CN116515344A - Environment-friendly water-based ink and preparation method thereof - Google Patents
Environment-friendly water-based ink and preparation method thereof Download PDFInfo
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- CN116515344A CN116515344A CN202310649275.7A CN202310649275A CN116515344A CN 116515344 A CN116515344 A CN 116515344A CN 202310649275 A CN202310649275 A CN 202310649275A CN 116515344 A CN116515344 A CN 116515344A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 229920002635 polyurethane Polymers 0.000 claims abstract description 78
- 239000004814 polyurethane Substances 0.000 claims abstract description 78
- 229920002472 Starch Polymers 0.000 claims abstract description 68
- 239000008107 starch Substances 0.000 claims abstract description 68
- 235000019698 starch Nutrition 0.000 claims abstract description 68
- 239000000839 emulsion Substances 0.000 claims abstract description 60
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 38
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229920005906 polyester polyol Polymers 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 7
- 239000008236 heating water Substances 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- -1 sodium fatty acid Chemical class 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 9
- 238000007790 scraping Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- 238000007646 gravure printing Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The application relates to the technical field of water-based ink, and in particular discloses environment-friendly water-based ink and a preparation method thereof, wherein the environment-friendly water-based ink comprises the following raw materials in parts by weight: 10-20 parts of modified aqueous polyurethane emulsion; 25-35 parts of starch; 0.5-0.8 part of sodium hydroxide; 0.4-0.7 part of oxidant; 5-10 parts of phthalocyanine blue; 0.1-0.3 part of urea; 0.1-0.6 part of defoaming agent; 1-5 parts of a surfactant; 10-18 parts of water, wherein the preparation step of the modified aqueous polyurethane emulsion comprises the step of chemically grafting polyethylene glycol on the surface of polyurethane. The environment-friendly water-based ink has the advantage of improving the solvent resistance, wear resistance and adhesive force of the water-based ink.
Description
Technical Field
The invention relates to the technical field of ink, in particular to environment-friendly water-based ink and a preparation method thereof.
Background
The water-based ink is used as one of environment-friendly ink, the main application fields are gravure printing and flexographic printing, 80% of gravure printing products in the United states use the water-based ink, 40% of plastic printing in the gravure field adopts the water-based ink, which shows that the water-based ink is increasingly applied to gravure printing abroad, and domestic plastic gravure ink mainly adopts solvent-based ink at present, because the plastic water-based gravure ink still has the problems of poor water resistance, solvent resistance, adhesive force and the like, the solvent-based ink has a plurality of hazards, the solvent-based ink contains a large amount of benzene, toluene, butanone, ethyl acetate and other organic solvents, the volatilized solvents pollute the air in the use process of the solvent-based ink, the health of operators is endangered, and the residual solvents in packaging products seriously pollute food in packages, so the development of the environment-friendly ink is imperative. The water-based ink is used as a novel packaging printing material, has the greatest advantages of no volatile organic solvent, reduces the amount of organic volatile matters (VOC), does not damage the health of ink manufacturers and printing operators, improves the environmental quality, and is called environment-friendly ink, so that the problems of the existing water-based gravure ink are urgently solved, and the application trend of the environment-friendly water-based ink cannot be blocked.
Disclosure of Invention
In order to improve solvent resistance, wear resistance and adhesive force of the water-based ink, the application provides environment-friendly water-based ink and a preparation method thereof.
The application provides an environmental protection water-based ink adopts following technical scheme:
an environment-friendly water-based ink comprises the following raw materials in parts by weight:
10-20 parts of modified aqueous polyurethane emulsion;
25-35 parts of starch;
0.5-0.8 part of sodium hydroxide;
0.4-0.7 part of oxidant;
5-10 parts of phthalocyanine blue;
0.1-0.3 part of urea;
0.1-0.6 part of defoaming agent;
1-5 parts of a surfactant;
10-18 parts of water;
the preparation method of the modified aqueous polyurethane emulsion comprises the step of chemically grafting polyethylene glycol on the surface of polyurethane.
By adopting the technical scheme, the aqueous polyurethane emulsion and the starch are both environment-friendly materials, the aqueous polyurethane emulsion and the starch are combined, the starch can form a stable composite emulsion structure with the aqueous polyurethane emulsion, the starch can ensure the viscosity and the adhesive force of the ink, the aqueous polyurethane increases the viscosity and the toughness of a starch binder, in addition, the polyethylene glycol chemically grafted on the surface of the aqueous polyurethane introduces ether bonds on the surface of the aqueous polyurethane, carboxyl groups and aldehyde base groups in starch chain segments, the increase of the polar groups increases the crosslinking density in polyurethane molecules, the combination between the molecular chain segments is firmer, the acting force between molecules is stronger, the wear resistance of the ink is improved, the swelling resistance of the polymer is also improved, and the aqueous ink has good solvent resistance.
Optionally, the environment-friendly water-based ink comprises the following raw materials in parts by weight:
15-18 parts of modified aqueous polyurethane emulsion;
25-32 parts of starch;
0.5-0.8 part of sodium hydroxide;
0.4-0.7 part of oxidant;
7-10 parts of phthalocyanine blue;
0.1-0.3 part of urea;
0.1-0.5 part of defoaming agent;
1-4 parts of a surfactant;
10-15 parts of water.
By adopting the technical scheme, the proportion of the modified aqueous polyurethane emulsion to the starch is adjusted, so that the components of the binder, the filler and the auxiliary agent of the aqueous ink are optimally matched, and the aqueous ink with good solvent resistance, wear resistance and adhesive force is obtained.
Optionally, the polyethylene glycol has a molecular weight of one of 200, 400 and 600.
By adopting the technical scheme, polyethylene glycol with low molecular weight is introduced to the surface of the water-based polyurethane, so that the winding between macromolecular chains is avoided, the viscosity of the polymer is increased, the fluidity and spreadability of the water-based ink are affected, and the polyethylene glycol is grafted, so that the quantity of polar groups introduced to the surface of the water-based polyurethane is increased, and the solvent resistance of the water-based ink is improved.
Optionally, the modified aqueous polyurethane emulsion comprises the following preparation steps: uniformly mixing polyethylene glycol, polyester polyol and a solvent, heating, adding toluene diisocyanate solution and a catalyst, reacting to obtain polyurethane prepolymer, adding acetone to reduce viscosity, adding a chain extender to react, neutralizing with triethylamine, adding water, stirring and emulsifying to obtain modified aqueous polyurethane emulsion.
By adopting the technical scheme, polyethylene glycol and polyester polyol are combined and react with toluene diisocyanate to generate polyurethane prepolymer, then the polyurethane prepolymer reacts with a chain extender to obtain aqueous polyurethane emulsion in an emulsifying step, and a large number of polar group ether bonds are introduced into polyurethane molecules through the steps, so that the polarity and intermolecular acting force of polymer molecules are improved, and further the solvent resistance, adhesive force and wear resistance of the ink are improved by taking starch as a binder of the aqueous ink.
Optionally, the mass ratio of the polyethylene glycol to the polyester polyol to the toluene diisocyanate is (0.5-1.2): 0.09-0.4): 1.5-2.2.
By adopting the technical scheme, the isocyanate groups in the toluene diisocyanate react with the hydroxyl groups, so that polyethylene glycol is combined with polyester polyol and is introduced onto polyurethane molecules, the number of polar groups on the polyurethane molecules is increased, the crosslinking density is increased, the binding force between molecular chain segments is firmer, and the solvent resistance and the wear resistance of the waterborne polyurethane are improved.
Optionally, the molecular weight of the polyester polyol is 2000-6000.
Alternatively, the hydroxyl value (mgKOH. G -1 ) An acid value of 56.+ -.4 (mgKOH. G) -1 ) Less than or equal to 0.5 percent and the mass fraction of water is less than or equal to 0.05 percent.
Optionally, the oxidant is one of sodium hypochlorite, hydrogen peroxide and potassium permanganate.
By adopting the technical scheme, the oxidant is added, the starch can be subjected to oxidation reaction with the oxidant, the oxidized starch contains carboxyl and aldehyde groups, the starch has good cohesiveness, stability and dispersibility due to the introduction of the carboxyl, and has good corrosion resistance due to the introduction of the aldehyde groups.
Optionally, the surfactant is one of sodium fatty acid, sodium dodecyl sulfate and sodium stearate.
By adopting the technical scheme, the surfactant can be adsorbed on the surface of the solution, so that the aim of reducing the surface tension of the liquid is fulfilled, and the uniform dispersibility of the pigment and the auxiliary agent in the water-based ink in the binder is improved.
In a second aspect, the present application provides a method for preparing an environment-friendly water-based ink, which adopts the following technical scheme:
the preparation method of the environment-friendly water-based ink comprises the following preparation steps:
preparation of aqueous ink: heating water, adding starch, stirring uniformly, adding oxidant, stirring uniformly, adding sodium hydroxide, and stirring to obtain starch slurry. And uniformly mixing the modified aqueous polyurethane emulsion and the starch slurry to obtain a connecting material, and adding phthalocyanine blue, urea, a defoaming agent and a surfactant into the connecting material to uniformly stir to obtain the aqueous ink.
Through adopting above-mentioned technical scheme, at first with starch heating stirring, the heating makes the inside that water molecule can freely get into starch granule, because starch granule has very high permeability, makes waterborne polyurethane and starch thick liquid interpenetration, then adds the oxidant, introduces polar group on starch molecule, and the sodium hydroxide can destroy starch's granule structure, makes starch molecule hydration and then dissolves in water.
And forming a composite emulsion structure by the starch slurry and the aqueous polyurethane emulsion, and then adding the pigment and the auxiliary agent, mixing and stirring to obtain the environment-friendly aqueous ink.
Optionally, in the step of heating the water and then adding the starch, the water is heated to a temperature of 70-85 ℃.
By adopting the technical scheme, the starch granules have very high permeability, can be dissolved in hot water, but are not dissolved in cold water, and in the hot water, water molecules can freely enter the starch granules, so that the starch is fully dissolved in the water.
Optionally, after the starch slurry is obtained, the modified aqueous polyurethane emulsion and the starch slurry are uniformly mixed in the step of uniformly mixing the modified aqueous polyurethane emulsion and the starch slurry at 25-35 ℃.
By adopting the technical scheme, the aqueous polyurethane emulsion and the starch slurry are mutually mixed and fully dissolved to form a composite emulsion structure which is used as a connecting material of the aqueous ink, so that the ink has good solvent resistance, wear resistance and adhesive force.
In summary, the present application has the following beneficial effects:
1. because the application adopts the combination of the aqueous polyurethane emulsion and the starch, the starch can form a stable composite emulsion structure with the aqueous polyurethane emulsion, the viscosity and the adhesive force of the printing ink can be ensured by the starch, and the viscosity and the toughness of the starch connecting material are increased by the aqueous polyurethane.
2. In the application, the polyethylene glycol is preferably chemically grafted on the surface of the waterborne polyurethane, ether bonds are introduced on the surface of the waterborne polyurethane, and the polar groups are increased, so that the crosslinking density in polyurethane molecules is increased, the acting force among molecules is strong, the combination among molecular chain segments is firm, the wear resistance of the ink is increased, the swelling resistance of the polymer is also improved, and the waterborne ink has good solvent resistance.
3. According to the method, the starch is heated and stirred, so that water molecules can freely enter the starch particles, and as the starch particles have high permeability, the water-based polyurethane and the starch slurry are mutually permeated, and the adhesive force of the connecting material is improved.
Detailed Description
The present application is described in further detail below in connection with examples and comparative examples.
Raw material sources of examples and comparative examples: the starting materials used in the examples and comparative examples are commercially available.
Preparation example of modified aqueous polyurethane emulsion
Preparation example 1
Preparation of modified aqueous polyurethane emulsion: 100g of polyethylene glycol with molecular weight of 400, 20g of polyester polyol and 40g of dimethylformamide are put into a four-neck flask, the temperature is raised to 80 ℃, and a solution of 70wt% of toluene diisocyanate is added dropwise in sequence, wherein the solvent is dimethylformamide, and the polyethylene glycol is: polyester polyol: toluene diisocyanate with the mass ratio of 1:0.2:2 and 0.95g dibutyl tin under the protection of nitrogen, reacting for 3 hours to obtain polyurethane prepolymer, adding 11g acetone to reduce the viscosity,adding 9g of chain extender 1, 4-butanediol for reaction for 2 hours, cooling to 40 ℃, adding 13g of triethylamine for neutralization, adding 30 ℃ of water for stirring and emulsifying, adding water to adjust the mass fraction to 32wt%, and distilling to remove acetone to obtain aqueous polyurethane emulsion, wherein the molecular weight of polyester polyol is 4000, and the hydroxyl value (mgKOH.g) -1 ) An acid value of 56.+ -.4 (mgKOH. G) -1 ) Less than or equal to 0.5 percent and the mass fraction of water is less than or equal to 0.05 percent.
Preparation example 2
In the preparation of the modified aqueous polyurethane emulsion, the molecular weight of polyethylene glycol is 200, the molecular weight of polyester polyol is 2000, the polyethylene glycol is 50g, the polyester polyol is 9g, the mass fraction of toluene diisocyanate solution is 70wt%, the solvent is dimethylformamide, and the polyethylene glycol: polyester polyol: the mass ratio of toluene diisocyanate was 0.5:0.09:1.5.
Preparation example 3
In the preparation of the modified aqueous polyurethane emulsion, the molecular weight of polyethylene glycol is 600, the molecular weight of polyester polyol is 6000, the polyethylene glycol is 120g, the polyester polyol is 40g, the mass fraction of toluene diisocyanate solution is 70wt%, the solvent is dimethylformamide, and the polyethylene glycol: polyester polyol: the mass ratio of toluene diisocyanate was 1.2:0.4:2.2.
Preparation example 4
The difference from preparation example 2 is that polyethylene glycol is 20g, polyester polyol is 5g, toluene diisocyanate solution is 70wt%, solvent is dimethylformamide, polyethylene glycol: polyester polyol: the mass ratio of toluene diisocyanate was 0.2:0.05:1.2.
Preparation example 5
The difference from preparation example 3 is that polyethylene glycol is 150g, polyester polyol is 70g, toluene diisocyanate solution is 70wt%, solvent is dimethylformamide, polyethylene glycol: polyester polyol: the mass ratio of toluene diisocyanate was 1.5:0.7:2.5.
Preparation example 6
The difference from preparation example 1 is that the molecular weight of polyethylene glycol is 2000.
Preparation example 7
The difference from preparation example 3 is that the molecular weight of the polyester polyol is 8000.
Examples
Example 1
The preparation method of the environment-friendly water-based ink comprises the following preparation steps:
preparation of aqueous ink: heating water to 80 ℃, then adding starch, stirring for 30min, adding oxidant sodium hypochlorite, stirring for 10min, then adding sodium hydroxide, stirring to obtain starch slurry, uniformly mixing modified aqueous polyurethane emulsion and the starch slurry at 30 ℃ to obtain a connecting material, wherein the modified aqueous polyurethane emulsion is prepared by adopting preparation example 1, cooling to room temperature, adding phthalocyanine blue, urea, defoamer polydimethylsiloxane and surfactant fatty acid sodium into the connecting material, and stirring for 35min to obtain the aqueous ink.
Example 2
A preparation method of environment-friendly water-based ink is different from that in the embodiment 1 in that an oxidant is hydrogen peroxide, a surfactant is sodium dodecyl sulfate, the molecular weight of polyethylene glycol is 200, water is heated, then the water is heated to 70 ℃ in the step of adding starch, and modified water-based polyurethane emulsion and starch slurry are uniformly mixed at 25 ℃ to obtain a connecting material, wherein the modified water-based polyurethane emulsion is prepared by adopting the preparation example 2.
Example 3
A preparation method of environment-friendly water-based ink is different from that in the embodiment 1 in that an oxidant is potassium permanganate, a surfactant is sodium stearate, the molecular weight of polyethylene glycol is 600, water is heated, then the water is heated to 85 ℃ in the step of adding starch, modified water-based polyurethane emulsion and starch slurry are uniformly mixed at 35 ℃ to obtain a connecting material, and the modified water-based polyurethane emulsion is prepared by adopting the preparation example 3.
Examples 1-3 the components of the raw materials and their corresponding parts by weight are shown in Table 1.
TABLE 1 weight (g) of the raw materials in examples 1-3
| Component (A) | Example 1 | Example 2 | Example 3 |
| Modified aqueous polyurethane emulsion | 15 | 10 | 20 |
| Starch | 30 | 25 | 35 |
| Sodium hydroxide | 0.6 | 0.8 | 0.5 |
| Oxidizing agent | 0.5 | 0.7 | 0.4 |
| Phthalocyanine blue | 8 | 10 | 5 |
| Urea | 0.2 | 0.3 | 0.1 |
| Defoaming agent | 0.4 | 0.6 | 0.1 |
| Surface active agent | 3 | 5 | 1 |
| Water and its preparation method | 15 | 18 | 10 |
Example 4
The preparation method of the environment-friendly water-based ink is different from that of the embodiment 1 in that the modified water-based polyurethane emulsion is prepared by adopting a preparation example 6.
Example 5
The preparation method of the environment-friendly water-based ink is different from that of the embodiment 1 in that the modified water-based polyurethane emulsion is prepared by adopting the preparation example 7.
Example 6
The preparation method of the environment-friendly water-based ink is different from that of the embodiment 1 in that the modified water-based polyurethane emulsion is prepared by adopting the preparation example 4.
Example 7
The preparation method of the environment-friendly water-based ink is different from that of the embodiment 1 in that the modified water-based polyurethane emulsion is prepared by adopting a preparation example 5.
Example 8
A preparation method of environment-friendly water-based ink is different from example 1 in that in the step of heating water and then adding starch, the temperature of heating water is 60 ℃.
Example 9
A preparation method of environment-friendly water-based ink is different from example 1 in that in the step of heating water and then adding starch, the temperature of heating water is 95 ℃.
Example 10
The preparation method of the environment-friendly water-based ink is different from the embodiment 1 in that the modified water-based polyurethane emulsion and the starch slurry are uniformly mixed at 45 ℃ to obtain the connecting material.
Example 11
The preparation method of the environment-friendly water-based ink is different from the embodiment 1 in that the modified water-based polyurethane emulsion and the starch slurry are uniformly mixed at 20 ℃ to obtain the binder.
Comparative example
Comparative example 1
The preparation method of the environment-friendly water-based ink is different from the embodiment 1 in that the specific preparation steps of the modified water-based polyurethane emulsion are as follows: 100g of polyethylene glycol with the molecular weight of 400 and 40g of dimethylformamide are put into a four-neck flask, the temperature is raised to 80 ℃, and 70wt% of toluene diisocyanate solution is added dropwise in sequence, wherein the solvent is dimethylformamide, and the polyethylene glycol is: the mass ratio of toluene diisocyanate is 1:2,0.95g of dibutyltin is reacted for 3 hours under the protection of nitrogen to obtain polyurethane prepolymer, then 11g of acetone is added to reduce the viscosity, then 9g of chain extender 1, 4-butanediol is added to react for 2 hours, the temperature is reduced to 40 ℃, 13g of triethylamine is added to neutralize, then 30 ℃ of water is added to stir and emulsify, the mass fraction of water is adjusted to be 32wt%, and acetone is distilled off to obtain modified aqueous polyurethane emulsion.
Comparative example 2
The preparation method of the environment-friendly water-based ink is different from the embodiment 1 in that the water-based polyurethane emulsion is not modified, and the specific preparation steps are as follows: 20g of polyester polyol and 40g of dimethylformamide are put into a four-neck flask, the temperature is raised to 80 ℃, and 70wt% of toluene diisocyanate solution is added dropwise in sequence, wherein the solvent is dimethylformamide, and the polyester polyol is prepared by the following steps: reacting for 3 hours under the protection of nitrogen and with 0.2:2 mass ratio of toluene diisocyanate and 0.95g of dibutyltin to obtain polyurethane prepolymer, adding 11g of acetone to reduce viscosity, adding 9g of chain extender 1, 4-butanediol to react for 2 hours, cooling to 40 ℃, adding 13g of triethylamine to neutralize, adding 30 ℃ of water to stir and emulsify, adding water to adjust the mass fraction to 32wt%, distilling to remove acetone to obtain modified aqueous polyurethane emulsion,
comparative example 3
A preparation method of environment-friendly water-based ink is different from that in the embodiment 1 in that the raw materials do not comprise starch. The preparation method of the water-based ink comprises the following steps: and uniformly stirring the modified aqueous polyurethane emulsion at 30 ℃ to obtain a connecting material, wherein the modified aqueous polyurethane emulsion is prepared by adopting preparation example 1, and after the temperature is reduced to room temperature, adding phthalocyanine blue, urea, a defoaming agent polydimethylsiloxane and a surfactant sodium fatty acid into the connecting material, and stirring for 35min to obtain the aqueous ink.
Performance test
Detection method
Abrasion resistance test: the test was carried out according to GB3960-83 standard with a test load of 20Kg. Attachment fastness was determined according to GB/T13217.7-2009; water resistance and solvent resistance test: the water resistance and solvent resistance of the water-based ink are tested by adopting a soaking method, the water-based ink prepared in the examples 1-11 and the comparative examples 1-3 is used as a test sample, the prepared water-based ink is placed above the sample scraping paper in a small amount by using an ink adjusting knife, the scraper is scraped on the sample paper from top to bottom to form a uniform sample scraping, the sample scraping is placed at normal temperature and dried for 24 hours, the dried sample scraping is sheared to be 3cm x 3cm in size, the dried sample scraping is respectively placed in 95% ethanol and deionized water, the dried sample scraping is taken out after being soaked for 24 hours, and is compared with the sample scraping which is not soaked, the color change of the sample scraping is detected, and the evaluation grade is the best grade 5 (no color change) and the worst grade 1 (severe color change).
TABLE 2 Performance test results
| Coefficient of friction | Water resistance | Ethanol resistance | Attachment fastness (%) | |
| Example 1 | 0.17 | Grade 5 | Grade 5 | 98 |
| Example 2 | 0.18 | Grade 5 | Grade 5 | 98 |
| Example 3 | 0.18 | Grade 5 | Grade 5 | 97 |
| Example 4 | 0.27 | Grade 4 | Grade 4 | 94 |
| Example 5 | 0.31 | Grade 4 | Grade 4 | 95 |
| Example 6 | 0.33 | Grade 4 | Grade 4 | 93 |
| Example 7 | 0.36 | Grade 4 | Grade 4 | 91 |
| Example 8 | 0.38 | 3 grade | 3 grade | 89 |
| Example 9 | 0.37 | 3 grade | 3 grade | 87 |
| Example 10 | 0.39 | 3 grade | 3 grade | 93 |
| Example 11 | 0.38 | 3 grade | 3 grade | 85 |
| Comparative example 1 | 0.69 | Level 1 | Level 2 | 69 |
| Comparative example 2 | 0.63 | Level 1 | Level 2 | 67 |
| Comparative example 3 | 0.68 | Level 1 | Level 2 | 62 |
It can be seen from the combination of examples 4 to 5 and example 1 and the combination of Table 2 that the molecular weight of polyethylene glycol and polyester polyol is not too high, which increases the viscosity of the prepared binder, leads to a decrease in the adhesion of the aqueous ink, an increase in defects after drying, and a decrease in other properties.
It can be seen from the combination of examples 6 to 7 and example 1 and the combination of Table 2 that the mass ratio of polyethylene glycol, polyester polyol and toluene diisocyanate determines the performance of the aqueous polyurethane emulsion as a binder, and that too low a mass of polyethylene glycol and polyester polyol results in a decrease in crosslinking density, and that both the solvent resistance and the adhesion of the binder are decreased, and that if the mass of both are too high, the viscosity is increased and the workability of the aqueous ink is decreased.
It can be seen from the combination of examples 8 to 11 and example 1 and the combination of table 2 that by adjusting the mixing temperature of the aqueous polyurethane emulsion and the starch slurry, the aqueous polyurethane emulsion and the starch slurry form a stable composite emulsion structure, and the aqueous polyurethane and the starch slurry are mutually penetrated due to the high permeability of the starch particles, so that the adhesive force, the wear resistance and the solvent resistance of the binder are improved.
It can be seen from the combination of comparative examples 1 to 3 of example 1 and Table 2 that the properties of example 1 are superior to those of comparative examples 1 to 3, polyethylene glycol with small molecular weight is selected to be chemically grafted onto the surface of polyurethane, and the introduction of polar groups greatly improves the wear resistance, solvent resistance and adhesion fastness of the aqueous ink. The high molecular weight polyethylene glycol increases the viscosity of the water-based ink, reduces the spreadability and fluidity of the ink, and reduces the overall performance of the ink.
The combination of starch and aqueous polyurethane emulsion ensures that each performance of the aqueous ink is optimal, carboxyl and aldehyde base groups in a starch chain segment and polyethylene glycol chemically grafted on the surface of the aqueous polyurethane are introduced into ether bond on the surface of the aqueous polyurethane, and the addition of the polar groups ensures that the combination between molecular chain segments is firmer, the acting force between molecules is stronger, the wear resistance of the ink is increased, the swelling resistance of a polymer is also improved, and the aqueous ink has good solvent resistance.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. An environment-friendly water-based ink, which is characterized in that: the material comprises the following raw materials in parts by weight:
10-20 parts of modified aqueous polyurethane emulsion;
25-35 parts of starch;
0.5-0.8 part of sodium hydroxide;
0.4-0.7 part of oxidant;
5-10 parts of phthalocyanine blue;
0.1-0.3 part of urea;
0.1-0.6 part of defoaming agent;
1-5 parts of a surfactant;
10-18 parts of water;
the preparation method of the modified aqueous polyurethane emulsion comprises the step of chemically grafting polyethylene glycol on the surface of polyurethane.
2. The environmentally-friendly water-based ink according to claim 1, wherein: the environment-friendly water-based ink comprises the following raw materials in parts by weight:
15-18 parts of modified aqueous polyurethane emulsion;
25-32 parts of starch;
0.5-0.8 part of sodium hydroxide;
0.4-0.7 part of oxidant;
7-10 parts of phthalocyanine blue;
0.1-0.3 part of urea;
0.1-0.5 part of defoaming agent;
1-4 parts of a surfactant;
10-15 parts of water.
3. The environmentally-friendly water-based ink according to claim 1, wherein: the polyethylene glycol molecular weight is 200, 400 and 600.
4. The environmentally-friendly water-based ink according to claim 1, wherein: the modified aqueous polyurethane emulsion comprises the following preparation steps: uniformly mixing polyethylene glycol, polyester polyol and a solvent, heating, adding toluene diisocyanate solution and a catalyst, reacting to obtain polyurethane prepolymer, adding acetone to reduce viscosity, adding a chain extender to react, neutralizing with triethylamine, adding water, stirring and emulsifying to obtain modified aqueous polyurethane emulsion.
5. The environmentally-friendly water-based ink according to claim 4, wherein: the mass ratio of polyethylene glycol to polyester polyol to toluene diisocyanate is (0.5-1.2) (0.09-0.4) (1.5-2.2).
6. The environmentally-friendly water-based ink according to claim 1, wherein: the surfactant is one of sodium fatty acid, sodium dodecyl sulfate and sodium stearate.
7. The environmentally-friendly water-based ink according to claim 1, wherein: the oxidant is one of sodium hypochlorite, hydrogen peroxide and potassium permanganate.
8. The method for preparing the environment-friendly water-based ink as claimed in any one of claims 1 to 7, which is characterized in that: the method comprises the following steps:
preparation of aqueous ink: heating water, adding starch, stirring uniformly, adding an oxidant, stirring uniformly, adding sodium hydroxide, stirring uniformly to obtain starch slurry, mixing modified aqueous polyurethane emulsion and starch slurry uniformly to obtain a connecting material, adding phthalocyanine blue, urea, a defoaming agent and a surfactant into the connecting material, and stirring uniformly to obtain the aqueous ink.
9. The method for preparing the environment-friendly water-based ink as claimed in claim 8, wherein the method comprises the following steps: the step of heating the water and then adding the starch is performed at a temperature of 70-85 ℃.
10. The method for preparing the environment-friendly water-based ink as claimed in claim 8, wherein the method comprises the following steps: after the starch slurry is obtained, the modified aqueous polyurethane emulsion and the starch slurry are uniformly mixed in the step of uniformly mixing the modified aqueous polyurethane emulsion and the starch slurry at 25-35 ℃.
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