CN116218281A - Environment-friendly film water-based ink and preparation method thereof - Google Patents
Environment-friendly film water-based ink and preparation method thereof Download PDFInfo
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- C09D11/02—Printing inks
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Abstract
The invention discloses an environment-friendly film water-based ink and a preparation method thereof, and relates to the technical field of ink, wherein the ink comprises the following raw materials: 10 to 20 parts of modified aqueous polyurethane emulsion, 20 to 40 parts of modified aqueous acrylic resin, 10 to 20 parts of pigment, 0.8 to 1.2 parts of triethanolamine, 0.4 to 0.8 part of film forming additive and 10 to 30 parts of water; the preparation method comprises the following steps: s1, mixing modified aqueous polyurethane emulsion, modified aqueous acrylic resin and water, and stirring for 30-60 min at 1500-2000 r/min; s2, continuously adding the pigment, the triethanolamine and the film forming auxiliary agent, and continuously stirring and uniformly mixing. The invention has the beneficial effects that the adhesive force of the water-based ink and the film can be improved and the water resistance of the ink can be improved by modifying the water-based acrylic acid and the water-based polyurethane and performing synergistic action with triethanolamine, a film forming additive and the like.
Description
Technical Field
The invention relates to the technical field of ink, in particular to environment-friendly film water-based ink and a preparation method thereof.
Background
In the current stage of China, the largest use amount of the printing and packaging of the food is chlorinated polypropylene ink, polyurethane ink and polyacrylate ink, the solvent type ink contains a large amount of benzene, toluene, butanone, ethyl acetate and other organic solvents, and in the use process of the solvent type ink, the volatilized solvents pollute the air and harm the body health of operators, and the residual solvents in packaging products can seriously pollute the food in the package. Under the circumstance that the environmental protection consciousness is gradually enhanced, particularly in the fields of food, children toys and medical packaging, development of environment-friendly ink is imperative.
Among the many environmental-friendly inks, aqueous inks are a more promising class. The main solvent of the water-based ink is water, the water is clean and pollution-free after volatilizing, operators are safe, healthy and nontoxic in the using process, the water has conductivity and can not accumulate static electricity, and the production site is very safe. The water-based ink has incomparable advantages on environmental protection, health and safety compared with solvent-based ink, and is a real green product.
Although the water-based ink is safe, healthy and nontoxic, as solvent water of the water-based ink is a polar material, the water-based ink is difficult to wet on the surface of a plastic film with low polarity, so that the adhesive force on the surface of the film is poor. The common water-based ink comprises water-based acrylic ink and water-based polyurethane ink, wherein the water-based acrylic ink has good adhesive force when printed on a high-density and low-density polyethylene film, but has poor adhesive force when printed on a polypropylene film, namely the water-based acrylic ink cannot be commonly used on films such as polyethylene, polypropylene, PET, PVC, aluminum foil and the like. When the water-based acrylic emulsion with poor re-solubility is selected to prepare the water-based plastic surface printing ink, the water resistance is good but the blocking phenomenon can occur after film formation, the workload of workers is increased, and the product is unqualified due to poor printing effect. When the aqueous acrylic emulsion with better re-solubility is selected to prepare the aqueous plastic surface printing ink, the problem that the printed finished product is not water-proof and can fade when rubbed with water can appear after film formation. When the acrylic emulsion with better re-solubility and the emulsion with worse re-solubility are selected to be matched to prepare the water-based plastic surface printing ink, the problem that the product is not water-resistant after being printed into a film and is slightly rubbed and discolored after meeting water still occurs. Although the aqueous polyurethane ink has good adhesion to PET and nylon films, the aqueous polyurethane ink has relatively poor adhesion to polypropylene printing films and poor water resistance. When the water resistance is too poor, the phenomenon of biting color occurs during printing, and when the water-based compound glue is used for compounding in the subsequent dry compounding process, the phenomenon that the water-based compound glue slightly dissolves the ink on the printed film to cause white spots occurs, so that the printed product is unqualified can also occur.
Therefore, how to improve the adhesive force of the water-based ink on the plastic film is a technical problem to be solved.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides an environment-friendly film water-based ink and a preparation method thereof.
The technical scheme of the invention is as follows:
the invention provides environment-friendly film water-based ink, which comprises the following raw materials in parts by weight:
10 to 20 parts of modified aqueous polyurethane emulsion, 20 to 40 parts of modified aqueous acrylic resin, 10 to 20 parts of pigment, 0.8 to 1.2 parts of triethanolamine, 0.4 to 0.8 part of film forming additive and 10 to 30 parts of water.
Preferably, the preparation method of the aqueous polyurethane emulsion comprises the following steps: adding an emulsifying agent into water to obtain emulsion; adding polyethylene wax particles into the emulsion, and uniformly dispersing; continuously adding polyurethane particles, and uniformly dispersing; finally adding a silane coupling agent and nano zinc oxide, and stirring for 1-3 hours at 60-80 ℃ to obtain the modified waterborne polyurethane emulsion.
Preferably, the mass ratio of polyurethane particles, polyethylene wax particles and nano zinc oxide to water is 3-4:1-2:0.6-1:20-40.
Preferably, the addition amount of the emulsifier is 4-8% of the mass of the polyurethane particles, and the addition amount of the silane coupling agent is 1-2% of the mass of the polyurethane particles.
Preferably, the preparation method of the modified aqueous acrylic resin comprises the following steps:
dissolving beta-cyclodextrin into deionized water, heating to 70-80 ℃ for dissolution, continuously adding modified nano particles and a silane coupling agent, performing ultrasonic dispersion for 30-60 min, and finally adding polyethylene glycol to obtain modified beta-cyclodextrin;
mixing acrylic acid, hydroxypropyl methacrylate, methyl methacrylate, diacetone acrylamide, glycerin fatty acid ester and deionized water, continuously adding modified beta-cyclodextrin, stirring and emulsifying to obtain a mixed solution I;
dissolving adipic acid dihydrazide and azodiisobutyronitrile in deionized water to prepare a mixed solution II;
heating the first mixed solution to 50-60 ℃, dripping the second mixed solution into the first mixed solution, continuously heating to 80-100 ℃, and reacting for 2-8 hours to obtain the modified aqueous acrylic resin.
Preferably, the preparation method of the modified nanoparticle comprises the following steps: dispersing nano titanium dioxide and nano silicon dioxide in water to form a dispersion liquid; adding a silane coupling agent into ethanol, and adding nanocellulose for high-speed dispersion; continuously adding the dispersion liquid, heating and reacting for 1-3 hours at 50-70 ℃, and cooling to obtain the modified nano particles.
Preferably, the mass ratio of the nano silicon dioxide to the nano titanium dioxide to the nano cellulose is 2-4:1-2:1-2, and the addition amount of the silane coupling agent is 1-3% of the total mass of the nano titanium dioxide, the nano silicon dioxide and the nano cellulose.
Preferably, the mass ratio of the modified nano particles to the beta-cyclodextrin to the polyethylene glycol to the silane coupling agent is 1-2:2-4:1-2:0.01-0.02.
Preferably, the mass ratio of the acrylic acid to the hydroxypropyl methacrylate, the methyl methacrylate, the diacetone acrylamide, the glycerin fatty acid ester, the adipic acid dihydrazide and the azodiisobutyronitrile is 2-6:2-6:4-8:0.4-0.8:0.8-1.2:0.4-0.6:0.4-0.6, and the addition amounts of the nano silicon dioxide and the beta-cyclodextrin are 3-7% and 5-9% of the mass of the acrylic acid respectively.
The second aspect of the invention provides a preparation method of environment-friendly film water-based ink, which comprises the following steps:
s1, mixing modified aqueous polyurethane emulsion, modified aqueous acrylic resin and water, and stirring for 30-60 min at 1500-2000 r/min;
s2, continuously adding the pigment, the triethanolamine and the film forming auxiliary agent, and continuously stirring and uniformly mixing.
The invention has at least one of the following beneficial effects:
the invention takes aqueous acrylic acid and aqueous polyurethane as a connecting material, and improves the adhesive force of the connecting material and a film by modifying the aqueous acrylic acid and the aqueous polyurethane, in particular:
on one hand, the invention adds the emulsifier into water to obtain emulsion, and adds polyethylene wax particles, polyurethane particles, silane coupling agent and nano zinc oxide into the emulsion to prepare modified aqueous polyurethane emulsion; the polyethylene wax can be used as a carrier of pigment, improves the dispersibility of the pigment and filler, has good anti-sedimentation effect, and improves the wear resistance of the ink; the silane coupling agent is adopted to carry out surface treatment on the nano zinc oxide, so that the silane coupling agent is successfully connected to the surface of the nano zinc oxide, and the nano zinc oxide and the water-based polyurethane can be tightly connected to form larger molecules, so that the water-based ink has more points to interact with a substrate, the adhesive force of the obtained water-based ink is improved, and the silane coupling agent contains a large amount of carbon-carbon double construction, so that the water-based ink can be crosslinked with the water-based polyurethane resin, the network density of the water-based polyurethane is improved, the penetration of water molecules is prevented, and the water resistance of the obtained water-based ink is improved; in addition, as the particle size of the nano zinc oxide is smaller, the particle size distribution is more uniform, and the dispersibility of the nano zinc oxide in the water-based ink is improved by adding the emulsifier and the silane coupling agent. Therefore, the dispersibility of the aqueous polyurethane and the nano zinc oxide can be improved by modification, the adhesion of the polyurethane and the film can be improved, and the water resistance of the ink can be improved.
On the other hand, by modifying the water-based acrylic resin, the modified nano particles not only can keep the good fluidity and fineness of the ink and prevent pigment sedimentation, but also can be uniformly dispersed in the water-based acrylic resin, so that the wear resistance and corrosion resistance of the ink can be improved, and the modified particles can be tightly connected with the water-based acrylic resin to form larger molecules, so that the water-based ink has more points to interact with a substrate, the adhesive force of the water-based ink and a film can be improved, and the water resistance of the ink can be improved; the beta-cyclodextrin is environment-friendly, the viscosity and the surface tension of the liquid can be increased, and the surface of the modified beta-cyclodextrin is provided with hydroxyl, so that the adhesive force of the water-based ink and the film can be improved.
In summary, the aqueous acrylic acid and the aqueous polyurethane are used as the connecting materials, and the aqueous acrylic acid and the aqueous polyurethane are modified and are synergistic with triethanolamine, a film forming additive and the like, so that the adhesive force of the aqueous ink and the film can be improved, and the water resistance of the ink can be improved.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, but the present invention is not limited to the following specific examples.
Example 1
Weighing the following raw materials in parts by weight:
10 parts of modified aqueous polyurethane emulsion, 20 parts of modified aqueous acrylic resin, 10 parts of phthalocyanine pigment, 0.8 part of triethanolamine, 0.4 part of film forming auxiliary agent dodecanol ester and 10 parts of water.
The preparation method of the aqueous polyurethane emulsion comprises the following steps: adding an emulsifier OP-10 into water to obtain emulsion; adding polyethylene wax particles into the emulsion, and uniformly dispersing; continuously adding polyurethane particles, and uniformly dispersing; and finally adding a silane coupling agent and nano zinc oxide, and stirring for 3 hours at 60 ℃ to obtain the modified waterborne polyurethane emulsion. The mass ratio of the polyurethane particles to the polyethylene wax particles to the nano zinc oxide to the water is 3:1:0.6:20. The addition amount of the emulsifier is 4% of the mass of the polyurethane particles, and the addition amount of the silane coupling agent is 1% of the mass of the polyurethane particles.
The preparation method of the modified aqueous acrylic resin comprises the following steps:
dispersing nano titanium dioxide and nano silicon dioxide in water to form a dispersion liquid; adding a silane coupling agent into ethanol, and adding nanocellulose for high-speed dispersion; and continuously adding the dispersion liquid, heating at 50 ℃ for reaction for 3 hours, and cooling to obtain the modified nano particles. The mass ratio of the nano silicon dioxide to the nano titanium dioxide to the nano cellulose is 2:1:1, and the addition amount of the silane coupling agent is 1% of the total mass of the nano titanium dioxide, the nano silicon dioxide and the nano cellulose.
Dissolving beta-cyclodextrin into deionized water, heating to 70 ℃ for dissolution, continuously adding modified nano particles and a silane coupling agent, performing ultrasonic dispersion for 30min, and finally adding polyethylene glycol to obtain the modified beta-cyclodextrin. The mass ratio of the modified nano particles to the beta-cyclodextrin to the polyethylene glycol to the silane coupling agent is 1:2:1:0.01.
Mixing acrylic acid, hydroxypropyl methacrylate, methyl methacrylate, diacetone acrylamide, glycerin fatty acid ester and deionized water, continuously adding modified beta-cyclodextrin, stirring and emulsifying to obtain a mixed solution I; the mass ratio of the acrylic acid to the hydroxypropyl methacrylate, the methyl methacrylate, the diacetone acrylamide and the glycerin fatty acid ester is 2:2:4:0.4:0.8, and the addition amounts of the nano silicon dioxide and the beta-cyclodextrin are respectively 3% and 5% of the mass of the acrylic acid.
Dissolving adipic acid dihydrazide and azodiisobutyronitrile in deionized water to prepare a mixed solution II; the mass ratio of the acrylic acid to the adipic acid dihydrazide to the azodiisobutyronitrile is 2:0.4:0.4.
And heating the first mixed solution to 50 ℃, dripping the second mixed solution into the first mixed solution, continuously heating to 80 ℃, and reacting for 2 hours to obtain the modified aqueous acrylic resin.
The preparation method of the environment-friendly film water-based ink comprises the following steps:
s1, mixing modified aqueous polyurethane emulsion, modified aqueous acrylic resin and water, and stirring for 30min at 1500 r/min;
s2, continuously adding the pigment, the triethanolamine and the film forming auxiliary agent, and continuously stirring and uniformly mixing.
Example 2
Weighing the following raw materials in parts by weight:
12 parts of modified aqueous polyurethane emulsion, 25 parts of modified aqueous acrylic resin, 12 parts of phthalocyanine pigment, 0.9 part of triethanolamine, 0.5 part of film forming auxiliary agent dodecanol ester and 15 parts of water.
The preparation method of the aqueous polyurethane emulsion comprises the following steps: adding an emulsifier OP-10 into water to obtain emulsion; adding polyethylene wax particles into the emulsion, and uniformly dispersing; continuously adding polyurethane particles, and uniformly dispersing; and finally adding a silane coupling agent and nano zinc oxide, and stirring for 2.5 hours at 65 ℃ to obtain the modified waterborne polyurethane emulsion. The mass ratio of the polyurethane particles to the polyethylene wax particles to the nano zinc oxide to the water is 3.2:1.2:0.7:25. The addition amount of the emulsifier is 5% of the mass of the polyurethane particles, and the addition amount of the silane coupling agent is 1.2% of the mass of the polyurethane particles.
The preparation method of the modified aqueous acrylic resin comprises the following steps:
dispersing nano titanium dioxide and nano silicon dioxide in water to form a dispersion liquid; adding a silane coupling agent into ethanol, and adding nanocellulose for high-speed dispersion; and continuously adding the dispersion liquid, heating at 55 ℃ for reaction for 1.5 hours, and cooling to obtain the modified nano particles. The mass ratio of the nano silicon dioxide to the nano titanium dioxide to the nano cellulose is 2.5:1.2:1.2, and the addition amount of the silane coupling agent is 1.5 percent of the total mass of the nano titanium dioxide, the nano silicon dioxide and the nano cellulose.
Dissolving beta-cyclodextrin into deionized water, heating to 72 ℃ for dissolution, continuously adding modified nano particles and a silane coupling agent, performing ultrasonic dispersion for 50min, and finally adding polyethylene glycol to obtain the modified beta-cyclodextrin. The mass ratio of the modified nano particles to the beta-cyclodextrin to the polyethylene glycol to the silane coupling agent is 1.2:2.5:1.2:0.012.
Mixing acrylic acid, hydroxypropyl methacrylate, methyl methacrylate, diacetone acrylamide, glycerin fatty acid ester and deionized water, continuously adding modified beta-cyclodextrin, stirring and emulsifying to obtain a mixed solution I; the mass ratio of the acrylic acid to the hydroxypropyl methacrylate, the methyl methacrylate, the diacetone acrylamide and the glycerin fatty acid ester is 3:3:5:0.5:0.9, and the addition amounts of the nano silicon dioxide and the beta-cyclodextrin are respectively 4% and 6% of the mass of the acrylic acid.
Dissolving adipic acid dihydrazide and azodiisobutyronitrile in deionized water to prepare a mixed solution II; the mass ratio of the acrylic acid to the adipic acid dihydrazide to the azodiisobutyronitrile is 3:0.5:0.5.
And heating the first mixed solution to 52 ℃, dripping the second mixed solution into the first mixed solution, continuously heating to 85 ℃, and reacting for 7 hours to obtain the modified aqueous acrylic resin.
The preparation method of the environment-friendly film water-based ink comprises the following steps:
s1, mixing modified aqueous polyurethane emulsion, modified aqueous acrylic resin and water, and stirring for 50min at 1500 r/min;
s2, continuously adding the pigment, the triethanolamine and the film forming auxiliary agent, and continuously stirring and uniformly mixing.
Example 3
Weighing the following raw materials in parts by weight:
15 parts of modified aqueous polyurethane emulsion, 30 parts of modified aqueous acrylic resin, 15 parts of phthalocyanine pigment, 1 part of triethanolamine, 0.6 part of film forming auxiliary agent dodecanol ester and 20 parts of water.
The preparation method of the aqueous polyurethane emulsion comprises the following steps: adding an emulsifier OP-10 into water to obtain emulsion; adding polyethylene wax particles into the emulsion, and uniformly dispersing; continuously adding polyurethane particles, and uniformly dispersing; and finally adding a silane coupling agent and nano zinc oxide, and stirring for 2 hours at 70 ℃ to obtain the modified waterborne polyurethane emulsion. The mass ratio of the polyurethane particles to the polyethylene wax particles to the nano zinc oxide to the water is 3.5:1.5:0.8:30. The addition amount of the emulsifier is 6% of the mass of the polyurethane particles, and the addition amount of the silane coupling agent is 1.5% of the mass of the polyurethane particles.
The preparation method of the modified aqueous acrylic resin comprises the following steps:
dispersing nano titanium dioxide and nano silicon dioxide in water to form a dispersion liquid; adding a silane coupling agent into ethanol, and adding nanocellulose for high-speed dispersion; and continuously adding the dispersion liquid, heating at 60 ℃ for reaction for 2 hours, and cooling to obtain the modified nano particles. The mass ratio of the nano silicon dioxide to the nano titanium dioxide to the nano cellulose is 3:1.5:1.5, and the addition amount of the silane coupling agent is 2% of the total mass of the nano titanium dioxide, the nano silicon dioxide and the nano cellulose.
Dissolving beta-cyclodextrin into deionized water, heating to 75 ℃ for dissolution, continuously adding modified nano particles and a silane coupling agent, performing ultrasonic dispersion for 45min, and finally adding polyethylene glycol to obtain the modified beta-cyclodextrin. The mass ratio of the modified nano particles to the beta-cyclodextrin to the polyethylene glycol to the silane coupling agent is 1.5:3:1.5:0.015.
Mixing acrylic acid, hydroxypropyl methacrylate, methyl methacrylate, diacetone acrylamide, glycerin fatty acid ester and deionized water, continuously adding modified beta-cyclodextrin, stirring and emulsifying to obtain a mixed solution I; the mass ratio of the acrylic acid to the hydroxypropyl methacrylate, the methyl methacrylate, the diacetone acrylamide and the glycerin fatty acid ester is 4:4:6:0.6:1, and the addition amounts of the nano silicon dioxide and the beta-cyclodextrin are respectively 5% and 7% of the mass of the acrylic acid.
Dissolving adipic acid dihydrazide and azodiisobutyronitrile in deionized water to prepare a mixed solution II; the mass ratio of the acrylic acid to the adipic acid dihydrazide to the azodiisobutyronitrile is 46:0.5:0.5.
And heating the first mixed solution to 55 ℃, dripping the second mixed solution into the first mixed solution, continuously heating to 90 ℃, and reacting for 5 hours to obtain the modified aqueous acrylic resin.
The preparation method of the environment-friendly film water-based ink comprises the following steps:
s1, mixing modified aqueous polyurethane emulsion, modified aqueous acrylic resin and water, and stirring for 45min at 1800 r/min;
s2, continuously adding the pigment, the triethanolamine and the film forming auxiliary agent, and continuously stirring and uniformly mixing.
Example 4
Weighing the following raw materials in parts by weight:
28 parts of modified aqueous polyurethane emulsion, 35 parts of modified aqueous acrylic resin, 18 parts of phthalocyanine pigment, 1.1 parts of triethanolamine, 0.7 part of film forming auxiliary agent dodecanol ester and 25 parts of water.
The preparation method of the aqueous polyurethane emulsion comprises the following steps: adding an emulsifier OP-10 into water to obtain emulsion; adding polyethylene wax particles into the emulsion, and uniformly dispersing; continuously adding polyurethane particles, and uniformly dispersing; and finally adding a silane coupling agent and nano zinc oxide, and stirring for 1.5h at 75 ℃ to obtain the modified waterborne polyurethane emulsion. The mass ratio of the polyurethane particles to the polyethylene wax particles to the nano zinc oxide to the water is 3.8:1.8:0.9:35. The addition amount of the emulsifier is 7% of the mass of the polyurethane particles, and the addition amount of the silane coupling agent is 1.8% of the mass of the polyurethane particles.
The preparation method of the modified aqueous acrylic resin comprises the following steps:
dispersing nano titanium dioxide and nano silicon dioxide in water to form a dispersion liquid; adding a silane coupling agent into ethanol, and adding nanocellulose for high-speed dispersion; and continuously adding the dispersion liquid, heating at 68 ℃ for reaction for 1.5 hours, and cooling to obtain the modified nano particles. The mass ratio of the nano silicon dioxide to the nano titanium dioxide to the nano cellulose is 3.5:1.5:1.5, and the addition amount of the silane coupling agent is 2.5 percent of the total mass of the nano titanium dioxide, the nano silicon dioxide and the nano cellulose.
Dissolving beta-cyclodextrin into deionized water, heating to 75 ℃ for dissolution, continuously adding modified nano particles and a silane coupling agent, performing ultrasonic dispersion for 40min, and finally adding polyethylene glycol to obtain the modified beta-cyclodextrin. The mass ratio of the modified nano particles to the beta-cyclodextrin to the polyethylene glycol to the silane coupling agent is 1.5:4:2:0.02.
Mixing acrylic acid, hydroxypropyl methacrylate, methyl methacrylate, diacetone acrylamide, glycerin fatty acid ester and deionized water, continuously adding modified beta-cyclodextrin, stirring and emulsifying to obtain a mixed solution I; the mass ratio of the acrylic acid to the hydroxypropyl methacrylate, the methyl methacrylate, the diacetone acrylamide and the glycerin fatty acid ester is 5:5:7:0.7:1.1, and the addition amounts of the nano silicon dioxide and the beta-cyclodextrin are respectively 6% and 8% of the mass of the acrylic acid.
Dissolving adipic acid dihydrazide and azodiisobutyronitrile in deionized water to prepare a mixed solution II; the mass ratio of the acrylic acid to the adipic acid dihydrazide to the azodiisobutyronitrile is 5:0.55:0.55.
And heating the first mixed solution to 58 ℃, dripping the second mixed solution into the first mixed solution, continuously heating to 95 ℃, and reacting for 4 hours to obtain the modified aqueous acrylic resin.
The preparation method of the environment-friendly film water-based ink comprises the following steps:
s1, mixing modified aqueous polyurethane emulsion, modified aqueous acrylic resin and water, and stirring for 30min at 2000 r/min;
s2, continuously adding the pigment, the triethanolamine and the film forming auxiliary agent, and continuously stirring and uniformly mixing.
Example 5
Weighing the following raw materials in parts by weight:
20 parts of modified aqueous polyurethane emulsion, 40 parts of modified aqueous acrylic resin, 20 parts of phthalocyanine pigment, 1.2 parts of triethanolamine, 0.8 part of film forming auxiliary agent dodecanol ester and 30 parts of water.
The preparation method of the aqueous polyurethane emulsion comprises the following steps: adding an emulsifier OP-10 into water to obtain emulsion; adding polyethylene wax particles into the emulsion, and uniformly dispersing; continuously adding polyurethane particles, and uniformly dispersing; and finally adding a silane coupling agent and nano zinc oxide, and stirring for 1h at 80 ℃ to obtain the modified waterborne polyurethane emulsion. The mass ratio of the polyurethane particles to the polyethylene wax particles to the nano zinc oxide to the water is 4:2:1:40. The addition amount of the emulsifier is 8% of the mass of the polyurethane particles, and the addition amount of the silane coupling agent is 2% of the mass of the polyurethane particles.
The preparation method of the modified aqueous acrylic resin comprises the following steps:
dispersing nano titanium dioxide and nano silicon dioxide in water to form a dispersion liquid; adding a silane coupling agent into ethanol, and adding nanocellulose for high-speed dispersion; and continuously adding the dispersion liquid, heating at 70 ℃ for reaction for 3 hours, and cooling to obtain the modified nano particles. The mass ratio of the nano silicon dioxide to the nano titanium dioxide to the nano cellulose is 4:2:2, and the addition amount of the silane coupling agent is 3% of the total mass of the nano titanium dioxide, the nano silicon dioxide and the nano cellulose.
Dissolving beta-cyclodextrin into deionized water, heating to 80 ℃ for dissolution, continuously adding modified nano particles and a silane coupling agent, performing ultrasonic dispersion for 30min, and finally adding polyethylene glycol to obtain the modified beta-cyclodextrin. The mass ratio of the modified nano particles to the beta-cyclodextrin to the polyethylene glycol to the silane coupling agent is 2:4:2:0.02.
Mixing acrylic acid, hydroxypropyl methacrylate, methyl methacrylate, diacetone acrylamide, glycerin fatty acid ester and deionized water, continuously adding modified beta-cyclodextrin, stirring and emulsifying to obtain a mixed solution I; the mass ratio of the acrylic acid to the hydroxypropyl methacrylate, the methyl methacrylate, the diacetone acrylamide and the glycerin fatty acid ester is 6:6:8:0.8:1.2, and the addition amounts of the nano silicon dioxide and the beta-cyclodextrin are respectively 7% and 9% of the mass of the acrylic acid.
Dissolving adipic acid dihydrazide and azodiisobutyronitrile in deionized water to prepare a mixed solution II; the mass ratio of the acrylic acid to the adipic acid dihydrazide to the azodiisobutyronitrile is 6:0.6:0.6.
And heating the first mixed solution to 60 ℃, dripping the second mixed solution into the first mixed solution, continuously heating to 100 ℃, and reacting for 8 hours to obtain the modified aqueous acrylic resin.
The preparation method of the environment-friendly film water-based ink comprises the following steps:
s1, mixing modified aqueous polyurethane emulsion, modified aqueous acrylic resin and water, and stirring for 60min at 2000 r/min;
s2, continuously adding the pigment, the triethanolamine and the film forming auxiliary agent, and continuously stirring and uniformly mixing.
Comparative example 1
The difference from example 1 is that: the procedure of example 1 was repeated except that the "modified aqueous acrylic resin" was changed to "aqueous acrylic resin" and the "modified aqueous polyurethane emulsion" was changed to "aqueous polyurethane", that is, the commercially available aqueous acrylic resin and aqueous polyurethane were used.
Performance testing
The aqueous inks obtained in examples 1 to 5 and comparative example 1 were printed on PE, PP, PET, PVC films, and the adhesion and water resistance were measured as follows:
attachment fastness detection: reference standard GB/T13217.7-2009;
and (3) water resistance detection: reference standard GB/T1733-1993, wherein the test procedure is referred to the A method.
The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the adhesion of the inks prepared in examples 1 to 5 of the present application to the PE, PP, PET, PVC film was 85% or more, and the abnormal phenomena such as falling off and air bubbles were not generated in the ink in the water resistance test for 72 hours, thus indicating that the inks prepared in examples 1 to 5 of the present application have good adhesion to the PE, PP, PET, PVC film and good water resistance. As can be seen by comparing examples 1-5 with comparative example 1, the adhesion fastness and water resistance of the ink prepared in examples 1-5 on PE, PP, PET, PVC film are obviously better than those of comparative example 1, so that whether modified aqueous acrylic resin and modified aqueous polyurethane emulsion are adopted or not influences the adhesion fastness and water resistance of the ink, and therefore, the ink has good adhesion fastness and water resistance through the combined action of the modified aqueous acrylic resin, the modified aqueous polyurethane emulsion, triethanolamine, a film forming auxiliary agent and the like.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The environment-friendly film water-based ink is characterized by comprising the following raw materials in parts by weight:
10 to 20 parts of modified aqueous polyurethane emulsion, 20 to 40 parts of modified aqueous acrylic resin, 10 to 20 parts of pigment, 0.8 to 1.2 parts of triethanolamine, 0.4 to 0.8 part of film forming additive and 10 to 30 parts of water.
2. The environment-friendly film water-based ink as claimed in claim 1, wherein the preparation method of the water-based polyurethane emulsion comprises the following steps: adding an emulsifying agent into water to obtain emulsion; adding polyethylene wax particles into the emulsion, and uniformly dispersing; continuously adding polyurethane particles, and uniformly dispersing; finally adding a silane coupling agent and nano zinc oxide, and stirring for 1-3 hours at 60-80 ℃ to obtain the modified waterborne polyurethane emulsion.
3. The environment-friendly film water-based ink as claimed in claim 2, wherein the mass ratio of polyurethane particles to polyethylene wax particles to nano zinc oxide to water is 3-4:1-2:0.6-1:20-40.
4. The environment-friendly film water-based ink as claimed in claim 2, wherein the addition amount of the emulsifier is 4-8% of the mass of the polyurethane particles, and the addition amount of the silane coupling agent is 1-2% of the mass of the polyurethane particles.
5. The environment-friendly film water-based ink as claimed in claim 1, wherein the preparation method of the modified water-based acrylic resin comprises the following steps:
dissolving beta-cyclodextrin into deionized water, heating to 70-80 ℃ for dissolution, continuously adding modified nano particles and a silane coupling agent, performing ultrasonic dispersion for 30-60 min, and finally adding polyethylene glycol to obtain modified beta-cyclodextrin;
mixing acrylic acid, hydroxypropyl methacrylate, methyl methacrylate, diacetone acrylamide, glycerin fatty acid ester and deionized water, continuously adding modified beta-cyclodextrin, stirring and emulsifying to obtain a mixed solution I;
dissolving adipic acid dihydrazide and azodiisobutyronitrile in deionized water to prepare a mixed solution II;
heating the first mixed solution to 50-60 ℃, dripping the second mixed solution into the first mixed solution, continuously heating to 80-100 ℃, and reacting for 2-8 hours to obtain the modified aqueous acrylic resin.
6. The environment-friendly thin film water-based ink as claimed in claim 5, wherein the preparation method of the modified nano particles comprises the following steps: dispersing nano titanium dioxide and nano silicon dioxide in water to form a dispersion liquid; adding a silane coupling agent into ethanol, and adding nanocellulose for high-speed dispersion; continuously adding the dispersion liquid, heating and reacting for 1-3 hours at 50-70 ℃, and cooling to obtain the modified nano particles.
7. The environment-friendly film water-based ink as claimed in claim 5, wherein the mass ratio of the nano silicon dioxide to the nano titanium dioxide to the nano cellulose is 2-4:1-2:1-2, and the addition amount of the silane coupling agent is 1-3% of the total mass of the nano titanium dioxide, the nano silicon dioxide and the nano cellulose.
8. The environment-friendly film water-based ink as claimed in claim 5, wherein the mass ratio of the modified nano particles to the beta-cyclodextrin to the polyethylene glycol to the silane coupling agent is 1-2:2-4:1-2:0.01-0.02.
9. The environment-friendly film water-based ink as claimed in claim 5, wherein the mass ratio of acrylic acid to hydroxypropyl methacrylate, methyl methacrylate, diacetone acrylamide, glycerin fatty acid ester, adipic acid dihydrazide and azodiisobutyronitrile is 2-6:2-6:4-8:0.4-0.8:0.8-1.2:0.4-0.6:0.4-0.6, and the addition amounts of nano silicon dioxide and beta-cyclodextrin are 3-7% and 5-9% of the mass of acrylic acid respectively.
10. The preparation method of the environment-friendly film water-based ink is characterized by comprising the following steps of:
s1, mixing modified aqueous polyurethane emulsion, modified aqueous acrylic resin and water, and stirring for 30-60 min at 1500-2000 r/min;
s2, continuously adding the pigment, the triethanolamine and the film forming auxiliary agent, and continuously stirring and uniformly mixing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118685072A (en) * | 2024-08-26 | 2024-09-24 | 烟台金富士水墨有限公司 | A method for preparing antibacterial water-based acrylic resin ink |
| CN118931295A (en) * | 2024-09-04 | 2024-11-12 | 广东佰合新材料科技股份有限公司 | Ink-absorbing coating on the surface of PE film or PET aluminized film and preparation method thereof |
| CN119286305A (en) * | 2024-11-06 | 2025-01-10 | 东莞市浩彩油墨科技有限公司 | A method for preparing abrasion-resistant and scratch-resistant water-based ink |
-
2023
- 2023-04-13 CN CN202310392666.5A patent/CN116218281A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118685072A (en) * | 2024-08-26 | 2024-09-24 | 烟台金富士水墨有限公司 | A method for preparing antibacterial water-based acrylic resin ink |
| CN118685072B (en) * | 2024-08-26 | 2024-10-29 | 烟台金富士水墨有限公司 | A method for preparing antibacterial water-based acrylic resin ink |
| CN118931295A (en) * | 2024-09-04 | 2024-11-12 | 广东佰合新材料科技股份有限公司 | Ink-absorbing coating on the surface of PE film or PET aluminized film and preparation method thereof |
| CN119286305A (en) * | 2024-11-06 | 2025-01-10 | 东莞市浩彩油墨科技有限公司 | A method for preparing abrasion-resistant and scratch-resistant water-based ink |
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