CN115491077A - 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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- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- 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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- C09D11/00—Inks
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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-aminoethyl piperazine diamine, 1-3 parts of N-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 for lithographic printing, is completely different from water-based inks of other printing modes such as gravure, flexography, silk screen and the like, has the characteristics of quick drying and high stability applicable to lithographic printing, which are not possessed by common water-based inks, and can adapt to the characteristics of high-speed operation of lithographic printing machines and no obvious physical concave-convex structure of lithographic plates.
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
Offset printing is one of the major printing methods at present and is also the most widely used printing method. Unlike traditional printing processes such as intaglio printing and letterpress printing, the blank part and the image-text part of the lithographic printing plate are almost on the same plane. The lithographic printing utilizes the law of mutual exclusion of oil and water to form an oleophilic and hydrophobic image-text part and a hydrophilic and oleophobic blank part on a printing plate on the same plane.
Lithographic printing inks are generally a homogeneous mixture of binders, pigments, fillers, solvents, auxiliaries and the like, and can be printed and dried on a substrate in the form of a slurry of colloid having a certain degree of fluidity and a certain colour. The water-based ink is prepared by partially or completely replacing original components such as mineral oil, resin and the like with pollution-free or degradable substances such as water and the like.
The water-based ink has some characteristics different from other inks due to the characteristics of the water solvent, and has the following advantages:
1) Green environment protection
The water-based ink does not use organic volatile solvents and hardly contains volatile organic compounds. This greatly improves the ink manufacturing and printing operating environment, ensuring physical health of the operator and end product user.
2) Printing characteristics
The water-based ink is stable, is not easy to corrode a plate roller, is easy to clean after printing, and is suitable for most printing modes.
3) Safety feature
The water-based ink does not contain organic solvent, the water-based system is relatively stable, and the safety problems of combustion, ignition and the like can not occur.
The lithographic printing mode has the principle limitation so far, and the printing performance and quality can not reach the standard of solvent-based ink. The reason is that the ink is difficult to wet and slow to dry due to the high surface tension of water, and the stability of the ink is poor, and particularly when the ink is applied to a plastic substrate, the conditions of poor adhesion and difficult stability guarantee are easy to occur.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a quick-drying high-stability printing ink and a preparation method thereof.
A 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-aminoethyl piperazine diamine, 1-3 parts of N-methylene bisacrylamide, 1-5 parts of photoinitiator, 1-2 parts of polymerization inhibitor and 1-2 parts of auxiliary agent.
Preferably, the pH of the fast drying highly stable printing ink is 7.1 to 7.4.
Preferably, the photoinitiator comprises an initiator TPO and an auxiliary initiator EDB, and the mass ratio of the initiator TPO to the auxiliary initiator EDB is 10:1-4.
Preferably, the auxiliary agent is at least one of a dispersant, a reactive diluent, an antifoaming agent, a mildewproof agent and a thixotropic agent.
Preferably, the dispersant is a polyester-based multi-chain high molecular polymer dispersant.
Preferably, the reactive diluent is trimethylolpropane triacrylate.
Preferably, the defoamer is a mineral oil type defoamer and/or a silicone type defoamer.
Preferably, the mildew inhibitor is at least one of sodium benzoate, sodium dehydroacetate, sodium sorbate and sodium pentachlorophenolate.
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-diethoxysilane in an ethanol water solution, adding nano silicon dioxide and organic pigment, stirring for 1-2h, filtering, washing and drying to obtain a pretreated pigment filler;
(2) Dispersing graphene oxide in deionized water, performing ultrasonic dispersion uniformly, adding N-aminoethyl piperazine diamine, stirring for 5-10h at 40-60 ℃, adding N-methylene bisacrylamide, continuing stirring, dialyzing, precipitating, and dispersing in deionized water to obtain pre-dispersed graphene oxide;
(3) Adding the pretreated pigment and filler into the pre-dispersed graphene oxide, stirring, standing for 2-6h, adding a photoinitiator, a polymerization inhibitor and an auxiliary agent, uniformly mixing, and performing filter pressing and dehydration to obtain slurry;
(4) Adding an acrylate monomer and polyester acrylic resin into the slurry, dispersing uniformly at a high speed, grinding until the fineness is less than 10 mu m, adding water to adjust the static viscosity of the system to be 30000-40000mPa & s, and obtaining the quick-drying high-stability printing ink.
The photoinitiator is a decisive factor of the curing rate, but the excessive photoinitiator does not increase the curing rate of the ink, but is not beneficial to the curing of the ink. According to the invention, the photoinitiator and the pre-dispersed graphene oxide are compounded, when light is irradiated, the proportion of the photoinitiator and the pre-dispersed graphene oxide is controlled, on the basis that the concentration of the photoinitiator is not too high, enough photoinitiated polymerization is ensured on the bottom layer, and meanwhile, the pre-dispersed graphene oxide is fully dispersed and combined in a polymerized polymer structure, so that the phenomena of no fracture, no falling off and the like in the coating structure are ensured.
Preferably, the solids content of the resulting fast drying highly stable printing ink is 6-9.2%.
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, in the filter-pressing dehydration process in the step (3), the pressure is 0.15-0.3MPa.
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 manner, the hyperbranched polymer not only has a highly branched structure and larger intramolecular voids, light transmission is effectively enhanced and reaches the bottom layer, the polymerization energy of the water-based ink and the base material is reduced, the adhesion difficulty is reduced, meanwhile, the molecular terminal contains a large number of active amino groups and is combined with the graphene oxide, and the 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 synergistic effect of the two layers is utilized to break through and prepare the high-stability ink, wherein the space effect embodied by the unique two-dimensional structure of the graphene oxide can effectively inhibit the movement of the polymer chain segment, 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-diethoxysilane is adopted to pretreat nano silicon dioxide and organic pigment, active amino groups are generated on the surface, and then self-assembly is carried out on the nano silicon dioxide and the organic pigment and pre-dispersed graphene oxide, due to the existence of a two-dimensional lamellar layer, hyperbranched polymers are combined on the surface of the pigment and filler to form a stacked structure, and strong interaction force exists among the stacked structures, so that the printed pattern has excellent bending resistance, the affinity of the pigment and filler in organic matters can be enhanced, meanwhile, the super-branched graphene oxide has better compatibility with water, the wettability is improved, the contact angle can be reduced, the adhesive force of water-based ink is improved, and the stability of a film layer is extremely high.
According to the invention, the pre-dispersed graphene oxide is compounded with the acrylate monomer and the polyester acrylic resin, so that an auxiliary crosslinking effect can be achieved during ultraviolet curing, the curing speed is high, the two-dimensional sheet structure and the highly branched structure of the pre-dispersed graphene oxide enable a system to form a continuous network structure more easily, and the compactness and stability of a film layer are effectively enhanced.
The water-based ink obtained by the invention is special water-based ink for lithographic printing, is completely different from water-based ink for gravure printing, flexo printing, silk-screen printing and other printing modes, has the characteristics of quick drying and high stability applicable to lithographic printing, which are not possessed by general water-based ink, and can adapt to the characteristics of high-speed operation of a lithographic printing machine and no obvious physical concave-convex structure of a lithographic plate. Compared with the prior art of lithographic printing ink, the invention does not need to use organic solvent with odor, toxicity and high boiling point, avoids the organic solvent from being volatilized and discharged into the atmosphere, does not cause pollution to the atmospheric environment, and has simple operation, economy and large-scale production.
Drawings
Fig. 1 is an infrared spectroscopic analysis chart of graphene oxide and pre-dispersed graphene oxide obtained in example 5.
FIG. 2 is a graph showing a comparison of the curing times of the printing inks obtained in example 5 and comparative examples 1 to 2.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
A fast drying highly stable printing ink having a pH 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-aminoethyl piperazine diamine, 1kg of N-methylene bisacrylamide, 1kg of photoinitiator, 1kg of polymerization inhibitor, 240000.5kg of lubrizol hyperdispersant and 0.5kg of trimethylolpropane triacrylate.
The photoinitiator is prepared from an initiator TPO and an auxiliary 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-diethoxysilane in 50kg of ethanol water 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 the pretreated pigment filler;
(2) Dispersing graphene oxide in 20kg of deionized water, performing ultrasonic dispersion uniformly, adding N-aminoethyl piperazine diamine, stirring at the temperature of 40 ℃ for 5 hours, adding N-methylene bisacrylamide, continuing stirring for 1 hour, dialyzing, precipitating, and dispersing in 20kg of deionized water to obtain pre-dispersed graphene oxide;
(3) Adding the pretreated pigment and filler into the pre-dispersed graphene oxide, stirring at the speed of 1000r/min for 10min, standing for 2h, adding a photoinitiator, a polymerization inhibitor, luboruzol hyperdispersant 24000 and trimethylolpropane triacrylate, uniformly mixing, and dehydrating the product under the pressure of 0.15MPa by using a filter press to obtain slurry;
(4) Adding an acrylate monomer and polyester acrylic resin into the slurry, uniformly dispersing at a high speed, wherein the dispersion speed is 1000r/min, adding the mixture into a three-roller machine, grinding the mixture to the fineness of less than 10 mu m, and adding water to adjust the static viscosity of the system to be 30350mPa & s, thereby obtaining the quick-drying high-stability printing ink.
Example 2
A fast drying highly stable printing ink having a pH of 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-aminoethyl piperazine diamine, 3kg of nitrogen methylene bisacrylamide, 5kg of photoinitiator, 2kg of polymerization inhibitor, 1.5kg of mineral oil defoamer and 0.5kg of sodium polyacrylate.
The photoinitiator is prepared from an initiator TPO and an auxiliary 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-diethoxysilane in 100kg of 90% ethanol aqueous solution, adding nano silicon dioxide and organic pigment, stirring for 2h, filtering, washing with deionized water for 4 times, and drying at 120 ℃ to obtain the pretreated pigment filler;
(2) Dispersing graphene oxide in 40kg of deionized water, performing ultrasonic dispersion uniformly, adding N-aminoethyl piperazine diamine, stirring at the temperature of 60 ℃ for 10 hours, adding N-methylene bisacrylamide, continuing stirring for 4 hours, dialyzing, precipitating, and dispersing in 50kg of deionized water to obtain pre-dispersed graphene oxide;
(3) Adding the pretreated pigment and filler into the pre-dispersed graphene oxide, stirring at the 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 the pressure of 0.3MPa to obtain slurry;
(4) Adding an acrylate monomer and polyester acrylic resin into the slurry, dispersing uniformly at a high speed of 5000r/min, adding the mixture into a three-roll mill, grinding the mixture until the fineness is less than 10 mu m, adding water to adjust the static viscosity of the system to be 39810mPa & s, and obtaining the quick-drying high-stability printing ink.
Example 3
A fast drying highly stable printing ink having a pH of 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-aminoethyl piperazine diamine, 2.5kg of N-methylene-bisacrylamide, 2kg of photoinitiator, 1.7kg of polymerization inhibitor, 1kg of mineral oil defoamer and 0.4kg of sodium benzoate.
The photoinitiator is prepared from an initiator TPO and an auxiliary initiator EDB according to the mass ratio of 10:3, and (3).
The preparation method of the quick-drying high-stability printing ink comprises the following steps:
(1) Dissolving 3-aminopropyl-diethoxysilane in 70kg of 88% ethanol water solution, adding nano silicon dioxide and organic pigment, stirring for 80min, filtering, washing with deionized water for 3 times, and drying at 115 ℃ to obtain the pretreated pigment filler;
(2) Dispersing graphene oxide in 25kg of deionized water, performing ultrasonic dispersion uniformly, adding N-aminoethyl piperazine diamine, stirring at the temperature of 55 ℃ for 6 hours, adding N-methylene bisacrylamide, continuing stirring for 3 hours, dialyzing, precipitating, and dispersing in 30kg of deionized water to obtain pre-dispersed graphene oxide;
(3) Adding the pretreated pigment and filler into the 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 under the pressure of 0.2MPa by using a filter press to obtain slurry;
(4) Adding an acrylate monomer and polyester acrylic resin into the slurry, uniformly dispersing at a high speed of 4000r/min, adding the mixture into a three-roll machine, grinding the mixture to a fineness of less than 10 mu m, adding water to adjust the static viscosity of the system to be 32360mPa & s, and obtaining the quick-drying high-stability printing ink.
Example 4
A fast drying highly stable printing ink having a pH of 7.19; the raw materials comprise: 18kg of polyester acrylic resin, 8kg of acrylate monomer, 18kg of nano silicon dioxide, 2.5kg of organic pigment, 3-aminopropyl-diethoxysilane, 2kg of graphene oxide, 2.5kg of N-aminoethyl piperazine diamine, 1.5kg of N-methylene-bisacrylamide, 4kg of photoinitiator, 1.3kg of polymerization inhibitor, 0.6kg of organic silicon defoamer, 0.6kg of sodium sorbate and 0.6kg of sodium carboxyethyl cellulose.
The photoinitiator is prepared from an initiator TPO and an auxiliary 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-diethoxysilane in 90kg of 82% ethanol water solution, adding nano silicon dioxide and organic pigment, stirring for 100min, filtering, washing with deionized water for 3 times, and drying at 105 ℃ to obtain the pretreated pigment filler;
(2) Dispersing graphene oxide in 35kg of deionized water, performing ultrasonic dispersion uniformly, adding N-aminoethyl piperazine diamine, stirring at 45 ℃ for 8 hours, adding N-methylene bisacrylamide, continuing stirring for 2 hours, dialyzing, precipitating, and dispersing in 40kg of deionized water to obtain pre-dispersed graphene oxide;
(3) Adding the pretreated pigment and filler into the pre-dispersed graphene oxide, stirring at the speed of 1200r/min for 17min, standing for 3h, adding a photoinitiator, a polymerization inhibitor, an organic silicon defoamer, sodium sorbate and sodium carboxyethyl cellulose, uniformly mixing, and dehydrating a product by using a filter press under the pressure of 0.26MPa to obtain slurry;
(4) Adding an acrylate monomer and polyester acrylic resin into the slurry, uniformly dispersing at a high speed of 2000r/min, adding the mixture into a three-roll machine, grinding until the fineness is less than 10 mu m, adding water to adjust the static viscosity of the system to be 37780mPa & s, and obtaining the quick-drying high-stability printing ink.
Example 5
A fast drying highly stable printing ink having a pH of 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-aminoethyl piperazine diamine, 2kg of N-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 lubrizol hyperdispersant.
The photoinitiator is prepared from an initiator TPO and an auxiliary 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-diethoxysilane in 80kg of 85% ethanol water solution, adding nano silicon dioxide and organic pigment, stirring for 90min, filtering, washing with deionized water for 3 times, and drying at 110 ℃ to obtain the pretreated pigment filler;
(2) Dispersing graphene oxide in 30kg of deionized water, performing ultrasonic dispersion uniformly, adding N-aminoethyl piperazine diamine, stirring at 50 ℃ for 7 hours, adding N-methylene bisacrylamide, continuing stirring for 2.5 hours, dialyzing, precipitating, and dispersing in 35kg of deionized water to obtain pre-dispersed graphene oxide;
infrared spectroscopic analysis is performed on the obtained pre-dispersed graphene oxide and graphene oxide, as shown in FIG. 1, N-H bond at 3280cm-1 and 2900cm- 1 At a C-H bond and 1525cm- 1 The peak values of the characteristic peaks at the C-N bond are increased, while the O-H characteristic peaks at 3410cm-1 and 1393cm-1 are decreased significantly. 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 nanosheets. In addition, the decrease of the peak value of the O — H peak indicates the decrease of carboxylic acid groups and hydroxyl groups on the graphene oxide, and thus it can be presumed that the modification of the graphene oxide by the hyperbranched polymer is mainly achieved by the reaction between the carboxylic acid groups and hydroxyl groups on the graphene oxide and amine groups on the hyperbranched polymer.
(3) Adding the pretreated pigment and filler into the pre-dispersed graphene oxide, stirring at the speed of 1500r/min for 15min, standing for 7h, adding a photoinitiator, a polymerization inhibitor, trimethylolpropane triacrylate, sodium sorbate, sodium carboxymethylcellulose and lubrizol hyper-dispersant 24000, uniformly mixing, and dehydrating a product under the pressure of 0.24MPa by using a filter press to obtain slurry;
(4) Adding an acrylate monomer and polyester acrylic resin into the slurry, uniformly dispersing at a high speed of 3000r/min, adding the mixture into a three-roll machine, grinding until the fineness is less than 10 mu m, adding water to adjust the static viscosity of the system to be 35080mPa & s, and thus 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-aminoethyl piperazine diamine, 2kg of N-methylene bisacrylamide, 3kg of photoinitiator, 1.5kg of polymerization inhibitor, 0.4kg of trimethylolpropane triacrylate, 0.6kg of sodium sorbate, 0.3kg of sodium carboxymethylcellulose and 240000.3kg of lubrizol hyperdispersant.
The photoinitiator is prepared from 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, performing ultrasonic dispersion uniformly, adding N-aminoethyl piperazine diamine, stirring at 50 ℃ for 7 hours, adding N-methylene bisacrylamide, continuing 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 the speed of 1500r/min for 15min, standing for 7h, adding a photoinitiator, a polymerization inhibitor, trimethylolpropane triacrylate, sodium sorbate, sodium carboxymethylcellulose and lubrizol hyper-dispersant 24000, uniformly mixing, and dehydrating a product under the pressure of 0.24MPa by using a filter press to obtain slurry;
(3) Adding an acrylate monomer and polyester acrylic resin into the slurry, uniformly dispersing at a high speed of 3000r/min, adding into a three-roll machine, grinding to a fineness of less than 10 mu m, adding water to adjust the static viscosity of the system to be 30000-40000mPa & s, and obtaining the 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 polyamide amine, 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 lubrozol hyperdispersant.
The photoinitiator is prepared from 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-diethoxysilane in 80kg of 85% ethanol water solution, adding nano silicon dioxide and organic pigment, stirring for 90min, filtering, washing with deionized water for 3 times, and drying at 110 ℃ to obtain a pretreated pigment filler;
(2) Dispersing graphene oxide in 30kg of deionized water, performing ultrasonic dispersion uniformly, adding polyamidoamine, and stirring at 50 ℃ for 7 hours to obtain pre-dispersed graphene oxide;
(3) Adding the pretreated pigment and filler into the pre-dispersed graphene oxide, stirring at the speed of 1500r/min for 15min, standing for 7h, adding a photoinitiator, a polymerization inhibitor, trimethylolpropane triacrylate, sodium sorbate, sodium carboxyethyl cellulose and Lubo lubrizol hyper-dispersant 24000, uniformly mixing, and dehydrating a product under the pressure of 0.24MPa by using a filter press to obtain slurry;
(4) Adding an acrylate monomer and polyester acrylic resin into the slurry, uniformly dispersing at a high speed of 3000r/r/min, adding into a three-roll machine, grinding until the fineness is less than 10 mu m, adding water to adjust the static viscosity of the system to be 30000-40000mPa & s, and obtaining the printing ink.
The printing inks obtained in example 5 and comparative examples 1 to 2 were coated on glass (thickness 30 μm) with a wire bar coater at room temperature and cured using a photo-curing machine (80W/cm) 2 10cm from the light source) was used to determine whether the coating was cured by finger touch and the time taken for curing was recorded.
As shown in fig. 2, the curing time of the printing ink obtained in example 5 is the shortest, which confirms that the hyperbranched polymer is grafted on the surface of the graphene oxide by using an in-situ polymerization method, so that the polymerization energy of the water-based ink and the base material is reduced, the adhesion difficulty is reduced, the affinity of the pigment and filler in organic matters can be enhanced, and the hyperbranched polymer has better compatibility with water, improves the wettability, reduces the contact angle, and accelerates the drying speed.
The printing ink obtained in the example 5 and the printing ink obtained in the comparative examples 1-2 are sprayed on the surface of a PVC plastic film, cured and dried, and then folded at 180 degrees, the printing ink obtained in the example 5 still does not fall off after being folded for 50 times, and the printing ink obtained in the comparative examples has phenomena of warping, falling off and the like. The printing ink obtained by the invention is proved to have good flexibility and adhesion.
The printing inks obtained in example 5 and comparative examples 1-2 were sprayed on the surface of a PVC plastic film and then tested, and the results are as follows:
the stability test of the printing ink obtained in example 5 and comparative examples 1-2 was conducted by standing at room temperature, and it was found that the printing ink obtained in example 5 was not changed after 6 months of storage, while the printing ink obtained in comparative examples 1-2 was dusty, coagulated, etc. after 6 months of storage, indicating that the printing ink obtained in the present invention was highly stable.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A 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-aminoethyl piperazine diamine, 1-3 parts of N-methylene bisacrylamide, 1-5 parts of photoinitiator, 1-2 parts of polymerization inhibitor and 1-2 parts of auxiliary agent.
2. The fast drying highly stable printing ink according to claim 1, wherein said fast drying highly stable printing ink has a pH of 7.1 to 7.4.
3. The fast drying highly stable printing ink according to claim 1, wherein the photoinitiator comprises initiator TPO and co-initiator EDB, and the mass ratio of the initiator TPO to the co-initiator EDB is 10:1-4.
4. The fast drying highly stable printing ink according to claim 1, wherein the auxiliary agent is at least one of a dispersant, a reactive diluent, an antifoaming agent, a mildewproof agent, and a thixotropic agent.
5. The fast drying highly stable printing ink according to claim 4, wherein the dispersant is a polyester type multi-chain high molecular polymer dispersant.
6. The fast drying highly stable printing ink according to claim 4, wherein the reactive diluent is trimethylolpropane triacrylate.
7. The quick-drying highly stable printing ink according to claim 4, wherein the defoaming agent is a mineral oil type defoaming agent and/or a silicone type defoaming agent.
8. The quick-drying highly stable printing ink according to claim 4, wherein the anti-mold agent is at least one of sodium benzoate, sodium dehydroacetate, sodium sorbate and sodium pentachlorophenol.
9. The fast drying highly stable printing ink according to claim 4, characterized in that the thixotropic agent is sodium carboxyethyl cellulose and/or sodium polyacrylate.
10. A process for the preparation of a fast drying highly stable printing ink according to any of claims 1 to 9, characterized in that it comprises the steps of:
(1) Dissolving 3-aminopropyl-diethoxysilane in an ethanol water solution, adding nano silicon dioxide and organic pigment, stirring for 1-2h, filtering, washing and drying to obtain a pretreated pigment filler;
(2) Dispersing graphene oxide in deionized water, performing ultrasonic dispersion uniformly, adding N-aminoethyl piperazine diamine, stirring at 40-60 ℃ for 5-10h, adding N-methylene-bisacrylamide, continuing stirring, dialyzing, precipitating, and dispersing in deionized water to obtain pre-dispersed graphene oxide;
(3) Adding the pretreated pigment and filler into the pre-dispersed graphene oxide, stirring, standing for 2-6h, adding a photoinitiator, a polymerization inhibitor and an auxiliary agent, uniformly mixing, and performing filter pressing and dehydration to obtain slurry;
(4) Adding acrylate monomers and polyester acrylic resin into the slurry, dispersing uniformly at a high speed, grinding until the fineness is less than 10 mu m, adding water to adjust the static viscosity of the system to be 30000-40000 mPa.s, and obtaining the quick-drying high-stability printing ink.
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