JP4996875B2 - Water repellent, water repellent processing method and water repellent fiber product - Google Patents
Water repellent, water repellent processing method and water repellent fiber product Download PDFInfo
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- JP4996875B2 JP4996875B2 JP2006120851A JP2006120851A JP4996875B2 JP 4996875 B2 JP4996875 B2 JP 4996875B2 JP 2006120851 A JP2006120851 A JP 2006120851A JP 2006120851 A JP2006120851 A JP 2006120851A JP 4996875 B2 JP4996875 B2 JP 4996875B2
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- water
- repellent
- water repellent
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- fluorine
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 178
- 239000005871 repellent Substances 0.000 title claims description 133
- 230000002940 repellent Effects 0.000 title claims description 102
- 239000000835 fiber Substances 0.000 title claims description 64
- 238000003672 processing method Methods 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims description 85
- 229920000642 polymer Polymers 0.000 claims description 66
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 58
- 229910052731 fluorine Inorganic materials 0.000 claims description 58
- 239000011737 fluorine Substances 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 40
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 26
- -1 acrylic ester Chemical class 0.000 claims description 26
- 239000003431 cross linking reagent Substances 0.000 claims description 24
- 239000004753 textile Substances 0.000 claims description 22
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229920006120 non-fluorinated polymer Polymers 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 238000012674 dispersion polymerization Methods 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 2
- 239000003814 drug Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 20
- 238000010526 radical polymerization reaction Methods 0.000 description 16
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 14
- 239000004815 dispersion polymer Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- PFKRTWCFCOUBHS-UHFFFAOYSA-N dimethyl(octadecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH+](C)C PFKRTWCFCOUBHS-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical group 0.000 description 12
- 239000003505 polymerization initiator Substances 0.000 description 12
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000004744 fabric Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 9
- 125000003709 fluoroalkyl group Chemical group 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002981 blocking agent Substances 0.000 description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- QASBHTCRFDZQAM-UHFFFAOYSA-N (2-isocyanato-2-methyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)N=C=O QASBHTCRFDZQAM-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- KPXFIETUTLCJAC-UHFFFAOYSA-N isocyanic acid;naphthalene Chemical compound N=C=O.C1=CC=CC2=CC=CC=C21 KPXFIETUTLCJAC-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、非フッ素系の撥水剤、撥水加工方法及び撥水性繊維製品に関するものである。 The present invention relates to a non-fluorinated water repellent, a water repellent processing method, and a water repellent fiber product.
従来、フッ素基を有するフッ素系撥水剤が知られており、かかるフッ素系撥水剤を繊維製品等に処理することにより、その表面に撥水性が付着された繊維製品が知られている。このようなフッ素系撥水剤は一般にフルオロアルキル基を有する単量体（モノマー）を重合（若しくは共重合）させることにより製造される。 Conventionally, a fluorine-based water repellent having a fluorine group is known, and a fiber product having water repellency attached to its surface by treating such a fluorine-based water repellent to a fiber product or the like is known. Such a fluorine-based water repellent is generally produced by polymerizing (or copolymerizing) a monomer having a fluoroalkyl group (monomer).
フッ素系撥水剤で処理された繊維製品は優れた撥水性を発揮するものの、撥水性を発現するためには、フルオロアルキル基の配向性を整える必要があるため、繊維製品に付着させた後に１３０℃以上で熱処理を施さなければならない。ところが、高温での熱処理には高いエネルギーを必要とし、国際的な省エネルギー化の流れにおいて問題がある Although textile products treated with fluorine-based water repellents exhibit excellent water repellency, in order to develop water repellency, it is necessary to align the orientation of the fluoroalkyl group. Heat treatment must be performed at 130 ° C or higher. However, heat treatment at high temperature requires high energy, and there are problems in the international trend of energy saving.
また、フルオロアルキル基を有する単量体は、高価であるため経済面においては満足のいくものではなく、更に、フルオロアルキル基を有する単量体は、難分解性であるため環境面においても問題がある。 In addition, a monomer having a fluoroalkyl group is not economically satisfactory because it is expensive, and a monomer having a fluoroalkyl group is difficult to decompose because it is difficult to decompose. There is.
そこで、近年、フッ素を含まない非フッ素系撥水剤について研究が進められている。例えば、非特許文献１には、パラフィンやワックスのような炭化水素化合物、脂肪酸金属塩又はアルキル尿素を乳化分散させた撥水剤が提案されている。
しかしながら、上記非特許文献１記載の非フッ素系撥水剤を繊維製品に付着させた場合であっても、十分な撥水性を得ることは困難であり、従来のフッ素系撥水剤を繊維製品に用いた場合の撥水性には及ばないものである。また、繊維製品に付着させた場合、繊維製品が硬くなる傾向にあり、風合が十分なものとはいえない。 However, it is difficult to obtain sufficient water repellency even when the non-fluorinated water repellent described in Non-Patent Document 1 is attached to a fiber product. It does not reach the water repellency when used in the above. Moreover, when it adheres to a fiber product, it exists in the tendency for a fiber product to become hard, and it cannot be said that a feeling is enough.
一方で撥水剤の分野においては、品質の安定化及びコスト削減のために、繊維製品に低い濃度や低い熱処理温度でも優れた撥水性を発揮することができる撥水剤が望まれている。 On the other hand, in the field of water repellents, water repellents that can exhibit excellent water repellency even at low concentrations and low heat treatment temperatures are desired in order to stabilize quality and reduce costs.
そこで、本発明は、繊維製品等に付着させた場合に、風合に優れ、かつ十分な撥水性を発揮する非フッ素系撥水剤、撥水加工方法及び撥水性繊維製品を提供することを目的とする。 Therefore, the present invention provides a non-fluorinated water repellent, a water repellent processing method, and a water repellent fiber product that are excellent in texture and exhibit sufficient water repellency when adhered to a fiber product or the like. Objective.
上記目的を達成するために、本発明は、エステル部分の炭素数が１２以上の（メタ）アクリル酸エステルを単量体単位として含む非フッ素系ポリマーからなる撥水剤であって、（メタ）アクリル酸エステルの構成割合が非フッ素系ポリマーを構成する単量体単位の全量に対して８０〜１００質量％であり、非フッ素系ポリマーは、重量平均分子量が１０万以上且つ１６０℃における溶融粘度が１０００Ｐａ・ｓ以下である撥水剤、を提供する。 In order to achieve the above object, the present invention provides a water repellent comprising a non-fluorine polymer containing a (meth) acrylic acid ester having an ester moiety having 12 or more carbon atoms as a monomer unit, wherein (meth) The constituent ratio of the acrylate ester is 80 to 100% by mass with respect to the total amount of monomer units constituting the non-fluorine polymer, and the non-fluorine polymer has a weight average molecular weight of 100,000 or more and a melt viscosity at 160 ° C. Provides a water repellent that is 1000 Pa · s or less.
本発明の撥水剤は、繊維製品等に付着させた場合に、風合に優れ、かつポリマーがフッ素基を有していないにもかかわらず、十分な撥水性を発揮させることができる。したがって、本発明の撥水剤は、従来のフッ素系撥水剤に代わるものとしての利用が可能であり、フルオロアルキル基を有する単量体を用いることによる経済面や環境面の負荷を抑制することができる。 The water repellent of the present invention is excellent in texture when adhered to textiles and the like, and can exhibit sufficient water repellency even though the polymer does not have a fluorine group. Therefore, the water repellent of the present invention can be used as an alternative to the conventional fluorine-based water repellent, and suppresses the economic and environmental burden caused by using a monomer having a fluoroalkyl group. be able to.
また、本発明の撥水剤を繊維製品等に付着させる場合、従来のフルオロアルキル基を有する単量体からなるフッ素系撥水剤を用いた場合のようにフルオロアルキル基の配向性を整える必要がないことから、繊維製品等を１３０℃以下の温和な条件下で熱処理した場合であっても、十分な撥水性を発揮させることができる。更には、繊維製品等を１３０℃以上の高温で熱処理する場合は、熱処理の時間が短くても良好な撥水性を発揮させることができ、繊維製品の変質も抑えられるので風合が柔軟となる。 In addition, when attaching the water repellent of the present invention to textiles, etc., it is necessary to arrange the orientation of the fluoroalkyl group as in the case of using a conventional fluorine-based water repellent composed of a monomer having a fluoroalkyl group. Therefore, even when the fiber product or the like is heat-treated under a mild condition of 130 ° C. or less, sufficient water repellency can be exhibited. Further, when heat-treating a fiber product or the like at a high temperature of 130 ° C. or higher, good water repellency can be exhibited even if the heat treatment time is short, and the quality of the fiber product can be suppressed, and the texture becomes flexible. .
撥水性及び風合をバランスよく向上させる観点からは、（メタ）アクリル酸エステルとして、アルキル基の炭素数が１２〜２４の（メタ）アクリル酸アルキルエステルの１又は２以上を用いるとよく、（メタ）アクリル酸エステルの構成割合が、非フッ素系ポリマーを構成する単量体単位の全量に対して１００質量％であるとよい。 From the viewpoint of improving water repellency and texture in a well-balanced manner, it is preferable to use one or more of (meth) acrylic acid alkyl esters having 12 to 24 carbon atoms as the (meth) acrylic acid ester, The constituent ratio of the (meth) acrylic acid ester is preferably 100% by mass with respect to the total amount of the monomer units constituting the non-fluorinated polymer.
非フッ素系ポリマーは、ヒドロキシル基、アミノ基、カルボキシル基、エポキシ基及びイソシアネート基からなる群より選ばれる少なくとも１種の官能基を有することが好ましい。これにより、本発明の撥水剤は、繊維製品等に付着させた場合に洗濯耐久性のある優れた撥水性を発現することができる。 The non-fluorinated polymer preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. Thereby, the water repellent of this invention can express the outstanding water repellency with washing durability, when it makes it adhere to textiles etc.
非フッ素系ポリマーは、上記官能基を有する反応性単量体を単量体単位として含んでおり、反応性単量体の構成割合が、前記非フッ素系ポリマーを構成する単量体単位の全量に対して１〜２０質量％であることが好ましい。なお、上述の（メタ）アクリル酸エステル単量体が上記官能基を有していてもよい。 The non-fluorinated polymer contains the reactive monomer having the functional group as a monomer unit, and the constituent ratio of the reactive monomer is the total amount of the monomer unit constituting the non-fluorinated polymer. It is preferable that it is 1-20 mass% with respect to. In addition, the above-mentioned (meth) acrylic acid ester monomer may have the said functional group.
上記撥水剤は種々の態様で用いることができ、例えば上記撥水剤からなる粒子が水中に分散された撥水剤組成物として適用してもよい。このような撥水剤組成物は、エステル部分の炭素数が１２以上の（メタ）アクリル酸エステルを含む単量体を、乳化又は分散重合させて製造できる。 The water repellent can be used in various modes, and for example, the water repellent may be applied as a water repellent composition in which particles comprising the water repellent are dispersed in water. Such a water repellent composition can be produced by emulsion or dispersion polymerization of a monomer containing a (meth) acrylic acid ester having an ester moiety having 12 or more carbon atoms.
本発明においては、繊維製品の撥水性の洗濯耐久性を更に向上させる観点から、撥水剤組成物を繊維製品に付着させて水を除去する工程と、架橋剤を繊維製品に付着させてこれを加熱する工程と、を含む繊維製品の撥水加工方法を提供する。架橋剤としては、メチロールメラミン及びイソシアネート基又はブロックドイソシアネート基を含有する化合物からなる群より選ばれる１種以上の化合物からなることが更に好ましい。 In the present invention, from the viewpoint of further improving the water-repellent washing durability of the textile product, the water repellent composition is attached to the textile product to remove water, and the crosslinking agent is adhered to the textile product. And a water repellent processing method for a textile product. More preferably, the crosslinking agent is composed of one or more compounds selected from the group consisting of methylolmelamine and a compound containing an isocyanate group or a blocked isocyanate group.
本発明の撥水剤は、繊維製品に付着させて用いるのに適している。すなわち、上記撥水剤が繊維製品に付着された撥水性繊維製品又は撥水剤組成物を繊維製品に付着させて水を除去してなる撥水性繊維製品は、優れた撥水効果を発揮するとともに風合に優れる。特に、本発明の撥水加工方法により撥水加工された撥水性繊維製品は、洗濯耐久性のある優れた撥水性を発揮するとともに風合に優れる。 The water repellent of the present invention is suitable for use on a textile product. That is, the water-repellent fiber product in which the water-repellent agent is adhered to the fiber product or the water-repellent fiber product in which the water-repellent composition is adhered to the fiber product to remove water exhibits an excellent water-repellent effect. Excellent texture. In particular, the water-repellent fiber product subjected to the water-repellent processing by the water-repellent processing method of the present invention exhibits excellent water repellency with durability to washing and excellent texture.
本発明の撥水剤は、フルオロアルキル基又はフッ素を有する化合物を含まない撥水剤でありながらも優れた撥水性を示し、フッ素系撥水撥油剤に代わるものとしての利用が可能であり、フッ素供給源や環境等への影響が懸念を解消することができる。なお、撥水剤を付着させた後は通常熱処理することが好ましいが、本発明の撥水剤はフルオロアルキル基を有する単量体を用いていないため、１３０℃以下の温和な条件で熱処理した場合であっても高い撥水性を発揮させることができ、また１３０℃以上の高温で熱処理した場合には、熱処理時間をフッ素系撥水撥油剤の場合よりも短くすることできる。したがって、被処理物の熱による変質が抑えられるため、風合が柔軟となり、しかも熱処理にかかる熱量を削減できる等コスト面での利点も期待される。 The water repellent of the present invention exhibits excellent water repellency while being a water repellent that does not contain a compound having a fluoroalkyl group or fluorine, and can be used as a substitute for a fluorine-based water and oil repellent, The influence on the fluorine supply source and the environment can solve the concern. In addition, although it is preferable to heat-process normally after attaching a water-repellent agent, since the water-repellent agent of this invention does not use the monomer which has a fluoroalkyl group, it heat-processed on mild conditions of 130 degrees C or less. Even in this case, high water repellency can be exhibited, and when heat treatment is performed at a high temperature of 130 ° C. or higher, the heat treatment time can be shortened compared to the case of a fluorine-based water and oil repellent agent. Therefore, since the alteration of the object to be processed due to heat is suppressed, the texture is flexible, and a cost advantage such as a reduction in the amount of heat required for the heat treatment is also expected.
以下、本発明の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
本発明の撥水剤は、エステル部分の炭素数が１２以上の（メタ）アクリル酸エステルを単量体単位として含む非フッ素系ポリマーからなるものである。この非フッ素系ポリマーは、（メタ）アクリル酸エステルの構成割合が非フッ素系ポリマーを構成する単量体単位の全量に対して８０〜１００質量％でなければならず、重量平均分子量が１０万以上且つ１６０℃における溶融粘度が１０００Ｐａ・ｓ以下でなければならない。 The water repellent of the present invention is composed of a non-fluorine polymer containing a (meth) acrylic acid ester having an ester moiety having 12 or more carbon atoms as a monomer unit. In this non-fluorine polymer, the constituent ratio of the (meth) acrylic acid ester must be 80 to 100% by mass with respect to the total amount of monomer units constituting the non-fluorine polymer, and the weight average molecular weight is 100,000. The melt viscosity at 160 ° C. must be 1000 Pa · s or less.
ここで、「（メタ）アクリル酸エステル」とは「アクリル酸エステル」又はそれに対応する「メタクリル酸エステル」を意味し、「（メタ）アクリル酸」、「（メタ）アクリルアミド」等においても同義である。また、「１６０℃における溶融粘度」とは、高架式フローテスター（例えば、島津製作所製ＣＦＴ−５００）を用い、ダイ（長さ１０ｍｍ、直径１ｍｍ）を取り付けたシリンダー内に非フッ素系ポリマーを１．５ｇ入れ、１６０℃で６分間保持し、プランジャーにより１００ｋｇ・ｆ／ｃｍ２の荷重を加えて測定したときの粘度をいう。 Here, “(meth) acrylic acid ester” means “acrylic acid ester” or “methacrylic acid ester” corresponding thereto, and is also synonymous in “(meth) acrylic acid”, “(meth) acrylamide” and the like. is there. In addition, “melt viscosity at 160 ° C.” means that a non-fluorinated polymer is 1 in a cylinder attached with a die (length 10 mm, diameter 1 mm) using an elevated flow tester (for example, CFT-500 manufactured by Shimadzu Corporation). The viscosity is measured when 0.5 g is added and held at 160 ° C. for 6 minutes, and a load of 100 kg · f / cm 2 is applied with a plunger.
本発明において使用される（メタ）アクリル酸エステル単量体は、上述したように炭素数が１２以上のエステル部分を有するが、このエステル部分は炭化水素基であることが好ましい。この炭化水素基は、直鎖状であっても分岐状であってもよく、飽和炭化水素であっても不飽和炭化水素であってもよく、更には脂環式又は芳香族の環状を有していてもよい。これらの中でも、直鎖状であるものが好ましく、直鎖状のアルキル基であるものがより好ましい。この場合、撥水性がより優れるものとなる。 The (meth) acrylic acid ester monomer used in the present invention has an ester moiety having 12 or more carbon atoms as described above, and this ester moiety is preferably a hydrocarbon group. This hydrocarbon group may be linear or branched, may be saturated or unsaturated, and has an alicyclic or aromatic ring. You may do it. Among these, those that are linear are preferable, and those that are linear alkyl groups are more preferable. In this case, the water repellency is more excellent.
上記エステル部分の炭素数は、１２〜２４であることが好ましい。炭素数が１２未満であると、撥水剤を繊維製品等に付着させた場合、十分な撥水性を発揮できない。一方、炭素数が２４を超えると、炭素数が上記範囲にある場合と比較して、撥水剤を繊維製品等に付着させた場合、繊維製品の風合が粗硬になる傾向にある。 The ester moiety preferably has 12 to 24 carbon atoms. When the number of carbon atoms is less than 12, sufficient water repellency cannot be exhibited when a water repellent is adhered to a textile product or the like. On the other hand, when the carbon number exceeds 24, the texture of the fiber product tends to become coarse when the water repellent is adhered to the fiber product or the like as compared with the case where the carbon number is in the above range.
エステル部分の炭素数は、１２〜２１であることがより好ましい。炭素数がこの範囲である場合は撥水性と風合が特に優れるようになる。エステル部分として得に好ましいのは、炭素数が１２〜１８の直鎖状のアルキル基である。 As for carbon number of an ester part, it is more preferable that it is 12-21. When the carbon number is within this range, the water repellency and texture are particularly excellent. Preferred as the ester moiety is a linear alkyl group having 12 to 18 carbon atoms.
本発明の撥水剤において、非フッ素系ポリマー中の（メタ）アクリル酸エステル単量体単位の構成割合は、非フッ素系ポリマーを構成する単量体単位の全量に対して８０〜１００質量％である。（メタ）アクリル酸エステル単量体単位の構成割合が、８０質量％未満であると、撥水剤を繊維製品等に付着させた場合、繊維製品等の撥水性が不十分となる。なお、上記（メタ）アクリル酸エステル単量体単位の構成割合は、８５〜１００質量％であることが好ましく、９０〜１００質量％であることがより好ましく、１００質量％が特に好ましい。 In the water repellent of the present invention, the constituent ratio of the (meth) acrylic acid ester monomer unit in the non-fluorine polymer is 80 to 100% by mass with respect to the total amount of the monomer units constituting the non-fluorine polymer. It is. When the constituent ratio of the (meth) acrylic acid ester monomer unit is less than 80% by mass, the water repellency of the fiber product or the like becomes insufficient when the water repellent is adhered to the fiber product or the like. In addition, it is preferable that the structural ratio of the said (meth) acrylic acid ester monomer unit is 85-100 mass%, It is more preferable that it is 90-100 mass%, 100 mass% is especially preferable.
非フッ素系ポリマーの重量平均分子量が等しい場合、非フッ素系（メタ）アクリル酸エステル単量体の割合が高い方が撥水性がより高くなる傾向にあり、共重合可能な非フッ素系単量体を共重合させることにより、撥水性についての洗濯耐久性、共重合体の乳化安定性、相溶性等の性能が向上する傾向にある。 When the weight average molecular weights of the non-fluorinated polymers are the same, the higher the ratio of the non-fluorinated (meth) acrylic acid ester monomer, the higher the water repellency, and the copolymerizable non-fluorinated monomer. By copolymerizing, there is a tendency to improve performance such as washing durability with respect to water repellency, emulsion stability of the copolymer, and compatibility.
撥水剤である非フッ素系ポリマーの重量平均分子量は１０万以上である。重量平均分子量が１０万未満であると、撥水剤を繊維製品等に付着させた場合、繊維製品等の撥水性が不十分となる。なお、上記重量平均分子量は、５０万以上であることが好ましい。この場合、撥水剤が付着された繊維製品等は、より十分に撥水性を発揮させることができる。重量平均分子量の上限は、通常５００万程度である。 The non-fluorinated polymer that is a water repellent has a weight average molecular weight of 100,000 or more. When the weight average molecular weight is less than 100,000, the water repellency of the fiber product or the like becomes insufficient when the water repellent is adhered to the fiber product or the like. The weight average molecular weight is preferably 500,000 or more. In this case, the fiber product or the like to which the water repellent is attached can exhibit water repellency more sufficiently. The upper limit of the weight average molecular weight is usually about 5 million.
本発明において、非フッ素系ポリマーの１６０℃における溶融粘度は１０００Ｐａ・ｓ以下である。１６０℃における溶融粘度が１０００Ｐａ・ｓを超えると、撥水剤を繊維製品に付着させた場合、繊維製品の風合が粗硬になる。また、上記非フッ素系ポリマーを乳化又は分散して撥水剤組成物とした場合、この非フッ素系ポリマーが析出したり沈降したりすることがあり、撥水剤組成物の安定性が低下する。なお、１６０℃における溶融粘度は、５００Ｐａ・ｓ以下であることが好ましい。この場合、撥水剤が付着された繊維製品等は、十分に撥水性を発揮しつつ、風合もより優れたものとなる。 In the present invention, the non-fluorinated polymer has a melt viscosity at 160 ° C. of 1000 Pa · s or less. When the melt viscosity at 160 ° C. exceeds 1000 Pa · s, the texture of the fiber product becomes coarse when the water repellent is adhered to the fiber product. Moreover, when the non-fluorine polymer is emulsified or dispersed to form a water repellent composition, the non-fluorine polymer may be precipitated or settled, resulting in a decrease in the stability of the water repellent composition. . The melt viscosity at 160 ° C. is preferably 500 Pa · s or less. In this case, the fiber product or the like to which the water repellent is attached exhibits a sufficient water repellency and a better texture.
本発明の撥水剤において、非フッ素系ポリマーは、エステル部分の炭素数が１２以上の（メタ）アクリル酸エステルの他に、これと共重合可能な単官能又は多官能の単量体を単量体単位として含んでいてもよい。 In the water repellent of the present invention, the non-fluorine-based polymer includes a monofunctional or polyfunctional monomer copolymerizable with the (meth) acrylic acid ester having an ester moiety having 12 or more carbon atoms. It may be included as a monomer unit.
共重合可能な単官能又は多官能の単量体としては、例えば、フマル酸エステル、マレイン酸エステル、炭素数１〜１１の炭化水素基を有する（メタ）アクリル酸エステル、（メタ）アクリル酸、フマル酸、マレイン酸、（メタ）アクリルアミド、Ｎ−メチロールアクリルアミド、ビニルエーテル類、ビニルエステル類、塩化ビニル、塩化ビニリデン、エチレン、スチレン等のフッ素を含まないビニル系単量体等が挙げられる。 Examples of copolymerizable monofunctional or polyfunctional monomers include, for example, fumaric acid ester, maleic acid ester, (meth) acrylic acid ester having 1 to 11 carbon atoms, (meth) acrylic acid, Examples include fumaric acid, maleic acid, (meth) acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, vinyl monomers not containing fluorine such as vinyl chloride, vinylidene chloride, ethylene, and styrene.
なお、炭素数１〜１１の炭化水素基を有する（メタ）アクリル酸エステルは、炭化水素基が、ビニル基、ヒドロキシル基、アミノ基、エポキシ基、イソシアネート基、ブロックドイソシアネート基、又は第４級アンモニウム基等の置換基を有していてもよく、エーテル結合、エステル結合、アミド結合、又はウレタン結合等を有していてもよい。 The (meth) acrylic acid ester having a hydrocarbon group having 1 to 11 carbon atoms has a hydrocarbon group such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, a blocked isocyanate group, or a quaternary group. It may have a substituent such as an ammonium group, and may have an ether bond, an ester bond, an amide bond, a urethane bond, or the like.
このような炭素数１〜１１の炭化水素基を有する（メタ）アクリル酸エステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸グリシジル、１，１−ビス（アクリロイルオキシメチル）エチルイソシアネート、エチレングリコールジ（メタ）アクリレート等が挙げられる。これらの単量体は、単独で使用してもよく、２以上を併用することもできる。 Examples of the (meth) acrylic acid ester having a hydrocarbon group having 1 to 11 carbon atoms include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( Examples include dimethylaminoethyl methacrylate, glycidyl (meth) acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and ethylene glycol di (meth) acrylate. These monomers may be used alone or in combination of two or more.
本発明の撥水剤において、非フッ素系ポリマーは、ヒドロキシル基、アミノ基、カルボキシル基、エポキシ基及びイソシアネート基からなる群より選ばれる少なくとも１種の官能基を有することが、繊維製品の撥水性の洗濯耐久性を向上させることから好ましい。イソシアネート基は、ブロック化剤で保護されたブロックドイソシアネート基を形成していてもよい。これら官能基は、例えば、これら官能基を有する反応性単量体を共重合させることによって、非フッ素系ポリマー中に導入される。反応性単量体としては、上に挙げた単量体のうち、後述する架橋剤や繊維製品との反応が可能な（メタ）アクリル酸２−ヒドロキシエチル、Ｎ−メチロールアクリルアミド、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸、（メタ）アクリル酸グリシジル、１，１−ビス（アクリロイルオキシメチル）エチルイソシアネートが挙げられる。そして反応性単量体の構成割合は、非フッ素系ポリマーを構成する単量体単位の全量に対して１〜２０質量％が好ましく、１〜１５質量％であることがより好ましく、特に２〜１０質量％であることが好ましい。また、上述したエステル部分の炭素数が１２以上である（メタ）アクリル酸エステルが上記官能基を有していてもよい。 In the water repellent of the present invention, the non-fluorine polymer has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group, so This is preferable because it improves the washing durability. The isocyanate group may form a blocked isocyanate group protected with a blocking agent. These functional groups are introduced into the non-fluorine polymer by, for example, copolymerizing a reactive monomer having these functional groups. As the reactive monomer, among the monomers listed above, 2-hydroxyethyl (meth) acrylate, N-methylolacrylamide, (meth) acrylic capable of reacting with a cross-linking agent and a fiber product described later. Examples include dimethylaminoethyl acid, (meth) acrylic acid, glycidyl (meth) acrylate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. The constituent ratio of the reactive monomer is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, particularly 2 to 2% by mass with respect to the total amount of monomer units constituting the non-fluorine polymer. It is preferable that it is 10 mass%. Moreover, the (meth) acrylic acid ester whose carbon number of the ester part mentioned above is 12 or more may have the said functional group.
次に、本発明の撥水剤の製造方法について説明する。 Next, the manufacturing method of the water repellent of this invention is demonstrated.
非フッ素系ポリマーは、ラジカル重合法により製造することができる。また、このラジカル重合法の中でも、得られる撥水剤の性能及び環境の面から乳化重合法又は分散重合法で重合することが好ましい。 The non-fluorine polymer can be produced by a radical polymerization method. Among these radical polymerization methods, it is preferable to perform polymerization by an emulsion polymerization method or a dispersion polymerization method from the viewpoint of performance and environment of the obtained water repellent.
乳化重合法又は分散重合法により、エステル部分の炭素数が１２以上の（メタ）アクリル酸エステル等の単量体を単独重合又は共重合させる場合は、媒体中に単量体と、乳化剤又は分散剤とを加え、この混合液を乳化又は分散させる。そして、乳化又は分散された混合液に、重合開始剤を加えることにより、重合反応が開始され、単量体を重合させることができる。なお、上述した混合液を乳化又は分散させる手段としては、ホモミキサー、高圧乳化機又は超音波等が挙げられる。 In the case of homopolymerizing or copolymerizing a monomer such as (meth) acrylic acid ester having 12 or more carbon atoms in the ester moiety by emulsion polymerization or dispersion polymerization, the monomer and emulsifier or dispersion in the medium An agent is added to emulsify or disperse the mixture. And a polymerization reaction is started by adding a polymerization initiator to the emulsified or dispersed liquid mixture, and the monomer can be polymerized. In addition, as a means for emulsifying or dispersing the above-described mixed liquid, a homomixer, a high-pressure emulsifier, an ultrasonic wave, or the like can be given.
上記乳化剤等としては、ノニオン界面活性剤、カチオン界面活性剤、アニオン界面活性剤、及び両性界面活性剤から選ばれる１以上を使用することができる。乳化剤等の含有量は、全単量体１００質量部に対して、０．５〜３０質量部であることが好ましく、１〜２０質量部であることがより好ましい。上記乳化剤等の量が０．５質量部未満であると、乳化剤等の量が上記範囲にある場合と比較して、混合液の分散安定性が低下する傾向にあり、乳化剤等の量が３０質量部を超えると、乳化剤等の量が上記範囲にある場合と比較して、得られる非フッ素系ポリマーからなる撥水剤は撥水性が低下する傾向にある。 As said emulsifier etc., 1 or more chosen from a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant can be used. It is preferable that content, such as an emulsifier, is 0.5-30 mass parts with respect to 100 mass parts of all monomers, and it is more preferable that it is 1-20 mass parts. When the amount of the emulsifier and the like is less than 0.5 parts by mass, the dispersion stability of the mixed solution tends to be lower than when the amount of the emulsifier is in the above range, and the amount of the emulsifier and the like is 30. When the amount exceeds mass parts, the water repellency of the obtained non-fluorinated polymer tends to decrease compared to the case where the amount of the emulsifier is in the above range.
乳化重合又は分散重合の媒体は、水が好ましい。媒体としては、必要に応じて水と有機溶剤とを混合してもよい。このときの有機溶剤としては、水と混和可能な有機溶剤であれば特に制限はないが、例えば、メタノールやエタノールなどのアルコール類、酢酸エチルなどのエステル類、アセトンやメチルエチルケトンなどのケトン類、ジエチルエーテルなどのエーテル類等、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール等のグリコール類が挙げられる。なお、水と有機溶剤の比率は特に限定されるものではない。 The medium for emulsion polymerization or dispersion polymerization is preferably water. As a medium, water and an organic solvent may be mixed as necessary. The organic solvent is not particularly limited as long as it is miscible with water. For example, alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, diethyl Examples include ethers such as ether, and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. In addition, the ratio of water and an organic solvent is not specifically limited.
上記重合開始剤としては、アゾ系、過酸化物系、又はレドックス系等の公知の重合開始剤を適宜使用できる。重合開始剤の含有量は、全単量体１００質量部に対して、重合開始剤０．０１〜２質量部であることが好ましい。重合開始剤の含有量が上記範囲であると、重量平均分子量が１０万以上である非フッ素系ポリマーを効率よく製造することができる。 As said polymerization initiator, well-known polymerization initiators, such as an azo type | system | group, a peroxide type | system | group, or a redox type | system | group, can be used suitably. It is preferable that content of a polymerization initiator is 0.01-2 mass parts of polymerization initiators with respect to 100 mass parts of all the monomers. When the content of the polymerization initiator is within the above range, a non-fluorine polymer having a weight average molecular weight of 100,000 or more can be produced efficiently.
また、重合反応において、分子量調整を目的として、ドデシルメルカプタン、ｔ−ブチルアルコール等の連鎖移動剤を用いてもよい。連鎖移動剤の含有量は、全単量体１００質量部に対して０．１質量部以下であることが好ましい。連鎖移動剤の含有量が０．１質量部を超えると、分子量の低下を招き、重量平均分子量が１０万以上である非フッ素系ポリマーを効率よく製造することが困難となる傾向にある。 In the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight. The content of the chain transfer agent is preferably 0.1 parts by mass or less with respect to 100 parts by mass of all monomers. When the content of the chain transfer agent exceeds 0.1 parts by mass, the molecular weight is lowered, and it tends to be difficult to efficiently produce a non-fluorinated polymer having a weight average molecular weight of 100,000 or more.
なお、分子量調整のためには重合禁止剤を使用してもよい。重合禁止剤の添加により所望の重量平均分子量を有する非フッ素系ポリマーを容易に得ることができる。 In order to adjust the molecular weight, a polymerization inhibitor may be used. By adding a polymerization inhibitor, a non-fluorinated polymer having a desired weight average molecular weight can be easily obtained.
重合反応の温度は、２０℃〜１５０℃が好ましい。温度が２０℃未満であると、温度が上記範囲にある場合と比較して、重合が不十分になる傾向にあり、温度が１５０℃を超えると、反応熱の制御が困難になる場合がある。 The temperature of the polymerization reaction is preferably 20 ° C to 150 ° C. When the temperature is less than 20 ° C., the polymerization tends to be insufficient as compared with the case where the temperature is in the above range, and when the temperature exceeds 150 ° C., it may be difficult to control the reaction heat. .
重合反応において、得られる非フッ素系ポリマーの重量平均分子量は、上述した重合開始剤、連鎖移動剤、重合禁止剤の含有量の増減により調整することができ、１６０℃における溶融粘度は、多官能単量体の含有量、重合開始剤の含有量の増減により調整することができる。なお、１６０℃における溶融粘度を低下させたい場合は、重合可能な官能基を２つ以上有する単量体の含有量を減らしたり、重合開始剤の含有量の増加させればよい。 In the polymerization reaction, the weight average molecular weight of the obtained non-fluorinated polymer can be adjusted by increasing / decreasing the content of the polymerization initiator, chain transfer agent and polymerization inhibitor described above, and the melt viscosity at 160 ° C. is polyfunctional. It can adjust by increase / decrease in content of a monomer and content of a polymerization initiator. In order to reduce the melt viscosity at 160 ° C., the content of the monomer having two or more polymerizable functional groups may be reduced or the content of the polymerization initiator may be increased.
乳化又は分散重合により非フッ素系ポリマーを得る場合は、非フッ素系ポリマーの含有割合を１０〜５０質量％（更には２０〜４０質量％）にするとよい。 When a non-fluorine polymer is obtained by emulsion or dispersion polymerization, the content ratio of the non-fluorine polymer is preferably 10 to 50% by mass (more preferably 20 to 40% by mass).
本発明の撥水剤には必要に応じて添加剤等を加えることも可能である。添加剤としては、他の撥水剤、架橋剤、抗菌防臭剤、難燃剤、帯電防止剤、柔軟剤、防皺剤等が挙げられる。 Additives and the like can be added to the water repellent of the present invention as necessary. Examples of the additive include other water repellents, crosslinking agents, antibacterial deodorants, flame retardants, antistatic agents, softeners, antifungal agents and the like.
次に、本発明の撥水性繊維製品について説明する。 Next, the water-repellent fiber product of the present invention will be described.
本発明の撥水性繊維製品は、上述した撥水剤が付着されることで得られる。かかる繊維製品の素材としては特に制限はなく、綿、麻、絹、羊毛などの天然繊維、レーヨン、アセテートなどの半合成繊維、ナイロン、ポリエステル、ポリウレタン、ポリプロピレンなどの合成繊維及びこれらの複合繊維、混紡繊維などが挙げられる。繊維製品の形態は繊維、糸、布、不織布、紙などのいずれの形態であってもよい。 The water-repellent fiber product of the present invention is obtained by attaching the above-described water-repellent agent. There are no particular restrictions on the material of such textile products, natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as nylon, polyester, polyurethane, and polypropylene, and composite fibers thereof. A blended fiber etc. are mentioned. The form of the fiber product may be any form such as fiber, yarn, cloth, non-woven fabric, and paper.
上記撥水剤を繊維製品に付着させる方法としては、例えば、浸漬、噴霧、塗布等の加工方法が挙げられる。また、撥水剤が水を含有する場合は、繊維製品に付着させた後に水を除去するために乾燥させることが好ましい。 Examples of the method for attaching the water repellent to the textile product include processing methods such as dipping, spraying, and coating. Moreover, when a water repellent contains water, it is preferable to make it dry in order to remove water, after making it adhere to textiles.
撥水剤の繊維製品への付着量は、要求される撥水性の度合いに応じて適宜調整可能であるが、繊維製品１００ｇに対して、撥水剤に含まれる非フッ素系ポリマーの付着量が０．０１〜１０ｇとなるように調整することが好ましく、０．０５〜５ｇとなるように調整することがより好ましい。非フッ素系ポリマーの付着量が０．０１ｇ未満であると、非フッ素系ポリマーの付着量が上記範囲にある場合と比較して、繊維製品が十分な撥水性を発揮できない傾向にあり、１０ｇを超えると、非フッ素系ポリマーの付着量が上記範囲にある場合と比較して、繊維製品の風合が粗硬になる傾向にある。 The amount of the water repellent attached to the fiber product can be appropriately adjusted according to the required degree of water repellency, but the amount of the non-fluorine polymer contained in the water repellent is 100 g relative to the fiber product. It is preferable to adjust so that it may become 0.01-10 g, and it is more preferable to adjust so that it may become 0.05-5 g. If the adhesion amount of the non-fluorine polymer is less than 0.01 g, the fiber product tends not to exhibit sufficient water repellency compared to the case where the adhesion amount of the non-fluorine polymer is in the above range. When it exceeds, compared with the case where the adhesion amount of a non-fluorine-type polymer exists in the said range, it exists in the tendency for the feel of a textile product to become coarse and hard.
また、本発明の撥水剤を繊維製品に付着させた後は、適宜熱処理することが好ましい。温度条件は特に制限はないが、本発明の撥水剤を用いると、１００〜１３０℃の温和な条件により繊維製品に十分良好な撥水性を発現させることができる。温度条件は１３０℃以上（好ましくは２００℃まで）の高温処理であってもよいが、かかる場合は、フッ素系撥水剤を用いた従来の場合よりも処理時間を短縮することが可能である。したがって、本発明の撥水性繊維製品によれば、熱による繊維製品の変質が抑えられ、撥水処理時の繊維製品の風合が柔軟となり、しかも温和な熱処理条件、すなわち低温キュア条件下で繊維製品に撥水性を発揮できる。 Moreover, after making the water repellent of this invention adhere to textiles, it is preferable to heat-process suitably. The temperature condition is not particularly limited, but when the water repellent of the present invention is used, sufficiently good water repellency can be expressed in the fiber product under mild conditions of 100 to 130 ° C. The temperature condition may be a high temperature treatment of 130 ° C. or higher (preferably up to 200 ° C.), but in such a case, the treatment time can be shortened compared to the conventional case using a fluorine-based water repellent. . Therefore, according to the water-repellent fiber product of the present invention, alteration of the fiber product due to heat is suppressed, the texture of the fiber product at the time of water-repellent treatment becomes flexible, and the fiber is subjected to mild heat treatment conditions, that is, low-temperature curing conditions The product can exhibit water repellency.
特に、撥水性の洗濯耐久性を向上させたい場合には、撥水剤組成物を繊維製品に付着させて水を除去する上述の工程と、メチロールメラミン、イソシアネート基又はブロックドイソシアネート基を１個以上有する化合物に代表される架橋剤を、繊維製品に付着させてこれを加熱する工程とを含む方法によって、繊維製品を撥水加工することが好ましい。更に、撥水性の洗濯耐久性をより向上させたい場合には、非フッ素系ポリマーからなる撥水剤として、上述の架橋剤と反応可能な官能基を有する単量体を共重合した非フッ素系ポリマーからなる撥水剤を用いることが好ましい。 In particular, when it is desired to improve the water-repellent washing durability, the water repellent composition is attached to the fiber product to remove water and one methylolmelamine, isocyanate group or blocked isocyanate group The fiber product is preferably water-repellent processed by a method comprising a step of adhering a crosslinking agent typified by the above-mentioned compound to the fiber product and heating it. Furthermore, when it is desired to further improve the water-repellent washing durability, a non-fluorine-based copolymer obtained by copolymerizing a monomer having a functional group capable of reacting with the above-mentioned crosslinking agent as a water-repellent agent comprising a non-fluorine-based polymer. It is preferable to use a water repellent made of a polymer.
イソシアネート基を１個以上有する化合物としては、ブチルイソシアネート、フェニルイソシアネート、トリルイソシアネート、ナフタレンイソシアネートなどのモノイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネートなどのジイソシアネート及びこれらのイソシアヌレート環である三量体や、トリメチロールプロパンアダクト体が挙げられる。また、ブロックドイソシアネート基を１個以上有する化合物としては、上記イソシアネート基を有する化合物をブロック化剤でイソシアネート基を保護した化合物が挙げられる。このとき用いられるブロック化剤としては、２級又は３級アルコール類、活性メチレン化合物、フェノール類、オキシム類、ラクタム類などの有機系ブロック化剤や、重亜硫酸ナトリウム、重亜硫酸カリウムなどの重亜硫酸塩が挙げられる。上述の架橋剤は、１種を単独で用いてもよいし、複数種を組み合わせてもよい。 Examples of the compound having at least one isocyanate group include monoisocyanates such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate, diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like. Examples include a trimer that is an isocyanurate ring and a trimethylolpropane adduct. Moreover, as a compound which has 1 or more of blocked isocyanate groups, the compound which protected the isocyanate group with the blocking agent for the compound which has the said isocyanate group is mentioned. Blocking agents used at this time include organic blocking agents such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, and lactams, and bisulfites such as sodium bisulfite and potassium bisulfite. Salt. The above crosslinking agents may be used alone or in combination of two or more.
架橋剤は、例えば、架橋剤を有機溶剤に溶解するか、水に乳化分散させた処理液に被処理物（繊維製品）を浸漬し、被処理物に付着した処理液を乾燥する方法により、被処理物に付着させることができる。そして、被処理物に付着した架橋剤を加熱することにより、架橋剤と被処理物や非フッ素系ポリマーとの反応を進行させることができる。架橋剤の反応を十分に進行させてより効果的に洗濯耐久性を向上させるために、このときの加熱は１１０〜１８０℃で１〜５分間行うのがよい。架橋剤の付着及び加熱の工程は、上述の撥水剤組成物で処理する工程と同時に行ってもよい。同時に行う場合、例えば、撥水剤組成物及び架橋剤を含有する処理液を被処理物に付着させ、水を除去した後、更に、被処理物に付着している架橋剤を加熱する。撥水加工工程の簡素化や、熱量の削減、経済性を考慮した場合、撥水剤組成物の処理工程と同時に行うことが好ましい。 The cross-linking agent is, for example, by dissolving the cross-linking agent in an organic solvent or immersing the object to be processed (fiber product) in a processing liquid emulsified and dispersed in water, and drying the processing liquid attached to the object to be processed. It can be attached to the workpiece. And the reaction with a to-be-processed object and a non-fluorine-type polymer can be advanced by heating the crosslinking agent adhering to to-be-processed object. In order to sufficiently advance the reaction of the crosslinking agent and more effectively improve the washing durability, the heating at this time is preferably performed at 110 to 180 ° C. for 1 to 5 minutes. The step of attaching and heating the cross-linking agent may be performed simultaneously with the step of treating with the above-described water repellent composition. In the case of carrying out simultaneously, for example, after the treatment liquid containing the water repellent composition and the crosslinking agent is adhered to the object to be treated and water is removed, the crosslinking agent adhered to the object to be treated is further heated. In view of simplification of the water repellent process, reduction of heat, and economy, it is preferable to perform the process simultaneously with the process of treating the water repellent composition.
また、架橋剤を過度に使用すると風合を損ねる恐れがある。上記架橋剤は、被処理物（繊維製品）に対して０．１〜５０質量％の量で用いることが好ましく、０．１〜１０質量％の量で用いることが特に好ましい。 Moreover, when a crosslinking agent is used excessively, there exists a possibility that a feeling may be impaired. The crosslinking agent is preferably used in an amount of 0.1 to 50% by mass, particularly preferably 0.1 to 10% by mass with respect to the object to be treated (textile product).
こうして得られる本発明の撥水性繊維製品は、屋外で長期間使用した場合であっても、十分に撥水性を発揮することができ、また、上記撥水性繊維製品はフッ素系の化合物を使用していないことから、環境にやさしいものとすることができる。 The water-repellent fiber product of the present invention thus obtained can sufficiently exhibit water repellency even when used outdoors for a long time, and the water-repellent fiber product uses a fluorine-based compound. Because it is not, it can be environmentally friendly.
以上、本発明の好適な実施形態について説明したが、本発明は上記実施形態に限定されるものではない。 The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.
例えば、本発明の撥水剤に含まれる非フッ素系ポリマーを製造する場合において、上記実施形態では、重合反応をラジカル重合により行っているが、紫外線、電子線、γ線のような電離性放射線などを照射する光重合により重合反応を行ってもよい。 For example, in the case of producing a non-fluorine polymer contained in the water repellent of the present invention, in the above embodiment, the polymerization reaction is performed by radical polymerization, but ionizing radiation such as ultraviolet rays, electron beams, and γ rays is used. The polymerization reaction may be carried out by photopolymerization with irradiation.
また、本発明においては、撥水剤が繊維製品に付着されて撥水性繊維製品としているが、撥水剤で処理される製品としては、繊維製品用途に限らず、金属、ガラス、樹脂等の物品であってもよい。 Further, in the present invention, the water repellent is attached to the fiber product to make the water repellent fiber product, but the product treated with the water repellent is not limited to the use of the fiber product, but may be metal, glass, resin, etc. It may be an article.
また、かかる場合、撥水剤を上記物品に付着させる方法や撥水剤の付着量は、被処理物の種類などに応じて、任意に定めることができる。 In such a case, the method of attaching the water repellent to the article and the amount of the water repellent attached can be arbitrarily determined according to the type of the object to be processed.
以下、本発明を実施例や比較例等で具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example, a comparative example, etc. demonstrate this invention concretely, this invention is not limited to these Examples.
（参考例１）
５００ｍＬフラスコに、アクリル酸ステアリル（単量体）７５ｇ、ステアリルジメチルアミン塩酸塩（カチオン界面活性剤）１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル（ノニオン界面活性剤）４ｇ、ドデシルメルカプタン（連鎖移動剤）０．１５ｇ、トリプロピレングリコール（有機溶媒）２５ｇ及び水（媒体）１４４．５ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩（重合開始剤）０．２５ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た。
( Reference Example 1)
In a 500 mL flask, stearyl acrylate (monomer) 75 g, stearyldimethylamine hydrochloride (cationic surfactant) 1 g, polyoxyethylene (10 mol) lauryl ether (nonionic surfactant) 4 g, dodecyl mercaptan (chain transfer agent) ) 0.15 g, tripropylene glycol (organic solvent) 25 g and water (medium) 144.5 g were mixed and stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.25 g of azobis (isobutylamidine) dihydrochloride (polymerization initiator) was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a polymer concentration of 30% by mass (non-fluorine-based). ) A polymer dispersion was obtained.
（実施例２）
５００ｍＬフラスコに、メタクリル酸ステアリル（単量体）７５ｇ、ステアリルジメチルアミン塩酸塩１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル４ｇ、ドデシルメルカプタン０．０５ｇ、トリプロピレングリコール２５ｇ及び水１４４．７ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩０．２５ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た。
(Example 2)
In a 500 mL flask, put 75 g of stearyl methacrylate (monomer), 1 g of stearyldimethylamine hydrochloride, 4 g of polyoxyethylene (10 mol) lauryl ether, 0.05 g of dodecyl mercaptan, 25 g of tripropylene glycol and 144.7 g of water, The mixture was stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a (non-fluorine-based) polymer dispersion having a polymer concentration of 30% by mass. Obtained.
（実施例３）
５００ｍＬフラスコに、メタクリル酸セチル（単量体）６５ｇ、メタクリル酸２−エチルヘキシル（単量体）１０ｇ、ステアリルジメチルアミン塩酸塩１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル４ｇ、トリプロピレングリコール２５ｇ及び水１４４．８ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩０．２５ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た。
(Example 3)
In a 500 mL flask, 65 g of cetyl methacrylate (monomer), 10 g of 2-ethylhexyl methacrylate (monomer), 1 g of stearyldimethylamine hydrochloride, 4 g of polyoxyethylene (10 mol) lauryl ether, 25 g of tripropylene glycol and water 144.8 g was added and mixed and stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a (non-fluorine-based) polymer dispersion having a polymer concentration of 30% by mass. Obtained.
（実施例４）
５００ｍＬフラスコに、メタクリル酸ステアリル５５ｇ、メタクリル酸ラウリル（単量体）２０ｇ、ステアリルジメチルアミン塩酸塩１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル４ｇ、トリプロピレングリコール２５ｇ及び水１４４．８ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩０．２５ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た。
Example 4
A 500 mL flask is charged with 55 g of stearyl methacrylate, 20 g of lauryl methacrylate (monomer), 1 g of stearyldimethylamine hydrochloride, 4 g of polyoxyethylene (10 mol) lauryl ether, 25 g of tripropylene glycol and 144.8 g of water. The mixture was stirred at 0 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a (non-fluorine-based) polymer dispersion having a polymer concentration of 30% by mass. Obtained.
（実施例５）
５００ｍＬフラスコに、アクリル酸ステアリル６５ｇ、アクリルアミド（単量体）３ｇ、アクリル酸メチル（単量体）７ｇ、ステアリルジメチルアミン塩酸塩１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル４ｇ、トリプロピレングリコール２５ｇ及び水１４４．９ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩０．１ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た
(Example 5)
In a 500 mL flask, 65 g of stearyl acrylate, 3 g of acrylamide (monomer), 7 g of methyl acrylate (monomer), 1 g of stearyldimethylamine hydrochloride, 4 g of polyoxyethylene (10 mol) lauryl ether, 25 g of tripropylene glycol and 144.9 g of water was added and mixed and stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.1 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a (non-fluorine-based) polymer dispersion having a polymer concentration of 30% by mass. Obtained
（実施例６）
５００ｍＬフラスコに、アクリル酸ステアリル６５ｇ、テトラメチロールメタンテトラアクリレート（単量体）５ｇ、アクリル酸ブチル（単量体）５ｇ、ステアリルジメチルアミン塩酸塩１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル４ｇ、トリプロピレングリコール２５ｇ及び水１４４．９ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩（重合開始剤）０．１ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た。
(Example 6)
In a 500 mL flask, 65 g of stearyl acrylate, 5 g of tetramethylolmethane tetraacrylate (monomer), 5 g of butyl acrylate (monomer), 1 g of stearyldimethylamine hydrochloride, 4 g of polyoxyethylene (10 mol) lauryl ether, 25 g of propylene glycol and 144.9 g of water were added and mixed and stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.1 g of azobis (isobutylamidine) dihydrochloride (polymerization initiator) was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a polymer concentration of 30% by mass (non-fluorine-based). ) A polymer dispersion was obtained.
（実施例７）
５００ｍＬフラスコに、メタクリル酸セチル（単量体）６５ｇ、メタクリル酸２−ヒドロキシエチル（ヒドロキシル基を有する単量体）１０ｇ、ステアリルジメチルアミン塩酸塩１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル４ｇ、トリプロピレングリコール２５ｇ及び水１４４．８ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩０．２５ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た。
(Example 7)
In a 500 mL flask, 65 g of cetyl methacrylate (monomer), 10 g of 2-hydroxyethyl methacrylate (monomer having a hydroxyl group), 1 g of stearyldimethylamine hydrochloride, 4 g of polyoxyethylene (10 mol) lauryl ether, 25 g of propylene glycol and 144.8 g of water were added and mixed and stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a (non-fluorine-based) polymer dispersion having a polymer concentration of 30% by mass. Obtained.
（実施例８）
５００ｍＬフラスコに、メタクリル酸セチル（単量体）６５ｇ、メタクリル酸ジメチルアミノエチル（アミノ基を有する単量体）１０ｇ、ステアリルジメチルアミン塩酸塩１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル４ｇ、トリプロピレングリコール２５ｇ及び水１４４．８ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩０．２５ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た。
(Example 8)
In a 500 mL flask, 65 g of cetyl methacrylate (monomer), 10 g of dimethylaminoethyl methacrylate (monomer having an amino group), 1 g of stearyldimethylamine hydrochloride, 4 g of polyoxyethylene (10 mol) lauryl ether, tripropylene 25 g of glycol and 144.8 g of water were added and mixed and stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a (non-fluorine-based) polymer dispersion having a polymer concentration of 30% by mass. Obtained.
（実施例９）
５００ｍＬフラスコに、メタクリル酸セチル（単量体）６５ｇ、メタクリル酸グリシジル（エポキシ基を有する単量体）１０ｇ、ステアリルジメチルアミン塩酸塩１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル４ｇ、トリプロピレングリコール２５ｇ及び水１４４．８ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩０．２５ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た。
Example 9
In a 500 mL flask, 65 g of cetyl methacrylate (monomer), 10 g of glycidyl methacrylate (monomer having an epoxy group), 1 g of stearyldimethylamine hydrochloride, 4 g of polyoxyethylene (10 mol) lauryl ether, 25 g of tripropylene glycol And 144.8 g of water were added and mixed and stirred at 45 ° C. to obtain a mixture. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a (non-fluorine-based) polymer dispersion having a polymer concentration of 30% by mass. Obtained.
（実施例１０）
５００ｍＬフラスコに、メタクリル酸セチル（単量体）７０ｇ、１，１−ビス（アクリロイルオキシメチル）エチルイソシアネートのメチルエチルケトンオキシムブロック化物（イソシアネート基を有する単量体）５ｇ、ステアリルジメチルアミン塩酸塩１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル４ｇ、トリプロピレングリコール２５ｇ及び水１４４．８ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩０．２５ｇを混合液に添加し、窒素雰囲気化で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た。
(Example 10)
In a 500 mL flask, 70 g of cetyl methacrylate (monomer), 5 g of 1,1-bis (acryloyloxymethyl) ethyl isocyanate blocked with methyl ethyl ketone oxime (monomer having an isocyanate group), 1 g of stearyldimethylamine hydrochloride, poly 4 g of oxyethylene (10 mol) lauryl ether, 25 g of tripropylene glycol and 144.8 g of water were added and mixed and stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours in a nitrogen atmosphere to obtain a (non-fluorine-based) polymer dispersion having a polymer concentration of 30% by mass. Obtained.
（比較例１）
５００ｍＬフラスコに下記化学式（１）：
で表され、ｎの平均値が８となる混合物（なお、当該混合物にはｎが６，８，１０，１２，１４の化合物が混合されている）７５ｇ、ステアリルトリメチルアンモニウムクロライド３ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル７．５ｇ、トリプロピレングリコール２５ｇ及び水１３８ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して上記混合物を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩１．５ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（フッ素系）ポリマー分散液を得た。
(Comparative Example 1)
In a 500 mL flask, the following chemical formula (1):
75 g of a mixture in which the average value of n is 8 (wherein n is a compound of 6, 8, 10, 12, 14), 3 g of stearyltrimethylammonium chloride, polyoxyethylene (10 mol) 7.5 g of lauryl ether, 25 g of tripropylene glycol and 138 g of water were added and mixed and stirred at 45 ° C. to obtain a mixed solution. The mixture was emulsified and dispersed by irradiating the mixture with ultrasonic waves. Next, 1.5 g of azobis (isobutylamidine) dihydrochloride is added to the mixed solution, and radical polymerization is performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a (fluorine) polymer dispersion having a polymer concentration of 30% by mass. It was.
（比較例２）
５００ｍＬフラスコに、セチルメタクリレート６５ｇ、２−エチルヘキシルメタクリレート１０ｇ、ステアリルジメチルアミン塩酸塩１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル４ｇ、トリプロピレングリコール２５ｇ、水１４４．３ｇ及びドデシルメルカプタン０．５ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩０．２５ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た。
(Comparative Example 2)
A 500 mL flask is charged with 65 g of cetyl methacrylate, 10 g of 2-ethylhexyl methacrylate, 1 g of stearyldimethylamine hydrochloride, 4 g of polyoxyethylene (10 mol) lauryl ether, 25 g of tripropylene glycol, 144.3 g of water and 0.5 g of dodecyl mercaptan, The mixture was stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a (non-fluorine-based) polymer dispersion having a polymer concentration of 30% by mass. Obtained.
（比較例３）
５００ｍＬフラスコに、メタクリル酸セチル６０ｇ、テトラメチロールメタンテトラアクリレート１０ｇ、アクリル酸ブチル５ｇ、ステアリルジメチルアミン塩酸塩１ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル４ｇ、トリプロピレングリコール２５ｇ及び水１４５．０ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して全単量体を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩（重合開始剤）０．０３ｇを混合液に添加し、窒素雰囲気下で５０℃にて６時間ラジカル重合させて、ポリマー濃度３０質量％の（非フッ素系）ポリマー分散液を得た。
(Comparative Example 3)
In a 500 mL flask, put 60 g of cetyl methacrylate, 10 g of tetramethylolmethane tetraacrylate, 5 g of butyl acrylate, 1 g of stearyldimethylamine hydrochloride, 4 g of polyoxyethylene (10 mol) lauryl ether, 25 g of tripropylene glycol and 145.0 g of water. The mixture was stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.03 g of azobis (isobutylamidine) dihydrochloride (polymerization initiator) was added to the mixed solution, and radical polymerization was performed at 50 ° C. for 6 hours under a nitrogen atmosphere to obtain a polymer concentration of 30% by mass (non-fluorine-based). ) A polymer dispersion was obtained.
（合成例１）：架橋剤（ブロックドイソシアネート基を分子内に１個以上含有する化合物）の合成
１Ｌのガラス反応容器に、ジフェニルメタンジイソシアネート２６０ｇと酢酸エチル３００ｇを採り、攪拌、昇温し、４０℃でメチルエチルケトンオキシム２００ｇを徐々に滴下する。滴下後、６０℃で３時間攪拌を続けて熟成反応し、得られた分散物を濾別し、アセトンで洗浄後、乾燥して粉末を得た。次に、ポリオキシエチレン（１０モル）ラウリルエーテル３ｇを水７０ｇに溶解した溶液中に、上記の乾燥した粉末３０ｇを攪拌しながら添加し、ブロックドイソシアネート基を分子内に１個以上有する化合物である架橋剤の分散物を得た。
(Synthesis example 1): Synthesis | combination of a crosslinking agent (compound containing 1 or more of blocked isocyanate groups in a molecule | numerator) Diphenylmethane diisocyanate 260g and ethyl acetate 300g are taken to 1L glass reaction container, and it stirs and heats up, 40 At 200C, 200 g of methyl ethyl ketone oxime is gradually added dropwise. After the dropwise addition, the mixture was stirred at 60 ° C. for 3 hours for aging reaction, and the resulting dispersion was filtered off, washed with acetone and dried to obtain a powder. Next, in a solution of 3 g of polyoxyethylene (10 mol) lauryl ether dissolved in 70 g of water, 30 g of the dried powder is added with stirring, and a compound having one or more blocked isocyanate groups in the molecule. A crosslinker dispersion was obtained.
なお、参考例１、実施例２〜１０及び比較例１〜３で得られたポリマー分散液中の各ポリマーは、ガスクロマトグラフ（ＧＣ−１５ＡＰＴＦ、（株）島津製作所製）により、いずれも全単量体の９８％以上が重合していることが確認された。 In addition, each polymer in the polymer dispersion liquid obtained in Reference Example 1, Examples 2 to 10 and Comparative Examples 1 to 3 was all united by gas chromatography (GC-15APTF, manufactured by Shimadzu Corporation). It was confirmed that 98% or more of the polymer was polymerized.
（評価方法）
参考例１、実施例２〜１０及び比較例１〜３で得られたポリマー分散液５０ｇにアセトン５００ｍＬを加えることによりポリマーと乳化剤とを分離させポリマーをろ取し、このポリマーを２５℃にて２４時間減圧乾燥させた。得られたポリマーを以下のように評価した。
(Evaluation method)
The polymer and the emulsifier are separated by adding 500 mL of acetone to 50 g of the polymer dispersions obtained in Reference Example 1, Examples 2 to 10 and Comparative Examples 1 to 3, and the polymer is collected by filtration. It was dried under reduced pressure for 24 hours. The obtained polymer was evaluated as follows.
溶融粘度の測定方法
参考例１、実施例２〜１０及び比較例２、３のポリマーについて、高架式フローテスターＣＦＴ−５００（（株）島津製作所製）を用い、ダイ（長さ１０ｍｍ、直径１ｍｍ）を取り付けたシリンダー内にポリマーを１．５ｇ入れ、１６０℃６分間保持し、プランジャーにより１００ｋｇ・ｆ／ｃｍ２の荷重を加えて１６０℃における溶融粘度を測定した。
Method for measuring melt viscosity
For the polymers of Reference Example 1, Examples 2 to 10 and Comparative Examples 2 and 3, an elevated flow tester CFT-500 (manufactured by Shimadzu Corporation) was used, and a cylinder attached with a die (length 10 mm, diameter 1 mm). 1.5 g of the polymer was put inside, kept at 160 ° C. for 6 minutes, a load of 100 kg · f / cm 2 was applied with a plunger, and the melt viscosity at 160 ° C. was measured.
重量平均分子量の測定方法
参考例１、実施例２〜１０及び比較例２、３のポリマーについて、ＧＰＣ装置（東ソー（株）製ＧＰＣ「ＨＬＣ−８０２０」）により、カラム温度４０℃、流量１．０ｍｌ／分の条件下で、溶離液にテトラヒドロフランを用いて測定し、標準ポリスチレン換算で重量平均分子量を測定した。なお、カラムは、東ソー（株）製の商品名ＴＳＫ−ＧＥＬ Ｇ５０００ＨＨＲ、Ｇ４０００ＨＨＲ、Ｇ３０００ＨＨＲの３本を接続して装着した。結果を表１に示す。
Method for measuring weight average molecular weight
For the polymers of Reference Example 1, Examples 2 to 10 and Comparative Examples 2 and 3, using a GPC apparatus (GPC “HLC-8020” manufactured by Tosoh Corporation), a column temperature of 40 ° C. and a flow rate of 1.0 ml / min. Then, the measurement was performed using tetrahydrofuran as an eluent, and the weight average molecular weight was measured in terms of standard polystyrene. In addition, three columns of TOS-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation were connected and attached to the column. The results are shown in Table 1.
撥水性の評価方法
ＪＩＳ Ｌ １０９２（１９９８）のスプレー法に準じてシャワー水温を２７℃として
試験をした。本試験においては、綿布又はポリエステル１００％布それぞれを、参考例１、実施例２〜１０又は比較例１〜３のポリマーの含有量が４質量％となるように水で希釈したものに浸漬処理（ピックアップ５０質量％）した後、１２０℃で２分間乾燥し、更に表１に示すような条件で熱処理して、得られた布の撥水性を評価した。結果は目視にて下記の等級で評価した。なお、特性がわずかに良好な場合は等級に「＋」をつけ、特性がわずかに劣る場合は等級に「−」をつけた。結果を表２に示す。
撥水性：状態
５： 表面に付着湿潤のないもの
４： 表面にわずかに付着湿潤を示すもの
３： 表面に部分的湿潤を示すもの
２： 表面に湿潤を示すもの
１： 表面全体に湿潤を示すもの
０： 表裏両面が完全に湿潤を示すもの
Evaluation method of water repellency The test was conducted at a shower water temperature of 27 ° C. according to the spray method of JIS L 1092 (1998). In this test, each cotton cloth or 100% polyester cloth was dipped in water diluted so that the polymer content of Reference Example 1, Examples 2 to 10 or Comparative Examples 1 to 3 was 4% by mass. (Pickup 50% by mass), dried at 120 ° C. for 2 minutes, and further heat-treated under the conditions shown in Table 1 to evaluate the water repellency of the resulting fabric. The results were visually evaluated according to the following grade. When the characteristics were slightly good, “+” was assigned to the grade, and when the characteristics were slightly inferior, “−” was assigned to the grade. The results are shown in Table 2.
Water repellency: State 5: No adhesion on the surface 4: Exhibit slight adhesion on the surface 3: Exhibit partial wetting on the surface 2: Exhibit wetting on the surface 1: Exhibit wetting on the entire surface Thing 0: Both front and back sides are completely wet
風合
風合は、ポリエステル布を参考例１、実施例２〜１０又は比較例１〜３のポリマーが４質量％となるように水で希釈したものに浸漬処理（ピックアップ５０質量％）した後、１２０℃で２分間乾燥し、更に１８０℃で３０秒間熱処理したものを用いて評価した。結果はハンドリングにて下記に示す５段階で評価した。結果を表２に示す。
１：硬い 〜 ５：柔らかい
Feeling After feeling the polyester fabric is dipped in water so that the polymer of Reference Example 1, Examples 2 to 10 or Comparative Examples 1 to 3 is 4% by mass (pickup 50% by mass). Evaluation was made using a sample dried at 120 ° C. for 2 minutes and further heat-treated at 180 ° C. for 30 seconds. The results were evaluated by handling in the following five stages. The results are shown in Table 2.
1: Hard ~ 5: Soft
撥水剤の安定性
参考例１、実施例２〜１０又は比較例１〜３で得られたポリマー分散液を４５℃で２週間保存した時の安定性を、以下の基準で評価した。結果を表２に示す。
Ａ： 外観変化のないもの
Ｂ： ポリマーの沈降物、分離、ゲル化等が認められるもの
Water repellent stability
The stability when the polymer dispersions obtained in Reference Example 1, Examples 2 to 10 or Comparative Examples 1 to 3 were stored at 45 ° C. for 2 weeks was evaluated according to the following criteria. The results are shown in Table 2.
A: No change in appearance B: Sedimentation, separation or gelation of polymer is observed
参考例１、実施例２〜１０の繊維製品は、熱処理した場合のみならず、熱処理しない場合であっても、従来のフッ素系撥水剤（比較例１）を用いた場合と同等以上の撥水性を発揮できることがわかった。更に、１６０℃における溶融粘度を１０００Ｐａ・ｓ以下とした実施例１〜１０では、比較例３と比較して、繊維製品の風合も良好なものであり、撥水剤とした場合の安定性にも優れるものであった。 The fiber products of Reference Example 1 and Examples 2 to 10 have the same or better repellent properties than the case of using the conventional fluorinated water repellent (Comparative Example 1), not only when heat-treated but also when not heat-treated. It was found that it can exhibit aqueous properties. Furthermore, in Examples 1 to 10 in which the melt viscosity at 160 ° C. was 1000 Pa · s or less, the texture of the fiber product was better than that of Comparative Example 3, and the stability when a water repellent was used. It was also excellent.
参考例１と実施例２とを比較すると、単量体組成が近いものであっても、ポリマーの重量平均分子量が異なる場合は、重量平均分子量が大きい方が、撥水性が優れていることがわかった。 Comparing Reference Example 1 and Example 2, when the weight average molecular weights of the polymers are different even if the monomer compositions are close, the water repellent property is better when the weight average molecular weight is larger. all right.
比較例２のポリマーは、実施例３のポリマーと単量体組成は同じであるが、ポリマーの重量平均分子量が異なり５万と小さいものであった。この場合、実施例３及び比較例２はいずれも繊維製品の風合は良好であるものの、比較例２の繊維製品は、撥水性が著しく劣ることがわかった。 The polymer of Comparative Example 2 had the same monomer composition as the polymer of Example 3, but the polymer had a weight average molecular weight different from that of Example 3 and was as small as 50,000. In this case, although both Example 3 and Comparative Example 2 have a good texture of the fiber product, it was found that the fiber product of Comparative Example 2 was remarkably inferior in water repellency.
比較例３のように、重量平均分子量が本発明範囲を満たす場合であっても溶融粘度が本発明の範囲を超える場合には、撥水性は良好であるものの、風合が著しく劣り、またポリマー分散液の安定性も劣ることがわかった。 Even if the weight average molecular weight satisfies the range of the present invention as in Comparative Example 3, if the melt viscosity exceeds the range of the present invention, the water repellency is good but the texture is remarkably inferior, and the polymer It was found that the stability of the dispersion was also poor.
撥水性の洗濯耐久性の評価
ＪＩＳ Ｌ １０９２（１９９８）のスプレー法に準じてシャワー水温を２７℃として試験をした。本試験においては、綿１００％布を、参考例１、実施例２〜１０又は比較例１〜３のポリマーの含有量が４質量％及び合成例１で得られた架橋剤の含有量が１質量％となるように水で希釈した処理液に浸漬処理（ピックアップ５０質量％）した後、１２０℃で２分間乾燥し、更に１６０℃で１分間熱処理して得られた布（Ｌ−０）、及びＪＩＳ Ｌ ０２１７（１９９５）の１０３法による洗濯を１０回（Ｌ−１０）行った後の布の撥水性を上記評価方法と同様に評価した。
また、ポリエステル１００％布を、参考例１、実施例２〜１０又は比較例１〜３のポリマーの含有量が４質量％及びメチロールメラミン（架橋剤）の含有量が０．３質量％となるように水で希釈した処理液に浸漬処理（ピックアップ５０質量％）した後、１２０℃で２分間乾燥し、更に１８０℃で３０秒間熱処理して得られた布（Ｌ−０）、及びＪＩＳ Ｌ ０２１７（１９９５）の１０３法による洗濯を１０回（Ｌ−１０）行った後の布の撥水性を上記評価方法と同様に評価した。結果を表３に示す。
Evaluation of water-repellent washing durability The test was conducted at a shower water temperature of 27 ° C. according to the spray method of JIS L 1092 (1998). In this test, the content of the polymer of Reference Example 1, Examples 2 to 10 or Comparative Examples 1 to 4% by mass and the content of the crosslinking agent obtained in Synthesis Example 1 was 100% for 100% cotton cloth. A cloth (L-0) obtained by immersing in a treatment solution diluted with water to a mass% (pickup 50 mass%), drying at 120 ° C. for 2 minutes, and further heat-treating at 160 ° C. for 1 minute. And the water repellency of the cloth after washing 10 times (L-10) by 103 method of JIS L 0217 (1995) was evaluated in the same manner as the above evaluation method.
Further, in the 100% polyester cloth, the content of the polymer of Reference Example 1, Examples 2 to 10 or Comparative Examples 1 to 3 is 4% by mass and the content of methylolmelamine (crosslinking agent) is 0.3% by mass. After being immersed in a treatment solution diluted with water (50% by mass of pickup), dried at 120 ° C. for 2 minutes and further heat treated at 180 ° C. for 30 seconds, and JIS L The water repellency of the fabric after 10 washings (L-10) according to the 103 method of 0217 (1995) was evaluated in the same manner as in the above evaluation method. The results are shown in Table 3.
架橋剤を併用した実施例３〜６は、従来のフッ素系撥水剤（比較例１）と同等の洗濯耐久性のある撥水性が得られる。そして、反応性単量体を共重合させた実施例７〜１０に架橋剤を併用することによって、更に洗濯耐久性の撥水性が改善されたことがわかった。 In Examples 3 to 6 in which a crosslinking agent is used in combination, water repellency with washing durability equivalent to that of a conventional fluorine-based water repellent (Comparative Example 1) is obtained. And it was found that the water repellency of washing durability was further improved by using a crosslinking agent in combination with Examples 7 to 10 in which reactive monomers were copolymerized.
以上より、本発明によれば、繊維製品等に付着させた場合に、十分な撥水性を発揮する撥水剤、それを用いた撥水加工方法、及びそれを用いた撥水性繊維製品を得られることが確認された。 As described above, according to the present invention, a water repellent that exhibits sufficient water repellency when adhered to a textile product, a water repellent processing method using the same, and a water repellent fiber product using the same are obtained. It was confirmed that
本発明の非フッ素系撥水剤は、特に繊維製品用途に効果的である。本発明の非フッ素系
撥水剤を繊維製品用途に用いた場合は、繊維製品を非フッ素系撥水剤で処理した後、低温
で熱処理しても十分優れた撥水性を発現できるため、熱に弱い特殊な繊維や天然繊維にお
いても十分に撥水性を発現させることができる。更に、架橋剤を併用したり、反応性単量体を共重合させることにより、撥水性の洗濯耐久性を向上させることができる。また、本発明の非フッ素系撥水剤は、フッ素基を含まないので低コストであり、人体や環境への悪影響が少ない撥水剤として有用である。
The non-fluorinated water repellent of the present invention is particularly effective for textile products. When the non-fluorinated water repellent of the present invention is used for textile products, it is possible to develop a sufficiently excellent water repellency even after heat treatment at a low temperature after treating the textile with a non-fluorinated water repellent. Water repellent properties can be sufficiently exhibited even in special fibers and natural fibers that are weak to water. Furthermore, the water-repellent washing durability can be improved by using a crosslinking agent together or copolymerizing a reactive monomer. In addition, the non-fluorinated water repellent of the present invention does not contain a fluorine group, is low in cost, and is useful as a water repellent with little adverse effect on the human body and the environment.
Claims (12)
前記（メタ）アクリル酸エステルの構成割合が前記非フッ素系ポリマーを構成する単量体単位の全量に対して８０〜１００質量％であり、
前記非フッ素系ポリマーは、重量平均分子量が５０万以上且つ１６０℃における溶融粘度が１０００Ｐａ・ｓ以下である、撥水剤。 A water repellent comprising a non-fluorine polymer containing a (meth) acrylic acid ester having 12 or more carbon atoms in the ester moiety as a monomer unit,
The composition ratio of the (meth) acrylic acid ester is 80 to 100% by mass with respect to the total amount of the monomer units constituting the non-fluorine polymer,
The non-fluorine-based polymer is a water repellent having a weight average molecular weight of 500,000 or more and a melt viscosity at 160 ° C. of 1000 Pa · s or less.
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