CN114437307A - Aqueous polyurethane dispersions, coating compositions and use thereof - Google Patents
Aqueous polyurethane dispersions, coating compositions and use thereof Download PDFInfo
- Publication number
- CN114437307A CN114437307A CN202011188098.XA CN202011188098A CN114437307A CN 114437307 A CN114437307 A CN 114437307A CN 202011188098 A CN202011188098 A CN 202011188098A CN 114437307 A CN114437307 A CN 114437307A
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- CN
- China
- Prior art keywords
- aqueous polyurethane
- iii
- formula
- polyurethane dispersion
- diol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920003009 polyurethane dispersion Polymers 0.000 title claims abstract description 68
- 239000008199 coating composition Substances 0.000 title claims abstract description 34
- -1 diol compound Chemical class 0.000 claims abstract description 75
- 238000000576 coating method Methods 0.000 claims abstract description 69
- 239000011248 coating agent Substances 0.000 claims abstract description 66
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 37
- 150000002009 diols Chemical class 0.000 claims abstract description 30
- 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 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 229920000728 polyester Polymers 0.000 claims abstract description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 229920000768 polyamine Polymers 0.000 claims description 10
- 150000001721 carbon Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 51
- 230000035699 permeability Effects 0.000 abstract description 29
- 238000005406 washing Methods 0.000 abstract description 25
- 230000000052 comparative effect Effects 0.000 description 26
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 11
- 239000004744 fabric Substances 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920005749 polyurethane resin Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229920000909 polytetrahydrofuran Polymers 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 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
- 239000008346 aqueous phase Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-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
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 230000008569 process Effects 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
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide 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
- 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
- 238000005516 engineering process 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
- 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
- 239000000463 material Substances 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000002987 primer (paints) Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 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
- 238000009941 weaving Methods 0.000 description 2
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 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
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000011717 all-trans-retinol Substances 0.000 description 1
- 235000019169 all-trans-retinol Nutrition 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
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 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
- 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
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000013530 defoamer Substances 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
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004826 seaming Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 210000004243 sweat Anatomy 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
- 239000002699 waste material Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 210000002268 wool Anatomy 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
-
- 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
- C08G18/4236—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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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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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
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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: polyisocyanate (A), diol compound (B), polyfunctional polyester polyol (C) and sulfonate diol (D). The diol compound (B) comprises polyester diol (B1) and/or 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, waterproofness 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 a waterproof moisture-permeable coating.
Background
In current aquatic product prevention, 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 imparted with a moisture-permeable function to allow the accumulated moisture to be discharged.
The waterproof and moisture permeable principle includes a microporous mechanism and a hydrophilic mechanism. In the microporous type mechanism, moisture (gaseous water molecules having a size of about 0.0004 micron) diffuses out through the pores of the coating layer having a diameter of less than 2 microns, and thereby blocks liquid water molecules (having a size of about more than 100 microns), thereby achieving the moisture permeability function. However, these micropores are easily clogged with dirt to reduce moisture permeability.
The hydrophilic mechanism is to apply a waterproof moisture-permeable coating on one side of a substrate (such as but not limited to fabric, etc.) to form a dense coating layer, thereby achieving the waterproof effect. Secondly, the coating has hydrophilic groups (such as carboxylic acid group, ester group or hydroxyl group) to absorb moisture and sweat discharged by the skin, and then the moisture is diffused to the other side of the substrate by diffusion so as to diffuse the moisture to the external environment, thereby achieving the moisture permeability effect. Therefore, compared to the microporous mechanism, the hydrophilic mechanism does not have a problem that the micropores are clogged with dirt, thereby reducing moisture permeability.
The waterproof moisture-permeable coating can be made of polyurethane resin, polyvinyl chloride resin and acryl resin, and the polyurethane resin is preferable based on the feeling of skin contact. Therefore, the waterproof film of a general waterproof product is made of polyurethane resin.
In recent years, due to the rise of environmental awareness, aqueous polyurethane dispersions using water as a main solvent are developed to replace oil-based polyurethanes using a large amount of solvents, so as to avoid energy consumption caused by organic solvent recovery, environmental problems caused by organic solvent waste and health concerns caused by organic solvent residues. Although the aqueous polyurethane dispersion has the advantage of solvent weight reduction, in a hydrophilic mechanism, since a hydrophilic functional group easily hydrolyzes an aqueous polyurethane coating, the water resistance, moisture permeability and water washing resistance of the aqueous polyurethane resin are still slightly insufficient compared with those of an oil-based polyurethane resin, and the water permeability, water resistance and water washing resistance cannot be achieved at the same time.
Accordingly, 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 problems, it is an aspect of the present invention to provide an aqueous polyurethane dispersion. Can provide the waterproof moisture-permeable coating and the waterproof moisture-permeable product which are prepared by the coating and the waterproof moisture-permeable product with good moisture permeability, waterproofness and washing resistance.
According to another aspect of the present invention, a coating composition is provided. The coating composition comprises the aforementioned aqueous polyurethane dispersion.
According to yet another aspect of the present invention, a waterproof moisture-permeable coating is provided. The waterproof moisture-permeable coating is prepared by utilizing the coating composition.
According to 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 moisture-permeable product comprises a substrate and the waterproof moisture-permeable coating. The waterproof moisture-permeable coating is arranged on the substrate.
According to one aspect of the present invention, an aqueous polyurethane dispersion is provided. The aqueous polyurethane dispersion comprises structural units derived from: polyisocyanate (a), diol compound (B), polyfunctional polyester polyol (C), and sulfonate diol (D). The diol compound (B) comprises polyester diol (B1) and/or 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 components of the aqueous polyurethane dispersion.
Further, the polyisocyanate (a) is used in an amount of 10 to 70 weight percent, the diol compound (B) is used in an amount of 10 to 70 weight percent, and the sulfonate diol (D) is used in an amount of 3 to 15 weight percent, based on 100 weight percent of the solid content of the aqueous polyurethane dispersion.
According to an embodiment of the present invention, the polyfunctional polyester polyol (C) has a structure represented by the following formula (I) or formula (II):
(R1)m-X-(R2)n (I)
in formula (I), X represents a tetravalent organic group, and X is a carbon atom or a silicon atom; r1Is a methylhydroxy group or an ethyl group, and the carbon atom of the methylhydroxy group is bonded to X; r2Represents 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.
In formula (II), with R1And R2The two carbon atoms bound being quaternary carbon atoms, R1And R2As 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 shown in the above formula (III) is as follows:
*-R21-R22 (III)
in formula (III), "represents R21Position bound to X or to a quaternary carbon atom of formula (II), R21Represents a structure represented by the following formula (III-1), formula (III-2) or formula (III-3), and R22Represents a structure represented by the following formula (III-3-1) or formula (III-3-2):
in the formulae (III-1), (III-2) and (III-3), "" represents R21And R22The position of the bond, a is an integer of 0 to 4, R31Each independently represents methyl or ethyl; b is an integer of 0 to 4, R32Each independently representsMethyl or ethyl; c is 0 to 2, R35Each independently represents methyl or ethyl, and R33And R34Each independently represents a hydrogen atom or a methyl group;
the structures shown by the above formulas (III-3-1) and (III-3-2) are shown below:
in the formulae (III-3-1) and (III-3-2), "" represents R22And R21Position of a bond, and a plurality of R4Each independently represents an alkyl group having a carbon number of 1 to 5.
According to another embodiment of the present invention, the polyfunctional polyester polyol (C) has a structure represented by the following formula (IV-1) or formula (IV-2):
in the formulae (IV-1) and (IV-2), a plurality of R4As defined above.
In order to improve the moisture permeability of waterproof moisture-permeable coatings and products made from aqueous polyurethane dispersions, according to yet another embodiment of the present invention, the aqueous polyurethane dispersion optionally comprises structural units derived from diol compounds (E) having polyethylene oxide groups in the side chains.
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 component of the aforementioned aqueous polyurethane dispersion.
According to still another embodiment of the present invention, the aforementioned aqueous polyurethane dispersion optionally contains a structural unit derived from the 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 yet another aspect of the present invention to provide a waterproof moisture-permeable coating. The waterproof moisture-permeable coating is prepared by utilizing the coating composition.
It is yet another aspect of the present invention 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 substrate.
The application of the aqueous polyurethane dispersion, the coating composition containing the aqueous polyurethane dispersion, the waterproof moisture-permeable coating prepared from the coating composition and the waterproof moisture-permeable product containing the waterproof moisture-permeable coating can effectively improve the moisture permeability, the waterproofness and the washability of the waterproof moisture-permeable coating and the product by controlling the using amount of the multifunctional polyester polyol (C) in the aqueous polyurethane dispersion.
Detailed Description
The making and using of embodiments of the present invention are discussed in detail below. It should be appreciated, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative and do not limit the scope of the invention.
The aqueous polyurethane dispersion of the present invention is obtained by reacting the reaction components described later, 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 is an environmentally friendly material because it 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.
The invention adopts a prepolymerization method to prepare the aqueous polyurethane dispersion. In some embodiments, the polyisocyanate (a) is prepolymerized with the diol compound (B), the polyfunctional polyester polyol (C) and the sulfonate diol (D) to form a polyurethane prepolymer having a certain viscosity range, and then the polyurethane prepolymer is dispersed in an aqueous medium, and then the polyurethane prepolymer is reacted with a chain extender, a crosslinking agent, etc. to perform chain extension, thereby preparing the aqueous polyurethane dispersion.
The polyisocyanates (A) according to the invention are organic compounds having at least 2 isocyanate groups. When the prepolymerization is carried out, the polyisocyanate (a) reacts with the hydroxyl groups of 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 part of the aqueous polyurethane dispersion, while the diol compound (B), the polyfunctional polyester polyol (C) and the sulfonate diol (D) constitute the soft segment part of the aqueous polyurethane dispersion.
In some embodiments, polyisocyanate (a) includes, but is not limited to, aliphatic polyisocyanates and/or aromatic polyisocyanates.
Specific examples of the aliphatic polyisocyanate include isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), Pentamethylene Diisocyanate (PDI), 4,4' -dicyclohexylmethane diisocyanate, 1, 4-cyclohexyl diisocyanate, norbornane diisocyanate (NBDI), 2-dimethylpentane diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 2,4, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1,6, 11-undecane triisocyanate and 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 Tolylene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Xylylene Diisocyanate (XDI), and triphenylmethane-4, 4', 4 ″ -triisocyanate (TTI). The aforementioned aromatic polyisocyanates may be used singly or in combination of plural kinds.
The polyisocyanates (A) of the invention are preferably HDI and IPDI, and more preferably IPDI, in order to impart better water resistance to the coating.
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 components of the aqueous polyurethane dispersion. When the amount of the polyisocyanate (a) used is too large, the moisture permeability of the coating layer is insufficient; when the amount of the polyisocyanate (A) used is too small, the water pressure resistance of the coating is poor.
The diol compound (B) used in the present invention comprises a polyester diol (B1) and/or a polyether diol (B2). Preferably, the diol compound (B) includes 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. Two hydroxyl groups of the polyester diol (B1) can react with isocyanate groups of the polyisocyanate (A), and the ester groups of the polyester diol (B1) can improve the mechanical properties of the prepared waterproof moisture-permeable coating and product.
The polyether glycol (B2) is a glycol compound having a Main chain (Main chain) with 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 diol (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 water 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 polyether glycol (B2) includes, but is not limited to, polytetramethylene ether glycol (PTMEG), polypropylene oxide condensate (PPG), and the like.
In some embodiments, the diol 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 components of the aqueous polyurethane dispersion. When the using amount of the diol compound (B) is 10 to 70 weight percent, the prepared waterproof moisture-permeable coating and product have good water pressure resistance, moisture permeability, mechanical properties, flexibility and water washing resistance. When the diol compound (B) is used in an excessively large amount, 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):
(R1)m-X-(R2)n (I)
in formula (I), X represents a tetravalent organic group, and X is a carbon atom or a silicon atom; r is1Is a methylhydroxy group or an ethyl group, and the carbon atom of the methylhydroxy group is bonded to X; r2Represents 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.
*—R21—R22 (III)
In formula (III), "represents R21Position bonded to X, R21Represents a structure represented by the following formula (III-1), formula (III-2) or formula (III-3), and R22Represents a structure represented by the following formula (III-3-1) or formula (III-3-2):
in the formulae (III-1), (III-2) and (III-3), "" represents R21And R22The position of the bond, a is an integer of 0 to 4, R31Each independently represents methyl or ethyl; b is an integer of 0 to 4, R32Each independently represents methyl or ethyl; c is 0 to 2, R35Each independently represents methyl or ethyl, and R33And R34Each independently represents a hydrogen atom or a methyl group;
in the formulae (III-3-1) and (III-3-2), "" represents R22And R21Position of a bond, and a plurality of R4Each independently represents an alkyl group having a carbon number of 1 to 5.
In other embodiments, the aforementioned polyfunctional polyester polyol (C) has a structure represented by the following formula (II):
in formula (II), with R1And R2The two bonded carbon atoms being quaternary carbon atoms, R1And R2As defined above, wherein R is represented by the formula (III)2Wherein represents R21A 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 polyfunctional polyester polyol (C) of the present invention has a structure represented by the following formula (IV-1) or formula (IV-2):
in the above formulae (IV-1) and (IV-2), a plurality of R4As defined above.
In the formula (I) and the formula (II), R is shown as the formula (III)2The aqueous polyurethane dispersion can form a three-dimensional structure so as 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 moisture 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. Thus, the waterproof and moisture permeable coating preparedAnd the product has good washing resistance and moisture permeability.
The polyfunctional polyester polyol (C) is obtained by the reaction: a polyol having at least three hydroxyl groups is subjected to a ring-opening reaction with a compound containing an anhydride of dicarboxylic acid (for example, 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 causes a ring-opening reaction of the oxirane group of the glycidyl versatate to produce the aforementioned polyfunctional polyester polyol (C). The polyol includes, but is not limited to, mono-pentaerythritol (MPE), dipentaerythritol, tripentaerythritol, Trimethylolpropane (TMP), ditrimethylolpropane, and the like. The compound containing an acid anhydride includes, but is not limited to, methyl hexahydrophthalic anhydride (MHHPA), phthalic 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 when converted to the aqueous phase. However, the subsequent extraction of organic solvent is still required, which increases energy consumption and has the problem of solvent treatment. However, the multifunctional polyester polyol (C) of the present invention can reduce the viscosity of the polyurethane prepolymer, thereby facilitating the dispersion of the polyurethane prepolymer in the aqueous phase, and can completely eliminate the use of organic solvents (e.g., acetone) in the process, thereby avoiding the environmental problems caused by the organic solvents. In addition, the multifunctional polyester polyol (C) can improve the pigment wettability and dispersibility of the prepared coating composition.
In some embodiments, the number average molecular weight of the polyfunctional polyester polyol (C) is from 400 g/mole to 4000 g/mole, and preferably from 1000 g/mole to 3000 g/mole. When the number average molecular weight of the polyfunctional 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, thereby solving the problem that the moisture permeability and the water washing resistance of the aqueous polyurethane dispersion cannot be achieved simultaneously.
In some embodiments, the polyfunctional polyester polyol (C) is used in an amount of 3 to 10 weight percent based on 100 weight percent of the solid components of the aqueous polyurethane dispersion, and specific examples thereof 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 weight percent. When the polyfunctional polyester polyol (C) is used in an amount of more than 10% by weight, steric hindrance caused by the polyfunctional 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 more bridges, which causes the resultant aqueous polyurethane dispersion to gel, and the coating composition containing the aqueous polyurethane dispersion has poor workability. When the amount of the polyfunctional polyester polyol (C) used is less than 3 weight percent, the water-repellent moisture-permeable coating and the product obtained therefrom have poor wash resistance.
In the above-mentioned preliminary polymerization method, the hydrophilic sulfonate group of the sulfonate diol (D) contributes to dispersion of the polyurethane prepolymer in the aqueous phase. 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 sulfonate diol (D) has a molecular weight of less than 1000 g/mole, and preferably from 300 to 500 g/mole. When the molecular weight of the sulfonate diol (D) is less than 1000 g/mol, the prepared waterproof moisture-permeable coating has better substrate adhesiveness, thereby improving the water washing resistance of the waterproof moisture-permeable coating and the product.
Specific examples of the sulfonate diol (D) include, but are not limited to, 2- (2-aminoethylamino) ethanesulfonic acid, polyethersulfonic acid, ethylenediamine-propyl-sulfonic acid, ethylenediamine-butylsulfonic acid, 1, 2-propylenediamine- β -ethanesulfonic acid, 1, 3-propylenediamine- β -ethanesulfonic acid, taurine and alkali metal salts and ammonium salts thereof, and the like. For example, a specific example of the sulfonate diol (D) may be bis-1,4- ((2-hydroxypropoxy) -2-propoxy) -butanesulfonic acid sodium salt (bis-1,4- ((2-hydroxyproxy) -2-proxy) -butane sulfonate sodium salt) manufactured by G N technology, and the model is GS-7Q.
In some embodiments, the sulfonate diol (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 components of the aqueous polyurethane dispersion. When the using amount of the sulfonate diol (D) is 3 to 15 weight percent, the prepared waterproof moisture-permeable coating and product have good 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 diol compound (E) having a polyethylene oxide group in a side chain is 400 g/mol to 3000 g/mol, and preferably 500 g/mol to 1500 g/mol.
In general, when polyethylene oxide is in the main chain, although Ethylene Oxide (EO) segment can be used as an excellent moisture channel to promote moisture permeability, since EO segment is highly hydrophilic, the water resistance of the resulting water-repellent moisture-permeable coating and product is significantly deteriorated with the increase of EO segment in the main chain. However, with respect to the diol compound (E) having a polyethylene oxide group in a side chain of the present invention, the polyethylene oxide group in a side chain does not affect the moisture permeability of the waterproof moisture-permeable coating layer and the product, and the water washing resistance of the waterproof moisture-permeable coating layer and the product can be improved.
Specific examples of the diol compound (E) having a polyethylene oxide group in a side chain may include, but are not limited to, a product manufactured by Perstorp 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 diol compound (E) having a polyethylene oxide group in a side chain 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 using amount of the diol compound (E) with the polyethylene oxide group on the side chain is 7 to 20 weight percent, the prepared waterproof moisture-permeable coating and product have good moisture permeability and washing resistance. When the diol compound (E) having a polyethylene oxide group in a side chain is used in an amount of more than 20% by weight, the water-washing resistance of the resulting water-repellent moisture-permeable coating and product will be significantly deteriorated. When the amount of the diol compound (E) having a polyethylene oxide group in a side chain is less than 7% by weight, the water-repellent moisture-permeable coating layer and the product obtained have poor moisture permeability.
In some embodiments, in the prepolymerization, the catalyst (G) can be used. The catalyst (G) includes, but is not limited to, organobismuth catalysts, organotin catalysts, organozinc catalysts, or the like. The catalyst may be, for example, bismuth methanesulfonate, dibutyltin dilaurate, ethyltin octoate, zinc oxalate or the like.
In some embodiments, after the prepolymerization, a neutralization step may optionally be performed. 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, potassium hydroxide or the like.
After the neutralization step, under the condition of high-speed stirring, adding a large quantity of water so as to make the polyurethane prepolymer produce self-emulsification action by means of the hydrophilicity of the above-mentioned sulfonate group and further disperse it in water 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, so that the mechanical property of the prepared waterproof moisture-permeable coating is improved, and the water washing resistance of the coating and the product is enhanced. Specific examples of the polyamine compound (F) may include, but are not limited to, ethylenediamine, hexamethylenediamine, 4-diphenylmethanediamine, hydroxyethylethylenediamine, di-n-butylamine and isophoronediamine or 2,2' -dimethylbis (p-aminocyclohexylamine) methane (2,2' -dimethyl 1-4,4' -methylene amine), 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 components of the aqueous polyurethane dispersion. When the polyamine compound (F) is used in an amount of 3 to 10% by weight, the obtained waterproof moisture-permeable coating and product have good wash-out resistance.
In the prepolymerization reaction of the invention, the formed polyurethane prepolymer still has hydroxyl groups, so when the coating composition containing the polyurethane prepolymer is coated and is further baked and cured, the hydroxyl groups in the polyurethane prepolymer can further react with a curing agent, thereby further improving the water washing resistance of the waterproof moisture-permeable coating and 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 tackifier. In other embodiments, the coating composition may further comprise a pigment and/or a biocide, and the like. The kinds and the usage amounts of the curing agent, the leveling agent, the defoaming agent, the tackifier, the pigment and the bactericide are not particularly limited, and may be those conventionally known to those skilled in the art of the present invention.
Specific examples of the curing agent 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 polydimethylsiloxanes. Specific examples of the defoaming agent include, but are not limited to, silicone-polyether copolymer type defoaming agents. Specific examples of the tackifier include, but are not limited to, urea-modified urethane. For example, the bridging agent may be a product manufactured by Lei-Dainig chemical company and having model number DN-950 or DN-980. The leveling agent may be a product manufactured by BYK chemical company and having a model number of BYK-333. The defoamer may be a BYK-093 product manufactured by Pico Chemicals, Inc. The tackifier may be a BYK-425 product manufactured by Pico chemical. The biocide may be a product manufactured by jiekang, uk, and having model number XL-2.
In some embodiments, the viscosity of the coating composition is adjusted to meet subsequent processing operations by controlling the amount of the adhesion promoter. For example, the viscosity is 20000 to 25000cps or 10000 to 15000 cps.
In some applications, the aforementioned coating compositions can be made into waterproof moisture-permeable coatings. The coating composition can be applied to a substrate by spraying, brushing, dipping, rolling or knife coating to form a waterproof moisture-permeable coating.
By means of the hydrophilic groups of the aqueous polyurethane dispersoid, the waterproof moisture-permeable coating can diffuse moisture exhausted by skin outwards so as to achieve the moisture-permeable effect. In the diffusion process, as the thickness of the waterproof moisture-permeable coating increases, the rate of diffusion decreases, resulting in a decrease in moisture permeability. In addition, the thickness of the waterproof moisture-permeable coating affects the processability of subsequent processes (e.g., cutting or seaming). In some embodiments, the thickness of the waterproof moisture-permeable coating may be 0.01mm to 0.03mm, and preferably 0.02 mm.
In some application examples, the waterproof moisture-permeable coating can be disposed on a substrate to produce a waterproof moisture-permeable product. In some embodiments, the substrate comprises fabric, leather, paper, and/or fibers. The fiber refers to a fiber which can be formed into a fabric after processing steps such as weaving or weaving. Specific examples of the fabric include, but are not limited to, fabrics of natural fibers and/or fabrics of artificial fibers, and the fabric may be, for example, wool fabric, cotton fabric, nylon fabric, or the like. The aforementioned leathers include, but are not limited to, natural leathers and/or synthetic leathers, and the leathers may be, for example, cow leathers, sheep leathers, polyvinyl chloride leathers, polyurethane leathers, and the like.
The following examples are provided to illustrate the present invention, but not to limit the invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention.
Synthesis of polyfunctional polyester polyol (C)
Production examples
161g of monopentaerythritol and 606g of phthalic anhydride were charged in a four-necked flask, 839g of glycidyl versatate were added dropwise at 150 ℃ and, after 5 hours of reaction, a polyfunctional polyester polyol (C) was obtained which had a number average molecular weight of about 1500 g/mol and a solids content of 98% by weight.
Production of aqueous polyurethane dispersions
Example 1
The amounts of the reaction components used are based on 100% by weight of the solid components of the aqueous polyurethane dispersion. 19.20 weight percent of a polyester diol (B1) (manufactured by Hakken materials industries, Inc., model number 5650-1000, and molecular weight 1000), 30.98 weight percent of a polyether diol (B2) (manufactured by Dakken chemicals industries, Inc., polytetramethylene ether glycol (PTMEG), model number 2000, and molecular weight about 2000) were added under nitrogen, 3.05 weight percent of polyfunctional polyester polyol (C), 5.20 weight percent of sulfonate diol (D) (manufactured by G N technology, model GS-7Q, and molecular weight of 420G/mol) and 13.31 weight percent of diol compound (E) having polyethylene oxide group at side chain (manufactured by Perstorp, model Ymer N120, and molecular weight of 1000G/mol) were mixed, heated to 120 ℃ and kept at 120 ℃ for 2 hours to remove water.
Subsequently, the temperature was reduced to 60 ℃ and polyisocyanate (A) (isophorone diisocyanate manufactured by Vanhua chemical Co., Ltd.) and one drop of catalyst (G) (dibutyltin dilaurate manufactured by Acon's practical Co., Ltd.) were added at 60 ℃. Then, the mixture was heated to 90 ℃ and held at 90 ℃ for 4 hours to conduct prepolymerization to produce a polyurethane prepolymer. Then, the temperature is reduced, and when the temperature is reduced to 60 ℃, 150 to 200 g of water is added to be dispersed in the water phase. The temperature was continuously decreased to 30 ℃ or lower, and 3 to 10 g of water and 5.82 wt% of a polyamine compound (F) (2,2' -dimethylbis (p-aminocyclohexylamine) methane, manufactured by Xiamenogrida chemical Co., Ltd.) were added to carry out a chain extension reaction. After 2 hours, the aqueous polyurethane dispersion of example 1 was obtained.
The aqueous polyurethane dispersion of example 1 was measured to have a solid content (n.v.) of 35 wt%, an R value (R-value) of 1.8, and a total solid content of 100 wt%, a soft segment content and a hard segment content of 72 wt% and 28 wt%, respectively, based on the aqueous polyurethane dispersion, by a detection method customary in the art to which the present invention pertains, wherein the R value was 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 carried out in the same manner as in example 1 except for the amounts of 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) used. Specific conditions for examples 2 to 8 and comparative examples 1 to 5 are shown in table 1.
Application example 1
Preparation of the coating composition
The coating compositions of the examples and comparative examples were prepared by uniformly mixing the aqueous polyurethane dispersions prepared in the examples and comparative examples with other compositions for adjusting coating properties.
Preparation of waterproof moisture-permeable coating and waterproof moisture-permeable product
100g of the aqueous polyurethane dispersions of the examples and comparative examples, 0.2g of a leveling agent (model No. BYK-333, manufactured by Bick chemical Co., Ltd.), and 0.3g of an antifoaming agent (model No. BYK-093, manufactured by Bick chemical Co., Ltd.) were separately added to a mixing tank and mixed uniformly. Then, 3g of cyclohexane diisocyanate (model No. DN-950, manufactured by Rizha chemical Co., Ltd.) was added thereto and mixed uniformly. Then, a tackifier (model number BYK-425, manufactured by BYK chemical) was added and the viscosity after mixing was measured to obtain an undercoat paint composition having a viscosity of 20000cps to 25000cps by controlling the amount of the tackifier used, and left to stand for 2 hours.
Next, the primer coating compositions of the examples and comparative examples were applied to Nylon cloth (70 d/160d Nylon, plain weave basis weight of 103 g/m) using a doctor blade2) Wherein the coating thickness is 0.02 m. Then, a heating step is performed. Firstly, useThe mixture was heated to 100 ℃ and held at 100 ℃ for 60 seconds to effect water removal. Then, the coating was heated to 150 ℃ for 60 seconds to perform a bridging reaction, and the primer waterproof moisture-permeable coating of each example and comparative example was formed.
Next, a topcoat coating composition is prepared. The preparation of the topcoat coating composition is in the same manner as the preparation of the basecoat coating 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 15000 cps. The top-coat coating composition was applied to the coating layer formed from the undercoating composition to form the top-coat waterproof moisture-permeable coating layers of each example and comparative example, wherein the coating thickness was 0.01 m.
The water-proof moisture-permeable coating of the top coating of each of the above examples and comparative examples is subjected to water removal and bridging reaction at the same temperature and time as the water-proof moisture-permeable coating of the bottom coating, so as to complete the preparation of the water-proof moisture-permeable products of each of the examples and comparative examples.
Evaluation method
Moisture permeability test
The moisture permeability of the waterproof moisture-permeable products of the foregoing examples and comparative examples was measured according to ASTM E-961995 BW standard test method, and the results thereof are shown in table 1.
Water resistance test
The water pressure resistance of the waterproof moisture-permeable products of the foregoing examples and comparative examples was measured in accordance with JIS L1092-.
Water wash resistance test
The waterproof moisture-permeable products prepared in the foregoing examples and comparative examples were washed with water and laundry detergent at 40 ℃ according to AATCC 135-2004(W0& W5) standard test method. After 5 times of washing, the water repellency of the waterproof moisture-permeable product was measured again in the above-described manner, and the change rate (d) of the water pressure resistance was calculated by the following formula (VI), and the results are shown in table 1.
In formula (VI), a represents a value of water pressure resistance before washing, and b represents a value of water pressure resistance after washing.
TABLE 1
Referring to table 1, the table shows the ratios of the reaction components of the aqueous polyurethane dispersions of the examples and comparative examples of the present invention, the detection of the aqueous polyurethane dispersions, and the evaluation results of the waterproof moisture-permeable products.
According to the evaluation results of each example and comparative example 1, the aqueous polyurethane dispersion obtained in comparative example 1 containing an excessive amount (used amount is 10.95 wt%) of the polyfunctional polyester polyol (C) gelled, and the coating composition of comparative example 1 was poor in workability and could not be uniformly applied to a substrate. In addition, according to the evaluation results of each example and comparative example 2, the waterproof moisture-permeable product of each example has better washing resistance than the waterproof moisture-permeable product obtained in comparative example 2 without using the polyfunctional polyester polyol (C).
According to the evaluation results of each example and comparative example 3, the waterproof moisture-permeable coating layer obtained in comparative example 3 in which the sulfonate diol (D) was not used could not be attached to the substrate. Therefore, the waterproof moisture-permeable products obtained in each example using the sulfonate diol (D) had good moisture permeability, water repellency, and water washing resistance, compared to the waterproof moisture-permeable product obtained in comparative example 3 not using the sulfonate diol (D).
According to the evaluation results of each example and comparative example 4, the moisture permeability of the waterproof moisture-permeable product obtained in comparative example 4 in which the diol compound (E) having a polyethylene oxide group in a side chain was not used was too low, and it was not applicable to the field of waterproof moisture permeability. Therefore, the waterproof moisture-permeable product obtained using each example having the polyoxyethylene-based diol compound (E) has good moisture permeability and washing resistance, compared to the waterproof moisture-permeable product obtained using comparative example 4 not having the polyoxyethylene-based diol compound (E).
In summary, by using the aqueous polyurethane dispersion, the coating composition containing the aqueous polyurethane dispersion, the waterproof moisture-permeable coating prepared from the coating composition, and the waterproof moisture-permeable product containing the waterproof moisture-permeable coating of the present invention, good moisture permeability, water resistance, and water washing resistance can be provided by controlling the specific usage amount of the multifunctional polyester polyol (C), the sulfonate diol (D), and the diol compound (E) having a polyethylene oxide group in a side chain.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. An aqueous polyurethane dispersion comprising structural units derived from:
a polyisocyanate (A);
a diol compound (B) comprising a polyester diol (B1) and/or a polyether diol (B2);
a polyfunctional polyester polyol (C); and
sulfonate diol (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 components of the aqueous polyurethane dispersion.
2. The aqueous polyurethane dispersion according to claim 1, wherein the polyisocyanate (a) is used in an amount of 10 to 70 weight percent, the diol compound (B) is used in an amount of 10 to 70 weight percent, and the sulfonate diol (D) is used in an amount of 3 to 15 weight percent, based on 100 weight percent of the solid content of the aqueous polyurethane dispersion.
3. The aqueous polyurethane dispersion according to claim 1, wherein the polyfunctional polyester polyol (C) has a structure represented by the following formula (I) or formula (II):
(R1)m-X-(R2)n (I)
in the formula (I), X represents a tetravalent organic group, and X is a carbon atom or a silicon atom; r1Is a methyl hydroxyl group or an ethyl group, and the carbon atom of the methyl hydroxyl group is bonded to X; r2Represents 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;
in said formula (II), with R1And R2The two bonded carbon atoms being quaternary carbon atoms, R1And R2As 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;
*-R21-R22 (III)
in said formula (III), "X" represents R21A position bonded to X or the quaternary carbon atom of the formula (II), R21Represents a structure represented by the following formula (III-1), formula (III-2) or formula (III-3), and R22Represents 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), "represents R21And R22The position of the bond, a is an integer of 0 to 4, R31Each independently represents methyl or ethyl; b is an integer of 0 to 4, R32Each independently represents methyl or ethyl; c is 0 to 2, R35Each independently represents methyl or ethyl, and R33And R34Each independently represents a hydrogen atom or a methyl group;
in the formulae (III-3-1) and (III-3-2),
represents R22And R21Position of a bond, and a plurality of R4Each independently represents an alkyl group having a carbon number of 1 to 5.
4. The aqueous polyurethane dispersion according to claim 3, wherein the polyfunctional polyester polyol (C) has a structure represented by the following formula (IV-1) or formula (IV-2):
in the formulae (IV-1) and (IV-2), a plurality of R4Is defined as in claim 2.
5. The aqueous polyurethane dispersion according to claim 1, further comprising structural units derived from a diol compound (E) having a polyethylene oxide group in a side chain.
6. The aqueous polyurethane dispersion according to claim 5, wherein 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 component of the aqueous polyurethane dispersion.
7. The aqueous polyurethane dispersion according to claim 1, further comprising structural units derived from a polyamine compound (F).
8. A coating composition comprising the aqueous polyurethane dispersion of any one of claims 1-7.
9. A waterproof moisture-permeable coating made using the coating composition of claim 8.
10. A waterproof, moisture permeable product comprising:
a substrate; and
the waterproof moisture-permeable coating of claim 9 disposed on the substrate.
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