CN115491077B - Quick-drying high-stability printing ink and preparation method thereof - Google Patents
Quick-drying high-stability printing ink and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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Abstract
The invention discloses quick-drying high-stability printing ink which comprises the following raw materials in parts by mass: 10-20 parts of polyester acrylic resin, 5-15 parts of acrylate monomer, 10-20 parts of nano silicon dioxide, 5-15 parts of organic pigment, 1-3 parts of 3-aminopropyl-diethoxysilane, 1-5 parts of graphene oxide, 1-3 parts of N-aminoethylpiperazine diamine, 1-3 parts of nitrogen-nitrogen methylene bisacrylamide, 1-5 parts of photoinitiator, 1-2 parts of polymerization inhibitor and 1-2 parts of auxiliary agent. The invention discloses a preparation method of the quick-drying high-stability printing ink. The water-based ink obtained by the invention is special water-based ink for lithography, is completely different from water-based ink for other printing modes such as gravure, flexography and silk screen printing, has the characteristics of applicability to quick drying and high stability of lithography, and is applicable to high-speed running of a lithography machine and no obvious physical concave-convex structure of a lithography plate.
Description
Technical Field
The invention relates to the technical field of water-based ink, in particular to quick-drying high-stability printing ink and a preparation method thereof.
Background
Lithographic printing is one of the main printing methods at present, and is also the most widely used printing method. Unlike traditional printing processes such as intaglio printing and relief printing, lithographic printing plates have blank portions and graphic portions on nearly the same plane. The lithographic printing is characterized in that a lipophilic and hydrophobic image-text part and a hydrophilic and oleophobic blank part are formed on the printing plate on the same plane by utilizing the principle of mutual exclusion of oil and water.
Lithographic printing inks generally consist of a homogeneous mixture of binders, pigments, fillers, solvents, auxiliaries, etc., which are capable of printing and drying on the object to be printed, and have a pasty colloid of a certain color and a certain degree of fluidity. The water-based ink is prepared by using water and other pollution-free or degradable substances to replace the original mineral oil, resin and other components partially or completely.
The water-based ink has some characteristics different from other inks due to the characteristics of the water solvent of the water-based ink, and has the following advantages:
1) Green environmental protection
The water-based ink does not use an organic volatile solvent and contains almost no volatile organic matters. This greatly improves the ink manufacturing and printing operating environment, ensuring the physical health of operators and end product users.
2) Printing characteristics
The water-based ink is relatively stable, is not easy to corrode the plate roller, is easy to clean after printing, and is suitable for most printing modes.
3) Safety of
The water-based ink does not contain an organic solvent, and the water-based system is stable and does not cause safety problems such as combustion, ignition and the like.
The printing performance and quality of the prior lithographic printing mode cannot meet the standard of solvent-based ink due to principle limitation. This is mainly due to the fact that the ink is difficult to wet and dry slowly due to the high surface tension of water, and the ink is poor in stability, and particularly when the ink is applied to a plastic substrate, the conditions of poor adhesive force and difficulty in guaranteeing stability are more likely to occur.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides quick-drying high-stability printing ink and a preparation method thereof.
The quick-drying high-stability printing ink comprises the following raw materials in parts by mass: 10-20 parts of polyester acrylic resin, 5-15 parts of acrylate monomer, 10-20 parts of nano silicon dioxide, 5-15 parts of organic pigment, 1-3 parts of 3-aminopropyl-diethoxysilane, 1-5 parts of graphene oxide, 1-3 parts of N-aminoethylpiperazine diamine, 1-3 parts of nitrogen-nitrogen methylene bisacrylamide, 1-5 parts of photoinitiator, 1-2 parts of polymerization inhibitor and 1-2 parts of auxiliary agent.
Preferably, the pH value of the quick-drying high-stability printing ink is 7.1-7.4.
Preferably, the photoinitiator comprises an initiator TPO and a co-initiator EDB, and the mass ratio of the initiator TPO to the co-initiator EDB is 10:1-4.
Preferably, the auxiliary agent is at least one of a dispersing agent, a reactive diluent, a defoaming agent, a mildew inhibitor and a thixotropic agent.
Preferably, the dispersant is a polyester type multi-chain high molecular polymer dispersant.
Preferably, the reactive diluent is trimethylolpropane triacrylate.
Preferably, the defoamer is a mineral oil defoamer and/or a silicone defoamer.
Preferably, the mildew inhibitor is at least one of sodium benzoate, sodium dehydroacetate, sodium sorbate and sodium pentachlorophenate.
Preferably, the thixotropic agent is sodium carboxyethyl cellulose and/or sodium polyacrylate.
The preparation method of the quick-drying high-stability printing ink comprises the following steps:
(1) Dissolving 3-aminopropyl-diethoxy silane in ethanol water solution, adding nano silicon dioxide and organic pigment, stirring for 1-2h, filtering, washing and drying to obtain pretreated pigment filler;
(2) Dispersing graphene oxide in deionized water, uniformly dispersing by ultrasonic, adding N-aminoethylpiperazine diamine, stirring for 5-10h at 40-60 ℃, adding nitrogen-nitrogen methylene bisacrylamide, continuously stirring, dialyzing, precipitating, and dispersing in deionized water to obtain pre-dispersed graphene oxide;
(3) Adding the pretreated pigment filler into the pre-dispersed graphene oxide, stirring, standing for 2-6 hours, adding the photoinitiator, the polymerization inhibitor and the auxiliary agent, uniformly mixing, and carrying out filter pressing and dehydration to obtain slurry;
(4) Adding acrylate monomer and polyester acrylic resin into the slurry, dispersing uniformly at high speed, grinding to fineness less than 10 mu m, and adding water to adjust the static viscosity of the system to 30000-40000 mPa.s to obtain the quick-drying high-stability printing ink.
Photoinitiators are determining factors for the curing rate, but excessive photoinitiators do not only increase the curing rate of the ink, but are detrimental to the curing of the ink. According to the invention, the photoinitiator and the pre-dispersed graphene oxide are compounded, when light is irradiated, by controlling the proportion of the photoinitiator and the pre-dispersed graphene oxide, on the basis of not too high concentration of the photoinitiator, the sufficient photoinitiation polymerization on the bottom layer is ensured, meanwhile, the pre-dispersed graphene oxide is fully dispersed and combined in a polymerized polymer structure, and the phenomena of breakage, falling-off and the like in the coating structure are ensured not to occur.
Preferably, the resulting fast drying high stability printing ink has a solids content of 6 to 9.2%.
Preferably, in the step (1), the mass fraction of the ethanol aqueous solution is 80-90%.
Preferably, in step (1), the drying temperature is 100-120 ℃.
Preferably, the pressure is 0.15-0.3Mpa in the filter-press dehydration process of step (3).
The technical effects of the invention are as follows:
according to the invention, the hyperbranched polymer is grafted on the surface of the graphene oxide in an in-situ polymerization mode, the hyperbranched polymer not only has a highly branched structure and larger intramolecular gaps, light transmission is effectively enhanced and reaches the bottom layer, polymerization energy of the water-based ink and a base material is reduced, adhesion difficulty is reduced, simultaneously, a large amount of active amino groups are contained at the molecular terminal of the hyperbranched polymer, and the hyperbranched polymer is combined with the graphene oxide, so that a lamellar structure of the graphene oxide can be fully dispersed into the branched structure of the hyperbranched polymer. According to the invention, the lamellar inorganic graphene oxide is introduced into the organic polymer separation layer, and the high-stability printing ink is broken through and prepared by means of the synergistic effect of the lamellar inorganic graphene oxide and the organic polymer separation layer, wherein the movement of the polymer chain segment can be effectively inhibited by the space effect represented by the unique two-dimensional structure of the graphene oxide, the stability of the hyperbranched polymer is improved, and the highly branched polymer chain segment endows the graphene oxide with certain flexibility.
According to the invention, 3-aminopropyl-diethoxy silane is adopted to pretreat nano silicon dioxide and organic pigment, active amino is generated on the surface, then self-assembly is carried out on the nano silicon dioxide and the organic pigment and the pre-dispersed graphene oxide, and due to the existence of a two-dimensional lamellar, hyperbranched polymers are combined on the surface of pigment and filler to form a stacked structure, and the stacked structure has strong interaction force, so that a printed pattern has excellent bending resistance, the affinity of pigment and filler in organic matters can be enhanced, meanwhile, the nano silicon dioxide and the organic pigment have good compatibility with water, the wettability is improved, the contact angle is reduced, the adhesive force of water-based ink is improved, and the stability of a film layer is extremely high.
The invention utilizes the pre-dispersed graphene oxide to be compounded with the acrylic ester monomer and the polyester acrylic resin, can play an auxiliary crosslinking role in ultraviolet light curing, has high curing speed, and the two-dimensional lamellar structure and the highly branched structure of the pre-dispersed graphene oxide can enable the system to form a continuous network structure more easily, thereby effectively enhancing the compactness and the stability of the film layer.
The water-based ink obtained by the invention is special water-based ink for lithography, is completely different from water-based ink for other printing modes such as gravure, flexography and silk screen printing, has the characteristics of applicability to quick drying and high stability of lithography, and is applicable to high-speed running of a lithography machine and no obvious physical concave-convex structure of a lithography plate. Compared with the prior art of lithographic printing ink, the invention does not need to use an organic solvent with odor, toxicity and high boiling point, avoids the volatilization and emission of the organic solvent into the atmosphere, does not pollute the atmospheric environment, and has simple and economic operation and large-scale production.
Drawings
FIG. 1 is an infrared spectrum analysis chart of graphene oxide and the pre-dispersed graphene oxide obtained in example 5.
FIG. 2 is a graph showing the comparison of the curing times of the printing inks obtained in example 5 and comparative examples 1 to 2.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1
A quick-drying high-stability printing ink has a pH value of 7.13; the raw materials comprise: 10kg of polyester acrylic resin, 5kg of acrylate monomer, 10kg of nano silicon dioxide, 5kg of organic pigment, 1kg of 3-aminopropyl-diethoxysilane, 1kg of graphene oxide, 1kg of N-aminoethylpiperazine diamine, 1kg of nitrogen-nitrogen methylene bisacrylamide, 1kg of photoinitiator, 1kg of polymerization inhibitor, 240000.5kg of Lu Borun lubrizol hyperdispersant and 0.5kg of trimethylolpropane triacrylate.
The photoinitiator consists of initiator TPO and co-initiator EDB according to the mass ratio of 10: 1.
The preparation method of the quick-drying high-stability printing ink comprises the following steps:
(1) Dissolving 3-aminopropyl-diethoxy silane in 50kg of ethanol aqueous solution with the mass fraction of 80%, adding nano silicon dioxide and organic pigment, stirring for 1h, filtering, washing with deionized water for 2 times, and drying at the temperature of 100 ℃ to obtain pretreated pigment filler;
(2) Dispersing graphene oxide in 20kg of deionized water, uniformly dispersing by ultrasonic, adding N-aminoethylpiperazine diamine, stirring at 40 ℃ for 5 hours, adding nitrogen-nitrogen methylene bisacrylamide, continuously stirring for 1 hour, dialyzing, precipitating, and dispersing in 20kg of deionized water to obtain pre-dispersed graphene oxide;
(3) Adding a pretreated pigment filler into pre-dispersed graphene oxide, stirring at a speed of 1000r/min for 10min, standing for 2h, adding a photoinitiator, a polymerization inhibitor, a Lubrizol hyperdispersant 24000 and trimethylolpropane triacrylate, uniformly mixing, and dehydrating the product under a pressure of 0.15MPa by using a filter press to obtain slurry;
(4) Adding acrylate monomer and polyester acrylic resin into the slurry, dispersing at a high speed of 1000r/min, grinding to fineness less than 10 μm in a three-roll machine, and adding water to adjust the static viscosity of the system to 30350 mPa.s to obtain the quick-drying high-stability printing ink.
Example 2
A quick-drying high-stability printing ink, the pH value of which is 7.37; the raw materials comprise: 20kg of polyester acrylic resin, 15kg of acrylate monomer, 20kg of nano silicon dioxide, 15kg of organic pigment, 3kg of 3-aminopropyl-diethoxysilane, 5kg of graphene oxide, 3kg of N-aminoethylpiperazine diamine, 3kg of nitrogen-nitrogen methylene bisacrylamide, 5kg of photoinitiator, 2kg of polymerization inhibitor, 1.5kg of mineral oil defoamer and 0.5kg of sodium polyacrylate.
The photoinitiator consists of initiator TPO and co-initiator EDB according to the mass ratio of 5: 2.
The preparation method of the quick-drying high-stability printing ink comprises the following steps:
(1) Dissolving 3-aminopropyl-diethoxy silane in 100kg of ethanol water solution with the mass fraction of 90%, adding nano silicon dioxide and organic pigment, stirring for 2 hours, filtering, washing with deionized water for 4 times, and drying at the temperature of 120 ℃ to obtain pretreated pigment filler;
(2) Dispersing graphene oxide in 40kg of deionized water, uniformly dispersing by ultrasonic, adding N-aminoethylpiperazine diamine, stirring at 60 ℃ for 10 hours, adding nitrogen-nitrogen methylene bisacrylamide, continuously stirring for 4 hours, dialyzing, precipitating, and dispersing in 50kg of deionized water to obtain pre-dispersed graphene oxide;
(3) Adding a pretreated pigment filler into pre-dispersed graphene oxide, stirring at a speed of 2000r/min for 20min, standing for 6h, adding a photoinitiator, a polymerization inhibitor, a mineral oil defoamer and sodium polyacrylate, uniformly mixing, and dehydrating a product by using a filter press under a pressure of 0.3MPa to obtain slurry;
(4) Adding acrylate monomer and polyester acrylic resin into the slurry, dispersing at a high speed of 5000r/min, grinding to fineness less than 10 μm in a three-roll machine, and adding water to adjust the static viscosity of the system to 39810 mPa.s to obtain the quick-drying high-stability printing ink.
Example 3
A quick-drying high-stability printing ink, the pH value of which is 7.29; the raw materials comprise: 14kg of polyester acrylic resin, 12kg of acrylate monomer, 12kg of nano silicon dioxide, 13kg of organic pigment, 1.5kg of 3-aminopropyl-diethoxysilane, 4kg of graphene oxide, 1.5kg of N-aminoethylpiperazine diamine, 2.5kg of nitrogen-nitrogen methylene bisacrylamide, 2kg of photoinitiator, 1.7kg of polymerization inhibitor, 1kg of mineral oil defoamer and 0.4kg of sodium benzoate.
The photoinitiator consists of initiator TPO and co-initiator EDB according to the mass ratio of 10: 3.
The preparation method of the quick-drying high-stability printing ink comprises the following steps:
(1) Dissolving 3-aminopropyl-diethoxy silane in 70kg of ethanol water solution with the mass fraction of 88%, adding nano silicon dioxide and organic pigment, stirring for 80min, filtering, washing with deionized water for 3 times, and drying at 115 ℃ to obtain pretreated pigment filler;
(2) Dispersing graphene oxide in 25kg of deionized water, uniformly dispersing by ultrasonic, adding N-aminoethylpiperazine diamine, stirring at 55 ℃ for 6 hours, adding nitrogen-nitrogen methylene bisacrylamide, continuously stirring for 3 hours, dialyzing, precipitating, and dispersing in 30kg of deionized water to obtain pre-dispersed graphene oxide;
(3) Adding a pretreated pigment filler into pre-dispersed graphene oxide, stirring at 1800r/min for 13min, standing for 5h, adding a photoinitiator, a polymerization inhibitor, a mineral oil defoamer and sodium benzoate, uniformly mixing, and dehydrating a product by using a filter press under the pressure of 0.2MPa to obtain slurry;
(4) Adding acrylate monomer and polyester acrylic resin into the slurry, dispersing at 4000r/min, grinding to fineness less than 10 μm in a three-roll machine, and adding water to adjust the static viscosity of the system to 32360 mPa.s to obtain the quick-drying high-stability printing ink.
Example 4
A quick-drying high-stability printing ink, the pH value of which is 7.19; the raw materials comprise: 18kg of polyester acrylic resin, 8kg of acrylate monomer, 18kg of nano silicon dioxide, 7kg of organic pigment, 2.5kg of 3-aminopropyl-diethoxysilane, 2kg of graphene oxide, 2.5kg of N-aminoethylpiperazine diamine, 1.5kg of nitrogen-nitrogen methylene bisacrylamide, 4kg of photoinitiator, 1.3kg of polymerization inhibitor, 0.6kg of organosilicon defoamer, 0.6kg of sodium sorbate and 0.6kg of sodium carboxyethyl cellulose.
The photoinitiator consists of initiator TPO and co-initiator EDB according to the mass ratio of 5: 1.
The preparation method of the quick-drying high-stability printing ink comprises the following steps:
(1) Dissolving 3-aminopropyl-diethoxy silane in 90kg of ethanol water solution with the mass fraction of 82%, adding nano silicon dioxide and organic pigment, stirring for 100min, filtering, washing with deionized water for 3 times, and drying at the temperature of 105 ℃ to obtain pretreated pigment filler;
(2) Dispersing graphene oxide in 35kg of deionized water, uniformly dispersing by ultrasonic, adding N-aminoethylpiperazine diamine, stirring at 45 ℃ for 8 hours, adding nitrogen-nitrogen methylene bisacrylamide, continuously stirring for 2 hours, dialyzing, precipitating, and dispersing in 40kg of deionized water to obtain pre-dispersed graphene oxide;
(3) Adding a pretreated pigment filler into pre-dispersed graphene oxide, stirring at a speed of 1200r/min for 17min, standing for 3h, adding a photoinitiator, a polymerization inhibitor, an organosilicon defoamer, sodium sorbate and sodium carboxyethyl cellulose, uniformly mixing, and dehydrating a product by using a filter press under a pressure of 0.26MPa to obtain slurry;
(4) Adding acrylate monomer and polyester acrylic resin into the slurry, dispersing at a high speed of 2000r/min, grinding to fineness less than 10 μm in a three-roll machine, and adding water to adjust the static viscosity of the system to 37780 mPa.s to obtain the quick-drying high-stability printing ink.
Example 5
A quick-drying high-stability printing ink, the pH value of which is 7.27; the raw materials comprise: 16kg of polyester acrylic resin, 10kg of acrylate monomer, 15kg of nano silicon dioxide, 10kg of organic pigment, 2kg of 3-aminopropyl-diethoxysilane, 3kg of graphene oxide, 2kg of N-aminoethylpiperazine diamine, 2kg of nitrogen-nitrogen methylene bisacrylamide, 3kg of photoinitiator, 1.5kg of polymerization inhibitor, 0.4kg of trimethylolpropane triacrylate, 0.6kg of sodium sorbate, 0.3kg of sodium carboxyethyl cellulose and 240000.3kg of Lu Borun lubrizol hyperdispersant.
The photoinitiator consists of initiator TPO and co-initiator EDB according to the mass ratio of 4: 1.
The preparation method of the quick-drying high-stability printing ink comprises the following steps:
(1) Dissolving 3-aminopropyl-diethoxy silane in 80kg of ethanol water solution with the mass fraction of 85%, adding nano silicon dioxide and organic pigment, stirring for 90min, filtering, washing with deionized water for 3 times, and drying at the temperature of 110 ℃ to obtain pretreated pigment filler;
(2) Dispersing graphene oxide in 30kg of deionized water, uniformly dispersing by ultrasonic, adding N-aminoethylpiperazine diamine, stirring at 50 ℃ for 7 hours, adding nitrogen-nitrogen methylene bisacrylamide, continuously stirring for 2.5 hours, dialyzing, precipitating, and dispersing in 35kg of deionized water to obtain pre-dispersed graphene oxide;
the obtained pre-dispersed graphene oxide and graphene oxide were subjected to infrared spectroscopic analysis, as shown in FIG. 1, and N-H bonds at 3280cm-1 and 2900cm- 1 C-H bond at 1525cm- 1 The characteristic peak-to-peak values of the C-N bonds are increased, while the characteristic peak values of the O-H at 3410cm-1 and 1393cm-1 are obviously decreased. Where N-H and C-N bonds are present in the amine functional groups, the increase in these peaks demonstrates that the hyperbranched polymer has been successfully grafted onto graphene oxide nanoplatelets. In addition, the decrease in the peak value of the O-H peak indicates the decrease in carboxylic acid groups and hydroxyl groups on the graphene oxide, and thus it is presumed that the modification of the graphene oxide by the hyperbranched polymer is mainly achieved by the reaction between carboxylic acid groups, hydroxyl groups on the graphene oxide and amine groups on the hyperbranched polymer.
(3) Adding a pretreated pigment filler into pre-dispersed graphene oxide, stirring at a speed of 1500r/min for 15min, standing for 7h, adding a photoinitiator, a polymerization inhibitor, trimethylolpropane triacrylate, sodium sorbate, sodium carboxyethyl cellulose and a lubrizol hyperdispersant 24000, uniformly mixing, and dehydrating a product by using a filter press under a pressure of 0.24MPa to obtain slurry;
(4) Adding acrylate monomer and polyester acrylic resin into the slurry, dispersing at high speed and uniform, adding into a three-roll machine, grinding to fineness less than 10 μm, adding water, regulating static viscosity of the system to 35080 mPa.s, and obtaining the quick-drying high-stability printing ink.
Comparative example 1
A printing ink comprises the following raw materials: 16kg of polyester acrylic resin, 10kg of acrylate monomer, 15kg of nano silicon dioxide, 10kg of organic pigment, 3kg of graphene oxide, 2kg of N-aminoethylpiperazine diamine, 2kg of nitrogen methylene bisacrylamide, 3kg of photoinitiator, 1.5kg of polymerization inhibitor, 0.4kg of trimethylolpropane triacrylate, 0.6kg of sodium sorbate, 0.3kg of sodium carboxyethyl cellulose and 240000.3kg of Lu Borun lubrizol hyperdispersant.
The photoinitiator consists of initiator TPO and co-initiator EDB according to the mass ratio of 4: 1.
The preparation method of the printing ink comprises the following steps:
(1) Dispersing graphene oxide in 30kg of deionized water, uniformly dispersing by ultrasonic, adding N-aminoethylpiperazine diamine, stirring at 50 ℃ for 7 hours, adding nitrogen-nitrogen methylene bisacrylamide, continuously stirring for 2.5 hours, dialyzing, precipitating, and dispersing in 35kg of deionized water to obtain pre-dispersed graphene oxide;
(2) Adding nano silicon dioxide and an organic pigment into pre-dispersed graphene oxide, stirring at a speed of 1500r/min for 15min, standing for 7h, adding a photoinitiator, a polymerization inhibitor, trimethylolpropane triacrylate, sodium sorbate, sodium carboxyethyl cellulose and a road-blon lubrizol hyperdispersant 24000, uniformly mixing, and dehydrating a product by using a filter press under a pressure of 0.24MPa to obtain slurry;
(3) Adding acrylate monomer and polyester acrylic resin into the slurry, dispersing at high speed and uniform, adding into a three-roll mill, grinding to fineness less than 10 μm, and adding water to adjust static viscosity of the system to 30000-40000 mPa.s to obtain printing ink.
Comparative example 2
A printing ink comprises the following raw materials: 16kg of polyester acrylic resin, 10kg of acrylate monomer, 15kg of nano silicon dioxide, 10kg of organic pigment, 2kg of 3-aminopropyl-diethoxysilane, 3kg of graphene oxide, 4kg of polyamidoamine, 3kg of photoinitiator, 1.5kg of polymerization inhibitor, 0.4kg of trimethylolpropane triacrylate, 0.6kg of sodium sorbate, 0.3kg of sodium carboxyethyl cellulose and 240000.3kg of Lu Borun lubrizol hyperdispersant.
The photoinitiator consists of initiator TPO and co-initiator EDB according to the mass ratio of 4: 1.
The preparation method of the printing ink comprises the following steps:
(1) Dissolving 3-aminopropyl-diethoxy silane in 80kg of ethanol water solution with the mass fraction of 85%, adding nano silicon dioxide and organic pigment, stirring for 90min, filtering, washing with deionized water for 3 times, and drying at the temperature of 110 ℃ to obtain pretreated pigment filler;
(2) Dispersing graphene oxide in 30kg of deionized water, uniformly dispersing by ultrasonic, adding polyamide amine, and stirring for 7 hours at 50 ℃ to obtain pre-dispersed graphene oxide;
(3) Adding a pretreated pigment filler into pre-dispersed graphene oxide, stirring at a speed of 1500r/min for 15min, standing for 7h, adding a photoinitiator, a polymerization inhibitor, trimethylolpropane triacrylate, sodium sorbate, sodium carboxyethyl cellulose and a lubrizol hyperdispersant 24000, uniformly mixing, and dehydrating a product by using a filter press under a pressure of 0.24MPa to obtain slurry;
(4) Adding acrylate monomer and polyester acrylic resin into the slurry, dispersing at high speed and uniform, wherein the dispersion speed is 3000r/r/min, adding into a three-roll machine, grinding to fineness less than 10 mu m, and adding water to adjust the static viscosity of the system to 30000-40000 mPa.s, thus obtaining the printing ink.
The printing inks obtained in example 5 and comparative examples 1-2 were applied to glass (thickness: 30 μm) at room temperature using a bar coater, and cured (80W/cm) 2 10cm from the light source), the coating was determined by finger touch to determine whether it was cured and the time taken for curing was recorded.
As shown in FIG. 2, the printing ink obtained in the embodiment 5 has the shortest curing time, and the invention proves that the in-situ polymerization mode is adopted to graft the hyperbranched polymer on the surface of the graphene oxide, so that the polymerization energy of the water-based ink and a base material is reduced, the adhesion difficulty is reduced, the affinity of pigment and filler in organic matters can be enhanced, meanwhile, the pigment and filler has better compatibility with water, the wettability is improved, the contact angle is reduced, and the drying speed is accelerated.
The printing ink obtained in the example 5 and the comparative examples 1-2 was sprayed on the surface of the PVC plastic film, and after curing and drying, the printing ink was folded at 180 degrees, and after 50 times of folding, the printing ink obtained in the example 5 still had no falling, while the printing ink obtained in the comparative example had phenomena such as tilting and falling. The printing ink obtained by the invention has good flexibility and adhesive force.
The printing inks obtained in example 5 and comparative examples 1 to 2 were tested after being sprayed on the surface of PVC plastic film, and the results were as follows:
the stability test was carried out by allowing the printing inks obtained in example 5 and comparative examples 1 to 2 to stand at normal temperature, and it was found that the printing ink obtained in example 5 was unchanged after storage for 6 months, whereas the printing ink obtained in comparative examples 1 to 2 was subjected to phenomena such as dust, coagulation, etc., indicating that the stability of the printing ink obtained in the present invention was high.
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 (9)
1. The quick-drying high-stability printing ink is characterized by comprising the following raw materials in parts by mass: 10-20 parts of polyester acrylic resin, 5-15 parts of acrylate monomer, 10-20 parts of nano silicon dioxide, 5-15 parts of organic pigment, 1-3 parts of 3-aminopropyl-diethoxysilane, 1-5 parts of graphene oxide, 1-3 parts of N-aminoethylpiperazine diamine, 1-3 parts of nitrogen-nitrogen methylene bisacrylamide, 1-5 parts of photoinitiator, 1-2 parts of polymerization inhibitor and 1-2 parts of auxiliary agent;
the method comprises the following steps:
(1) Dissolving 3-aminopropyl-diethoxy silane in ethanol water solution, adding nano silicon dioxide and organic pigment, stirring for 1-2h, filtering, washing and drying to obtain pretreated pigment filler;
(2) Dispersing graphene oxide in deionized water, uniformly dispersing by ultrasonic, adding N-aminoethylpiperazine diamine, stirring for 5-10h at 40-60 ℃, adding nitrogen-nitrogen methylene bisacrylamide, continuously stirring, dialyzing, precipitating, and dispersing in deionized water to obtain pre-dispersed graphene oxide;
(3) Adding the pretreated pigment filler into the pre-dispersed graphene oxide, stirring, standing for 2-6 hours, adding the photoinitiator, the polymerization inhibitor and the auxiliary agent, uniformly mixing, and carrying out filter pressing and dehydration to obtain slurry;
(4) Adding acrylate monomer and polyester acrylic resin into the slurry, dispersing uniformly at high speed, grinding to fineness less than 10 mu m, and adding water to adjust the static viscosity of the system to 30000-40000 mPa.s to obtain the quick-drying high-stability printing ink.
2. The quick-drying, high-stability printing ink according to claim 1, wherein the pH of the quick-drying, high-stability printing ink is 7.1-7.4.
3. The quick-drying high-stability printing ink according to claim 1, wherein the photoinitiator comprises an initiator TPO and a co-initiator EDB, and the mass ratio of the initiator TPO to the co-initiator EDB is 10:1-4.
4. The quick-drying high-stability printing ink according to claim 1, wherein the auxiliary agent is at least one of a dispersing agent, a reactive diluent, a defoaming agent, a mildew-proof agent and a thixotropic agent.
5. The quick-drying high-stability printing ink according to claim 4, wherein the dispersant is a polyester type multi-chain high-molecular polymer dispersant.
6. The quick-drying, high-stability printing ink of claim 4 wherein the reactive diluent is trimethylolpropane triacrylate.
7. The quick-drying high-stability printing ink according to claim 4, wherein the defoamer is a mineral oil defoamer and/or a silicone defoamer.
8. The quick-drying high-stability printing ink according to claim 4, wherein the mildew preventive is at least one of sodium benzoate, sodium dehydroacetate, sodium sorbate and sodium pentachlorophenate.
9. The quick-drying high-stability printing ink according to claim 4, wherein the thixotropic agent is sodium carboxyethyl cellulose and/or sodium polyacrylate.
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