylolmelamine short carbon chain alcohol etherate and aliphatic Long carbon chain Alcohol, aliphatic Long carbon chain carboxylic acid or the reaction of aliphatic Long carbon chain N- methylol amides obtain.
- 4. the fabric free-floride water-proof finish lotion as described in claim 1, it is characterised in that：The component b) is cation-modified Long carbon chain amino resins be by hexamethylolmelamine or hexamethylolmelamine short carbon chain alcohol etherate and quaternary ammonium salt It is or anti-with aliphatic Long carbon chain alcohol or aliphatic Long carbon chain carboxylic acid or aliphatic Long carbon chain N- methylol amides again after reactive tertiary amine It should be made.
- 5. the fabric free-floride water-proof finish lotion as described in claim 3 or 4, it is characterised in that：The hexamethylol trimerization The short carbon chain alcohol etherate of cyanamide obtains for the reaction of the fatty alcohol of hexamethylolmelamine and C1-C8；The aliphatic Long carbon chain alcohol, aliphatic Long carbon chain carboxylic acid or carbon number contained by aliphatic Long carbon chain N- methylol amides are C12-C20。
- 6. the fabric free-floride water-proof finish lotion as described in claim 4, it is characterised in that：The knot of the quaternary ammonium salt or tertiary amine Respectively containing a hydroxyl, a rosin group in structure；Or the aliphatic Long carbon chain of a hydroxyl and C12-C20.
- 7. the fabric free-floride water-proof finish lotion as described in claim 6, it is characterised in that：The quaternary ammonium of the group containing rosin Salt is quaternary ammonium salt shown in the quaternary ammonium salt shown in I or formula IIFormula IIn formula, R8,R9=C1-C20 alkyl, R6For rosin acid groups；Formula IIIn formula, R8,R9=C1-C20 alkyl, R7For dehydrogenated rosin amine groups；The tertiary amine of the group containing rosin is tertiary amine shown in the tertiary amine shown in III or formula IV,Formula IIIIn formula, R8=C1-C20 alkyl, R6For rosin acid groups；Formula IVIn formula, R8=C1-C20 alkyl, R7For dehydrogenated rosin amine groups.
- 8. the fabric free-floride water-proof finish lotion as described in claim 1, it is characterised in that：Component c) the Long carbon chain carboxylic acids Metal complex is (RCOO)nM, wherein, R is C12-C20 straight-chain aliphatics carboxylic acid or C12-C20 containing 1-3 unsaturation The carboxylic acid of double or triple bonds, n 1-4, M are metal ion.
- 9. the fabric free-floride water-proof finish lotion as described in claim 1, it is characterised in that：Cation in the component e) Emulsifying agent is C8-C20 quaternary ammonium salt cationic emulsifying agents, wherein, the anion of quaternary ammonium salt is chlorion or Methylsulfate base；Group Polyoxyethylene ether, tween and the sapn that nonionic emulsifier in dividing f) is C8-C20.
- A kind of 10. application of the floride-free water-proof finish lotion of fabric described in claim 1, it is characterised in that：The lotion exists Application as waterproofing agent in blended fabric, artificial board or the preparation process of papermaking.
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