CN118994531A - Waterborne polyurethane polyurea dispersion - Google Patents
Waterborne polyurethane polyurea dispersion Download PDFInfo
- Publication number
- CN118994531A CN118994531A CN202310572493.5A CN202310572493A CN118994531A CN 118994531 A CN118994531 A CN 118994531A CN 202310572493 A CN202310572493 A CN 202310572493A CN 118994531 A CN118994531 A CN 118994531A
- Authority
- CN
- China
- Prior art keywords
- aqueous polyurethane
- polyurethane polyurea
- polyurea dispersion
- weight
- component
- 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.)
- Pending
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- 229920002396 Polyurea Polymers 0.000 title claims abstract description 144
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 138
- 239000004814 polyurethane Substances 0.000 title claims abstract description 138
- 239000006185 dispersion Substances 0.000 title claims abstract description 119
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 61
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 61
- -1 silane compound Chemical class 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 229920005862 polyol Polymers 0.000 claims abstract description 30
- 150000003077 polyols Chemical class 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 229910000077 silane Inorganic materials 0.000 claims abstract description 28
- 239000000853 adhesive Substances 0.000 claims abstract description 22
- 230000001070 adhesive effect Effects 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000976 ink Substances 0.000 claims abstract description 13
- 150000002433 hydrophilic molecules Chemical class 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 34
- 125000001931 aliphatic group Chemical group 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229920000570 polyether Polymers 0.000 claims description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 22
- 125000003277 amino group Chemical group 0.000 claims description 21
- 238000012360 testing method Methods 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 10
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 8
- 239000000523 sample Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229920005906 polyester polyol Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 238000005227 gel permeation chromatography Methods 0.000 claims description 4
- 238000010998 test method Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000012470 diluted sample Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 238000011067 equilibration Methods 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 230000004580 weight loss Effects 0.000 claims description 3
- NNLRDVBAHRQMHK-UHFFFAOYSA-N 3-(2-aminoethylamino)propanoic acid Chemical compound NCCNCCC(O)=O NNLRDVBAHRQMHK-UHFFFAOYSA-N 0.000 claims description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- RWLDCNACDPTRMY-UHFFFAOYSA-N 3-triethoxysilyl-n-(3-triethoxysilylpropyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCCC[Si](OCC)(OCC)OCC RWLDCNACDPTRMY-UHFFFAOYSA-N 0.000 claims description 2
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 239000002318 adhesion promoter Substances 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 239000003899 bactericide agent Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000006224 matting agent Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 150000004072 triols Chemical class 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 150000001414 amino alcohols Chemical class 0.000 claims 1
- 201000006747 infectious mononucleosis Diseases 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 11
- 238000007639 printing Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 238000007789 sealing Methods 0.000 abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 93
- 239000012948 isocyanate Substances 0.000 description 28
- 150000002513 isocyanates Chemical class 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 229920000728 polyester Polymers 0.000 description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- VRRABDXZDGRGPC-UHFFFAOYSA-M sodium;2-(2-aminoethylamino)ethanesulfonate Chemical compound [Na+].NCCNCCS([O-])(=O)=O VRRABDXZDGRGPC-UHFFFAOYSA-M 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000003010 ionic group Chemical group 0.000 description 6
- 229920003009 polyurethane dispersion Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 108090000765 processed proteins & peptides Proteins 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 229940009098 aspartate Drugs 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 2
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 2
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- 150000004985 diamines Chemical group 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
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- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 description 1
- OAWJNGTVHKRBAT-UHFFFAOYSA-N 1,1-bis(isocyanatomethylsulfanyl)ethane Chemical compound O=C=NCSC(C)SCN=C=O OAWJNGTVHKRBAT-UHFFFAOYSA-N 0.000 description 1
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 description 1
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- LTKBJFRCZZYLJY-UHFFFAOYSA-N 1,2,3-tris(isocyanatomethylsulfanyl)propane Chemical compound O=C=NCSCC(SCN=C=O)CSCN=C=O LTKBJFRCZZYLJY-UHFFFAOYSA-N 0.000 description 1
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ZHWJTCDUSSCFOZ-UHFFFAOYSA-N isocyanato(isocyanatomethylsulfanylmethylsulfanyl)methane Chemical compound O=C=NCSCSCN=C=O ZHWJTCDUSSCFOZ-UHFFFAOYSA-N 0.000 description 1
- WQRXRVXLCHRFMC-UHFFFAOYSA-N isocyanato(sulfonyl)methane Chemical compound O=C=NC=S(=O)=O WQRXRVXLCHRFMC-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4236—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
-
- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/65—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/65—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to aqueous polyurethane-polyurea dispersions comprising polyurethane-polyureas, to a process for their preparation and to their use, in particular in the field of coatings, adhesives or inks, and to articles or articles obtained by coating, bonding, sealing or printing with the aqueous polyurethane-polyurea dispersions. The polyurethane polyurea of the aqueous polyurethane polyurea dispersion comprising the polyurethane polyurea is obtained by reacting a system comprising the following components: two polyisocyanates; a polymer; a polyol; a silane compound and a hydrophilic compound containing 2 to 3 isocyanate-reactive groups. The aqueous polyurethane polyurea dispersoid has good adhesiveness and hydrolysis resistance.
Description
Technical Field
The present invention relates to aqueous polyurethane polyurea dispersions, to a process for their preparation and their use, in particular in the field of coatings, adhesives or inks, and to articles or articles obtained by coating, bonding, sealing or printing with the aqueous polyurethane polyurea dispersions.
Background
The aqueous polyurethane polyurea dispersion can be widely applied to the fields of coating, adhesive, sealant and printing ink. Compared with the traditional solvent polyurethane, the polyurethane has the advantages of environmental protection, non-inflammability, explosive property, safe storage, high solid content and the like. However, the aqueous polyurethane-polyurea dispersion contains a hydrolyzable group, and is easily hydrolyzed when stored under ambient conditions, and the metal ions (e.g., metal ions introduced in a catalyst) present in the system promote hydrolysis of the hydrolyzable group on the aqueous polyurethane-polyurea dispersion, which results in a decrease in application properties, and is particularly effective in the fields of paint products, which affect adhesion, stain resistance, scratch resistance, impact resistance, elongation at break, water washing resistance, etc., and in the fields of sealants and adhesive products, which affect the application properties, heat resistance, hydrolysis resistance, etc., of sealants and adhesives.
The patent DE 19954500, DE 4410557 or EP 792908 et al propose to introduce carboxylate salts in polyurethane polyurea dispersions, which are obtained by adding dimethylolpropionic acid to the polyurethane polyurea, and then compounding with carbodiimide to improve the adhesion properties. The reactivity of the reactive carboxyl group with carbodiimide is low.
US5066705 describes the use of carboxyl-containing polymers, carboxyl-containing polyurethanes and polycarbodiimides for producing weather-resistant aqueous lacquers for plastic substrates.
CN 108250390B describes that by adding a non-sterically hindered difunctional silane and introducing a polyethoxy segment with a terminal as hydrophilic agent, a self-crosslinkable aqueous polyurethane dispersion is obtained.
CN 109081897A describes that by adding a non-sterically hindered difunctional, monofunctional silane, the introduction of a polyethoxy segment with a terminal as hydrophilic agent, a self-crosslinkable aqueous polyurethane dispersion is obtained.
EP 3026071 A1 describes a process for preparing aqueous polyurethane dispersions which are obtained from a mixture comprising at least one readily crystallizable polyester polyol and at least one polyether polyol, wherein the polyether polyol is a polyalkylene glycol homo-or copolymer containing ethylene oxide units.
WO 201635162 A1 describes a method for producing aqueous peptide-functionalized polyurethane dispersions (PUDs) useful as adhesives, in particular for metal surfaces, which are produced by reacting maleimide-terminated polyurethane prepolymers with one or more peptides. The amino acid side chain in the peptide and the maleimide group are subjected to coupling reaction, and the adsorption quality of the peptide on the surface of the substrate is improved by utilizing the adsorption characteristic of the peptide. The reaction mixture contains at least a polyether polyol, which may be a polyalkylene glycol homo-or copolymer, and a polyester polyol, which may be a crystalline/semi-crystalline polyol.
US 10640702 BB describes a method of making and using coated particles as proppants in hydraulic fracturing to optimize capital and equipment costs and improve production efficiency. The coated particles consist of substrate particles having a particle size of not more than 3 mesh and a coating comprising a crystalline or semi-crystalline polyester/polyurethane having a decrystallization temperature of at least 35 ℃ and modified with an aminosilane. The crystalline or semi-crystalline polyester/polyurethane may contain monofunctional or difunctional polyether polyols polymerized from ethylene oxide or copolymerized with ethylene oxide and propylene oxide.
Disclosure of Invention
The object of the present invention is to provide an aqueous polyurethane polyurea dispersion, a process for its preparation and its use, in particular in the field of coatings, adhesives or inks, and also to articles or articles obtained by coating, bonding, sealing or printing with the aqueous polyurethane polyurea dispersion.
The aqueous polyurethane polyurea dispersion according to the invention comprising polyurethane polyureas which are obtained by reacting a system comprising:
a. At least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, the weight ratio of the at least one aliphatic polyisocyanate and the at least one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, the weight ratio of the one aliphatic polyisocyanate and the one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1;
b. a polymer conforming to the structure of formula I:
Wherein n is 10-75, R 1 is alkyl containing 1-10 carbon atoms, R 2 is a structure containing at least two isocyanate-reactive groups;
c. a polyol different from component b), said polyol having a hydroxyl functionality of from 1.5 to 4;
d. A silane compound comprising an isocyanate reactive group and at least two methoxy and/or ethoxy groups attached to a silicon atom;
e. A hydrophilic compound different from polymer b) containing 2 to 3 isocyanate-reactive groups, the hydrophilic group of the hydrophilic compound comprising one or more of the following: one or more of ionic groups, potentially ionic groups, and nonionic groups; and
An optional f. compounds containing 1-3 amino groups and/or hydroxyl groups, preferably 1-3 amino groups.
According to one aspect of the present invention, there is provided a process for preparing an aqueous polyurethane polyurea dispersion comprising polyurethane polyurea according to the present invention, comprising the steps of: i. reacting component a) at least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, the weight ratio of the at least one aliphatic polyisocyanate and the at least one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, the weight ratio of the one aliphatic polyisocyanate and the one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1, component b) a polymer conforming to the structure of formula I and component c) some or all of a polyol different from component b) to obtain a prepolymer;
ii) reacting the prepolymer, component d) a silane compound, component e) a hydrophilic compound containing 2 to 3 isocyanate-reactive groups different from polymer b) and optionally component f) a compound containing 1 to 3 amino groups and/or hydroxyl groups, preferably 1 to 3 amino groups to obtain the polyurethane polyurea; and
Introducing water before, during or after step ii to obtain the aqueous polyurethane polyurea dispersion.
According to another aspect of the present invention there is provided a coating, adhesive or ink comprising an aqueous polyurethane polyurea dispersion comprising polyurethane polyurea according to the present invention.
According to a further aspect of the present invention there is provided the use of an aqueous polyurethane polyurea dispersion comprising polyurethane polyurea according to the present invention for the preparation of a coated, bonded or printed product.
According to a further aspect of the present invention there is provided an article or article comprising a substrate prepared, coated, bonded, sealed or printed with an aqueous polyurethane polyurea dispersion comprising polyurethane polyurea according to the present invention.
According to a further aspect of the present invention, there is provided a printing method comprising the steps of: the aqueous polyurethane-polyurea dispersion comprising polyurethane-polyurea provided according to the invention is printed onto a substrate surface and subsequently cured.
According to yet another aspect of the present invention, there is provided a printed product comprising a substrate and a coating formed by printing an aqueous polyurethane polyurea dispersion comprising polyurethane polyurea provided according to the present invention onto the substrate.
The aqueous polyurethane polyurea dispersion of the invention has good adhesion and hydrolysis resistance, is suitable for use as a coating, adhesive or ink, and is particularly suitable for use as a binder, especially a shoe polish.
Detailed Description
The present invention provides an aqueous polyurethane polyurea dispersion comprising polyurethane polyurea, which polyurethane polyurea is obtained by the reaction of a system comprising:
a. At least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, the weight ratio of the at least one aliphatic polyisocyanate and the at least one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, the weight ratio of the one aliphatic polyisocyanate and the one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1;
b. a polymer conforming to the structure of formula I:
Wherein n is 10-75, R 1 is alkyl containing 1-10 carbon atoms, R 2 is a structure containing at least two isocyanate-reactive groups;
c. a polyol different from component b), said polyol having a hydroxyl functionality of from 1.5 to 4;
d. A silane compound comprising an isocyanate reactive group and at least two methoxy and/or ethoxy groups attached to a silicon atom;
e. A hydrophilic compound different from polymer b) containing 2 to 3 isocyanate-reactive groups, the hydrophilic group of the hydrophilic compound comprising one or more of the following: one or more of ionic groups, potentially ionic groups, and nonionic groups; and
An optional f. compounds containing 1-3 amino groups and/or hydroxyl groups, preferably 1-3 amino groups.
The invention also provides a preparation method and application of the aqueous polyurethane polyurea dispersion, particularly application in the fields of paint, adhesives or printing ink, and an article or a product obtained by coating, bonding, sealing or printing by using the aqueous polyurethane polyurea dispersion.
The term "curing" as used herein refers to the process of a liquid substance from a liquid state to a cured state.
The term "coating" as used herein refers to a substance that can be applied to the surface of an article using different application processes to form a solid, continuous coating that adheres well, has a certain strength.
The term "adhesive" as used herein refers to a chemical substance that is capable of being applied to the surface of an article by a different application process, forming a coating on the surface of the article itself or one article with another, and bonding the article itself or one article with another article surface, and also serves as a synonym for adhesives and/or sealants and/or binders.
The term "polyurethane polyurea" as used herein refers to polyurethane and/or polyurethane urea and/or polyurea.
The term "aqueous polyurethane polyurea dispersion" as used herein refers to an aqueous polyurethane dispersion and/or an aqueous polyurethane urea dispersion and/or an aqueous polyurea dispersion.
The content of polyurethane polyurea in the aqueous polyurethane polyurea dispersion described herein is equivalent to the solid component content of the aqueous polyurethane polyurea dispersion.
The term "solid component" as used herein refers to a solid or an active component.
The term "isocyanate-reactive compound" as used herein refers to a component containing groups reactive towards isocyanate groups, i.e. a component containing Zerevitinov-active hydrogen, the definition of Zerevitinov-active hydrogen being given in Rompp' S CHEMICAL Dictionary (Rommp Chemie Lexikon), 10th ed., georg THIEME VERLAG Stuttgart,1996. Generally, zerevitinov-active hydrogen-containing groups are understood in the art to mean hydroxyl (OH), amino (NH x) and thiol (SH).
The term "isocyanate-reactive group" as used herein refers to a group which is reactive towards isocyanate groups, i.e.a group containing Zerevitinov-active hydrogen, zerevitinov-active hydrogen being defined by reference Rompp' S CHEMICAL Dictionary (Rommp Chemie Lexikon), 10th ed., georg THIEME VERLAG Stuttgart,1996. Generally, zerevitinov-active hydrogen containing groups are understood in the art to mean hydroxyl (OH), amino (NHx) and thiol (SH).
Aqueous polyurethane polyurea dispersions
The amount of organic solvent in the aqueous polyurethane polyurea dispersion is preferably less than 1% by weight relative to the total weight of the aqueous polyurethane polyurea dispersion.
The aqueous polyurethane polyurea dispersion preferably has a solids content of 15% to 70% by weight, most preferably 30% to 60% by weight, relative to the total weight of the aqueous polyurethane polyurea dispersion, using an HS153 moisture meter from Mettler Toledo company according to DIN-EN ISO 3251:2019 is performed at a heating temperature of 120 ℃ and the test endpoint is determined when the sample weight loss is less than 1mg/140 seconds.
The aqueous polyurethane polyurea dispersion has a pH in the range from 4 to 11, preferably in the range from 5 to 9, most preferably in the range from 6.0 to 7.5, according to DIN ISO 976:2016-12 was measured at 23℃using a PB-10pH meter from Sartorius Corp.
The aqueous polyurethane polyurea dispersions preferably have an average particle diameter of from 20nm to 750nm, more preferably from 50nm to 450nm, most preferably from 100nm to 250nm, as determined by laser correlation (laser particle sizer) according to the ZEN 1600 tester from Malvern, UK, according to ISO 13321:1996 test method 1 drop (about 0.05 g) of sample was added to 50ml of ultrapure water, and the diluted sample was tested at 23.0.+ -. 0.1 ℃; materials: polystyrene latex (RI: 1.590; absorptivity: 0.010), dispersant: water (temperature: 23.0 ℃ C.; viscosity: 0.9308cP; RI: 0.330), equilibration time: 60 seconds, using disposable cuvette DTS0012, positioning method: automatic attenuation selection, finding the best position: the analytical model is: universal (normal resolution), measurement angle: 173 ° backscatter (NIBS default), run times: 3 times, run duration: 10 seconds, number of measurements: 10 times.
The viscosity of the aqueous polyurethane polyurea dispersion is preferably in the range of 30 mPa-s to 3500 mPa-s, more preferably in the range of 1000 mPa-s to 3500 mPa-s, according to the use of a DV-ii+pro. Rotational viscometer from Brookfield company according to ISO 2555:2018 measured at 23 ℃, rotor type: s 62-64, rotating speed: 30RPM, test temperature: 23 ℃.
Component a) polyisocyanates
The polyisocyanate preferably has an isocyanate functionality of not less than 2, more preferably from 2 to 4, most preferably 2.
The component a) comprises at least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, the weight ratio of the at least one aliphatic polyisocyanate to the at least one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, the weight ratio of the one aliphatic polyisocyanate to the one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1, preferably a mixture of hexamethylene diisocyanate and isophorone diisocyanate.
The weight ratio of the aliphatic polyisocyanate to the alicyclic polyisocyanate is preferably 10:1 to 20:1.
The aliphatic polyisocyanate is preferably one or more of the following: hexamethylene diisocyanate, 1, 5-pentanediisocyanate, 2-dimethylpentanediisocyanate, 2, 4-trimethylhexamethylene diisocyanate, butene diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, 2, 4-trimethyl 1, 6-hexamethylene diisocyanate, 1,6, 11-undecyltriacrylate, 1,3, 6-hexamethylene triisocyanate, 1, 8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanatoethylyl) carbonate, bis (isocyanatoethylyl) ether, lysine methyldiisocyanate, lysine triisocyanate, bis (isocyanatomethylyl) sulfide, bis (isocyanatoethylyl) sulfide, bis (isocyanatopropylsulfide, bis (isocyanatohexylyl) sulfide, bis (isocyanatomethylyl) sulfone, bis (isocyanatomethylyl) disulfide, bis (isocyanatoethyldisulfide, bis (isocyanatopropyldisulfide), bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1, 5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2, 3-tris (isocyanatomethylthio) propane, 1,2, 3-tris (isocyanatoethylthio) propane, 3, 5-dithia-1, 2,6, 7-heptane tetraisocyanate, 2, 6-methyl diisocyanate-3, 5-dithia-1, 7-heptane diisocyanate, 2, 5-diisocyanate methylthiophene and isocyanatoethylthio-2, 6-dithia-1, 8-octane diisocyanate; most preferred is hexamethylene diisocyanate.
The cycloaliphatic polyisocyanate is preferably one or more of the following: 2, 5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, 2, 6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 4-dicyclohexylmethane diisocyanate, 2, 5-diisocyanato-1, 4-dithiane, 4, 5-diisocyanato-1, 3-dithiolane, 4, 5-bis (isocyanatomethyl) -1, 3-dithiolane, 4, 5-diisocyanato-2-methyl-1, 3-dithiolane, norbornane diisocyanate (NBPPDI), hydrogenated xylylene diisocyanate (H 6 XDI) and 1, 4-cyclohexyldiisocyanate (H 6 I); and most preferably isophorone diisocyanate.
The aliphatic polyisocyanate and the alicyclic polyisocyanate are most preferably hexamethylene diisocyanate and isophorone diisocyanate.
The weight ratio of hexamethylene diisocyanate to isophorone diisocyanate is preferably 10:1 to 20:1.
The amount of component a) is preferably 9% to 18% by weight, most preferably 10% to 12% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
Component b) polymers of formula I
N of formula I is 10-75, which may or may not be an integer, preferably 10-40, more preferably 10-30.
The at least two isocyanate-reactive groups are preferably selected from at least two amino groups, at least two hydroxyl groups or at least one amino group and at least one hydroxyl group.
When the polymer of component b) having the structure of formula I comprises three or more isocyanate-reactive groups, the isocyanate-reactive groups may be two amino groups and one or more amino or other isocyanate-reactive groups, may be two hydroxyl groups and one or more hydroxyl or other isocyanate-reactive groups, and may be one amino group, one hydroxyl group and one or more amino, hydroxyl or other isocyanate-reactive groups.
The polymer conforming to the structure of formula I most preferably one or more of the following: a polymer conforming to the structure of formula II and a polymer conforming to the structure of formula III,
Wherein a in formula II is 10-75, a may be an integer or not, b is 0-50, and b may be an integer or not; in formula III, x is 10-75, x may be an integer or not, y is 1-50, and y may be an integer or not.
The number average molecular weight of the polymer of component b) which corresponds to the structure of formula I is preferably 500g/mol to 4000g/mol, most preferably 600g/mol to 1500g/mol, the number average molecular weight being measured according to gel permeation chromatography using tetrahydrofuran as mobile phase and calculating the molecular weight based on polystyrene as standard, the component having a molecular weight of 200 or more being selected for calculation and measured by means of a differential refractive detector (RI detector).
The functionality of the polymers of component b) which correspond to the structure of formula I is preferably 2.
The amount of the polymer of component b) which corresponds to the structure of the formula I is preferably from 0.9% by weight to 4% by weight, most preferably from 1% by weight to 2% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
Component c) a polyol different from component b)
The polyol different from component b) is preferably one or more of the following: diols having a number average molecular weight of 62 to 15000 and polyols having a number average molecular weight of 62 to 15000, more preferably one or more of the following: diols having a number average molecular weight of 62 to 5000 and triols having a number average molecular weight of 92 to 5000, most preferably one or more of the following: a polyester polyol having 2 to 3 hydroxyl groups and a number average molecular weight of 500 to 2500, a polycarbonate polyol having 2 to 3 hydroxyl groups and a number average molecular weight of 400 to 2500, a polyether polyol having 2 to 3 hydroxyl groups and a number average molecular weight of 200 to 2500, a polylactone polyol having 2 to 3 hydroxyl groups and a small molecular alcohol, the number average molecular weight being measured by gel permeation chromatography, using tetrahydrofuran as a mobile phase, and calculating a molecular weight based on polystyrene as a standard, selecting a component having a molecular weight of 200 or more for calculation, and measuring by a differential refractive detector (RI detector).
The polyether polyol having a number average molecular weight of 200 to 2500 and having 2 to 3 hydroxyl groups is preferably polytetrahydrofuran polyol having a number average molecular weight of 200 to 2500 and having 2 to 3 hydroxyl groups.
The melting enthalpy of the polyols different from component b) is preferably not less than 15J/g, most preferably from 25J/g to 100J/g, obtained by the first temperature increase profile from 20℃to 100℃by DSC according to DIN65467, with a loading of from 10 to 20 mg and a heating rate of 20K/min.
The amount of component c) is preferably from 5% to 94% by weight, most preferably from 70% to 90% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
Component d) silane compound
The silane compound comprises one isocyanate reactive group and at least two methoxy groups attached to a silicon atom; or the silane comprises one isocyanate reactive group and at least two ethoxy groups attached to a silicon atom; or the silane comprises an isocyanate reactive group and at least one methoxy group attached to a silicon atom and one ethoxy group attached to a silicon atom.
The silane compound most preferably comprises only one isocyanate reactive group and at least two methoxy and/or ethoxy groups attached to the silicon atom.
The silane compound of component d) is preferably one or more of the following: bis (3-triethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) amine, (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, 3-aminopropyl (diethoxy) methylsilane and 3-aminopropyl methyldimethoxysilane, most preferably one or more of the following: (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane and 3-aminopropyl methyldimethoxysilane.
In addition, the corresponding aspartate (formula IV) which can be synthesized from the above-described amino-functional silane and an ester of an unsaturated dicarboxylic acid such as maleic acid can be used.
Wherein X is the same or different and is methoxy, ethoxy, methyl or ethyl, provided that at least two groups are methoxy and/or ethoxy; wherein Q is alkyl, preferably n-propyl, and Z is alkoxy, preferably methoxy or ethoxy.
Further preferred compounds are diethyl N- (3-triethoxysilylpropyl) aspartate, diethyl N- (3-trimethoxysilylpropyl) aspartyl and propyl N- (3-dimethoxymethylsilylpropyl) aspartate.
The amount of the silane compound of component d) is preferably from 0.12% to 0.7% by weight, most preferably from 0.18% to 0.4% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
Component e) hydrophilic compounds containing 2 to 3 isocyanate-reactive groups
The hydrophilic group of the hydrophilic compound preferably comprises one or more of the following: ionic groups, potentially ionic groups, and nonionic groups.
The hydrophilic compounds of component e) containing 2 to 3 isocyanate-reactive groups are preferably one or more of the following: n- (2-aminoethyl) -2-aminoethane sulfonate, dimethylol propionate and (N- (2-aminoethyl) -2-aminoethane carboxylate.
The amount of component e) is preferably from 0.2% to 50% by weight, most preferably from 1% to 5% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
Component f) compounds containing 1 to 3 amino groups and/or hydroxyl groups, preferably 1 to 3 amino groups
The compounds of component f) containing 1 to 3 amino groups and/or hydroxyl groups preferably contain at least one amino group; further preferred are one or more of the following: aliphatic monoamines, cycloaliphatic monoamines, aliphatic primary and/or secondary diamines, aliphatic primary and/or secondary triamines, aliphatic primary and/or secondary amino alcohols, cycloaliphatic primary and/or secondary diamines, cycloaliphatic primary and/or secondary triamines, cycloaliphatic primary and/or secondary amino alcohols; most preferably one or more of the following: isophorone diamine, N- (2-hydroxyethyl) ethylene diamine, and diethanolamine.
The amount of component f) is preferably not more than 10% by weight, most preferably from 0.5% to 3% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
Method for producing aqueous polyurethane-polyurea dispersions containing polyurethane-polyurea
The preparation process may further comprise a step iv. Introducing a water-miscible but inert to isocyanate groups during or after step i, and removing the organic solvent from the aqueous polyurethane polyurea dispersion.
The organic solvent is preferably a solvent miscible with water but inert to isocyanate groups, further preferably one or more of the following: acetone, butanone, propylene glycol dimethyl ether, other ethers and esters that do not contain hydroxyl functionality; most preferably one or more of the following: acetone and butanone.
The organic solvent preferably does not contain an N-methyl or N-ethyl pyrrolidone compound.
The organic solvent is preferably removed partially or completely by distillation, preferably at a temperature of from 10 ℃ to 100 ℃ and for a time of from 1 hour to 12 hours.
The distillation temperature is most preferably from 25℃to 60 ℃.
The distillation time is most preferably 2 hours to 7 hours.
The rectification pressure is preferably from 500mbar to 50mbar, most preferably from 200mbar to 60mbar.
The amount of residual organic solvent in the aqueous polyurethane polyurea dispersion is preferably less than 1.0% by weight relative to the total weight of the aqueous polyurethane polyurea dispersion.
In order to accelerate the reaction rate of step i, catalysts customary in prepolymer preparation can be used, for example triethylamine, 1, 4-diazabicyclo- [2, 2] -octane, sebacic acid or bismuth neodecanoate, tin dioctanoate, tin (II) chloride or dibutyltin dilaurate, most preferably tin (II) chloride and bismuth neodecanoate.
The catalyst may be placed in the reactor simultaneously with the components of step i or may be added later.
The degree of conversion of the components of step i can be obtained by testing the NCO content of the components. To this end, spectroscopic measurements, such as infrared or near-infrared spectra, and refractive index measurements or chemical analyses, such as titration, may be performed simultaneously on the extracted sample.
The prepolymer may be in a solid state or a liquid state at ordinary temperature.
The degree of neutralization of the prepolymer may be 50mol% to 125mol%, preferably 65mol% to 105mol%.
Coatings, adhesives or inks
The coating, adhesive or ink preferably further comprises an additive. The additive is preferably one or more of the following: emulsifiers, light stabilizers, antioxidants, bactericides, fillers, antisettling agents, defoamers, wetting agents, flow regulators, reactive diluents, plasticizers, neutralizing agents, catalysts, auxiliary solvents, thickeners, pigments, dyes, matting agents and adhesion promoters. The additives may be added during and/or after the production of the polyurethane polyurea dispersion.
The additive selection and use metering are in principle known to the person skilled in the art and are readily determinable.
The aqueous polyurethane polyurea dispersions of the invention can also be mixed with and used with other aqueous or solvent-containing oligomers or polymers, for example aqueous or solvent-containing polyesters, polyurethanes, polyurethane-polyacrylates, polyethers, polyester-polyacrylates, alkyd resins, addition polymers, polyamide/imides or polyepoxides. The compatibility of such mixtures must be tested in each case using simple preliminary tests.
The aqueous polyurethane polyurea dispersions of the invention can also be mixed together and used together with other compounds containing functional groups, such as carboxyl groups, hydroxyl groups and/or blocked isocyanate groups.
The coatings, binders or inks according to the invention are processed according to methods known to the person skilled in the art.
Coated, bonded or printed products
The substrate is preferably one or more of the following: wood, metal, glass, fiber, textile, imitation leather, paper, plastic, rubber, foam, ceramic, and various polymer coatings, most preferably one or more of the following: textiles, plastics, ceramics, metals, dermis, artificial leather and various polymer coatings.
The coating may be a coating of the coating, binder or ink onto the entire surface of the substrate or onto only one or more portions of the surface of the substrate.
The coating may be brushing, dipping, spraying, rolling, knife coating, flow coating, pouring or printing.
Drawings
The invention is described and explained in more detail below with reference to the attached drawing figures, wherein:
fig. 1 is a schematic diagram of spline bonding.
FIG. 2 is a schematic illustration of a spline hydrolysis resistance test.
Fig. 3 is a schematic view of a sample adhesion test, fig. 3a is a schematic view of coating, and fig. 3b is a schematic view of doubling up and attaching a substrate.
Examples
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that the definitions of terms in this specification are inconsistent with the ordinary understanding of those skilled in the art to which this invention pertains, the definitions described herein control.
Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties to be obtained.
As used herein, "and/or" means one or all of the elements mentioned.
The use of "including" and "comprising" herein encompasses both the situation in which only the elements are mentioned and the situation in which other elements not mentioned are present in addition to the elements mentioned.
As used in this specification, the terms "a," "an," "the," and "the" are intended to include "at least one" or "one or more," unless otherwise specified. For example, "a component" refers to one or more components, and thus more than one component may be considered and possibly employed or used in the practice of the embodiments.
All percentages in the present invention are by weight unless otherwise indicated.
Analytical measurements according to the invention were carried out at 23.+ -. 2 ℃ unless otherwise indicated.
Method for testing the solids content (solids content) of dispersions of aqueous polyurethane polyureas: the HS153 moisture meter from Mettler Toledo was used in accordance with DIN-EN ISO 3251:2019 is performed at a heating temperature of 120 ℃ and the test endpoint is determined when the sample weight loss is less than 1mg/140 seconds.
The average particle diameter of the aqueous polyurethane polyurea dispersion is measured by the following method: measured by laser correlation (laser particle sizer) using the ZEN 1600 tester from Malvern, uk, according to ISO 13321:1996 test method 1 drop (about 0.05 g) of sample was added to 50ml of ultrapure water, and the diluted sample was tested at 23.0.+ -. 0.1 ℃; materials: polystyrene latex (RI: 1.590; absorptivity: 0.010), dispersant: water (temperature: 23.0 ℃ C.; viscosity: 0.9308cP; RI: 0.330), equilibration time: 60 seconds, using disposable cuvette DTS0012, positioning method: automatic attenuation selection, finding the best position: the analytical model is: universal (normal resolution), measurement angle: 173 ° backscatter (NIBS default), run times: 3 times, run duration: 10 seconds, number of measurements: 10 times.
The method for testing the pH value of the aqueous polyurethane polyurea dispersion comprises the following steps: according to DIN ISO 976:2016-12 was measured at 23℃using a PB-10pH meter from Sartorius Corp.
The viscosity test method of the aqueous polyurethane polyurea dispersion comprises the following steps: using a DV-ii+pro. Rotational viscometer from Brookfield, according to ISO 2555:2018 measured at 23 ℃, rotor type: s 62-64, rotating speed: 30RPM, test temperature: 23 ℃.
Isocyanate group (NCO) content according to DIN-EN ISO 11909:2007 by volume.
Raw materials and reagents
Polyester I: based on the semi-crystalline forms of adipic acid and 1, 4-butanediol, the difunctional polyester polyol has a number average molecular weight Mn 2250g/mol, a hydroxyl number of 50mg KOH/g, a glass transition temperature of-61℃and a melting temperature of 49℃and a melting enthalpy of 80J/g.
Polyester II: difunctional polyester polyol based on adipic acid, 1, 6-hexanediol and neopentyl glycol (molar ratio of 1, 6-hexanediol to neopentyl glycol of 3:2), number average molecular weight Mn1700g/mol, hydroxyl number 66mg KOH/g, glass transition temperature-63 ℃, melting temperature 26 ℃, melting enthalpy 55J/g.
Polyether I: ymer N120,120, a difunctional polyether containing pendant methoxy polyethylene oxide chains, having a number average molecular weight of 1000g/mol, obtainable from Perstorp Chemitec AB (SE).
Polyether II: ymer N90A difunctional polyether containing pendant methoxy polyethylene oxide chains with a number average molecular weight of 1200g/mol is commercially available from Perstorp Chemitec AB (SE).
Polyether III: MPEG750, monofunctional polyethoxy ether, number average molecular weight 750g/mol, available from Shanghai Dong chemical Co., ltd.
Isocyanate I: H, hexamethylene diisocyanate, available from Kogyo Co., ltd.
Isocyanate II: isophorone diisocyanate is available from Cork, inc., germany.
Silane I: PC1110, 3-aminopropyl trimethoxysilane, commercially available from sisbo silicone.
Silane II: PC1100, 3-aminopropyl triethoxysilane, commercially available from sisbo silicone.
Silane III: PC1200, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, is commercially available from sisbo silicone.
Lucramul 1820 and liquid: emulsifiers, fatty alcohol poly (ethylene glycol/propylene glycol) ethers, supplied as 15% -20% aqueous solutions, are commercially available from Levaco GmbH, germany.
Sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid: VESTAMIN A95A concentration of 49% in water, commercially available from Yingzhang, germany.
Diethanolamine: analytical grade specifications are available from national pharmaceutical systems and chemical reagents, inc.
Hydroxyethyl ethylenediamine: analytical grade specifications are available from national pharmaceutical systems and chemical reagents, inc.
Isophorone diamine: analytical grade specifications are available from national pharmaceutical systems and chemical reagents, inc.
Borchigel Gel L75N: thickeners, clear liquids, 25% strength, are available from Borchers.
Preparation of aqueous polyurethane polyurea dispersions
The weight of the raw materials in the following examples is the weight comprising water if they are aqueous emulsions or aqueous solutions.
Aqueous polyurethane polyurea dispersion 1
510.82G of polyester I,20.32g of polyester II and 6.27g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and, while stirring, cooled. 64.16g of isocyanate I and 3.56g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.7% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. A solution of 14.02g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.03g of diethanolamine, 3.38g of hydroxyethylethylenediamine in 51.57g of water and a solution of 1.26g of silane I in 12.6g of acetone were added to the acetone solution in which the prepolymer was dissolved, respectively, while stirring vigorously. The mixture was stirred for 30min and then dispersed by adding 560g of water. Acetone was separated by distillation for a further 5 hours, after which the acetone content was less than 1.0% by weight, and 40g Lucramul 1820 liquid was added again, to obtain an aqueous polyurethane polyurea dispersion having a solids content of 50.5% by weight and an average particle diameter of 135nm in the dispersed phase, a pH value of 6.8 and a viscosity of 2567 mPa.s.
Aqueous polyurethane polyurea dispersion 2
542.81G of polyester I and 7.5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and cooled while stirring. 59.49g of isocyanate I and 3.77g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.47g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.21g isophoronediamine, 2.30g hydroxyethylethylenediamine in 50g water and 1.26g silane II in 12.6g acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated off again by distillation for 4.5 hours, after which the ketone content was less than 1.0% by weight, and 40g Lucramu1 1820 liquid was added again, to obtain an aqueous polyurethane polyurea dispersion having a solids content of 50.5% by weight and an average particle diameter of 166nm in the dispersed phase, a pH value of 6.8 and a viscosity of 1692 mPa.s.
Aqueous polyurethane polyurea dispersion 3
531.56G of polyester I and 12.5g of polyether II are dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol are added and, while stirring, cooled. 69.17g of isocyanate I and 5.83g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 2.2% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 14.98g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 5.23g isophoronediamine, a solution of 3.1g hydroxyethyl ethylenediamine in 50g water and a solution of 1.26g silane I in 12.6g acetone were added separately to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 580g of water. Acetone was separated by distillation for 5 hours, and after having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid was added to obtain an aqueous polyurethane polyurea dispersion having a solids content of 49.2% by weight and an average particle diameter of 210nm in the dispersed phase, a pH of 6.8 and a viscosity of 3012 mPas.
Comparative aqueous polyurethane polyurea Dispersion 1
542.81G of polyester I and 7.5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and cooled while stirring. 62.35g of isocyanate I are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.47g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.21g isophoronediamine, 2.30g hydroxyethylethylenediamine in 50g water and 1.26g silane I in 12.6g acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated by distillation for a further 4 hours, after which the acetone content was less than 1.0% by weight, and 40g Lucramul 1820 liquid was added again, to obtain an aqueous polyurethane polyurea dispersion having a solids content of 49.8% by weight and an average particle diameter of 170nm in the disperse phase, a pH value of 7.0 and a viscosity of 1680 mPas.
Comparative aqueous polyurethane polyurea Dispersion 2
542.81G of polyester I and 7.5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and cooled while stirring. 53.82g of isocyanate I and 10.69g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.47g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.21g isophoronediamine, 2.30g hydroxyethylethylenediamine in 50g water and 1.26g silane I in 12.6g acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated by distillation for 5 hours, and after having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid was added to obtain an aqueous polyurethane polyurea dispersion having a solids content of 50.2% by weight and an average particle diameter of 148nm in the dispersed phase, a pH of 6.6 and a viscosity of 2347 mPas.
Comparative aqueous polyurethane polyurea Dispersion 3
542.81G of polyester I and 7.5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and cooled while stirring. 44.02g of isocyanate I and 24.21g of isocyanate II were added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% was reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.47g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.21g isophoronediamine, 2.30g hydroxyethylethylenediamine in 50g water and 1.26g silane I in 12.6g acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated by distillation for 4 hours, and after having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid was added to obtain an aqueous polyurethane polyurea dispersion having a solids content of 50.7% by weight and an average particle diameter of 204nm in the dispersed phase, a pH of 6.8 and a viscosity of 1472 mPas.
Comparative aqueous polyurethane polyurea Dispersion 4
542.81G of polyester I and 7.5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and cooled while stirring. 67.30g of isocyanate I and 8.1g of isocyanate II were added at 60℃and stirred at 80-90℃until an isocyanate content of 2.2% was reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 14.98g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 5.23g isophoronediamine, a solution of 3.1g hydroxyethyl ethylenediamine in 50g water and a solution of 1.26g silane I in 12.6g acetone were added separately to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 580g of water. Acetone was separated by distillation for 5 hours, and after having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid was added to obtain an aqueous polyurethane polyurea dispersion having a solids content of 50.0% by weight and an average particle diameter of 159nm in the dispersed phase, a pH of 6.7 and a viscosity of 2612 mPas.
Comparative aqueous polyurethane polyurea Dispersion 5
548.4G of polyester I and 5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and, while stirring, cooled. 59.49g of isocyanate I and 3.77g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.47g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.87g of hydroxyethylethylene diamine, 1.26g of diethanolamine in 50g of water and 1.26g of silane III in 12.6g of acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated off again by distillation for 4 hours, after which the acetone content was less than 1.0% by weight, and 40g Lucramul 1820 liquid was added again, to obtain an aqueous polyurethane polyurea dispersion having a solids content of 49.7% by weight and an average particle diameter of 152nm in the disperse phase, a pH value of 6.9 and a viscosity of 1392mPas.
Comparative aqueous polyurethane polyurea Dispersion 6
542.8G of polyester I and 12.6g of polyether III were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and cooled while stirring. 59.49g of isocyanate I and 3.77g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.47g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, a solution of 2.81g of hydroxyethylethylene diamine in 50g of water and a solution of 1.26g of silane I in 12.6g of acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated off again by distillation for 6 hours, after which the acetone content was less than 1.0% by weight, and 40g Lucramul 1820 liquid was added again, giving an aqueous polyurethane polyurea dispersion having a solids content of 50.5% by weight and an average particle diameter of 134nm in the disperse phase, a pH value of 6.7 and a viscosity of 5403mPas.
Method for preparing the adhesive of examples and comparative examples
According to the components shown in Table 1, 0.7g BorchiL Gel L75N was added to 100g of an aqueous polyurethane polyurea dispersion (the aqueous polyurethane polyurea dispersion was allowed to stand and age for 7 days at room temperature in advance) while stirring at 600rpm, and further stirred at 1200rpm for 10 minutes to 15 minutes to be sufficiently and uniformly mixed, and the viscosity was adjusted to 5000 mPas to 10000 mPas for use.
Hydrolysis resistance test
The base materials 1 (black rubber) and 2 (black rubber) with the length of 120mm and the width of 20mm are mechanically polished, then a rubber treatment agent (the rubber treatment agent obtained by dissolving trichloroisocyanuric acid (B powder) in ethyl acetate) is coated, after drying, the adhesive is brushed on the base materials 1 and 2 by using a brush, and the brushing area is 100mm x 20mm. The adhesive was dried and heat activated by heating substrate 1 and substrate 2 at 60 ℃ for 3 minutes, and then substrate 1 and substrate 2 were attached at a pressure of 4bar for 10 seconds, resulting in a test bar as shown in fig. 1. After storing the test bars at room temperature (22.+ -. 2 ℃ C., 50.+ -. 5% RH) for 72 hours, 1kg weight was loaded on one end of the substrate, as shown in FIG. 2, and the test bars were placed in an oven at 70 ℃ C., 95% humidity for the time required for complete detachment of the test bars. The test bars were qualified with a time greater than 8 hours required to completely disengage.
Adhesion test
As shown in FIG. 3a, a black rubber having a length of 60mm and a width of 20mm was mechanically polished, and then a rubber treating agent (a rubber treating agent obtained by dissolving trichloroisocyanuric acid (B powder) in ethyl acetate) was applied thereto, and after drying, a brush was used to brush an adhesive containing the present invention at both ends of the substrate at a length of 25mm and a width of 20 mm. The test substrate was heated at 60 ℃ for 3 minutes, the adhesive was dried and heat activated and removed, and the substrates were manually folded in half and attached at room temperature (22±2 ℃,50±5%rh) for 0 minutes, 2 minutes, 4 minutes, 6 minutes, 8 minutes and 10 minutes, respectively (fig. 3 b). The speed of spline detachment and distance of detachment were recorded and the test was scored 1-5. The score of 5 is the best, the score of 1 is the worst, and the score of 4 and more than 4 are qualified. If the base material is sprung from both ends within 5 seconds after attaching (or is not attached at all), the base material can be kept to be sprung from both ends for more than 5 seconds and less than 120 seconds after attaching, the base material is sprung from both ends for 2 minutes, if the base material is not sprung from both ends after attaching for not less than 120 seconds, the glue-opening distance is 16mm-25mm, the base material is 3 minutes, if the base material is not sprung from both ends after attaching for not less than 120 seconds, the glue-opening distance is not less than 6mm but less than 16mm, the base material is 4 minutes, and if the base material is not totally sprung from both ends after attaching for not less than 120 seconds or the glue-opening distance is less than 6mm, the base material is5 minutes.
Table 1 shows the results of evaluation of the adhesiveness and hydrolysis resistance of the adhesives of examples 1 to 3 of the present invention and comparative examples 1 to 6.
TABLE 1 evaluation of the binders of examples 1-3 and comparative examples 1-6
Remarks: the amount of aqueous polyurethane polyurea dispersions of both examples and comparative examples in table 1 was 100 grams.
The aqueous polyurethane polyurea dispersions of the examples of the present application have good adhesion and hydrolysis resistance.
Comparative example 2 and comparative example 1, when the system for preparing the aqueous polyurethane polyurea dispersion contains only one polyisocyanate hexamethylene diisocyanate, the aqueous polyurethane polyurea dispersion has poor adhesion.
From comparative examples 2 to 4, it is understood that when the system for preparing the aqueous polyurethane polyurea dispersion contains the aliphatic polyisocyanate and the alicyclic polyisocyanate in a weight ratio of less than 10:1, the aqueous polyurethane polyurea dispersion cannot achieve both of the adhesiveness and the hydrolysis resistance.
As is clear from comparative example 5, when the system for preparing the aqueous polyurethane polyurea dispersion contains a silane compound having two isocyanate-reactive groups, the aqueous polyurethane polyurea dispersion is poor in hydrolysis resistance without the silane compound having one isocyanate-reactive group.
From comparative example 6, it is clear that when the system for preparing the aqueous polyurethane polyurea dispersion comprises a polyether polyol having one isocyanate-reactive group, the aqueous polyurethane polyurea dispersion has poor hydrolysis resistance without the polymer conforming to the structure of formula I.
It will be evident to those skilled in the art that the invention is not limited to the precise details set forth, and that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description; and therefore any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (26)
1. An aqueous polyurethane polyurea dispersion comprising polyurethane polyurea, the polyurethane polyurea resulting from a system reaction comprising:
a. At least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, the weight ratio of the at least one aliphatic polyisocyanate and the at least one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, the weight ratio of the one aliphatic polyisocyanate and the one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1;
b. a polymer conforming to the structure of formula I:
Wherein n is 10-75, R 1 is alkyl containing 1-10 carbon atoms, R 2 is a structure containing at least two isocyanate-reactive groups;
c. a polyol different from component b), said polyol having a hydroxyl functionality of from 1.5 to 4;
d. A silane compound comprising an isocyanate reactive group and at least two methoxy and/or ethoxy groups attached to a silicon atom;
e. a hydrophilic compound containing 2 to 3 isocyanate-reactive groups which is different from the polymer b); and
An optional f. compounds containing 1-3 amino groups and/or hydroxyl groups, preferably 1-3 amino groups.
2. The aqueous polyurethane polyurea dispersion according to claim 1, wherein component a) is a mixture of hexamethylene diisocyanate and isophorone diisocyanate.
3. The aqueous polyurethane polyurea dispersion according to claim 2, wherein the weight ratio of hexamethylene diisocyanate to isophorone diisocyanate is from 10:1 to 20:1.
4. An aqueous polyurethane polyurea dispersion according to any one of claims 1 to 3 characterised in that the isocyanate functionality of the component a) polyisocyanate is not less than 2, more preferably 2 to 4 and most preferably 2.
5. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 4, wherein said at least two isocyanate-reactive groups are selected from at least two amino groups, at least two hydroxyl groups or at least one amino group and at least one hydroxyl group.
6. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 5, wherein the polymer conforming to the structure of formula I is one or more of the following: a polymer conforming to the structure of formula II and a polymer conforming to the structure of formula III,
Wherein a in formula II is 10-75, b is 0-50; in the formula III, x is 10-75, and y is 1-50.
7. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 6, wherein the polymer of component b) which corresponds to the structure of formula I has a number average molecular weight of 500g/mol to 4000g/mol, the number average molecular weight being measured according to gel chromatography using tetrahydrofuran as mobile phase and calculating the molecular weight based on polystyrene as standard, the component having a molecular weight of 200 or higher being selected for calculation and measured with a differential refractive detector (RI detector).
8. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 7, wherein component d) the silane compound is one or more of the following: bis (3-triethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) amine, (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, 3-aminopropyl (diethoxy) methylsilane and 3-aminopropyl methyldimethoxysilane, most preferably one or more of the following: (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane and 3-aminopropyl methyldimethoxysilane.
9. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 8, wherein the polyol different from component b) is one or more of the following: diols having a number average molecular weight of 62 to 15000 and polyols having a number average molecular weight of 62 to 15000, more preferably one or more of the following: diols having a number average molecular weight of 62 to 5000 and triols having a number average molecular weight of 92 to 5000, most preferably one or more of the following: a polyester polyol having 2 to 3 hydroxyl groups and a number average molecular weight of 500 to 2500, a polycarbonate polyol having 2 to 3 hydroxyl groups and a number average molecular weight of 400 to 2500, a polyether polyol having 2 to 3 hydroxyl groups and a number average molecular weight of 200 to 2500, a polylactone polyol having 2 to 3 hydroxyl groups and a small molecular alcohol, the number average molecular weight being 250 to 5000, being measured by gel chromatography, using tetrahydrofuran as a mobile phase, and calculating a molecular weight based on polystyrene as a standard, selecting a component having a molecular weight of 200 or more for calculation, and measuring by a differential refractive detector (RI detector).
10. Aqueous polyurethane polyurea dispersion according to any one of claims 1 to 9, characterised in that the polyol different from component b) has a melting enthalpy of not less than 15J/g, most preferably from 25J/g to 100J/g, obtained by the first temperature rise profile from 20 ℃ to 100 ℃ by DSC according to method a in DIN65467, a loading of 10 to 20 mg and a heating rate of 20K/min.
11. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 10, wherein the hydrophilic compound of component e) containing 2 to 3 isocyanate-reactive groups which is different from polymer b) is one or more of the following: n- (2-aminoethyl) -2-aminoethane sulfonate, dimethylol propionate and (N- (2-aminoethyl) -2-aminoethane carboxylate.
12. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 11, wherein the component f) compound containing 1 to 3 amino groups and/or hydroxyl groups is one or more of the following: aliphatic and/or cycloaliphatic primary and/or secondary mono-or di-or tri-amines or amino-alcohols, most preferably one or more of the following: isophorone diamine, N- (2-hydroxyethyl) ethylene diamine, and diethanolamine.
13. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 12, wherein the amount of component a) is from 9% to 18% by weight, most preferably from 10% to 12% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
14. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 13, wherein the amount of component b) is from 0.9% to 4% by weight, most preferably from 1% to 2% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
15. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 14, wherein the amount of component c) is from 5% to 94% by weight, most preferably from 70% to 90% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
16. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 15, wherein the amount of component d) is from 0.12% to 0.7% by weight, most preferably from 0.18% to 0.4% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
17. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 16, wherein the amount of component e) is from 0.2% to 50% by weight, most preferably from 1% to 5% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
18. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 17, wherein the amount of component f) is not more than 10% by weight, most preferably from 0.5% to 3% by weight, relative to the total weight of the solid components of the aqueous polyurethane polyurea dispersion.
19. The aqueous polyurethane polyurea dispersion according to any one of claims 1 to 18, wherein the aqueous polyurethane polyurea dispersion meets at least one of the following characteristics:
the solids content is from 15% to 70% by weight, most preferably from 30% to 60% by weight, relative to the total weight of the aqueous polyurethane polyurea dispersion, using an HS153 moisture meter from Mettler Toledo company according to DIN-ENISO 3251:2019, heating to 120 ℃, and determining a test endpoint when the weight loss of the sample is less than 1mg/140 seconds;
pH value of 4-11, most preferably 5-10, measured at 23deg.C according to PB-10pH meter from Sartorius Corp., germany;
Average particle size of 20nm to 750nm, more preferably 50nm to 450nm, most preferably 100nm to 250nm, as determined by laser correlation (laser particle sizer) according to the ZEN 1600 tester from Malvern, uk, according to ISO 13321:1996 test method 1 drop (about 0.05 g) of sample was added to 50ml of ultrapure water, and the diluted sample was tested at 23.0.+ -. 0.1 ℃; materials: polystyrene latex (RI: 1.590; absorptivity: 0.010), dispersant: water (temperature: 23.0 ℃ C.; viscosity: 0.9308cP; RI: 0.330), equilibration time: 60 seconds, using disposable cuvette DTS0012, positioning method: automatic attenuation selection, finding the best position: the analytical model is: universal (normal resolution), measurement angle: 173 ° backscatter (NIBS default), run times: 3 times, run duration: 10 seconds, number of measurements: 10 times; and
The viscosity is 1000 mPas-3500 mPas, according to DV-II+Pro. Rotational viscometer from Brookfield company, ISO 2555:2018 measured at 23 ℃, rotor type: s 62-64, rotating speed: 30RPM, test temperature: 23 ℃.
20. A process for preparing an aqueous polyurethane polyurea dispersion comprising polyurethane polyurea according to any one of claims 1 to 19, comprising the steps of:
i. reacting component a) at least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, the weight ratio of the at least one aliphatic polyisocyanate and the at least one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, the weight ratio of the one aliphatic polyisocyanate and the one cycloaliphatic polyisocyanate being in the range of 10:1 to 20:1, component b) a polymer conforming to the structure of formula I and component c) some or all of a polyol different from component b) to obtain a prepolymer;
ii) reacting the prepolymer, component d) a silane compound, component e) a hydrophilic compound containing 2 to 3 isocyanate-reactive groups different from polymer b) and optionally component f) a compound containing 1 to 3 amino groups and/or hydroxyl groups, preferably 1 to 3 amino groups to obtain the polyurethane polyurea; and
Introducing water before, during or after step ii to obtain the aqueous polyurethane polyurea dispersion.
21. The method of claim 20, further comprising a step iv. Introducing a water miscible organic solvent that is inert to isocyanate groups during or after step i, and removing the organic solvent from the aqueous polyurethane polyurea dispersion.
22. The preparation process according to claim 21, characterized in that the organic solvent is partly or completely removed by distillation at a temperature of 10 ℃ to 100 ℃, most preferably 25 ℃ to 60 ℃, for a time of 1 hour to 12 hours, most preferably 2 hours to 7 hours, and at a distillation pressure of 500mbar to 50mbar, most preferably 200mbar to 60mbar.
23. A coating, adhesive or ink comprising an aqueous polyurethane polyurea dispersion comprising polyurethane polyurea according to any one of claims 1 to 19.
24. The coating, adhesive or ink of claim 23, further comprising an additive that is one or more of the following: emulsifiers, light stabilizers, antioxidants, bactericides, fillers, antisettling agents, defoamers, wetting agents, flow regulators, reactive diluents, plasticizers, neutralizing agents, catalysts, auxiliary solvents, thickeners, pigments, dyes, matting agents and adhesion promoters.
25. Use of an aqueous polyurethane polyurea dispersion comprising polyurethane polyurea according to any one of claims 1 to 19 for the preparation of a coated product, a bonded product or a printed product.
26. An article or article comprising the aqueous polyurethane-polyurea dispersion comprising polyurethane-polyurea according to any one of claims 1 to 19 prepared, coated, bonded, sealed or printed substrate.
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| CN202310572493.5A CN118994531A (en) | 2023-05-19 | 2023-05-19 | Waterborne polyurethane polyurea dispersion |
| PCT/EP2023/080763 WO2024099927A1 (en) | 2022-11-09 | 2023-11-06 | Aqueous polyurethane-polyurea dispersion |
| TW112142778A TW202434662A (en) | 2022-11-09 | 2023-11-07 | Aqueous polyurethane-polyurea dispersion |
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