TWI667264B - Sulfonic acid based aqueous polyurethane emulsion and process of producing the same - Google Patents
Sulfonic acid based aqueous polyurethane emulsion and process of producing the same Download PDFInfo
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- TWI667264B TWI667264B TW106125400A TW106125400A TWI667264B TW I667264 B TWI667264 B TW I667264B TW 106125400 A TW106125400 A TW 106125400A TW 106125400 A TW106125400 A TW 106125400A TW I667264 B TWI667264 B TW I667264B
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- Prior art keywords
- sulfonic acid
- aqueous polyurethane
- polyurethane emulsion
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- 239000000839 emulsion Substances 0.000 title claims abstract description 108
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 108
- 239000004814 polyurethane Substances 0.000 title claims abstract description 108
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims description 19
- 239000004970 Chain extender Substances 0.000 claims description 53
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 33
- 229920000570 polyether Polymers 0.000 claims description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 25
- -1 Potassium 2-ethoxybutanesulfonate Chemical compound 0.000 claims description 25
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 21
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 239000005056 polyisocyanate Substances 0.000 claims description 15
- 229920001228 polyisocyanate Polymers 0.000 claims description 15
- 150000005846 sugar alcohols Polymers 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 13
- 150000003077 polyols Chemical class 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 7
- 150000003384 small molecules Chemical group 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004971 Cross linker Substances 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 claims description 2
- CJVKAEYGNINWLI-UHFFFAOYSA-N 1,2-diisocyanatoethane 1,2,3,4-tetramethylbenzene Chemical compound C(CN=C=O)N=C=O.CC1=C(C(=C(C=C1)C)C)C CJVKAEYGNINWLI-UHFFFAOYSA-N 0.000 claims description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- BLCJBICVQSYOIF-UHFFFAOYSA-N 2,2-diaminobutanoic acid Chemical compound CCC(N)(N)C(O)=O BLCJBICVQSYOIF-UHFFFAOYSA-N 0.000 claims description 2
- MBVGJZDLUQNERS-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound FC(F)(F)C1=NC(C#N)=C(C#N)N1 MBVGJZDLUQNERS-UHFFFAOYSA-N 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- PECYZEOJVXMISF-UHFFFAOYSA-N 3-aminoalanine Chemical compound [NH3+]CC(N)C([O-])=O PECYZEOJVXMISF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920006295 polythiol Polymers 0.000 claims description 2
- NWWAJXCJQQOLIU-UHFFFAOYSA-M sodium;2,3-diaminobenzenesulfonate Chemical compound [Na+].NC1=CC=CC(S([O-])(=O)=O)=C1N NWWAJXCJQQOLIU-UHFFFAOYSA-M 0.000 claims description 2
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 2
- KPTLPIAOSCGETM-UHFFFAOYSA-N benzene 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O.c1ccccc1 KPTLPIAOSCGETM-UHFFFAOYSA-N 0.000 claims 1
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 claims 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 14
- 230000007062 hydrolysis Effects 0.000 abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 7
- 230000003472 neutralizing effect Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004383 yellowing Methods 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000004945 emulsification Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 2
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- CBBNYJHIAFHIFC-UHFFFAOYSA-N N=C=O.N=C=O.C(C=C1)=CC2=C1NN=CC=C2 Chemical compound N=C=O.N=C=O.C(C=C1)=CC2=C1NN=CC=C2 CBBNYJHIAFHIFC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- QILXPCHTWXAUHE-UHFFFAOYSA-N [Na].NCCN Chemical compound [Na].NCCN QILXPCHTWXAUHE-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- DXHPZXWIPWDXHJ-UHFFFAOYSA-N carbon monosulfide Chemical compound [S+]#[C-] DXHPZXWIPWDXHJ-UHFFFAOYSA-N 0.000 description 1
- 125000005521 carbonamide group Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
本發明係關於一種全環保磺酸型水性聚氨酯乳液及其製備方法，本發明之磺酸型水性聚氨酯乳液的優點在於，其可大量減少有機溶劑、羧酸及中和劑之用量，且製備方法簡單並對環境友好；本發明之磺酸型水性聚氨酯乳液另具有良好之穩定性，因此，由其製得之膠膜具有更佳的耐水解性及耐黃變性。 The invention relates to a full environmental protection sulfonic acid type aqueous polyurethane emulsion and a preparation method thereof, and the sulfonic acid type aqueous polyurethane emulsion of the invention has the advantages that the amount of the organic solvent, the carboxylic acid and the neutralizing agent can be greatly reduced, and the preparation method It is simple and environmentally friendly; the sulfonic acid type aqueous polyurethane emulsion of the present invention has good stability, and therefore, the film obtained therefrom has better hydrolysis resistance and yellowing resistance.
Description
本發明涉及聚合物材料領域，具體而言係涉及一種水性聚氨酯乳液，本發明另涉及一種水性聚氨酯乳液的製備方法。 The invention relates to the field of polymer materials, in particular to an aqueous polyurethane emulsion, and to a preparation method of an aqueous polyurethane emulsion.
聚氨酯廣泛應用於塗料、膠黏劑、油墨、皮革加工、紡織等領域，性能表現優異，目前工業上仍大量採用有機溶劑型聚氨酯，以降低體系黏度或溶解反應物，常用有機溶劑主要包括丙酮、N,N-二甲基甲醯胺及/或N-甲基吡咯烷酮等，丙酮在水性聚氨酯乳液製備結束後透過減壓蒸餾的方式部分或全部除去，而N,N-二甲基甲醯胺及N-甲基吡咯烷酮由於沸點相對較高，則一般殘留在乳液中。因此目前工業製備的水性聚氨酯乳液都並非真正意義上之無有機溶劑參與的水乳液體系，亦即，其在製備和使用過程中均存在一定程度的揮發性有機化合物(VOC)的釋放，而造成對施工人員和消費者的健康構成嚴重的威脅，各國政府亦已立法限制聚氨酯製品中揮發性有機化合物或有害空氣污染物(HAP)的含量。 Polyurethane is widely used in coatings, adhesives, inks, leather processing, textiles, etc. It has excellent performance. At present, organic solvent-based polyurethanes are still widely used in the industry to reduce the viscosity of the system or dissolve the reactants. Commonly used organic solvents mainly include acetone. N,N-dimethylformamide and/or N-methylpyrrolidone, etc., acetone is partially or completely removed by vacuum distillation after the preparation of the aqueous polyurethane emulsion, and N,N-dimethylformamide And N-methylpyrrolidone generally remains in the emulsion because of its relatively high boiling point. Therefore, the currently prepared aqueous polyurethane emulsions are not in the true sense of the organic emulsion-free aqueous emulsion system, that is, there is a certain degree of release of volatile organic compounds (VOC) during preparation and use, resulting in It poses a serious threat to the health of construction workers and consumers, and governments have also legislated to limit the content of volatile organic compounds or harmful air pollutants (HAP) in polyurethane products.
水性聚氨酯乳液以係水為分散介質，具有無毒、不具可燃性、環境友好、及成本低等優點，已成為當今聚氨酯領域的重要研究方向。水性聚氨酯乳液保留傳統有機溶劑型聚氨酯之高光澤度、高強度、高耐磨性、高 彈性、高黏接性、耐低溫性、及耐疲勞性等特點，且具有運輸安全、操作環境好、黏度與聚合物分子量無關等優勢，同時避免有機溶劑型聚氨酯因在使用過程中產生之大量揮發性有機溶劑所造成之環境污染問題。 Water-based polyurethane emulsion has the advantages of non-toxic, non-flammable, environmentally friendly, and low cost, and has become an important research direction in the field of polyurethane. Waterborne polyurethane emulsion retains the high gloss, high strength, high wear resistance and high density of traditional organic solvent polyurethane Elasticity, high adhesion, low temperature resistance, and fatigue resistance, and has the advantages of safe transportation, good operating environment, and viscosity independent of polymer molecular weight, while avoiding the large amount of organic solvent-based polyurethanes produced during use. Environmental pollution caused by volatile organic solvents.
傳統水性聚氨酯乳液係由低聚物二元醇、二異氰酸酯、親水性擴鏈劑及小分子擴鏈劑等成分，透過加成聚合及水中分散而製得，且與有機溶劑型聚氨酯乳液相比，除所使用之分散介質不同外，水性聚氨酯乳液之合成關鍵在於使用親水性擴鏈劑，該親水性擴鏈劑可在聚氨酯分子結構中引入親水基團，以使水性聚氨酯乳液具有良好的分散性或自乳化性能。舉例言之，先前技術US 5470907 A及US 6017998 A即揭露一種以二羥甲基丙酸(DMPA)為親水擴鏈劑的水性聚氨酯乳液的製備方法；CN 101475678 A另揭露一種以乙二胺基乙磺酸鈉(AAS)為主要親水擴鏈劑的水性聚氨酯乳液的製備方法；US 4870129 A揭露一種以二羥甲基丙酸及乙二胺基乙磺酸鈉為共親水擴鏈劑的水性聚氨酯乳液的製備方法；US 2006/0036054 A1揭露一種磺酸鹽官能聚酯多元醇的製備方法，可用在聚氨酯的軟段上。 The conventional waterborne polyurethane emulsion is prepared by addition polymerization and dispersion in water by oligomeric diol, diisocyanate, hydrophilic chain extender and small molecular chain extender, and compared with organic solvent type polyurethane emulsion. In addition to the different dispersion media used, the key to the synthesis of aqueous polyurethane emulsions is the use of a hydrophilic chain extender which introduces hydrophilic groups into the molecular structure of the polyurethane to provide good dispersion of the aqueous polyurethane emulsion. Sexual or self-emulsifying properties. For example, prior art US 5,470,907 A and US Pat. No. 6,017,998 A disclose the preparation of an aqueous polyurethane emulsion using dimethylolpropionic acid (DMPA) as a hydrophilic chain extender; CN 101475678 A further discloses an ethylenediamine group. A method for preparing an aqueous polyurethane emulsion containing sodium sulfonate (AAS) as a main hydrophilic chain extender; US Pat. No. 4,870,129 A discloses an aqueous solution using dimethylolpropionic acid and sodium ethylenediamine sulfonate as a co-hydrophilic chain extender A method for preparing a polyurethane emulsion; US 2006/0036054 A1 discloses a process for preparing a sulfonate-functional polyester polyol which can be used on a soft segment of polyurethane.
目前水性聚氨酯乳液所涉之陰離子型親水性擴鏈劑主要分為羧酸型擴鏈劑及磺酸鹽型擴鏈劑二種，相較於羧酸型擴鏈劑(如，DMPA/DMBA)，磺酸鹽型擴鏈劑具有更佳的親水性，因此在製備親水性程度相當之聚氨酯時，相較於羧酸型擴鏈劑，磺酸鹽型擴鏈劑所涉之莫耳用量更少，且由於聚氨酯鏈上的離子減少，靜電斥力減弱，因此水合體積不會迅速增大致使系統黏度上升，故磺酸鹽型擴鏈劑更有利於製備高固含量的水性聚氨酯乳液。 At present, the anionic hydrophilic chain extenders involved in waterborne polyurethane emulsions are mainly classified into two types of carboxylic acid type chain extenders and sulfonate type chain extenders, compared to carboxylic acid type chain extenders (eg, DMPA/DMBA). The sulfonate type chain extender has better hydrophilicity, so when preparing a polyurethane having a hydrophilic degree, the sulfonate type chain extender is more involved than the carboxylic acid type chain extender. Since the ion on the polyurethane chain is reduced and the electrostatic repulsion is weakened, the hydration volume does not increase rapidly and the viscosity of the system is increased. Therefore, the sulfonate type chain extender is more advantageous for preparing a high solid content aqueous polyurethane emulsion.
此外，使用羧酸型擴鏈劑(如，DMPA/DMBA)在加水乳化步驟之 前，額外需提供中和成鹽步驟。目前廣泛使用之中和劑為三乙胺，然，使用三乙胺中和成鹽後，再經乳化而製得之水性聚氨酯乳液中，仍可能殘留三乙胺，致使該水性聚氨酯乳液具有難聞刺激性氣味之缺點，且三乙胺在乳液儲存過程中亦可能發生分解及揮發，從而降低水性聚氨酯乳液之穩定性。相較於此，由於磺酸鹽型擴鏈劑為中性，因此在乳液分散過程中則毋需另添加中和劑，可有效避免前述具有難聞刺激性氣味或分解、揮發之問題；再者由於磺酸鹽型擴鏈劑具有良好的儲存穩定性且不受外部環境(如，溫度)影響，因此製得之水性聚氨酯乳液物性上偏差較小，水性聚氨酯乳液產品具有更高的再現性及穩定性，可有效監控品質並有利於大量生產。 In addition, a carboxylic acid type chain extender (eg, DMPA/DMBA) is used in the water emulsification step. Before, an additional neutralization salt step is required. At present, the widely used neutralizing agent is triethylamine. However, after neutralizing the salt with triethylamine and then emulsification, the aqueous polyurethane emulsion may still have residual triethylamine, making the aqueous polyurethane emulsion difficult. The shortcomings of irritating odors, and triethylamine may also decompose and volatilize during emulsion storage, thereby reducing the stability of the aqueous polyurethane emulsion. Compared with this, since the sulfonate type chain extender is neutral, it is not necessary to add a neutralizing agent in the emulsion dispersion process, which can effectively avoid the above-mentioned problem of unpleasant irritating odor or decomposition and volatilization; Since the sulfonate type chain extender has good storage stability and is not affected by the external environment (for example, temperature), the obtained aqueous polyurethane emulsion has less physical property deviation, and the aqueous polyurethane emulsion product has higher reproducibility. And stability, can effectively monitor the quality and facilitate mass production.
然，現存技術中用之磺酸鹽型擴鏈劑，在分散過程仍需使丙酮調節系統黏度，然，為符合當前環保型聚合物材料之要求，因此在製成磺酸型水性聚氨酯產品後，需額外經減壓蒸餾步驟以移除丙酮。但前述分離丙酮所涉之製程繁瑣、耗時且增加製造成本，且透過減壓蒸餾所移除之丙酮，仍有VOC排放之虞，換言之，事實上現存製造水性聚氨酯乳液之製程並非全環保製程。 However, the sulfonate type chain extender used in the existing technology still needs to adjust the viscosity of the acetone in the dispersion process. However, in order to meet the requirements of the current environmentally friendly polymer materials, after the preparation of the sulfonic acid type waterborne polyurethane product, An additional vacuum distillation step is required to remove the acetone. However, the above-mentioned process for separating acetone is cumbersome, time consuming, and increases the manufacturing cost, and the acetone removed by vacuum distillation still has the VOC emission. In other words, the existing process for manufacturing the waterborne polyurethane emulsion is not an environmentally friendly process. .
為解決前述問題，本發明之一目的即欲提供一種全環保之磺酸型水性聚氨酯乳液其製品及製造方法，在較佳情況下，本發明之製造磺酸型水性聚氨酯乳液的製程中毋需添加任何有機溶劑、羧酸及/或中和劑，本發明之製造方法簡單且對環境友好，而製得之乳液亦具有良好的穩定性，製得之膠膜更具有合意之耐水解性及耐黃變性。本發明之磺酸型水性聚氨酯乳液及其製造方法不僅從製造端即全環保之目的，本發明磺酸型水性聚氨酯乳液可廣泛使用於塗料或接著劑等產品。 In order to solve the foregoing problems, it is an object of the present invention to provide an environmentally friendly sulfonic acid type aqueous polyurethane emulsion, a product thereof, and a method for producing the same, and preferably, in the process for producing a sulfonic acid type aqueous polyurethane emulsion of the present invention, Adding any organic solvent, carboxylic acid and/or neutralizing agent, the manufacturing method of the invention is simple and environmentally friendly, and the prepared emulsion also has good stability, and the obtained film has more desirable hydrolysis resistance and Yellowing resistance. The sulfonic acid type aqueous polyurethane emulsion of the present invention and the method for producing the same are not only used for the purpose of environmental protection at the manufacturing end, but also the sulfonic acid type aqueous polyurethane emulsion of the present invention can be widely used for products such as paints or adhesives.
本發明係關於合成全環保磺酸型水性聚氨酯乳液及其製備方法，本發明之磺酸型水性聚氨酯乳液的優點在於，其可大量減少有機溶劑、羧酸及中和劑之用量，且製備方法簡單並對環境友好；本發明之磺酸型水性聚氨酯乳液另具有良好之穩定性，因此，由其製得之膠膜具有更佳的耐水解性及耐黃變性。 The invention relates to a synthetic environmentally-friendly sulfonic acid type aqueous polyurethane emulsion and a preparation method thereof, and the sulfonic acid type aqueous polyurethane emulsion of the invention has the advantages that the amount of the organic solvent, the carboxylic acid and the neutralizing agent can be greatly reduced, and the preparation method It is simple and environmentally friendly; the sulfonic acid type aqueous polyurethane emulsion of the present invention has good stability, and therefore, the film obtained therefrom has better hydrolysis resistance and yellowing resistance.
為達成上述目的，本發明之磺酸型水性聚氨酯乳液，其包含多異氰酸酯、聚多元醇、磺酸鹽官能聚醚二元醇型親水擴鏈劑及溶劑。 In order to achieve the above object, the sulfonic acid type aqueous polyurethane emulsion of the present invention comprises a polyisocyanate, a polyhydric alcohol, a sulfonate functional polyether glycol type hydrophilic chain extender, and a solvent.
本發明另提供一種磺酸型水性聚氨酯乳液之製備方法，其包括以下步驟：1.混合聚多元醇及磺酸鹽官能聚醚二元醇型親水擴鏈劑；2.加入多異氰酸酯於該混合物中，以製得聚氨酯預聚物；及3.將溶劑加入該聚氨酯預聚物中，乳化該聚氨酯預聚物以製得磺酸型水性聚氨酯乳液。 The invention further provides a preparation method of a sulfonic acid type aqueous polyurethane emulsion, which comprises the following steps: 1. mixing a polyhydric alcohol and a sulfonate functional polyether glycol type hydrophilic chain extender; 2. adding a polyisocyanate to the mixture a polyurethane prepolymer is prepared; and 3. a solvent is added to the polyurethane prepolymer, and the polyurethane prepolymer is emulsified to obtain a sulfonic acid type aqueous polyurethane emulsion.
圖1：本發明非限制性實例1至3所示範之製備磺酸型水性聚氨酯乳液的反應溫度曲線及原料添加流程。 Figure 1 : Reaction temperature profile and feedstock addition procedure for preparing a sulfonic acid type aqueous polyurethane emulsion as exemplified in the non-limiting examples 1 to 3 of the present invention.
本發明之首要目的係為克服現有技術的缺點與不足，而提供一種包含多異氰酸酯、聚多元醇、磺酸鹽官能聚醚二元醇型親水擴鏈劑及溶劑的磺酸型水性聚氨酯乳液。 The primary object of the present invention is to overcome the shortcomings and deficiencies of the prior art and to provide a sulfonic acid type aqueous polyurethane emulsion comprising a polyisocyanate, a polyhydric alcohol, a sulfonate functional polyether glycol type hydrophilic chain extender, and a solvent.
本發明之磺酸型水性聚氨酯乳液中，對於多異氰酸酯並無特別要 求。本發明適用的多異氰酸酯較佳包括二異氰酸酯，其係選自由以下各項所組成之群：甲苯二異氰酸酯(TDI)、1,4-四亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯(HDI)、1,12-十二亞甲基二異氰酸酯、環己烷-1,3-二異氰酸酯、環己烷-1,4-二異氰酸酯、異佛爾酮二異氰酸酯(IPDI)、二苯基甲烷4,4-二異氰酸酯(MDI)、雙環己基甲烷二異氰酸酯(HMDI)、1,6-己二異氰酸酯(HDI)、多亞甲基多苯基異氰酸酯(PAPI)、苯二亞甲基二異氰酸酯(XDI)、萘-1,5-二異氰酸酯(NDI)、甲基環己基二異氰酸酯(HTDI)、四甲基苯二亞甲基二異氰酸酯(TMXDI)、及其混合物。較佳的多異氰酸酯為異佛爾酮二異氰酸酯(IPDI)、甲苯二異氰酸酯(TDI)、1,6-六亞甲基二異氰酸酯(HDI)、雙環己基甲烷二異氰酸酯(HMDI)、二苯基甲烷4,4-二異氰酸酯(MDI)、或甲苯二異氰酸酯(TDI)。 In the sulfonic acid type aqueous polyurethane emulsion of the present invention, there is no particular need for polyisocyanate begging. The polyisocyanate to which the present invention is applicable preferably includes a diisocyanate selected from the group consisting of toluene diisocyanate (TDI), 1,4-tetramethylene diisocyanate, 1,6-hexamethylene group. Diisocyanate (HDI), 1,12-dodecylene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), Diphenylmethane 4,4-diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), polymethylene polyphenyl isocyanate (PAPI), benzodiazepine Diisocyanate (XDI), naphthalene-1,5-diisocyanate (NDI), methylcyclohexyl diisocyanate (HTDI), tetramethylbenzene dimethylene diisocyanate (TMXDI), and mixtures thereof. Preferred polyisocyanates are isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), diphenylmethane. 4,4-diisocyanate (MDI), or toluene diisocyanate (TDI).
根據本發明之一態樣，基於該磺酸型水性聚氨酯乳液之總固含量計，該多異氰酸酯之含量為5至35重量%，如：6重量%、8重量%、10重量%、12重量%、14重量%、16重量%、18重量%、20重量%、22重量%、24重量%、26重量%、28重量%、30重量%、32重量%、或34重量%，較佳為10至30重量%，尤佳為15至25重量%。 According to one aspect of the present invention, the polyisocyanate is contained in an amount of 5 to 35% by weight based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion, such as: 6% by weight, 8% by weight, 10% by weight, and 12% by weight. %, 14% by weight, 16% by weight, 18% by weight, 20% by weight, 22% by weight, 24% by weight, 26% by weight, 28% by weight, 30% by weight, 32% by weight, or 34% by weight, preferably 10 to 30% by weight, particularly preferably 15 to 25% by weight.
本發明之磺酸型水性聚氨酯乳液中，對於聚多元醇並無特別要求。本發明適用的聚多元醇包括選自由以下各項所組成之群之聚多元醇：聚酯多元醇、聚內酯多元醇、聚醚多元醇、聚碳酸酯多元醇、聚硫醚多醇、聚醚和聚酯的混聚物多元醇、及其混合物。該聚多元醇較佳包括聚乙二醇、聚氧化丙烯二醇、聚四氫夫喃醚二醇、聚丁二酸丁二醇酯、聚己二酸己二 醇酯、聚己二酸丁二醇酯、聚己二酸乙二醇丁二醇酯、聚碳酸亞丙酯二元醇、或其混合物，可依不同成品特性做選擇。 In the sulfonic acid type aqueous polyurethane emulsion of the present invention, there is no particular requirement for the polyhydric alcohol. The polyhydric alcohol to which the present invention is applicable includes a polyhydric alcohol selected from the group consisting of polyester polyols, polylactone polyols, polyether polyols, polycarbonate polyols, polythioether polyols, A mixture of polyether and polyester polyols, and mixtures thereof. The polyhydric alcohol preferably comprises polyethylene glycol, polyoxypropylene diol, polytetrahydrofurfuryl ether diol, polybutylene succinate, polyhexamethylene adipate Alcohol esters, polybutylene adipate, polyethylene butylene glycol adipate, poly(propylene carbonate) glycols, or mixtures thereof, may be selected depending on the properties of the finished product.
根據本發明之一態樣，該聚多元醇分子量為600至5,000，如：800、1000、1200、1400、1600、1800、2000、2200、2400、2600、2800、3000、3200、3400、3600、3800、4000、4200、4400、4600、或4800，較佳為1,000至4,000。 According to one aspect of the present invention, the polyhydric alcohol has a molecular weight of 600 to 5,000, such as: 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, 3400, 3600, 3800, 4000, 4200, 4400, 4600, or 4800, preferably 1,000 to 4,000.
根據本發明之一態樣，基於該磺酸型水性聚氨酯乳液之總固含量計，該聚多元醇之含量為45至80重量%，如：46重量%、48重量%、50重量%、52重量%、54重量%、56重量%、58重量%、60重量%、62重量%、64重量%、66重量%、68重量%、70重量%、72重量%、或74重量%，較佳為50至75重量%，尤佳為55至70重量%。 According to an aspect of the present invention, the polyhydric alcohol is contained in an amount of 45 to 80% by weight based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion, such as 46% by weight, 48% by weight, 50% by weight, and 52% by weight. By weight, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, or 74% by weight, preferably It is 50 to 75% by weight, particularly preferably 55 to 70% by weight.
根據本發明之一較佳態樣，該磺酸鹽官能聚醚二元醇型親水擴鏈劑具有如式II所示之雙-1,4-(2-羥基丙氧基)-2-丙氧基丁烷磺酸鹽(Bis-1,4-(2-hydroxypropoxy)-2propoxybutane sulfonate)。 According to a preferred embodiment of the present invention, the sulfonate-functional polyether glycol type hydrophilic chain extender has bis-1,4-(2-hydroxypropoxy)-2-propene as shown in Formula II. Bis-1,4-(2-hydroxypropoxy)-2propoxybutane sulfonate).
根據本發明之一態樣，基於該磺酸型水性聚氨酯乳液之總固含量計，該磺酸鹽官能聚醚二元醇型親水擴鏈劑之含量為1至35重量%，如：2重量%、4重量%、6重量%、8重量%、10重量%、12重量%、14重量%、16重量%、18重量%、20重量%、22重量%、24重量%、26重量%、28重量%、30重量%、32重量%、或34重量%，較佳為5至25重量%，尤佳為10至20重量%。 According to one aspect of the present invention, the sulfonate-functional polyether glycol type hydrophilic chain extender is contained in an amount of from 1 to 35% by weight, such as 2 weight, based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion. %, 4% by weight, 6% by weight, 8% by weight, 10% by weight, 12% by weight, 14% by weight, 16% by weight, 18% by weight, 20% by weight, 22% by weight, 24% by weight, 26% by weight, 28% by weight, 30% by weight, 32% by weight, or 34% by weight, preferably 5 to 25% by weight, particularly preferably 10 to 20% by weight.
上述本發明所定義之該磺酸鹽官能聚醚二元醇型親水擴鏈劑，其有益效果在於：相較於習知之胺基磺酸鹽型親水擴鏈劑，該磺酸鹽官能聚醚二元醇型親水擴鏈劑在反應過程中，其羥基與多異氰酸酯之反應更為溫和，因此不會突然增加所形成之預聚物的黏度，可更容易控制反應進行，且在較佳狀況下毋需要添加大量的丙酮以降低系統黏度。 The sulfonate-functional polyether glycol type hydrophilic chain extender defined by the above-mentioned invention has the beneficial effects that the sulfonate-functional polyether is compared with the conventional amine sulfonate type hydrophilic chain extender. The glycol type hydrophilic chain extender reacts more gently with the polyisocyanate during the reaction, so that the viscosity of the formed prepolymer is not suddenly increased, and the reaction can be controlled more easily, and in a better condition. The squat needs to add a large amount of acetone to reduce the system viscosity.
另一方面，相較於其他磺酸鹽官能聚醚二元醇型親水擴鏈劑，上述定義之該磺酸鹽官能聚醚二元醇型親水擴鏈劑具有更低的分子量，因此少 量添加即可引入磺酸基團，以降低製造成本；此外，在製備磺酸型水性聚氨酯乳液之過程，選用如上文定義之磺酸鹽官能聚醚二元醇型親水擴鏈劑，則可避免使用大量的有機溶劑，且毋需進行額外的中和成鹽步驟，省略複雜的除雜步驟程序，並簡化合成工藝。 On the other hand, the sulfonate-functional polyether diol type hydrophilic chain extender as defined above has a lower molecular weight than other sulfonate-functional polyether diol type hydrophilic chain extenders, and thus has less The addition of the sulfonic acid group can be introduced to reduce the manufacturing cost; in addition, in the process of preparing the sulfonic acid type aqueous polyurethane emulsion, the sulfonate functional polyether glycol type hydrophilic chain extender as defined above can be used. Avoid the use of large amounts of organic solvents, and eliminate the need for additional neutralization steps, omitting complex impurity removal procedures and simplifying the synthesis process.
本發明之磺酸型水性聚氨酯乳液可視需要地額外包括催化劑。適用於本發明之磺酸型水性聚氨酯乳液的催化劑包括選自由以下各項所組成之群之催化劑：叔胺催化劑、有機錫催化劑、非錫類金屬化合物催化劑、及其混合物。較佳包括辛酸亞錫或二月桂酸二丁基錫。 The sulfonic acid type aqueous polyurethane emulsion of the present invention may additionally include a catalyst as needed. The catalyst suitable for the sulfonic acid type aqueous polyurethane emulsion of the present invention comprises a catalyst selected from the group consisting of a tertiary amine catalyst, an organotin catalyst, a non-tin metal compound catalyst, and a mixture thereof. Preferably, stannous octoate or dibutyltin dilaurate is included.
關於本發明之一態樣，基於該磺酸型水性聚氨酯乳液之總固含量計，該催化劑之含量為0至200重量ppm，如：10重量ppm、20重量ppm、30重量ppm、40重量ppm、50重量ppm、60重量ppm、70重量ppm、80重量ppm、90重量ppm、100重量ppm、110重量ppm、120重量ppm、130重量ppm、140重量ppm、150重量ppm、160重量ppm、170重量ppm、180重量ppm、或190重量ppm，較佳為0至150重量ppm，尤佳為0至100重量ppm。 With respect to one aspect of the present invention, the catalyst is contained in an amount of from 0 to 200 ppm by weight based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion, such as 10 ppm by weight, 20 ppm by weight, 30 ppm by weight, and 40 ppm by weight. 50 ppm by weight, 60 ppm by weight, 70 ppm by weight, 80 ppm by weight, 90 ppm by weight, 100 ppm by weight, 110 ppm by weight, 120 ppm by weight, 130 ppm by weight, 140 ppm by weight, 150 ppm by weight, 160 ppm by weight, 170 The weight ppm, 180 ppm by weight, or 190 ppm by weight, preferably 0 to 150 ppm by weight, particularly preferably 0 to 100 ppm by weight.
本發明之磺酸型水性聚氨酯乳液可視需要地額外包括小分子擴鏈劑。根據本發明之一態樣，該小分子擴鏈劑包括選自由以下各項所組成之群之小分子擴鏈劑：乙二胺、己二胺、苯二胺、二乙醇胺、聚氧丙烯三 胺、二乙烯三胺、異佛爾酮二胺、間苯二甲胺、甲基二乙醇胺、及其混合物。 The sulfonic acid type aqueous polyurethane emulsion of the present invention optionally additionally includes a small molecule chain extender. According to an aspect of the present invention, the small molecule chain extender comprises a small molecule chain extender selected from the group consisting of ethylenediamine, hexamethylenediamine, phenylenediamine, diethanolamine, and polyoxypropylene. Amine, diethylenetriamine, isophoronediamine, m-xylylenediamine, methyldiethanolamine, and mixtures thereof.
根據本發明之一態樣，基於該磺酸型水性聚氨酯乳液之總固含量計，該小分子擴鏈劑之含量為0.1至20重量%，如：0.2重量%、0.3重量%、0.4重量%、0.5重量%、0.6重量%、0.7重量%、0.8重量%、0.9重量%、1重量%、2重量%、3重量%、4重量%、5重量%、6重量%、7重量%、8重量%、9重量%、10重量%、11重量%、12重量%、13重量%、14重量%、15重量%、16重量%、17重量%、18重量%、或19重量%，較佳為0.5至15重量%，尤佳為1至10重量%。 According to an aspect of the present invention, the content of the small molecule chain extender is 0.1 to 20% by weight, such as 0.2% by weight, 0.3% by weight, 0.4% by weight, based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion. 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8 % by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, or 19% by weight, preferably It is from 0.5 to 15% by weight, particularly preferably from 1 to 10% by weight.
本發明之磺酸型水性聚氨酯乳液包括非磺酸鹽官能聚醚二元醇型親水擴鏈劑之其他親水性擴鏈劑。根據本發明之一態樣，該其他親水性擴鏈劑包括選自由以下各項所組成之群的親水性擴鏈劑：二羥甲基丙酸、二羥甲基丁酸、二羥基半酯、乙二氨基乙磺酸鈉、二氨基苯磺酸鈉、二氨基丙酸、二氨基丁酸、及其混合物。 The sulfonic acid type aqueous polyurethane emulsion of the present invention comprises other hydrophilic chain extenders of a non-sulfonate functional polyether glycol type hydrophilic chain extender. According to one aspect of the invention, the other hydrophilic chain extender comprises a hydrophilic chain extender selected from the group consisting of: dimethylolpropionic acid, dimethylolbutanoic acid, dihydroxy half ester Sodium ethylenediaminoethanesulfonate, sodium diaminobenzenesulfonate, diaminopropionic acid, diaminobutyric acid, and mixtures thereof.
關於本發明之一態樣，基於該磺酸型水性聚氨酯乳液之總固含量計，該其他親水性擴鏈劑之含量為0.1至20重量%，如：0.2重量%、0.3重量%、0.4重量%、0.5重量%、0.6重量%、0.7重量%、0.8重量%、0.9重量%、1重量%、2重量%、3重量%、4重量%、5重量%、6重量%、7重量%、8重量%、9重量%、10重量%、11重量%、12重量%、13重量%、14重量%、15重量%、16重量%、17重量%、18重量%、或19重量%，較佳為0.5至15重量%，尤佳為1至10重量%。 With respect to one aspect of the present invention, the content of the other hydrophilic chain extender is 0.1 to 20% by weight, such as 0.2% by weight, 0.3% by weight, 0.4% by weight based on the total solid content of the sulfonic acid type aqueous polyurethane emulsion. %, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, or 19 wt%, It is preferably from 0.5 to 15% by weight, particularly preferably from 1 to 10% by weight.
本發明之磺酸型水性聚氨酯乳液可視需要地額外包括交聯劑，以提升交聯密度，增加水性聚氨酯乳液的耐水解性。根據本發明之一態樣，該交聯劑包括選自由以下各項所組成之群的交聯劑：脂肪族異氰酸鹽、聚氮丙啶、水性環氧基交聯劑、碳亞醯胺交聯劑、三聚氰胺-甲醛樹脂(美耐皿)、及其混合物。該碳亞醯胺交聯劑較佳為GSI型碳亞醯胺。 The sulfonic acid type aqueous polyurethane emulsion of the present invention may additionally include a crosslinking agent as needed to increase the crosslinking density and increase the hydrolysis resistance of the aqueous polyurethane emulsion. According to one aspect of the invention, the crosslinking agent comprises a crosslinking agent selected from the group consisting of aliphatic isocyanates, polyaziridines, aqueous epoxy crosslinking agents, carbon arylene. Amine crosslinker, melamine-formaldehyde resin (melamine), and mixtures thereof. The carbon sulfide crosslinking agent is preferably a GSI type carbon amide.
關於本發明之一態樣，基於該磺酸型水性聚氨酯乳液之總重量計，該交聯劑含量為0至20重量%，如：1重量%、2重量%、3重量%、4重量%、5重量%、6重量%、7重量%、8重量%、9重量%、10重量%、11重量%、12重量%、13重量%、14重量%、15重量%、16重量%、17重量%、18重量%、或19重量%，較佳為2至15重量%，尤佳為5至10重量%。 With respect to one aspect of the present invention, the crosslinking agent is present in an amount of from 0 to 20% by weight based on the total weight of the sulfonic acid type aqueous polyurethane emulsion, such as: 1% by weight, 2% by weight, 3% by weight, and 4% by weight. 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 The weight%, 18% by weight, or 19% by weight, preferably 2 to 15% by weight, particularly preferably 5 to 10% by weight.
適用於本發明之磺酸型水性聚氨酯乳液的溶劑包括水，較佳該溶劑實質上係由水所組成。 The solvent suitable for the sulfonic acid type aqueous polyurethane emulsion of the present invention includes water, and preferably the solvent is substantially composed of water.
關於本發明之一態樣，基於該磺酸型水性聚氨酯乳液之總重量計，該溶劑含量為55至80重量%，如：56重量%、58重量%、60重量%、62重量%、64重量%、66重量%、68重量%、70重量%、72重量%、74重量%、76重量%、或78重量%，較佳為60至75重量%，尤佳為65至70重量%。 With respect to one aspect of the present invention, the solvent content is 55 to 80% by weight, such as 56% by weight, 58% by weight, 60% by weight, 62% by weight, based on the total weight of the sulfonic acid type aqueous polyurethane emulsion. % by weight, 66% by weight, 68% by weight, 70% by weight, 72% by weight, 74% by weight, 76% by weight, or 78% by weight, preferably 60 to 75% by weight, particularly preferably 65 to 70% by weight.
根據本發明之一較佳態樣，基於該磺酸型水性聚氨酯乳液之總重量計，該溶劑中所含之有機溶劑的含量為5.0重量%或更少，如：4.5重量%或更少、4.0重量%或更少、3.5重量%或更少、3.0重量%或更少、2.5重量%或更少、2.0重量%或更少、1.5重量%或更少、1.0重量%或更少、 0.9重量%或更少、0.8重量%或更少、0.7重量%或更少、0.6重量%或更少、0.5重量%或更少、0.4重量%或更少、0.3重量%或更少、0.2重量%或更少、或0.1重量%或更少，較佳為1.0重量%或更少，尤佳完全不含任何有機溶劑。 According to a preferred embodiment of the present invention, the content of the organic solvent contained in the solvent is 5.0% by weight or less, such as 4.5% by weight or less, based on the total weight of the sulfonic acid type aqueous polyurethane emulsion. 4.0% by weight or less, 3.5% by weight or less, 3.0% by weight or less, 2.5% by weight or less, 2.0% by weight or less, 1.5% by weight or less, 1.0% by weight or less, 0.9% by weight or less, 0.8% by weight or less, 0.7% by weight or less, 0.6% by weight or less, 0.5% by weight or less, 0.4% by weight or less, 0.3% by weight or less, 0.2 It is preferably % or less, or 0.1% by weight or less, preferably 1.0% by weight or less, and particularly preferably completely free of any organic solvent.
根據本發明之一較佳態樣，基於該磺酸型水性聚氨酯乳液之總重量計，該溶劑中所含之丙酮、N,N-二甲基甲醯胺及/或N-甲基吡咯烷酮的含量為5.0重量%或更少，如：4.5重量%或更少、4.0重量%或更少、3.5重量%或更少、3.0重量%或更少、2.5重量%或更少、2.0重量%或更少、1.5重量%或更少、1.0重量%或更少、0.9重量%或更少、0.8重量%或更少、0.7重量%或更少、0.6重量%或更少、0.5重量%或更少、0.4重量%或更少、0.3重量%或更少、0.2重量%或更少、或0.1重量%或更少，較佳為1.0重量%或更少，尤佳完全不含任何丙酮、N,N-二甲基甲醯胺及/或N-甲基吡咯烷酮。 According to a preferred embodiment of the present invention, based on the total weight of the sulfonic acid type aqueous polyurethane emulsion, acetone, N,N-dimethylformamide and/or N-methylpyrrolidone contained in the solvent The content is 5.0% by weight or less, such as: 4.5% by weight or less, 4.0% by weight or less, 3.5% by weight or less, 3.0% by weight or less, 2.5% by weight or less, 2.0% by weight or Less, 1.5% by weight or less, 1.0% by weight or less, 0.9% by weight or less, 0.8% by weight or less, 0.7% by weight or less, 0.6% by weight or less, 0.5% by weight or more Less, 0.4% by weight or less, 0.3% by weight or less, 0.2% by weight or less, or 0.1% by weight or less, preferably 1.0% by weight or less, and particularly preferably completely free of any acetone, N , N-dimethylformamide and / or N-methylpyrrolidone.
因此，本發明之磺酸型水性聚氨酯乳液可展現以下有益效果： Therefore, the sulfonic acid type aqueous polyurethane emulsion of the present invention can exhibit the following beneficial effects:
A.本發明水性聚氨酯乳液採用磺酸鹽做為親水基團，可省略習知之羧酸鹽成分所額外涉及之中和反應，且由於乳液中所形成之聚氨酯預聚物包括磺酸鹽親水基團，該聚氨酯預聚物具有親水性，故可以直接溶於水，毋需額外添加丙酮降黏，因此本發明之磺酸型水性聚氨酯乳液更符合環保訴求。另外，由於本發明水性聚氨酯乳液所形成之聚氨酯預聚物可溶於水，因此當僅使用水作為溶劑時，可利用現有攪拌機提高攪拌速率，毋須另使用均質機，即可成功製得磺酸型水性聚氨酯乳液。 A. The aqueous polyurethane emulsion of the present invention uses a sulfonate as a hydrophilic group, and the conventional carboxylate component may be omitted to additionally involve a neutralization reaction, and the polyurethane prepolymer formed in the emulsion includes a sulfonate hydrophilic group. The polyurethane prepolymer has hydrophilicity, so it can be directly dissolved in water, and no additional acetone is added to reduce viscosity. Therefore, the sulfonic acid type aqueous polyurethane emulsion of the present invention is more in line with environmental protection demands. In addition, since the polyurethane prepolymer formed by the aqueous polyurethane emulsion of the present invention is soluble in water, when only water is used as the solvent, the stirring rate can be increased by using an existing mixer, and the sulfonic acid can be successfully produced without using a homogenizer. Type waterborne polyurethane emulsion.
B.本發明水性聚氨酯乳液較佳使用直鏈型磺酸鹽官能聚醚二元醇 型親水擴鏈劑，可增加所形成之膠膜的柔軟性。 B. The aqueous polyurethane emulsion of the present invention preferably uses a linear sulfonate functional polyether diol A hydrophilic chain extender that increases the softness of the formed film.
C.本發明水性聚氨酯乳液可視需要地包含交聯劑，以提昇原本偏向水溶性之聚氨酯的交聯密度，增加耐水解性。 C. The aqueous polyurethane emulsion of the present invention may optionally contain a crosslinking agent to increase the crosslinking density of the originally water-soluble polyurethane and increase the hydrolysis resistance.
D.本發明磺酸型水性聚氨酯乳液尤其適用於塗料及接著劑等產品，其功能性強且具有廣泛的應用前景。 D. The sulfonic acid type aqueous polyurethane emulsion of the invention is especially suitable for products such as coatings and adhesives, and has strong functions and wide application prospects.
因此，本發明之另一目的係欲提供一種用於軟質材料之印墨樹脂、塗層、底料、熱熔膠、接著用樹脂之膠膜，該膠膜其係由如上文定義之磺酸型水性聚氨酯乳液所製得。 Therefore, another object of the present invention is to provide a film for an ink resin, a coating, a primer, a hot melt adhesive, and a resin for a soft material, which is a sulfonic acid as defined above. A waterborne polyurethane emulsion is prepared.
本發明之又一目的係欲提供一種製備磺酸型水性聚氨酯乳液的方法，其包括以下步驟：1.混合聚多元醇及磺酸鹽官能聚醚二元醇型親水擴鏈劑；2.加入多異氰酸酯於該混合物中，以製得聚氨酯預聚物；及3.將溶劑加入該聚氨酯預聚物中，乳化該聚氨酯預聚物以製得磺酸型水性聚氨酯乳液。 Another object of the present invention is to provide a method for preparing a sulfonic acid type aqueous polyurethane emulsion, which comprises the steps of: 1. mixing a polyhydric alcohol and a sulfonate functional polyether glycol type hydrophilic chain extender; Polyisocyanate is added to the mixture to prepare a polyurethane prepolymer; and 3. A solvent is added to the polyurethane prepolymer to emulsify the polyurethane prepolymer to prepare a sulfonic acid type aqueous polyurethane emulsion.
根據本發明之一態樣，上述步驟1之混合步驟較佳於50℃或更高，尤佳於60℃或更高之溫度下進行。 According to an aspect of the present invention, the mixing step of the above step 1 is preferably carried out at a temperature of 50 ° C or higher, particularly preferably 60 ° C or higher.
根據本發明之一態樣，上述步驟2較佳於50℃或更高，尤佳於65至95℃之溫度下進行，且在反應時間為1至7小時內，尤佳為2至5小時內，即可獲致聚氨酯預聚物產物。 According to an aspect of the present invention, the above step 2 is preferably carried out at a temperature of 50 ° C or higher, particularly preferably at a temperature of 65 to 95 ° C, and preferably within a period of from 1 to 7 hours, particularly preferably from 2 to 5 hours. Within, a polyurethane prepolymer product is obtained.
根據本發明之一態樣，如上文定義之催化劑可於步驟2中加入。 According to one aspect of the invention, a catalyst as defined above can be added in step 2.
根據本發明之一態樣，上述步驟3之乳化步驟中，所選用之溶劑包括水，較佳該溶劑實質上係由水所組成。 According to an aspect of the present invention, in the emulsification step of the above step 3, the solvent selected includes water, and preferably the solvent is substantially composed of water.
根據本發明之一態樣，如上文定義之小分子擴鏈劑，例如乙二胺， 可於步驟3之乳化步驟後加入。 According to one aspect of the invention, a small molecule chain extender as defined above, such as ethylenediamine, It can be added after the emulsification step of step 3.
根據本發明之一較佳態樣，本發明磺酸型水性聚氨酯乳液之製備方法所涉之其中該聚多元醇、磺酸鹽官能聚醚二元醇型親水擴鏈劑、多異氰酸酯及/或溶劑係如上文所定義。 According to a preferred embodiment of the present invention, the method for preparing a sulfonic acid type aqueous polyurethane emulsion of the present invention is characterized in that the polyhydric alcohol, a sulfonate functional polyether glycol type hydrophilic chain extender, a polyisocyanate and/or The solvent is as defined above.
根據本發明之一較佳態樣，本發明之製備磺酸型水性聚氨酯乳液的方法不包括加入有機溶劑，例如丙酮、N,N-二甲基甲醯胺及/或N-甲基吡咯烷酮，之步驟。 According to a preferred embodiment of the present invention, the method for preparing a sulfonic acid type aqueous polyurethane emulsion of the present invention does not include adding an organic solvent such as acetone, N,N-dimethylformamide and/or N-methylpyrrolidone. The steps.
根據本發明之一較佳態樣，本發明之製備磺酸型水性聚氨酯乳液的方法不包括移除有機溶劑，例如減壓蒸餾，之步驟。 According to a preferred embodiment of the present invention, the method for producing a sulfonic acid type aqueous polyurethane emulsion of the present invention does not include a step of removing an organic solvent such as distillation under reduced pressure.
以下透過實施例對本發明進行進一步的具體描述。有必要在此指出的是以下實施例只用於對本發明做進一步的說明，不能理解為對本發明保護範圍的限制，該領域技術熟練人員根據上述本發明內容對本發明做出一些非本質的改進和調整，仍屬於本發明的保護範圍。在討論本發明之若干非限制性實施例之前，應理解，本發明在其申請上不限於本文中所示及所論述之特定非限制性實施例的細節，因為本發明可具有其他實施例。此外，在本文中用於論述本發明之術語係出於描述而非限制之目的。再此外，除非另外指明，否則以下類似數字之論述係指類似要素。 The invention is further described in detail below by way of examples. It is to be noted that the following examples are merely illustrative of the present invention and are not to be construed as limiting the scope of the invention. Adjustments still fall within the scope of protection of the present invention. Before discussing several non-limiting embodiments of the present invention, it is to be understood that the invention is not limited to the details of the specific non-limiting embodiments shown and described herein, as the invention may have other embodiments. In addition, the terminology used herein to describe the invention is for the purpose of description and not limitation. Further, unless otherwise indicated, the following discussion of similar numbers refers to similar elements.
在本說明書及申請專利範圍中所使用的表達含量、比例、物理特徵等之所有數字應理解為在所有情況下經術語「約」修飾。因此，除非有相反指示，否則在以下說明書及申請專利範圍中所闡述之數值可視本發明設法獲得之及/或所需特性而變化。至少，且不試圖將等效原則之應用限制於申請專利範圍之範圍，各數值參數至少應根據所揭露之有效數位的數目 且藉由應用一般捨入技術來解釋。 All numbers expressing levels, ratios, physical characteristics, and the like, used in the specification and claims are to be understood as being modified by the term "about" in all instances. Accordingly, the numerical values set forth in the following description and claims are to be construed as a At the very least, and without attempting to limit the application of the equivalent principles to the scope of the claims, the And explained by applying general rounding techniques.
本文中所揭示之所有範圍均應理解為涵蓋其中所包含之任何及所有次範圍。舉例而言，「1至10」之所述範圍應視為包含最小值1與最大值10之間的任何及所有次範圍且包含最大值1及最大值10；亦即，以1或大於1之最小值開始且以10或小於10之最大值結束的所有次範圍，例如：1至6.7、3.2至8.1或5.5至10，以及該範圍內之任何數字，例如：2.6、4.7或7.3。 All ranges disclosed herein are to be understood as encompassing any and all sub-ranges For example, the range of "1 to 10" shall be taken to include any and all sub-ranges between the minimum value 1 and the maximum value 10 and include a maximum value of 1 and a maximum value of 10; that is, 1 or greater than 1 All sub-ranges starting at the minimum and ending with a maximum of 10 or less, for example: 1 to 6.7, 3.2 to 8.1 or 5.5 to 10, and any number within the range, for example: 2.6, 4.7 or 7.3.
秤取300g經真空乾燥脫水處理之聚己二酸乙二醇丁二醇酯(分子量：2,000)及28g雙-1,4-(2-羥基丙氧基)-2-丙氧基丁烷磺酸鈉攪拌均勻並加熱至60℃，秤取61.71g異佛爾酮二異氰酸酯(IPDI)，保持溫度95℃進行聚合反應，反應時間為4小時，反應至NCO含量達到理論值，製得聚氨酯預聚物；提高攪拌速率，將470g水直接滴加入該聚氨酯預聚物，乳化10分鐘轉水相後，加入1.6g乙二胺，製得磺酸型水性聚氨酯乳液，塗膜前添加5重量%(基於該乳液之總固含量計)之脂肪族異氰酸鹽交聯劑以提升乾膜之耐水解性，上述反應之溫度曲線及流程係如圖1所示。 300 g of poly(ethylene glycol adipate) dehydrated by vacuum drying (molecular weight: 2,000) and 28 g of bis-1,4-(2-hydroxypropoxy)-2-propoxybutane sulfonate Sodium salt was stirred uniformly and heated to 60 ° C. 61.71 g of isophorone diisocyanate (IPDI) was weighed and the temperature was maintained at 95 ° C for 4 hours. The reaction was carried out until the NCO content reached the theoretical value. Polymer; increasing the stirring rate, adding 470g of water directly to the polyurethane prepolymer, emulsification for 10 minutes to the aqueous phase, adding 1.6g of ethylenediamine to obtain a sulfonic acid type aqueous polyurethane emulsion, adding 5% by weight before coating The aliphatic isocyanate crosslinking agent (based on the total solid content of the emulsion) is used to improve the hydrolysis resistance of the dry film, and the temperature profile and flow of the above reaction are shown in FIG.
秤取經真空乾燥脫水處理之聚己二酸丁二醇酯(分子量：2,000)和聚己二酸乙二醇丁二醇酯(分子量：2,000)共300g及61.09g雙-1,4-(2-羥基丙氧基)-2-丙氧基丁烷磺酸鈉攪拌均勻並加熱至60℃，秤取97.97g異佛爾酮二異氰酸酯(IPDI)，加入0.04g二月桂酸二丁基錫催化劑，保持溫度95℃進行聚合反應，反應時間為2小時，反應至NCO含量達到理論值，製得聚氨酯預聚物；提高攪拌速率，將1100g水直接滴加入該聚氨酯 預聚物，乳化10分鐘轉水相後，加入2.05g二乙烯三胺及7.06g乙二胺，製得磺酸型水性聚氨酯乳液，塗膜前添加5重量%(基於該乳液之總固含量計)之脂肪族異氰酸鹽交聯劑以提升乾膜之耐水解性，上述反應之溫度曲線及流程係如圖1所示。 The mixture was subjected to vacuum drying and dehydration treatment of polybutylene adipate (molecular weight: 2,000) and polybutylene adipate (molecular weight: 2,000), 300 g and 61.09 g of bis-1,4-(2). Sodium hydroxypropoxy)-2-propoxybutane sulfonate was stirred uniformly and heated to 60 ° C. 97.97 g of isophorone diisocyanate (IPDI) was weighed and 0.04 g of dibutyltin dilaurate catalyst was added to maintain The polymerization was carried out at a temperature of 95 ° C for 2 hours, and the reaction was carried out until the NCO content reached a theoretical value to obtain a polyurethane prepolymer; the stirring rate was increased, and 1100 g of water was directly added dropwise to the polyurethane. Prepolymer, after emulsification for 10 minutes, the aqueous phase was added, 2.05 g of diethylenetriamine and 7.06 g of ethylenediamine were added to prepare a sulfonic acid type aqueous polyurethane emulsion, and 5% by weight was added before coating (based on the total solid content of the emulsion) The aliphatic isocyanate cross-linking agent is used to improve the hydrolysis resistance of the dry film. The temperature profile and the flow of the above reaction are shown in FIG.
秤取200g經真空乾燥脫水處理之聚四甲基醚二醇(分子量：2,000)及41.43g雙-1,4-(2-羥基丙氧基)-2-丙氧基丁烷磺酸鈉攪拌均勻並加熱至60℃，秤取74.22g 1,6-六亞甲基二異氰酸酯(HDI)，加入0.02g二月桂酸二丁基錫催化劑，保持溫度95℃進行聚合反應，反應時間為1.5小時，反應至NCO含量達到理論值，製得聚氨酯預聚物；提高攪拌速率，將282g水直接滴加入該聚氨酯預聚物，乳化10分鐘轉水相後加入2g聚氧丙烯三胺及21g異佛爾酮二胺，製得磺酸型水性聚氨酯乳液，塗膜前添加5重量%(基於該乳液之總固含量計)之碳亞醯胺交聯劑以提升乾膜耐水解性，上述反應之溫度曲線及流程係如圖1所示。 200 g of polytetramethyl ether glycol (molecular weight: 2,000) and 41.43 g of sodium bis-1,4-(2-hydroxypropoxy)-2-propoxybutanesulfonate were stirred and dried under vacuum drying. Uniformly and heated to 60 ° C, weighing 74.22g 1,6-hexamethylene diisocyanate (HDI), adding 0.02g of dibutyltin dilaurate catalyst, maintaining the temperature at 95 ° C for polymerization, the reaction time is 1.5 hours, the reaction To the theoretical value of NCO, the polyurethane prepolymer was prepared; the stirring rate was increased, 282 g of water was directly added dropwise to the polyurethane prepolymer, and the aqueous phase was emulsified for 10 minutes, and then 2 g of polyoxypropylene triamine and 21 g of isophorone were added. Diamine, prepared sulfonic acid type waterborne polyurethane emulsion, adding 5% by weight (based on the total solid content of the emulsion) of a carbamate crosslinker before coating to improve the hydrolysis resistance of the dry film, the temperature curve of the above reaction And the process is shown in Figure 1.
秤取300g經真空乾燥脫水處理之聚內酯多元醇(分子量：2,000)及73g雙-1,4-(2-羥基乙氧基)-2-乙氧基丁烷磺酸鉀攪拌均勻並加熱至60℃，秤取83.6g二苯基甲烷4,4-二異氰酸酯(MDI)，保持溫度95℃進行聚合反應，反應時間為2小時，反應至NCO含量達到理論值，製得聚氨酯預聚物；提高攪拌速率，將1570g水直接滴加入該聚氨酯預聚物，乳化10分鐘轉水相後，加入13.2g乙二胺及9.8g間苯二甲胺，製得磺酸型水性聚氨酯乳液，塗膜前添加重量5%(基於該乳液之總固含量計)之美耐皿交聯劑以提升乾膜之耐水解性，上述反應之溫度曲線及流程係如圖1所示。 Weigh 300g of polylactone polyol (molecular weight: 2,000) which has been vacuum dried and dehydrated, and 73g of potassium bis-1,4-(2-hydroxyethoxy)-2-ethoxybutanesulfonate. Stir and heat. At 60 ° C, 83.6 g of diphenylmethane 4,4-diisocyanate (MDI) was weighed and the polymerization was carried out at a temperature of 95 ° C for 2 hours. The reaction was carried out until the NCO content reached a theoretical value to obtain a polyurethane prepolymer. The stirring rate was increased, 1570 g of water was directly added dropwise to the polyurethane prepolymer, and after emulsification for 10 minutes, the aqueous phase was added, and 13.2 g of ethylenediamine and 9.8 g of m-xylylenediamine were added to prepare a sulfonic acid type aqueous polyurethane emulsion. A 5% by weight (based on the total solid content of the emulsion) of the melamine cross-linking agent was added to enhance the hydrolysis resistance of the dry film. The temperature profile and the flow of the above reaction are shown in FIG.
秤取300g經真空乾燥脫水處理之聚醚多元醇(分子量：2,000)及52g雙-1,4-(2-羥基乙氧基)-2-乙氧基丁烷磺酸鈉攪拌均勻並加熱至60℃，秤取71.1g甲苯二異氰酸酯(TDI)，保持溫度95℃進行聚合反應，反應時間為2.5小時，反應至NCO含量達到理論值，製得聚氨酯預聚物；提高攪拌速率，將1320g水直接滴加入該聚氨酯預聚物，乳化10分鐘轉水相後，加入12.6g己二胺及8.8g苯二胺，製得磺酸型水性聚氨酯乳液，塗膜前添加5重量%(基於該乳液之總固含量計)之碳亞醯胺交聯劑可提升乾膜耐水解性，上述反應之溫度曲線及流程係如圖1所示。 300 g of polyether polyol (molecular weight: 2,000) subjected to vacuum drying and dehydration treatment and 52 g of sodium bis-1,4-(2-hydroxyethoxy)-2-ethoxybutanesulfonate were uniformly stirred and heated to At 60 ° C, 71.1 g of toluene diisocyanate (TDI) was weighed and maintained at a temperature of 95 ° C for a reaction time of 2.5 hours. The reaction was carried out until the NCO content reached a theoretical value to obtain a polyurethane prepolymer; the stirring rate was increased, and 1320 g of water was obtained. The polyurethane prepolymer was directly added dropwise, and after emulsification for 10 minutes, the aqueous phase was added, 12.6 g of hexamethylenediamine and 8.8 g of phenylenediamine were added to prepare a sulfonic acid type aqueous polyurethane emulsion, and 5 wt% was added before the film coating (based on the emulsion). The total solid content of the carbon amide amine crosslinking agent can improve the hydrolysis resistance of the dry film, and the temperature profile and the flow of the above reaction are shown in FIG. 1 .
取乾燥的表面皿，稱其重量記為m，然後稱取1.5~2.0g水性聚氨酯乳液平鋪於表面皿中稱重量為m0，放入烘箱中120℃乾燥2小時，取出稱重量記為m1，固含量係按以下方式計算：固含量(%)=[(m 1 -m)/m 0 ]x 100%。 Take a dry watch glass, weigh it as m, then weigh 1.5~2.0g of water-based polyurethane emulsion and spread it in a watch glass. Weigh it at m 0 and put it in an oven at 120 °C for 2 hours. m 1 , the solid content is calculated as follows: solid content (%) = [(m 1 -m) / m 0 ] x 100% .
將乾膜進行ISO 1419：1995耐水解性測試(Jungle test)，溼度95%，溫度70℃，放置一週檢測物性保持率。 The dry film was subjected to ISO 1419:1995 Jungle test, humidity 95%, temperature 70 ° C, and the physical property retention rate was measured for one week.
將100g乳液在室溫(25℃)下存放，每隔一週觀察是否有沉澱析出，析出沉澱所用時間越長，穩定性越好。 100 g of the emulsion was stored at room temperature (25 ° C), and it was observed every other week whether or not precipitation occurred, and the longer the time for precipitation, the better the stability.
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