CN114437307B - Aqueous polyurethane dispersion, coating composition and application thereof - Google Patents
Aqueous polyurethane dispersion, coating composition and application thereof Download PDFInfo
- Publication number
- CN114437307B CN114437307B CN202011188098.XA CN202011188098A CN114437307B CN 114437307 B CN114437307 B CN 114437307B CN 202011188098 A CN202011188098 A CN 202011188098A CN 114437307 B CN114437307 B CN 114437307B
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- iii
- aqueous polyurethane
- polyurethane dispersion
- moisture
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- 229920003009 polyurethane dispersion Polymers 0.000 title claims abstract description 68
- 239000008199 coating composition Substances 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 70
- 239000011248 coating agent Substances 0.000 claims abstract description 67
- -1 diol compound Chemical class 0.000 claims abstract description 57
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 37
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 26
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- 229920000728 polyester Polymers 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 26
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 229920000768 polyamine Polymers 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- MNLAVFKVRUQAKW-UHFFFAOYSA-N VR nerve agent Chemical compound CCN(CC)CCSP(C)(=O)OCC(C)C MNLAVFKVRUQAKW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 229910052710 silicon Chemical group 0.000 claims description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 54
- 230000035699 permeability Effects 0.000 abstract description 29
- 238000005406 washing Methods 0.000 abstract description 26
- 150000002009 diols Chemical class 0.000 abstract description 24
- 230000000052 comparative effect Effects 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000010985 leather Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 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 description 6
- 239000002904 solvent Substances 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920005749 polyurethane resin Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002318 adhesion promoter Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 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 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 239000002987 primer (paints) Substances 0.000 description 3
- 238000007655 standard test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 2
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 1
- AFGNPFWWBHDPEN-UHFFFAOYSA-N 1,6-dioxacyclododecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCCCO1 AFGNPFWWBHDPEN-UHFFFAOYSA-N 0.000 description 1
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- IVGRSQBDVIJNDA-UHFFFAOYSA-N 2-(2-aminoethylamino)ethanesulfonic acid Chemical compound NCCNCCS(O)(=O)=O IVGRSQBDVIJNDA-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- GZDFHIJNHHMENY-UHFFFAOYSA-N Dimethyl dicarbonate Chemical compound COC(=O)OC(=O)OC GZDFHIJNHHMENY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241001081179 Litsea Species 0.000 description 1
- 235000012854 Litsea cubeba Nutrition 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- DTGZJGZYPXAZTG-UHFFFAOYSA-N bicyclo[2.2.1]heptane;1,2-diisocyanatoethane Chemical compound C1CC2CCC1C2.O=C=NCCN=C=O DTGZJGZYPXAZTG-UHFFFAOYSA-N 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- MNMKEULGSNUTIA-UHFFFAOYSA-K bismuth;methanesulfonate Chemical compound [Bi+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O MNMKEULGSNUTIA-UHFFFAOYSA-K 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 235000010300 dimethyl dicarbonate Nutrition 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- ISRXMEYARGEVIU-UHFFFAOYSA-N n-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C)C(C)C ISRXMEYARGEVIU-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000004826 seaming Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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Abstract
The invention relates to an aqueous polyurethane dispersion, a coating composition, a waterproof moisture-permeable coating and application thereof. The aqueous polyurethane dispersion comprises structural units derived from: a polyisocyanate (A), a diol compound (B), a polyfunctional polyester polyol (C) and a sulfonate diol (D). The diol compound (B) contains a polyester diol (B1) and/or a polyether diol (B2). The invention also relates to a waterproof moisture-permeable coating containing the aqueous polyurethane dispersion, and the waterproof moisture-permeable coating has good moisture permeability, waterproof property and water washing resistance.
Description
Technical Field
The invention relates to an aqueous polyurethane dispersion, a coating composition containing the aqueous polyurethane dispersion and application thereof, in particular to an aqueous polyurethane dispersion suitable for waterproof moisture-permeable coating.
Background
In the current waterproof products, the waterproof effect is generally achieved by attaching or coating a waterproof film to a substrate. However, to further enhance the user's evaluation, the waterproof product is given a moisture permeable function to allow the accumulated moisture to be discharged.
The waterproof moisture-permeable principle comprises a micro-porous mechanism and a hydrophilic mechanism. In the micro-porous mechanism, moisture (the size of gaseous water molecules is about 0.0004 microns) is discharged through the out-diffusion of a plurality of micropores with diameters smaller than 2 microns on the coating, and thereby liquid water molecules (the size is about more than 100 microns) are blocked, so that the function of moisture permeability is achieved. However, these micropores are easily clogged with dirt, and the moisture permeability is reduced.
The hydrophilic mechanism is to apply a waterproof moisture-permeable coating on one side of a substrate (such as but not limited to a fabric, etc.) to form a dense coating to achieve the waterproof effect. Secondly, the paint itself has hydrophilic groups (such as carboxylic acid groups, ester groups or hydroxyl groups, etc.), so that the paint can absorb moisture and sweat discharged by skin, and then diffuse the moisture and sweat to the other side of the substrate by diffusion so as to release the moisture into the external environment, thereby achieving the effect of moisture permeability. Therefore, the hydrophilic mechanism does not have a problem of reduced moisture permeability due to clogging of micropores by dirt, compared to the microporous mechanism.
The waterproof moisture-permeable coating can be prepared from polyurethane resin, polyvinyl chloride resin and acrylic resin, and the polyurethane resin is preferable based on the feeling of skin contact. Therefore, the waterproof film of the general waterproof product is made of polyurethane resin.
In recent years, due to the rising environmental awareness, aqueous polyurethane dispersions using water as a main solvent are developed to replace oily polyurethane using a large amount of solvent, so as to avoid the energy consumption caused by recycling the organic solvent, the environmental protection problem of discarding the organic solvent and the health concern caused by residual organic solvent. Although the aqueous polyurethane dispersion has the advantage of the aforementioned solvent reduction, in the hydrophilic mechanism, since the hydrophilic functional group easily hydrolyzes the aqueous polyurethane coating, the water resistance, moisture permeability and water resistance of the aqueous polyurethane resin are slightly insufficient as compared with the oily polyurethane resin, and the moisture permeability and water resistance often cannot be combined.
Thus, there is a need for new aqueous polyurethane dispersions, coating compositions, coatings and products that ameliorate the aforementioned disadvantages.
Disclosure of Invention
In view of the above, it is an aspect of the present invention to provide an aqueous polyurethane dispersion. The waterproof moisture-permeable coating and the waterproof moisture-permeable product prepared by the waterproof moisture-permeable coating can provide good moisture permeability, waterproof property and water washing resistance.
According to another aspect of the present invention, a coating composition is presented. The coating composition comprises the aforementioned aqueous polyurethane dispersion.
According to yet another aspect of the present invention, a waterproof moisture-permeable coating is presented. The waterproof moisture-permeable coating is prepared by using the coating composition.
According to yet another aspect of the present invention, a waterproof moisture permeable product is provided. The waterproof moisture-permeable product comprises the waterproof moisture-permeable coating. The waterproof and moisture-permeable product comprises a substrate and the waterproof and moisture-permeable coating. The waterproof moisture-permeable coating is arranged on the base material.
According to one aspect of the present invention, an aqueous polyurethane dispersion is provided. The aqueous polyurethane dispersion comprises structural units derived from: a polyisocyanate (A), a diol compound (B), a polyfunctional polyester polyol (C) and a sulfonate diol (D). The diol compound (B) contains a polyester diol (B1) and/or a polyether diol (B2). The polyfunctional polyester polyol (C) is used in an amount of 3 to 10 weight percent based on 100 weight percent of the solid component of the aqueous polyurethane dispersion.
Further, the polyisocyanate (a) is used in an amount of 10 to 70% by weight, the diol compound (B) is used in an amount of 10 to 70% by weight, and the sulfonate diol (D) is used in an amount of 3 to 15% by weight, based on 100% by weight of the solid content of the aqueous polyurethane dispersion.
According to an embodiment of the present invention, the multifunctional polyester polyol (C) has a structure represented by the following formula (I) or formula (II):
(R 1 ) m -X-(R 2 ) n (I)
in formula (I), X represents a tetravalent organic group, and X is a carbon atom or a silicon atom; r is R 1 Is methyl or ethyl, and the carbon atom of the methyl is bonded with X; r is R 2 Represents a structure represented by the following formula (III); m represents 0 or 1, n generationTable 3 or 4, and the sum of m and n is 4.
In the formula (II), with R 1 R is R 2 The two carbon atoms bound are quaternary carbon atoms, R 1 R is R 2 Is as defined above; p1 represents an integer of 0 to 2, p2 represents an integer of 1 to 3, and the sum of p1 and p2 is 3; q1 represents an integer of 0 to 2, q2 represents an integer of 1 to 3, the sum of q1 and q2 is 3, and the sum of p2 and q2 is an integer of 3 to 6.
The structure of formula (III) above is as follows:
*-R 21 -R 22 (III)
in formula (III), R represents 21 The position bonded to X or a quaternary carbon atom of formula (II), R 21 Represents a structure represented by the following formula (III-1), formula (III-2) or formula (III-3), and R 22 Represents a structure represented by the following formula (III-3-1) or formula (III-3-2):
in the formula (III-1), the formula (III-2) and the formula (III-3), R represents 21 And R is R 22 The bonding position, a is an integer from 0 to 4, R 31 Each independently represents methyl or ethyl; b is an integer of 0 to 4, R 32 Each independently represents methyl or ethyl; c is 0 to 2, R 35 Each independently represents methyl or ethyl, and R 33 R is R 34 Each independently represents a hydrogen atom or a methyl group;
the structure of the above formula (III-3-1) and formula (III-3-2) is shown below:
in the formula (III-3-1) and the formula (III-3-2), R is represented by 22 And R is R 21 Bonding positions, and a plurality of R 4 Each independently represents an alkyl group having 1 to 5 carbon atoms.
According to another embodiment of the present invention, the multifunctional polyester polyol (C) has a structure represented by the following formula (IV-1) or formula (IV-2):
in the formula (IV-1) and the formula (IV-2), a plurality of R 4 Is defined as before.
In order to improve the moisture permeability of waterproof moisture permeable coatings and products made from aqueous polyurethane dispersions optionally comprising structural units derived from glycol compounds (E) having polyethylene oxide groups in the side chains, according to yet another embodiment of the present invention.
According to still another embodiment of the present invention, the diol compound (E) having a polyethylene oxide group in a side chain is used in an amount of 7 to 20 weight percent based on 100 weight percent of the solid content of the aforementioned aqueous polyurethane dispersion.
According to a further embodiment of the present invention, the aforementioned aqueous polyurethane dispersion optionally comprises structural units derived from a polyamine compound (F).
Another aspect of the present invention is to provide a coating composition. The coating composition comprises the aqueous polyurethane dispersion.
It is a further aspect of the present invention to provide a waterproof moisture permeable coating. The waterproof moisture-permeable coating is prepared by the coating composition.
Yet another aspect of the present invention is to provide a waterproof moisture permeable product. The waterproof moisture-permeable product comprises a substrate and the waterproof moisture-permeable coating. The waterproof moisture-permeable coating is arranged on the base material.
The water-based polyurethane dispersion, the coating composition containing the water-based polyurethane dispersion, the waterproof moisture-permeable coating prepared from the coating composition and the waterproof moisture-permeable product containing the waterproof moisture-permeable coating are applied, and the moisture permeability, the water resistance and the water washing resistance of the waterproof moisture-permeable coating and the product are effectively improved by controlling the using amount of the multifunctional polyester polyol (C) in the water-based polyurethane dispersion.
Detailed Description
The making and using of the embodiments of the present invention are discussed in detail below. However, it is to be understood that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The particular embodiments discussed are merely illustrative and are not meant to limit the scope of the invention.
The aqueous polyurethane dispersion of the present invention is prepared by reacting the following reaction components, wherein the reaction components comprise polyisocyanate (A), diol compound (B), polyfunctional polyester polyol (C) and sulfonate diol (D).
The aqueous polyurethane dispersion of the present invention uses an aqueous medium, such as deionized water, ultrapure water, ion-exchanged water, reverse osmosis water (Reverse Osmosis Water) or distilled water, preferably deionized water, as a solvent, and is thus an environmentally friendly material.
The invention adopts a prepolymerization method to prepare the aqueous polyurethane dispersoid. In some embodiments, the aqueous polyurethane dispersion is prepared by pre-polymerizing the polyisocyanate (A) with the diol compound (B), the multifunctional polyester polyol (C) and the sulfonate diol (D) to form a polyurethane prepolymer with a certain viscosity range, dispersing the prepolymer in an aqueous medium, and then reacting the prepolymer with a chain extender, a cross-linking agent and the like for chain extension.
The polyisocyanate (a) of the present invention refers to an organic compound having at least 2 isocyanate groups. When the aforementioned prepolymerization reaction is carried out, the polyisocyanate (A) is prepared by reacting an isocyanate group with a hydroxyl group in the diol compound (B), the polyfunctional polyester polyol (C) and the sulfonate diol (D) to form a polyurethane prepolymer. The polyisocyanate (A) constitutes the hard segment portion of the aqueous polyurethane dispersion, while the diol compound (B), the polyfunctional polyester polyol (C) and the sulfonate diol (D) constitute the soft segment portion of the aqueous polyurethane dispersion.
In some embodiments, the polyisocyanate (a) includes, but is not limited to, aliphatic polyisocyanates and/or aromatic polyisocyanates.
Specific examples of the aliphatic polyisocyanate include isophorone diisocyanate (isophorone diisocyanate, IPDI), hexamethylene diisocyanate (hexamethylene diisocyanate, HDI), pentamethylene diisocyanate (pentamethylene diisocyanate, PDI), 4' -dicyclohexylmethane diisocyanate, 1, 4-cyclohexyl diisocyanate, norbornane diisocyanate (norbornane dimethyleneisocyanate, NBDI), 2-dimethylpentane diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1,6, 11-undecane triisocyanate, 1,3, 6-hexamethylene triisocyanate and the like. The aforementioned aliphatic polyisocyanates may be used singly or in combination of plural kinds.
Specific examples of the aromatic polyisocyanate include toluene diisocyanate (toluene diisocyanate, TDI), diphenylmethane diisocyanate (methylene diphenyl diisocyanate, MDI), xylene diisocyanate (xylylene diisocyanate, XDI), triphenylmethane-4,4',4"-triisocyanate (TTI), and the like. The aforementioned aromatic polyisocyanates may be used singly or in combination of plural kinds.
The polyisocyanates (A) according to the invention are preferably HDI and IPDI, and more preferably IPDI, in order to give the coating better water resistance.
In some embodiments, the polyisocyanate (a) is used in an amount of 10 to 70 weight percent, preferably 12 to 28 weight percent, and more preferably 18 to 25 weight percent, based on 100 weight percent of the solid component of the aqueous polyurethane dispersion. When the amount of polyisocyanate (a) used is too large, the moisture permeability of the coating layer is insufficient; when the amount of polyisocyanate (a) used is too small, the water pressure resistance of the coating layer is poor.
The diol compound (B) used in the present invention contains a polyester diol (B1) and/or a polyether diol (B2). Preferably, the diol compound (B) contains both the polyester diol (B1) and the polyether diol (B2).
The molecular weight of the aforementioned polyester diol (B1) is 500 g/mol to 5000 g/mol, and preferably 1000 g/mol to 3000 g/mol. The two hydroxyl groups of the polyester diol (B1) can react with the isocyanate groups of the polyisocyanate (A), and the mechanical properties of the waterproof moisture-permeable coating and the product prepared by the ester groups of the polyester diol (B1) are improved.
The polyether glycol (B2) is a glycol compound having a Main chain (Main chain) having a polyalkylene oxide group (poly (alkylene oxide)), and has a molecular weight of 200 g/mol to 5000 g/mol, and preferably 1000 g/mol to 3000 g/mol. The two hydroxyl groups of the polyether glycol (B2) can react with the isocyanate groups of the polyisocyanate (A) to endow the prepared waterproof moisture-permeable coating and product with good flexibility and washing resistance.
In some embodiments, the polyester diol (B1) includes, but is not limited to, poly (hexamethylene succinate), poly (butylene adipate), poly (butylene succinate), and the like.
In some embodiments, the aforementioned polyether glycol (B2) includes, but is not limited to, polytetramethylene ether glycol (poly (tetramethylene ether) glycol, PTMEG), propylene oxide condensate (polypropylene glycol, PPG), and the like.
In some embodiments, the glycol compound (B) is used in an amount of 10 to 70 weight percent, and preferably 40 to 60 weight percent, based on 100 weight percent of the solid component of the aqueous polyurethane dispersion. When the amount of the glycol compound (B) is 10 to 70 weight percent, the waterproof moisture-permeable coating and the product prepared have good water pressure resistance, moisture permeability, mechanical properties, flexibility and water washing resistance. When the amount of the glycol compound (B) used is too large, the water pressure resistance of the coating layer is poor; when the amount of the diol compound (B) used is too small, the moisture permeability of the coating layer is poor.
The polyfunctional polyester polyol (C) used in the present invention has a structure represented by the following formula (I):
(R 1 ) m -X-(R 2 ) n (I)
in formula (I), X represents a tetravalent organic group, and X is a carbon atom or a silicon atom; r is R 1 Is methyl or ethyl, and the carbon atom of the methyl is bonded with X; r is R 2 Represents a structure represented by the following formula (III); m represents 0 or 1, n represents 3 or 4, and the sum of m and n is 4.
*—R 21 —R 22 (III)
In formula (III), R represents 21 The position bonded to X, R 21 Represents a structure represented by the following formula (III-1), formula (III-2) or formula (III-3), and R 22 Represents a structure represented by the following formula (III-3-1) or formula (III-3-2):
in the formula (III-1), the formula (III-2) and the formula (III-3), R represents 21 And R is R 22 The bonding position, a is an integer from 0 to 4, R 31 Each independently represents methyl or ethyl; b is an integer of 0 to 4, R 32 Each independently represents methyl or ethyl; c is 0 to 2, R 35 Each independently represents methyl or ethyl, and R 33 R is R 34 Each independently represents a hydrogen atom or a methyl group;
in the formula (III-3-1) and the formula (III-3-2), R is represented by 22 And R is R 21 Bonding positions, and a plurality of R 4 Each independently represents an alkyl group having 1 to 5 carbon atoms.
In other embodiments, the foregoing multifunctional polyester polyol (C) has a structure represented by the following formula (II):
in the formula (II), with R 1 R is R 2 The two carbon atoms bound are quaternary carbon atoms, R 1 R is R 2 Wherein R is represented by formula (III) 2 Wherein ":" represents R 21 A position bonded to a quaternary carbon atom of formula (II); p1 represents an integer of 0 to 2, p2 represents an integer of 1 to 3, and the sum of p1 and p2 is 3; q1 represents an integer of 0 to 2, q2 represents an integer of 1 to 3, the sum of q1 and q2 is 3, and the sum of p2 and q2 is an integer of 3 to 6.
Preferably, the multifunctional polyester polyol (C) of the present invention has a structure represented by the following formula (IV-1) or formula (IV-2):
in the above formula (IV-1) and formula (IV-2), a plurality of R 4 Is defined as before.
In the formula (I) and the formula (II), R is as shown in the formula (III) 2 The aqueous polyurethane dispersion can be formed into a three-dimensional structure to enhance the water washing resistance and chemical resistance of the prepared waterproof moisture-permeable coating and product. Secondly, the diffusion rate of the prepared waterproof moisture-permeable coating to water vapor can be enhanced by a large amount of hydrophilic groups (such as hydroxyl groups) in the multifunctional polyester polyol (C), so that the moisture permeability of the coating is improved. Therefore, the prepared waterproof moisture-permeable coating and the product have the effects of good water washing resistance and moisture permeability.
The multifunctional polyester polyol (C) is prepared by the following reaction: the polyol having at least three hydroxyl groups is first subjected to a ring opening reaction with a compound containing a dicarboxylic anhydride (e.g., a polycyclic compound) to produce a polycarboxylic acid compound having at least three carboxylic acid functional groups. Then, the carboxylic acid group of the polycarboxylic acid compound undergoes a ring-opening reaction on the ethylene oxide group of the glycidyl versatate to produce the foregoing multifunctional polyester polyol (C). The polyhydric alcohols include, but are not limited to, mono-pentaerythritol (MPE), dipentaerythritol, tripentaerythritol, trimethylolpropane (TMP), and di (trimethylolpropane). Compounds containing a dicarboxylic anhydride include, but are not limited to, methyl hexahydrophthalic anhydride (methyl hexahydrophthalic anhydride, MHHPA), phthalic anhydride, hexahydrophthalic anhydride (hexahydrophthalic anhydride, HHPA), and the like.
Traditionally, aqueous polyurethane dispersions often require the addition of solvents (e.g., acetone) during synthesis to reduce the viscosity of the prepolymer for subsequent dispersion into the aqueous phase. However, the organic solvent still needs to be pumped out later, which increases energy consumption and has problems of solvent treatment. However, the multifunctional polyester polyol (C) of the present invention can reduce the viscosity of the polyurethane prepolymer, so as to facilitate the dispersion of the polyurethane prepolymer in the aqueous phase, and can avoid environmental problems caused by organic solvents (such as acetone) during the process. In addition, the multifunctional polyester polyol (C) can improve pigment wettability and dispersibility of the prepared coating composition.
In some embodiments, the number average molecular weight of the multifunctional polyester polyol (C) is 400 g/mol to 4000 g/mol, and preferably 1000 g/mol to 3000 g/mol. When the number average molecular weight of the multifunctional polyester polyol (C) is 400 g/mol to 4000 g/mol, the prepared waterproof moisture-permeable coating and product have good moisture permeability and water washing resistance, so that the problem that the moisture permeability and water washing resistance of the aqueous polyurethane dispersion cannot be achieved is solved.
In some embodiments, the multifunctional polyester polyol (C) is used in an amount of 3 to 10 weight percent based on 100 weight percent of the solid component of the aqueous polyurethane dispersion, and specific examples of its use may be 3, 4, 5, 6, 7, 8, 9, 10 weight percent. Further, the polyfunctional polyester polyol (C) may be preferably used in an amount of 4 to 8% by weight. When the amount of the multifunctional polyester polyol (C) used is more than 10% by weight, the steric hindrance caused by the multifunctional polyester polyol (C) causes incomplete reaction of other components, resulting in poor water resistance of the coating film. Furthermore, the hydroxyl groups of the polyfunctional polyester polyol (C) react with the isocyanate groups of the polyisocyanate (A) to form bridges which increase the gelation of the aqueous polyurethane dispersion obtained, and the workability of the coating composition comprising the aqueous polyurethane dispersion is deteriorated. When the amount of the multifunctional polyester polyol (C) used is less than 3% by weight, the waterproof moisture-permeable coating and the product obtained are poor in water-washing resistance.
In the foregoing prepolymerization process, the hydrophilic sulfonate groups of the sulfonate glycol (D) help disperse the polyurethane prepolymer in the aqueous phase. And secondly, the sulfonate dihydric alcohol (D) can enhance the adhesiveness of the prepared waterproof moisture-permeable coating to a substrate, and can improve the water-washing resistance of the waterproof moisture-permeable coating and a product. In some embodiments, the molecular weight of sulfonate glycol (D) is less than 1000 grams/mole, and preferably 300 to 500 grams/mole. When the molecular weight of the sulfonate dihydric alcohol (D) is less than 1000 g/mol, the prepared waterproof moisture-permeable coating has better substrate adhesiveness, so that the waterproof moisture-permeable coating and the water washing resistance of the product are improved.
Specific examples of the sulfonate glycol (D) include, but are not limited to, 2- (2-aminoethylamino) ethane sulfonic acid, polyether sulfonic acid, ethylenediamine-propyl-sulfonic acid, ethylenediamine-butyl sulfonic acid, 1, 2-propylenediamine- β -ethyl sulfonic acid, 1, 3-propylenediamine- β -ethyl sulfonic acid, taurine, alkali metal salts and ammonium salts thereof, and the like. For example, a specific example of sulfonate glycol (D) may be bis-1,4- ((2-hydroxypropoxy) -2-propoxy) -butanesulfonic acid sodium salt (bis-1, 4- ((2-hydroxypropyl) -2-propoxy) -butane sulfonate sodium salt, manufactured by G N technology, inc.), and model GS-7Q.
In some embodiments, the sulfonate glycol (D) is used in an amount of 3 to 15 weight percent, and preferably 4 to 10 weight percent, based on 100 weight percent of the solid component of the aqueous polyurethane dispersion. When the sulfonate glycol (D) is used in an amount of 3 to 15 weight percent, the waterproof moisture-permeable coating and the product prepared have good water-washing resistance.
The aforementioned reaction component may optionally contain a diol compound (E) having a polyethylene oxide group in a side chain. In some embodiments, the molecular weight of the glycol compound (E) having polyethylene oxide groups in the side chains is 400 to 3000 g/mol, and preferably 500 to 1500 g/mol.
Generally, when polyethylene oxide is on the main chain, although Ethylene Oxide (EO) segments can serve as excellent moisture channels to enhance moisture permeability, the water-resistant and moisture-permeable coating and product produced will be significantly deteriorated in water-resistant property with the increase of EO segments on the main chain because the EO segments are highly hydrophilic. However, with respect to the diol compound (E) having a polyethylene oxide group in the side chain of the present invention, the polyethylene oxide group in the side chain does not affect the moisture permeability of the waterproof moisture permeable coating and the product, and the water washing resistance of the waterproof moisture permeable coating and the product can be improved.
Specific examples of the diol compound (E) having a polyethylene oxide group in the side chain may include, but are not limited to, a product manufactured by Perston corporation and having a model number of Ymer N120, and a product manufactured by Evonik corporation and having a model number of Tegomer D3404.
In some embodiments, the glycol compound (E) having polyethylene oxide groups in the side chains is used in an amount of 7 to 20 weight percent, and preferably 10 to 15 weight percent, based on 100 weight percent of the solid component of the aqueous polyurethane dispersion. When the amount of the glycol compound (E) having a polyethylene oxide group in the side chain is 7 to 20% by weight, the waterproof moisture-permeable coating and the product obtained have both good moisture permeability and water washing resistance. When the amount of the glycol compound (E) having a polyethylene oxide group in the side chain is more than 20% by weight, the water-and-wet-resistant property of the obtained water-and-wet-resistant coating and product will be remarkably deteriorated. When the amount of the glycol compound (E) having a polyethylene oxide group in the side chain is less than 7% by weight, the water-proof moisture-permeable coating and the product obtained are poor in moisture permeability.
In some embodiments, in the prepolymerization, a catalyst (G) may be used. The catalyst (G) includes, but is not limited to, an organobismuth catalyst, an organotin catalyst, an organozinc catalyst, or the like. The catalyst may be, for example, bismuth methylsulfonate, dibutyltin dilaurate, ethyltin octoate, zinc oxalate or the like.
In some embodiments, the neutralization step may optionally be performed after the prepolymerization. Specific examples of neutralizing agents used include, but are not limited to, amines or alkali metal bases. The neutralizing agent may be, for example, trimethylamine, triethylamine, methyldiethylamine, tripropylamine, N-methylmorpholine, methyldiisopropylamine, ethyldiisopropylamine, diisopropylethylamine, sodium hydroxide or potassium hydroxide, etc.
After the neutralization step, a large amount of water is added under high-speed stirring to cause self-emulsification of the polyurethane prepolymer by the hydrophilicity of the sulfonate groups described above, and further dispersion in the aqueous phase. Then, the polyamine compound (F) is added. The amine group of the polyamine compound (F) can react with the hydroxyl group of the polyurethane prepolymer to carry out chain extension, and the polyamine compound (F) can form a hard segment part of the aqueous polyurethane dispersion, thereby improving the mechanical property of the prepared waterproof moisture-permeable coating and enhancing the washing resistance of the coating and the product. Specific examples of the polyamine compound (F) may include, but are not limited to, ethylenediamine, hexamethylenediamine, 4-diphenylmethane diamine, hydroxyethylethylenediamine, di-n-butylamine, isophoronediamine or 2,2' -dimethylbis (p-aminocyclohexylamine) methane (2, 2' -dimethyl1-4, 4' -methylenebis (cyclohexylamine), DMDC), and the like.
In some embodiments, the polyamine compound (F) is used in an amount of 3 to 10 weight percent, and preferably 4 to 7 weight percent, based on 100 weight percent of the solid component of the aqueous polyurethane dispersion. When the polyamine compound (F) is used in an amount of 3 to 10% by weight, the resulting waterproof moisture-permeable coating and product have good water-washing resistance.
In the prepolymerization reaction of the invention, the polyurethane prepolymer still has hydroxyl groups, so when the coating composition containing the polyurethane prepolymer is coated and baked and cured, the hydroxyl groups in the polyurethane prepolymer can further react with the curing agent, thereby further improving the water-proof and moisture-permeable coating and the water-washing resistance of the product. In other words, the polyurethane prepolymer of the present invention can be fully cured by further reacting with a curing agent, so that the polyurethane dispersion of the present invention has better process flexibility.
The coating composition of the present invention comprises the aforementioned aqueous polyurethane dispersion. In some embodiments, the coating composition further comprises a curing agent, a leveling agent, an antifoaming agent, and/or a adhesion promoter. In other embodiments, the coating composition may further comprise pigments and/or bactericides, and the like. The types and the amounts of the curing agent, leveling agent, defoamer, adhesion promoter, pigment and bactericide are not particularly limited, and may be those known to those skilled in the art of the present invention.
Specific examples of curing agents include, but are not limited to, hexamethylene diisocyanate. Specific examples of leveling agents include, but are not limited to, polysiloxane-polyether copolymers, such as polyether modified polydimethylsiloxane. Specific examples of defoamers include, but are not limited to, silicone-polyether copolymer-based defoamers. Specific examples of tackifiers include, but are not limited to, urea-modified urethanes. For example, the bridging agent may be a product manufactured by Likagaku, inc. and having a model number of DN-950 or DN-980. The leveling agent may be a product manufactured by Pick chemical company and model number BYK-333. The defoamer may be a product manufactured by Pick chemical company and model BYK-093. The adhesion promoter may be a product manufactured by Pick chemical company and model number BYK-425. The germicide may be a product manufactured by the company British Jiekang, model XL-2.
In some embodiments, the viscosity of the coating composition is adjusted to match the subsequent processing operations by controlling the amount of adhesion promoter used. For example, the viscosity is 20000 to 25000cps or 10000 to 15000cps, etc.
In some applications, the foregoing coating compositions may be formulated as waterproof moisture-permeable coatings. The coating composition can be coated on a substrate by using methods such as spraying, brushing, dip coating, roller coating or knife coating to form a waterproof and moisture permeable coating.
The waterproof moisture-permeable coating can diffuse the moisture discharged by the skin to the outside by the hydrophilic group of the aqueous polyurethane dispersoid, thereby achieving the moisture-permeable effect. In the diffusion process, the diffusion rate gradually decreases with the increase of the thickness of the waterproof moisture-permeable coating, resulting in a decrease in moisture permeability. In addition, the thickness of the waterproof moisture-permeable coating can affect the processability of subsequent processes (e.g., cutting or seaming, etc.). In some embodiments, the thickness of the waterproof moisture permeable coating may be 0.01mm to 0.03mm, and preferably 0.02mm.
In some applications, the waterproof moisture-permeable coating can be disposed on a substrate to form a waterproof moisture-permeable product. In some embodiments, the substrate comprises fabric, leather, paper, and/or fiber. The aforementioned fibers are fibers that can be formed into a fabric after processing steps such as braiding or weaving. Specific examples of the aforementioned fabrics include, but are not limited to, natural fiber fabrics and/or artificial fiber fabrics, and the fabrics may be, for example, wool fabrics, cotton fabrics, nylon fabrics, or the like. The aforementioned leather includes, but is not limited to, natural leather and/or synthetic leather, and the leather may be, for example, bovine leather, ovine leather, polyvinyl chloride leather, polyurethane leather, and the like.
The following examples are set forth to illustrate the practice of the invention and are not intended to limit the invention thereto, as various modifications and adaptations may be made by those skilled in the art without departing from the spirit and scope of the invention.
Synthesis of multifunctional polyester polyol (C)
Production example
161g of monopentaerythritol and 606g of phthalic anhydride were added to a four-necked flask, and 839g of glycidyl versatate was added dropwise at 150℃to react for 5 hours, to obtain a multifunctional polyester polyol (C) having a number average molecular weight of about 1500 g/mol and a solid content of 98% by weight.
Production of aqueous polyurethane dispersions
Example 1
The amounts of the respective reaction components used are based on 100% by weight of the solid content of the aqueous polyurethane dispersion. Under nitrogen, 19.20 weight percent of polyester diol (B1) (model 5650-1000 and molecular weight 1000, manufactured by chang materials industry Co., ltd.), 30.98 weight percent of polyether diol (B2) (model 2000 and molecular weight about 2000, manufactured by Dailin chemical industry Co., ltd.), 3.05 weight percent of polyfunctional polyester polyol (C), 5.20 weight percent of sulfonate diol (D) (model GS-7Q and molecular weight 420G/mol), and 13.31 weight percent of diol compound (E) (model Ymer N120, manufactured by Perstorp, and molecular weight 1000G/mol) were mixed, and then heated to 120 ℃ for 2 hours at 120 ℃ to remove water.
Then, the temperature was lowered to 60℃and polyisocyanate (A) (isophorone diisocyanate manufactured by Wanhua chemical Co., ltd.) and one drop of catalyst (G) (dibutyltin dilaurate manufactured by An Feng Co., ltd.) were added at 60 ℃. Then, the mixture was heated to 90℃and held at 90℃for 4 hours to carry out a prepolymerization reaction to give a polyurethane prepolymer. Then, the temperature is lowered, and when the temperature is lowered to 60 ℃, 150 to 200 g of water is added to disperse in the water phase. Continuously cooling to below 30 ℃, adding 3 to 10 g of water and 5.82 weight percent of polyamine compound (F) (2, 2' -dimethyl di (p-amino cyclohexylamine) methane manufactured by Xiamen Geruida chemical Co., ltd.) to perform chain extension reaction. After 2 hours, the aqueous polyurethane dispersion of example 1 was obtained.
The aqueous polyurethane dispersion of example 1 was determined by a detection method customary in the art to which the present invention pertains to have a solids content (n.v.) of 35% by weight, an R value (R-value) of 1.8 and a total solids content of 100% by weight, a soft segment content and a hard segment content of 72% by weight and 28% by weight, respectively, based on the aqueous polyurethane dispersion, wherein the R value is calculated by the following formula (V).
Examples 2 to 8 and comparative examples 1 to 5
Examples 2 to 8 and comparative examples 1 to 5 were conducted in the same manner as in example 1 except that the polyisocyanate (A), the diol compound (B), the polyfunctional polyester polyol (C), the sulfonate diol (D), the diol compound (E) having a polyethylene oxide group in a side chain, and the polyamine compound (F) were used in the amounts. The specific conditions for examples 2 to 8 and comparative examples 1 to 5 are shown in table 1.
Application example 1
Preparation of coating compositions
The coating compositions of each example and comparative example were formed by uniformly mixing the aqueous polyurethane dispersions prepared in each example and comparative example with other compositions for adjusting the coating properties.
Waterproof moisture-permeable coating and preparation of waterproof moisture-permeable product
100g of the aqueous polyurethane dispersion of each of the foregoing examples and comparative examples, 0.2g of a leveling agent (manufactured by Pick chemical Co., ltd., model BYK-333) and 0.3g of a defoaming agent (manufactured by Pick chemical Co., ltd., model BYK-093) were added to each mixing tank, and mixed uniformly. Next, 3g of cyclohexane diisocyanate (manufactured by Litsea chemical Co., ltd., model DN-950) was added and mixed uniformly. Then, a viscosity increasing agent (manufactured by Pick chemical Co., ltd., and model number BYK-425) was added, and the viscosity after mixing was measured to obtain a primer coating composition having a viscosity of 20000cps to 25000cps by controlling the amount of the viscosity increasing agent to be used, and left for 2 hours.
Next, the primer coating compositions of the foregoing examples and comparative examples were applied to Nylon cloths (fabric gauge 70d/160d Nylon, and plain weave basis weight 103g/m, respectively, using a doctor blade 2 ) And wherein the coating thickness was 0.02m. Then, a heating step is performed. Heating to 100deg.C, and maintaining at 100deg.C for 60 s to remove water. Then, the mixture was heated to 150℃and held at 150℃for 60 seconds to carry out a bridging reaction, and the primer waterproof moisture-permeable coating of each of examples and comparative examples was formed.
Next, a topcoat composition is prepared. The preparation of the top coat composition is the same as the preparation of the base coat composition, except that: the leveling agent of the top coating composition was used in an amount of 0.3g, cyclohexane diisocyanate was used in an amount of 2g, and the viscosity thereof was controlled to 10000cps to 15000cps. The top coat coating composition was applied to the coating layer formed by the base coat coating composition to form the top coat waterproof moisture-permeable coating layer of each of examples and comparative examples, wherein the coating thickness was 0.01m.
The waterproof moisture-permeable coating of the top coat of each of the examples and the comparative examples is subjected to water removal and bridging reactions at the same temperature and time as the waterproof moisture-permeable coating of the bottom coat, so as to complete the preparation of the waterproof moisture-permeable products of each of the examples and the comparative examples.
Evaluation method
Moisture permeability test
The moisture permeability of the waterproof moisture permeability products of the foregoing examples and comparative examples was measured according to ASTM E-96 1995BW Standard test method, and the results are shown in Table 1.
Waterproof test
The water pressure resistance of the waterproof moisture-permeable products of the foregoing examples and comparative examples was measured according to JIS L1092-2009B standard test methods to evaluate the water resistance, and the results are shown in table 1.
Test of Water washing resistance
The waterproof and moisture permeable products prepared in the foregoing examples and comparative examples were washed with water at 40℃and laundry detergent according to AATCC 135-2004 (W0 & W5) standard test method. After washing 5 times, the water repellency of the waterproof moisture-permeable product was measured again by the aforementioned method, and the rate of change (d) in water pressure resistance was calculated by the following formula (VI), and the results are shown in table 1.
In the formula (VI), a represents a value of the water pressure resistance before water washing, and b represents a value of the water pressure resistance after water washing.
TABLE 1
Referring to Table 1, the proportions of the respective reaction components of the aqueous polyurethane dispersions, the detection of the aqueous polyurethane dispersions, and the evaluation results of the waterproof and moisture-permeable products of the examples and comparative examples of the present invention are shown.
According to the evaluation results of each example and comparative example 1, the aqueous polyurethane dispersion prepared in comparative example 1, in which the multifunctional polyester polyol (C) was excessively used (in an amount of 10.95 weight percent), gelled, and the coating composition of comparative example 1 was deteriorated in handleability and could not be uniformly coated on a substrate. Furthermore, according to the evaluation results of each example and comparative example 2, the waterproof and moisture-permeable products of each example had better water-washing resistance than the waterproof and moisture-permeable products of comparative example 2, which did not use the polyfunctional polyester polyol (C).
According to the evaluation results of each example and comparative example 3, the waterproof moisture-permeable coating of comparative example 3, which did not use the sulfonate diol (D), could not be attached to the substrate. Thus, the waterproof and moisture-permeable products prepared in each example using the sulfonate diol (D) had good moisture permeability, water repellency, and water washing resistance, as compared to the waterproof and moisture-permeable products prepared in comparative example 3 in which the sulfonate diol (D) was not used.
According to the evaluation results of examples and comparative example 4, the waterproof moisture-permeable product produced in comparative example 4, which did not use the diol compound (E) having a polyethylene oxide group in the side chain, was too low in moisture permeability to be applied to the waterproof moisture-permeable field. Therefore, the waterproof and moisture-permeable products obtained by each example using the polyol compound (E) have good moisture permeability and water-washing resistance, compared with the waterproof and moisture-permeable products obtained by comparative example 4 not using the polyol compound (E) having polyethylene oxide.
In summary, the aqueous polyurethane dispersion, the coating composition containing the aqueous polyurethane dispersion, the waterproof and moisture permeable coating prepared from the coating composition and the waterproof and moisture permeable product containing the waterproof and moisture permeable coating can provide good moisture permeability, waterproof property and washing resistance by controlling the specific using amount of the multifunctional polyester polyol (C), the sulfonate glycol (D) and the glycol compound (E) with the polyethylene oxide group on the side chain of the aqueous polyurethane dispersion.
Although the present invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, but may be modified and altered by persons skilled in the art without departing from the spirit and scope of the invention.
Claims (9)
1. An aqueous polyurethane dispersion comprising structural units derived from:
a polyisocyanate (A);
a glycol compound (B) comprising a polyester glycol (B1) and a polyether glycol (B2);
a multifunctional polyester polyol (C); and
sulfonate glycol (D);
wherein the polyfunctional polyester polyol (C) is used in an amount of 3 to 10 weight percent based on 100 weight percent of the solid component of the aqueous polyurethane dispersion;
wherein the multifunctional polyester polyol (C) has a structure represented by the following formula (I) or formula (II):
(I)
in the formula (I), X represents a tetravalent organic group, and X is a carbon atom or a silicon atom; r is R 1 Is hydroxymethyl or ethyl, and the carbon atom of the hydroxymethyl is bonded to X; r is R 2 Represents a structure represented by the following formula (III); m represents 0 or 1, n represents 3 or 4, and the sum of m and n is 4;
(II)
in the formula (II), R is the same as that of 1 R is R 2 The two carbon atoms bound are quaternary carbon atoms, R 1 R is R 2 Is as defined above; p1 represents an integer of 0 to 2, p2 represents an integer of 1 to 3, and the sum of p1 and p2 is 3; q1 represents an integer of 0 to 2, q2 represents an integer of 1 to 3, the sum of q1 and q2 is 3, and the sum of p2 and q2 is an integer of 3 to 6;
(III)
in the formula (III), R is represented by 21 The position bonded to X or the quaternary carbon atom of formula (II), R 21 Represents a structure represented by the following formula (III-1), formula (III-2) or formula (III-3), and R 22 Represents a structure represented by the following formula (III-3-1) or formula (III-3-2):
(III-1)
(III-2)
(III-3)
in the formula (III-1), the formula (III-2) and the formula (III-3), R is represented by 21 And R is R 22 The bonding position, a is an integer from 0 to 4, R 31 Each independently represents methyl or ethyl; b is an integer of 0 to 4, R 32 Each independently represents methyl or ethyl; c is 0 to 2, R 35 Each independently represents methyl or ethyl, and R 33 R is R 34 Each independently represents a hydrogen atom or a methyl group;
(III-3-1)
(III-3-2)
in the formula (III-3-1) and the formula (III-3-2), R is represented by 22 And R is R 21 Bonding positions, and a plurality of R 4 Each independently represents an alkyl group having 1 to 5 carbon atoms.
2. The aqueous polyurethane dispersion according to claim 1, wherein the polyisocyanate (a) is used in an amount of 10 to 70% by weight, the diol compound (B) is used in an amount of 10 to 70% by weight, and the sulfonate diol (D) is used in an amount of 3 to 15% by weight, based on 100% by weight of the solid content of the aqueous polyurethane dispersion.
3. The aqueous polyurethane dispersion according to claim 1, wherein the multifunctional polyester polyol (C) has a structure represented by the following formula (IV-1) or formula (IV-2):
in the formula (IV-1) and the formula (IV-2), a plurality of R 4 Is defined as in claim 1.
4. The aqueous polyurethane dispersion according to claim 1, wherein the aqueous polyurethane dispersion further comprises a structural unit derived from a diol compound (E) having a polyethylene oxide group in a side chain.
5. The aqueous polyurethane dispersion according to claim 4, wherein the glycol compound (E) having a polyethylene oxide group in the side chain is used in an amount of 7 to 20% by weight based on 100% by weight of the solid content of the aqueous polyurethane dispersion.
6. The aqueous polyurethane dispersion according to claim 1, wherein the aqueous polyurethane dispersion further comprises structural units derived from a polyamine compound (F).
7. A coating composition comprising the aqueous polyurethane dispersion of any one of claims 1-6.
8. A waterproof moisture-permeable coating made using the coating composition of claim 7.
9. A waterproof moisture-permeable product comprising:
a substrate; and
the waterproof moisture-permeable coating of claim 8, disposed on the substrate.
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