CN117701065A - Water-based polyurethane ink binder and preparation method and application thereof - Google Patents
Water-based polyurethane ink binder and preparation method and application thereof Download PDFInfo
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- CN117701065A CN117701065A CN202311582466.2A CN202311582466A CN117701065A CN 117701065 A CN117701065 A CN 117701065A CN 202311582466 A CN202311582466 A CN 202311582466A CN 117701065 A CN117701065 A CN 117701065A
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- polyurethane ink
- aqueous polyurethane
- unsaturated
- water
- polyol
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 123
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 123
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000011230 binding agent Substances 0.000 title claims abstract description 37
- 229920005862 polyol Polymers 0.000 claims abstract description 36
- 150000003077 polyols Chemical class 0.000 claims abstract description 36
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 22
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012948 isocyanate Substances 0.000 claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 16
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 239000004971 Cross linker Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000049 pigment Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 13
- 238000004945 emulsification Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims description 3
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 claims description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 3
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- BQRPSOKLSZSNAR-UHFFFAOYSA-N ethenyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C=C BQRPSOKLSZSNAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 3
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 3
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 3
- YWZHEUFCDPRCAD-OWOJBTEDSA-N (e)-pent-2-ene-1,5-diol Chemical compound OCC\C=C\CO YWZHEUFCDPRCAD-OWOJBTEDSA-N 0.000 claims description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 2
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 239000000945 filler Substances 0.000 abstract description 5
- 239000000976 ink Substances 0.000 description 101
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 53
- 239000002245 particle Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 14
- 235000012239 silicon dioxide Nutrition 0.000 description 13
- 239000005543 nano-size silicon particle Substances 0.000 description 12
- 229920005906 polyester polyol Polymers 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000001023 inorganic pigment Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- -1 t-butylperoxy Chemical group 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920000616 Poly(1,4-butylene adipate) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a water-based polyurethane ink binder, a preparation method and application thereof, and belongs to the technical field of water-based ink. The preparation raw materials of the aqueous polyurethane ink binder provided by the invention comprise: a polymeric polyol, a hydrophilic crosslinker, a chain extender, and an isocyanate; the hydrophilic cross-linking agent is formed by copolymerizing unsaturated polyol, unsaturated siloxane and unsaturated organic sulfonate. The aqueous polyurethane ink binder provided by the invention can effectively improve the mechanical property, thermal stability, flame retardance and adhesive force of a film layer formed by the aqueous polyurethane ink binder, and simultaneously improve the wrapping property of the aqueous polyurethane ink binder on a filler. The invention also provides a preparation method and application of the aqueous polyurethane ink binder.
Description
Technical Field
The invention relates to the technical field of water-based ink, in particular to a water-based polyurethane ink binder, and a preparation method and application thereof.
Background
In the ink industry, volatile organic compounds can cause a number of safety problems in the manufacture and use of conventional solvent-based inks, such as: food safety, environmental pollution, transportation safety and the like. Therefore, solvent-based inks are being phased out, and at the same time, the research and application range of water-based inks is steadily increasing, and the use of solvent-based inks will be gradually replaced in the future. The water-based ink is considered as the most promising printing ink because of its low environmental pollution, high solid content, high gloss, low viscosity, and the like.
The water-based ink mainly comprises four parts of pigment, ink binder, auxiliary agent and water. The ink vehicle is referred to as the "core" of the ink, and many properties of the ink are provided by the vehicle, such as the pigment being uniformly dispersed in the vehicle and providing adhesion to the surface of the print substrate while transferring the pigment during printing. The ink vehicle plays a decisive role in the performance of the aqueous ink, such as coating viscosity, gloss, pigment dispersibility, dry film formation, adhesion, etc. For better performance and environmental friendliness, development of high-performance aqueous ink vehicles is required.
The most widely used water-based inks are water-based polyurethane inks, water-based acrylic inks, and the like. In recent years, waterborne polyurethane has different properties due to the variability of the soft segment and the hard segment, is suitable for different purposes, and therefore attracts the interest of researchers in the packaging and printing industries. Aqueous polyurethanes are useful as coatings or adhesives in printing and packaging, particularly as printing ink vehicles, and have become one of the most important matters in aqueous ink research efforts.
Although the aqueous polyurethane ink binder has been widely studied and used, the aqueous polyurethane ink binder still has the technical problems of mechanical property, thermal stability, flame retardance, poor packing property for filler and the like.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides the water-based polyurethane ink binder, which can effectively improve the mechanical property, the thermal stability, the flame retardance and the adhesive force of a film layer formed by the water-based polyurethane ink binder, and simultaneously improve the wrapping property of the water-based polyurethane ink binder on the filler.
The invention also provides a preparation method of the water-based polyurethane ink binder.
The invention also provides the water-based polyurethane ink prepared from the water-based polyurethane ink binder.
According to an embodiment of the first aspect of the present invention, there is provided an aqueous polyurethane ink vehicle, the preparation raw materials of the aqueous polyurethane ink vehicle include:
a polymeric polyol, a hydrophilic crosslinker, a chain extender, and an isocyanate;
the hydrophilic cross-linking agent is formed by copolymerizing unsaturated polyol, unsaturated siloxane and unsaturated organic sulfonate.
The aqueous polyurethane ink binder provided by the embodiment of the invention has at least the following beneficial effects:
(1) The hydrophilic cross-linking agent adopted by the invention contains a large number of hydroxyl groups and sulfonate groups, so that the prepared water-based polyurethane ink binder has good hydrophilicity; and the hydrophilic group comprises sulfonate instead of sulfonic acid, so that only a small amount of neutralizing agent is needed to be added in the preparation process, and the side effect of the neutralizing agent on the aqueous polyurethane ink vehicle is obviously reduced.
(2) In the hydrophilic cross-linking agent adopted by the invention, unsaturated siloxane is polymerized; in the water adding emulsification in the preparation process, siloxane can be automatically hydrolyzed and polymerized to form nano silicon dioxide; the silica is chemically linked to the molecular chain of the aqueous polyurethane, and the particle size and the dispersibility are very uniform.
The nano silicon dioxide can improve the mechanical property, the thermal stability, the flame retardance and the adhesive force of a film layer formed by the water-based polyurethane ink binder; in addition, the nano silicon dioxide can be used as an intermediate connector between inorganic pigment and other organic components in the aqueous polyurethane ink, and can be filled in gaps formed by the solid pigment; finally, the dispersibility of the pigment in the water-based polyurethane ink and the wrapping effect of organic matters on the pigment are obviously improved; the coverage, storage stability and adhesion fastness of the obtained aqueous polyurethane ink are obviously improved from the appearance.
(3) In the prior art, silica dispersion liquid and polyurethane dispersion liquid are directly mixed to form silica modified polyurethane, so that the silica has certain contribution to mechanical property, thermal stability and the like of the film layer, but because the silica and the polyurethane exist independently, phase separation is easy to generate, and the silica and the polyurethane are difficult to be effectively compatible with other inorganic fillers such as pigment and the like, the comprehensive performance of the obtained film layer is not very excellent based on the silica and the polyurethane. The invention polymerizes the silicon dioxide nano particles on the polyurethane molecular chain, thereby fundamentally overcoming the technical problems.
According to some embodiments of the invention, the polymeric polyol comprises at least one of a polyester polyol and a polyether polyol.
According to some embodiments of the invention, the polymeric polyol is a mixture of a polyester polyol and a polyether polyol. The polyester polyol has poor water resistance and high strength; polyether polyols have good toughness but poor strength; the water-based polyurethane ink binder with excellent water resistance, strength and toughness can be obtained by combining the water-based polyurethane ink binder with the water-based polyurethane ink binder.
Wherein the mass ratio of the polyester polyol to the polyether polyol is 1:0.8-1.2. For example, it may be about 1:1. In this range, the aqueous polyurethane ink vehicle has a strong adhesion to a substrate.
According to some embodiments of the invention, the polyester polyol comprises at least one of a poly (neopentyl glycol adipate) glycol (PNA, CAS: 27925-07-1) and a poly (1, 4-butylene glycol) adipate glycol (PBA, CAS: 150923-12-9).
According to some embodiments of the invention, the polyether polyol comprises at least one of polypropylene glycol (PPG, CAS: 25322-69-4) and polyethylene glycol (PEG, CAS: 25322-68-3).
According to some embodiments of the invention, the polymeric polyol has a weight average molecular weight of 1800 to 2200. For example, it may be about 2000.
According to some embodiments of the invention, the molar ratio of the polymeric polyol to the hydrophilic cross-linking agent is from 10:1 to 5. For example, it may be about 10:1.5, 10:2, 10:2.5, 10:3, 10:4 or 10:4.5.
Since the molar mass of the polymer is not a point value, the ratio of the mass to the weight average molecular weight is used as the amount of the substance in the actual feeding process, and the molar amount is calculated further in combination with the mass.
According to some embodiments of the invention, the molar ratio of the unsaturated polyol to the unsaturated siloxane is from 10:4 to 6. For example, the ratio may be specifically 10:4.5 to 5.5. And more specifically may be about 2:1.
According to some embodiments of the invention, the molar ratio of the unsaturated polyol to the unsaturated sulfonate is 10:4-6. For example, the ratio may be specifically 10:4.5 to 5.5. And more specifically may be about 2:1.
In the molar ratio range, at least one siloxane group and at least one sulfonate group can be ensured in each hydrophilic cross-linking agent molecule, thereby ensuring the hydrophilic performance of the hydrophilic cross-linking agent, and providing a basis for the subsequent generation of nano silicon dioxide with uniform particle size distribution and stable dispersion.
According to some embodiments of the invention, the unsaturated polyol includes at least one of 1, 4-butene diol (CAS: 110-64-5), 2-pentene-1, 5-diol (CAS: 187806-17-3), glycerol monomethacrylate (CAS: 5919-74-4), and 2, 3-dihydroxypropyl acrylate (CAS: 10095-20-2).
According to some embodiments of the invention, the unsaturated siloxane includes at least one of vinyltrichlorosilane (CAS: 75-94-5), vinyltrimethoxysilane (CAS: 2768-02-7), vinyltriethoxysilane (CAS: 78-08-0), vinyltris (beta-methoxyethoxy) silane (CAS: 1067-53-4), vinyltri-t-butoxysilane (CAS: 5356-88-7), vinyltri-t-butylperoxy silane (CAS: 15188-09-7), and vinyltriacetoxy silane (CAS: 4130-08-9).
According to some embodiments of the invention, the unsaturated organic sulfonate includes at least one of sodium vinylsulfonate (CAS: 3039-83-6), sodium allylsulfonate (CAS: 2495-39-8), sodium p-styrenesulfonate (CAS: 2695-37-6), and 2-acrylamido-2-methylpropanesulfonic acid (CAS: 15214-89-8).
According to some embodiments of the invention, the hydrophilic cross-linking agent has a weight average molecular weight of 500 to 1500. For example, it may be about 1000.
According to some embodiments of the invention, the molar ratio of the polymeric polyol to the chain extender is from 100:16 to 260. For example, the ratio may be specifically 100:18 to 25. And more specifically may be about 5:1.
According to some embodiments of the invention, the chain extender is a glycol. The dihydric alcohol includes at least one of 1, 4-butanediol (BDO, CAS: 110-63-4) and 1, 3-propanediol (CAS: 504-63-2).
According to some embodiments of the invention, the isocyanate comprises at least one of isophorone diisocyanate (IPDI, CAS: 4098-71-9), hexamethylene diisocyanate (HDI, CAS: 822-06-0), and diphenylmethane diisocyanate (MDI, CAS: 101-68-8).
According to some embodiments of the invention, the aqueous polyurethane ink vehicle is prepared from isocyanate and hydroxyl materials in a ratio of 1.2 to 1.5:1. For example, the ratio may be specifically 1.25 to 1.35:1. And more specifically may be about 1.3:1.
According to some embodiments of the invention, the aqueous polyurethane ink vehicle is prepared from raw materials, and further comprises a catalyst, acetone, water and a neutralizing agent.
According to some embodiments of the invention, the catalyst comprises at least one of an organotin catalyst and an organobismuth catalyst. Thereby accelerating the reaction rate between isocyanate and hydroxyl groups.
According to some embodiments of the invention, the mass ratio of the catalyst to the isocyanate is 1:3000-5000. For example, it may be about 1:4000.
According to some embodiments of the invention, the organotin catalyst comprises dibutyltin dilaurate (CAS: 77-58-7).
According to some embodiments of the invention, the acetone accounts for 10-15% of the total mass of other preparation raw materials except the water.
According to some embodiments of the invention, the neutralizing agent comprises triethylamine (CAS: 121-44-8).
According to some embodiments of the invention, the hard segment content of the aqueous polyurethane ink vehicle is 25-45%. For example, the content may be specifically 30 to 35%. And more specifically may be about 32% or 33%.
According to some embodiments of the invention, the aqueous polyurethane ink vehicle has a viscosity of 30 to 55 mPa-s.
According to some embodiments of the invention, the aqueous polyurethane ink vehicle has a solids content of 40 to 45%.
According to some embodiments of the invention, the solid particles in the aqueous polyurethane ink vehicle have a particle size of 40-150 nm. For example, it may be about 80nm, 100nm or 120nm. If not specified, the particle size of the solid in the aqueous polyurethane ink vehicle is D V 50 particle size.
According to an embodiment of the second aspect of the present invention, there is provided a preparation method of the aqueous polyurethane ink vehicle, the preparation method including the steps of:
s1, polymerizing the unsaturated polyol, unsaturated siloxane and unsaturated organic sulfonate under the action of an initiator to obtain the hydrophilic cross-linking agent;
s2, primarily reacting the polymeric polyol and the isocyanate;
s3, adding the hydrophilic cross-linking agent into the mixture obtained in the step S2 to continue the reaction;
s4, adding the chain extender into the mixture obtained in the step S3 for reacting again, and then adjusting the pH;
s5, adding water into the mixture obtained in the step S4 for emulsification.
The mechanism of the preparation method is as follows: step S3, hydroxyl, sulfonate and siloxane groups in the hydrophilic cross-linking agent are introduced into polyurethane molecular chains, pH adjustment in step S4 provides a basis for subsequent siloxane hydrolysis and nano silicon dioxide formation, and in step S5, hydrolysis conditions are provided for siloxane hydrolysis in the water-adding emulsification process, and nano silicon dioxide is formed on polyurethane molecular chains in the step.
In the preparation method, the step S1 and the step S2 are only for convenience in description and do not represent the sequence of the steps; in actual production, step S1 may be performed before step S3, and step S1 and step S2 may be performed sequentially or simultaneously.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects:
in the preparation method, the generation of nano silicon dioxide and the water adding emulsification of polyurethane can be performed simultaneously, so that the operation time is shortened.
The preparation method provided by the invention is simple to operate, easy to realize and convenient for industrial popularization.
According to some embodiments of the invention, the preparation method is performed in a protective atmosphere. The protective atmosphere includes at least one of nitrogen and argon.
According to some embodiments of the invention, in step S1, the method further comprises dissolving the unsaturated organic sulfonate in a polar solvent. The polar solvent includes at least one of an alcohol and acetonitrile. Wherein the concentration of the organic sulfonate is 3-10wt%.
According to some embodiments of the invention, in step S1, the initiator comprises at least one of dilauryl peroxide (CAS: 105-74-8), dibenzoyl peroxide (CAS: 13495-28-8), 1-bis (t-butylperoxy) cyclohexane (CAS: 3006-86-8), and 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane (CAS: 6731-36-8).
According to some embodiments of the invention, in step S1, the initiator comprises 0.1 to 1% by mass of the mixture obtained in step S1. For example, the content may be specifically 0.2 to 0.5%.
According to some embodiments of the invention, in step S1, the polymerization temperature is 50-70 ℃. For example, the temperature may be specifically 55 to 65 ℃. And more specifically may be about 60 c.
According to some embodiments of the invention, in step S1, the polymerization is carried out for a reaction period of 2 to 4 hours. For example, the time period may be specifically 2.5 to 3.5 hours. And more specifically may be about 3 hours.
According to some embodiments of the invention, in step S2, the preliminary reaction is carried out under the action of a catalyst. The catalyst comprises at least one of an organobismuth catalyst and an organotin catalyst.
According to some embodiments of the invention, in step S2, the preliminary reaction comprises a mixture of the polymeric polyol and the isocyanate, and a reaction after mixing with the catalyst. Wherein,
the temperature of the mixing is 60-70 ℃. For example, the temperature may be specifically 62 to 68 ℃. And more specifically may be about 65 deg.c.
And the catalyst is mixed and reacted for 30 to 120 minutes. For example, the time period may be 60 to 100 minutes. Further specifically, about 90 minutes may be used.
The reaction temperature after mixing with the catalyst is 80 to 90 ℃, for example, 82 to 88 ℃ can be used. And more specifically may be about 85 deg.c.
According to some embodiments of the invention, in step S3, the temperature of the continued reaction is 60-80 ℃. For example, the temperature may be 65 to 75 ℃. And more specifically may be about 70 c.
According to some embodiments of the invention, in step S3, the duration of the continuous reaction is 30-90 min. For example, the time period may be specifically 50 to 70 minutes. Further specifically, about 60 minutes may be used.
According to some embodiments of the invention, in step S4, no temperature adjustment is performed. I.e. the reaction temperature in step S3 is maintained, but still a small temperature change is brought about due to the addition of the material.
According to some embodiments of the invention, in step S4, in the re-reaction, the reaction is stopped when the mass percentage of isocyanate in the reaction system reaches a theoretical value. The theoretical value is calculated according to the ratio of the amounts of isocyanate and hydroxyl substances.
According to some embodiments of the invention, in step S4, the reagent used to adjust the pH is Triethylamine (TEA).
According to some embodiments of the invention, in step S4, the pH of the resulting mixture is between 6 and 8. For example, it may be about 7.
According to some embodiments of the present invention, acetone may be added as a solvent in steps S1 to S4 according to the viscosity and the like.
According to some embodiments of the invention, the mass of the acetone accounts for 10-15% of the mass of the mixture obtained in the step S4. For example, it may be about 12%.
In the steps S1 to S4, the stirring may be performed in a stirring state at a rotation speed of 200 to 300rpm in order to promote mass transfer. For example, it may be about 250rpm.
According to some embodiments of the invention, in step S5, the emulsification with water is performed under stirring, and the stirring speed is 800-2000 rpm. For example, it may be about 1000rpm. The emulsification effect can be improved due to the higher rotating speed, and the obtained aqueous polyurethane ink binder is more thoroughly emulsified, wherein the particle size of solid particles is smaller.
According to some embodiments of the invention, in step S5, the water is added to emulsify, and the amount of water is determined according to the solids content and viscosity of the aqueous polyurethane ink vehicle.
According to some embodiments of the invention, the method further comprises performing reduced pressure distillation after step S5. To remove acetone from the mixture obtained in step S5.
According to some embodiments of the invention, the method of preparation comprises the steps of:
S1.
s1a, forming acetonitrile dispersion liquid by the organic sulfonate according to the mass concentration of 3-10wt%;
s1b, mixing the unsaturated polyol, the unsaturated siloxane and the acetonitrile dispersion liquid obtained in the step S1a, and heating to 50-70 ℃;
s1c, adding the initiator into the system obtained in the step S1b according to the mass percentage of 0.1-1% of all the mixtures, and continuing to react for 2-4 h;
S2.
s2. mixing the polymeric polyol and the isocyanate at a temperature of 60-70 ℃;
s2b, mixing the mixture obtained in the step S2a with a catalyst, heating to 80-90 ℃ and reacting for 30-120 min;
s3, adding the hydrophilic cross-linking agent into the mixture obtained in the step S2 to continue the reaction; the temperature of the continuous reaction is 60-80 ℃ and the duration is 30-90 min;
S4.
s4a, maintaining the temperature of the step S3, and adding the chain extender into the mixture obtained in the step S3 to react again until the concentration of isocyanic acid radical in the obtained mixture reaches the standard;
s4b, adding triethylamine into the mixture obtained in the step S4a, and adjusting the pH to 6-8;
s5, adding water into the mixture obtained in the step S4 for emulsification; the water adding emulsification is carried out under the stirring condition, and the rotating speed of the stirring state is 800-2000 rpm.
According to an embodiment of the third aspect of the present invention, there is provided an aqueous polyurethane ink, wherein the preparation raw materials of the aqueous polyurethane ink include the aqueous polyurethane ink vehicle.
The aqueous polyurethane ink adopts all the technical schemes of the aqueous polyurethane ink binder of the embodiment, so that the aqueous polyurethane ink has at least all the beneficial effects brought by the technical schemes of the embodiment.
According to some embodiments of the invention, the preparation raw materials of the aqueous polyurethane ink further comprise pigment, and the mass ratio of the aqueous polyurethane ink binder to the pigment is 100:5-25. For example, it may be about 100:15 to 22. And more specifically may be about 100:20.
According to some embodiments of the invention, the pigment comprises at least one of an organic pigment, an inorganic pigment, and a metallic pigment.
According to some embodiments of the invention, the pigment has a particle size of 20 μm or less.
According to some embodiments of the invention, the pigment comprises at least one of carbon black and titanium dioxide.
According to some embodiments of the invention, the aqueous polyurethane ink has a solids content of 30-60%. For example, the content may be specifically 35 to 45%. And more specifically may be about 40%.
According to some embodiments of the invention, the preparation raw materials of the aqueous polyurethane ink further comprise an auxiliary agent and water.
According to some embodiments of the invention, the adjuvant includes at least one of a wetting agent, an antifoaming agent, a dispersing agent, and a leveling agent.
According to some embodiments of the invention, the mass ratio of the aqueous polyurethane ink vehicle and the auxiliary agent is 100:1-5. For example, it may be about 100:2.
According to some embodiments of the invention, the preparation of the aqueous polyurethane ink comprises mixing raw materials for preparing the aqueous polyurethane ink and grinding until the raw materials reach a target particle size.
The grinding can improve the dispersion uniformity of the pigment in the aqueous polyurethane ink.
The term "about" as used herein, unless otherwise specified, means that the tolerance is within + -2%, for example, about 100 is actually 100 + -2%. Times.100.
Unless otherwise specified, the term "between … …" in the present invention includes the present number, for example "between 2 and 3" includes the end values of 2 and 3.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
The water-based polyurethane ink binder is prepared according to the preparation method, wherein the proportions of the preparation raw materials are shown in table 1, and the specific steps are as follows:
s1, synthesizing a hydrophilic cross-linking agent:
s1a, forming acetonitrile dispersion liquid by organic sulfonate according to the mass concentration of 5 wt%;
s1b, mixing unsaturated polyol, unsaturated siloxane and acetonitrile dispersion liquid obtained in the step S1a, and heating to 60 ℃;
s1c, adding an initiator into the system obtained in the step S1b according to the mass percentage of 0.2% of all the mixtures, and continuing to react for 3 hours;
the hydrophilic cross-linking agent obtained in this step has a weight average molecular weight of about 1000.
The proportions of the preparation raw materials used in this example are shown in Table 2.
S2, preliminary reaction:
s2. mixing the polymerized polyol and isocyanate in a system of acetone at 65 ℃;
s2b, mixing the mixture obtained in the step S2a with a catalyst, and heating to 85 ℃ for reaction for 90min;
s3, continuing the reaction: adding a hydrophilic cross-linking agent into the mixture obtained in the step S2 to continue the reaction; the temperature of the continuous reaction is 70 ℃ and the duration is 60min;
s4, reacting again:
s4a, maintaining the temperature of the step S3, and adding a chain extender into the mixture obtained in the step S3 to react again until the concentration of isocyanate groups in the obtained mixture reaches the standard;
s4b, adding triethylamine to the mixture obtained in the step S4a, and adjusting the pH to about 7;
s5, emulsifying: adding water into the mixture obtained in the step S4 for emulsification; the water adding emulsification is carried out under the stirring condition, and the rotating speed of the stirring state is 800-2000 rpm;
s6, decompressing and distilling the mixture obtained in the step S5, and removing the acetone;
the viscosity of the obtained aqueous polyurethane ink binder is 40 mPas; the solids content was about 41% and the average particle size was about 80nm.
Steps S1 to S4 in this example were performed in a nitrogen-protected atmosphere.
Example 2
The water-based polyurethane ink binder is prepared in this example, and the specific difference from example 1 is that:
the types and amounts of the partial preparation raw materials are different, and are shown in tables 1 to 2.
Comparative example 1
The water-based polyurethane ink binder is prepared in this example, and the specific difference from example 1 is that:
the types and amounts of the partial preparation raw materials are different, and are shown in tables 1 to 2.
Table 1 raw materials for preparing the aqueous polyurethane ink vehicles of examples and comparative examples
In table 1, the hard segment content is calculated as: [1- (polymeric polyol)/(aqueous polyurethane ink vehicle×solid content) ]×100%.
In Table 1, the polyester is a polyester polyol selected from the group consisting of poly (1, 4-butylene adipate) glycol (PBA) having a weight average molecular weight of 2000; the polyether is polyether polyol selected from polypropylene glycol (PPG) with weight average molecular weight of 2000; and (3) polyester: polyether, which means the mass ratio of polyester polyol to polyether polyol.
In Table 1, the amount of catalyst used represents the mass percent of catalyst to isocyanate.
The amount of acetone is expressed as mass percent of the mixture obtained in step S4. Acetone may be added in any of steps S2 to S4 as long as the required viscosity for stirring and the like is satisfied.
Table 2 examples and comparative examples preparation of aqueous crosslinkers starting materials for preparation
Comparative example 2
The specific steps of this example for preparing a polyurethane ink vehicle and the differences from example 1 are:
(1) In step S1, no unsaturated siloxane is added.
(2) After step S5, the same amount of unsaturated siloxane as in step S1 is mixed with the product obtained in step S5, and the stirring speed of step S5 is maintained for 20min.
The average particle size of the obtained aqueous polyurethane ink vehicle is 200nm.
Comparative example 3
This example prepared an organosilicon modified polyurethane ink vehicle, which differs from example 1 in particular in that:
(1) In step S1, no unsaturated siloxane is added.
(2) The polyester polyol used was replaced with an equal mass of silicone modified polyester polyol, wherein the silicone modified polyester polyol was prepared by the method disclosed in CN102101969a, specifically:
60% of silane coupling agent and 15% of absolute ethyl alcohol are added into a three-mouth bottle, after the temperature is raised to 70 ℃, mixed solution of 10% of deionized water and 15% of absolute ethyl alcohol is added dropwise, and the dropping speed is controlled to be finished within half an hour. After the reaction was continued for 3 hours, the reaction was stopped. Then distilling under normal pressure, and stopping distilling after the temperature of the residual liquid in the bottle is raised to 125 ℃. The organosilicon oligomer is prepared.
The silicone oligomer, polyester polyol (same as in example 1 of the present invention) and solvent (xylene: cyclohexanone=1:1 volume ratio) prepared above were added in a mass ratio of 10:100 in a four-necked flask. The reaction is carried out for 4 hours at 75 ℃ to dealcoholize. Obtaining the organosilicon modified polyester polyol.
The average particle size of the obtained aqueous polyurethane ink vehicle is about 100nm.
Application example
The aqueous polyurethane ink is prepared from the following raw materials in parts by weight:
100 parts of a water-based polyurethane ink binder; from examples or comparative examples;
20 parts of filler; titanium dioxide, purchased from Shanghai river-jumping titanium dioxide chemical products limited;
water: the solid content was adjusted to 40%.
The preparation method comprises the following steps: mixing the above raw materials, and grinding until the particle size is less than or equal to 20 μm.
Test case
Average particle size test: the average particle diameters of the aqueous polyurethane ink vehicles obtained in examples and comparative examples were analyzed by a laser particle size tester, and the test results are shown in table 1. Although example 2 reduced the amount of unsaturated siloxane used in the preparation of the hydrophilic crosslinking agent as compared to example 1, the amount of hydrophilic crosslinking agent was increased in the preparation of the aqueous polyurethane ink vehicle; the particle size of the aqueous polyurethane ink vehicle obtained as a whole increases. In comparative example 1, unsaturated siloxane is not included, that is, nano silicon dioxide is not formed in the aqueous polyurethane ink vehicle, but rather the particle size of the aqueous polyurethane ink vehicle is increased, so that it is predicted that the nano silicon dioxide is integrated into polyurethane molecular chains, the dispersing agent is also used, and aggregation of a large number of polyurethane molecular chains is avoided. In comparative example 2, silica produced by in situ hydrolysis was added externally; because of the lack of the limit function of polyurethane molecular chains, the nano silicon dioxide is easy to agglomerate, so that the particle size of comparative example 2 is larger. In comparative example 3, the preparation method and other embodiments are different, and the effect of the nano silica is not involved, and the particle size of the obtained aqueous polyurethane ink vehicle is about 100nm.
Preparation of polyurethane test strips: pouring the polyurethane ink binder obtained in the example or the comparative example into a mould, naturally drying for 48 hours at room temperature, transferring into a vacuum drying oven at 60 ℃ for continuous drying for 24 hours, and putting into a dryer after the dry film quality is constant; the test strip is used as a raw material to test the water absorption, tensile property, thermal stability and flame retardance.
Water absorption test: at an ambient temperature of 25 ℃, the polyurethane test strip is soaked in deionized water for 6 days, and the water absorption of the film is calculated according to the formula: w= (W) t -W 0 )/W 0 X 100%; wherein W is t G is the mass of the wet film; w (W) 0 G is the mass of the initial dry film.
Tensile property test: the stretching speed was 50mm/min as measured in accordance with GB/T528-2009.
The thermal stability was measured by thermogravimetric method and the temperature at which the polyurethane test strip lost 5% of weight was recorded.
Flame retardant properties: the test was performed according to the vertical burning test (94V-0, VTM) of the UL94 chapter 11 thin material.
The performance of the aqueous polyurethane ink obtained in the application example was also tested in this example, wherein:
attachment fastness, tested with reference to GB/T13217.7;
storage stability, namely sealing and storing the obtained water-based polyurethane ink at 40 ℃ for 6 months, judging whether sediment exists or not, and testing adhesive force by referring to GB/T13217.7 if sediment does not exist;
the hiding power was measured using a black and white grid, and the dry film thickness of the coating was 10. Mu.m.
The results of the above tests are shown in Table 3.
Table 3 properties of aqueous polyurethane ink vehicles obtained in examples and comparative examples and aqueous polyurethane inks obtained in application examples
According to the results, the water-based polyurethane ink binder provided by the invention has higher water resistance, strength, thermal stability and flame retardance, and the water-based polyurethane ink comprising the water-based polyurethane ink binder has higher storage stability, adhesion fastness and coverage.
Compared with example 1, the example 2 adopts a single type of polymer polyol, and the strength, thermal stability and other properties of the obtained test strip are reduced; in addition, the adhesion of the aqueous polyurethane ink after storage is remarkably reduced because the single type of polymeric polyol reduces the coating property of the pigment added to the ink, so that after storage at high temperature, the coating property of the polyurethane molecule to the inorganic pigment is reduced although no delamination occurs, and finally the adhesion is reduced.
As is clear from comparative example 1 and comparative example 1, if unsaturated siloxane is not included in the raw materials for preparing the hydrophilic crosslinking agent, nano silica cannot be generated, and thus the strength, water resistance, and heat resistance of the obtained aqueous polyurethane ink vehicle are all lowered; furthermore, due to the lack of the intermediation of the nano silicon dioxide between the polyurethane molecular chain and the inorganic pigment, the storage stability of the obtained water-based polyurethane ink is reduced; furthermore, the coverage of the obtained water-based polyurethane ink is obviously reduced due to the lack of the effect of filling gaps by the nano silicon dioxide.
As is clear from comparative examples 1 and 2, the silica in comparative example 2 is not bonded to polyurethane molecular chain, silica is also equivalent to filler, dispersion stability in aqueous polyurethane ink is poor, and obvious delamination and precipitation occur at high temperature storage stage; and the acting force between the organic component and the inorganic component in the water-based polyurethane ink is weak, so that the adhesive force is obviously reduced. However, the addition of silica still has a certain gap filling effect, and also has a remarkable reinforcing effect on strength and the like.
Comparative examples 1 and 3 it is known that in comparative example 3, no additional solid silica was introduced, but a silicone polymer segment was introduced into the polyurethane molecular chain; therefore, the improvement in strength, water resistance, adhesion and the like caused by the organosilicon group is provided, but the overall performance is inferior to that of examples 1 to 2 of the present invention.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The water-based polyurethane ink binder is characterized by comprising the following raw materials:
a polymeric polyol, a hydrophilic crosslinker, a chain extender, and an isocyanate;
the hydrophilic cross-linking agent is formed by copolymerizing unsaturated polyol, unsaturated siloxane and unsaturated organic sulfonate.
2. The aqueous polyurethane ink vehicle of claim 1, wherein the molar ratio of the unsaturated polyol to the unsaturated siloxane is from 10:4 to 6; and/or the molar ratio of the unsaturated polyol to the unsaturated sulfonate is 10:4-6.
3. The aqueous polyurethane ink vehicle of claim 1, wherein the unsaturated polyol comprises at least one of 1, 4-butene diol, 2-pentene-1, 5-diol, glycerol monomethacrylate, and 2, 3-dihydroxypropyl acrylate.
4. The aqueous polyurethane ink vehicle of claim 1, wherein the unsaturated siloxane comprises at least one of vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β -methoxyethoxy) silane, vinyltri-t-butoxysilane, vinyltri-t-butylperoxy silane, and vinyltriacetoxy silane.
5. The aqueous polyurethane ink vehicle of claim 1, wherein the unsaturated organic sulfonate comprises at least one of sodium vinyl sulfonate, sodium allyl sulfonate, sodium p-styrene sulfonate, and 2-acrylamido-2-methylpropane sulfonic acid.
6. The aqueous polyurethane ink vehicle according to any one of claims 1 to 5, wherein the hydrophilic cross-linking agent has a weight average molecular weight of 500 to 1500; and/or the ratio of the amount of the isocyanate to the amount of the hydroxyl in the raw materials for preparing the aqueous polyurethane ink vehicle is 1.2-1.5:1.
7. A method for preparing the aqueous polyurethane ink vehicle according to any one of claims 1 to 6, comprising the steps of:
s1, polymerizing the unsaturated polyol, unsaturated siloxane and unsaturated organic sulfonate under the action of an initiator to obtain the hydrophilic cross-linking agent;
s2, primarily reacting the polymeric polyol and the isocyanate;
s3, adding the hydrophilic cross-linking agent into the mixture obtained in the step S2 to continue the reaction;
s4, adding the chain extender into the mixture obtained in the step S3 for reacting again, and then adjusting the pH;
s5, adding water into the mixture obtained in the step S4 for emulsification.
8. The method according to claim 7, wherein in the step S1, the polymerization temperature is 50 to 70 ℃; and/or, in step S1, further comprising dissolving the unsaturated organic sulfonate in a polar solvent.
9. An aqueous polyurethane ink, wherein the preparation raw materials of the aqueous polyurethane ink comprise the aqueous polyurethane ink binder according to any one of claims 1 to 6.
10. The aqueous polyurethane ink according to claim 9, wherein the preparation raw materials of the aqueous polyurethane ink further comprise pigment, and the mass ratio of the aqueous polyurethane ink binder to the pigment is 100:5-25; and/or the solid content of the water-based polyurethane ink is 30-60%.
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| JP2020196852A (en) * | 2019-06-03 | 2020-12-10 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Composition for manufacturing polyurethane foam |
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