阅读说明：本技术 一种改良版复合油墨及其制备方法 (Improved composite printing ink and preparation method thereof ) 是由 王伟生 于 2020-06-03 设计创作，主要内容包括：本发明公开了一种改良版复合油墨,由如下重量份原料制成：20-30份改性水性环氧树脂、12-15份复合填料、3-4份聚乙烯蜡乳液、1-2份消泡剂、15-20份无水乙醇、20-25份去离子水；本发明还公开了该复合油墨的制备方法。本发明的复合油墨采用改性水性环氧树脂作为高聚物连接料,该树脂不仅能够溶于水,而且能够提高油墨涂层的耐刮、耐磨性和耐水性,以无水乙醇作为树脂稀释剂,水作为溶剂,不会挥发有机物,使油墨安全、环保,同时,采用复合填料替代传统的金红石型钛白粉,能够更好地发挥钛白粉的作用,提高钛白粉对油墨涂层的补强、防老化、抗紫外线等能力,制得的复合油墨是一种环保、稳定、综合性能强的改良版油墨。(The invention discloses an improved composite printing ink which is prepared from the following raw materials in parts by weight: 20-30 parts of modified waterborne epoxy resin, 12-15 parts of composite filler, 3-4 parts of polyethylene wax emulsion, 1-2 parts of defoaming agent, 15-20 parts of absolute ethyl alcohol and 20-25 parts of deionized water; the invention also discloses a preparation method of the composite ink. The composite ink of the invention adopts the modified waterborne epoxy resin as the high polymer binder, the resin can be dissolved in water and can improve the scratch resistance, the wear resistance and the water resistance of an ink coating, the absolute ethyl alcohol is used as a resin diluent, the water is used as a solvent, and organic matters can not be volatilized, so that the ink is safe and environment-friendly, meanwhile, the composite filler is adopted to replace the traditional rutile titanium dioxide, the function of the titanium dioxide can be better exerted, the reinforcing, anti-aging, anti-ultraviolet and other capabilities of the titanium dioxide to the ink coating are improved, and the prepared composite ink is an improved printing ink with environmental protection, stability and strong comprehensive performance.)

1. The improved composite printing ink is characterized by being prepared from the following raw materials in parts by weight: 20-30 parts of modified waterborne epoxy resin, 12-15 parts of composite filler, 3-4 parts of polyethylene wax emulsion, 1-2 parts of defoaming agent, 15-20 parts of absolute ethyl alcohol and 20-25 parts of deionized water;

the improved plate composite ink is prepared by the following steps:

firstly, mixing modified waterborne epoxy resin, absolute ethyl alcohol and deionized water, stirring for 10min at the temperature of 15-25 ℃ and at the speed of 150r/min, adding a defoaming agent, and continuously stirring for 15min to obtain a premix;

and step two, simultaneously adding the composite filler and the polyethylene wax emulsion into the premix, increasing the rotating speed to 200r/min, stirring for 30-40min, and performing ultrasonic dispersion treatment at the temperature of 15-25 ℃ for 150-160min to obtain the improved plate composite ink.

2. An improved plate composite ink according to claim 1, characterized in that the modified aqueous epoxy resin is prepared by the following method:

(1) preparing modified kaolinite, namely preparing mixed acid by using 98% concentrated sulfuric acid and 70% concentrated nitric acid according to the mass ratio of 1: 1, putting the kaolinite into the mixed acid according to the solid-liquid ratio of 1 g: 8m L, stirring and reacting for 120min in a 80 ℃ water bath, repeatedly centrifuging and washing by using deionized water until the pH value of washing liquor is 6.6-7, drying for 24h in a 60 ℃ drying box, crushing and sieving by using a 120-mesh sieve to obtain the modified kaolinite;

(2) adding waterborne epoxy resin and hydroquinone under a nitrogen seal piece in a four-neck flask provided with a dropping funnel, a stirrer and a reflux condenser, slowly heating to 96 ℃, adding triphenylphosphine after the epoxy resin is fully melted, slowly dropwise adding metered acrylic acid, and fully reacting for 6-7 hours after dropwise adding is finished to obtain pretreated waterborne epoxy resin; wherein the mass ratio of the water-based epoxy resin to the acrylic acid is 1: 2;

(3) uniformly mixing the pretreated waterborne epoxy resin with metered methyl methacrylate, butyl acrylate, hydroxymethyl acrylamide, modified kaolin and 4/5 ammonium persulfate to obtain a reaction mixture;

(4) adding a small amount of absolute ethyl alcohol into a four-neck flask provided with a dropping funnel, a stirrer and a reflux condenser, stirring and heating to the reflux temperature of 78 ℃, slowly dripping 1/4 reaction mixture after the reflux is stable, reacting for 15min, dripping the rest reaction mixture, heating the system to 80 ℃ after the dripping is finished, adding the rest 1/5 ammonium persulfate, carrying out heat preservation reaction for 2h, then adding n-butyl alcohol, stirring for about 10min until the mixture is uniform, cooling to 50-60 ℃, then dripping 50 ℃ of deionized water under uniform stirring at 1000r/min, carrying out heat preservation stirring for 10min, and discharging to obtain the modified waterborne epoxy resin.

3. An improved composite ink as claimed in claim 2, wherein the mass ratio of the pre-treated aqueous epoxy resin, the monomer, the modified kaolin, the ammonium persulfate, the n-butanol and the deionized water at 50 ℃ is 4: 1: 0.1: 0.15: 0.05: 0.1, and the mass ratio of the methyl methacrylate, the butyl acrylate and the methacrylamide is 4: 7: 1.

4. An improved plate composite ink as claimed in claim 1, wherein said composite filler is prepared by:

adding calcium carbonate, hydroxypropyl cellulose and water into a sand mill according to a corresponding proportion, grinding the mixture at a high speed for 2 hours, adding titanium dioxide into the mixture, increasing the rotating speed, continuously grinding the mixture for 2 hours, and finally dehydrating, filtering and drying the mixture to obtain the composite filler.

5. The improved composite ink as claimed in claim 4, wherein the mass ratio of calcium carbonate, hydroxypropyl cellulose, water and titanium dioxide is 2: 0.3-0.4: 2-3: 1.

6. The preparation method of the improved composite ink is characterized by comprising the following steps of:

firstly, mixing modified waterborne epoxy resin, absolute ethyl alcohol and deionized water, stirring for 10min at the temperature of 15-25 ℃ and at the speed of 150r/min, adding a defoaming agent, and continuously stirring for 15min to obtain a premix;

and step two, simultaneously adding the composite filler and the polyethylene wax emulsion into the premix, increasing the rotating speed to 200r/min, stirring for 30-40min, and performing ultrasonic dispersion treatment at the temperature of 15-25 ℃ for 150-160min to obtain the improved plate composite ink.

Technical Field

The invention belongs to the technical field of printing ink, and particularly relates to improved plate composite printing ink and a preparation method thereof.

Background

In modern economic life, commodity packaging becomes an important component of commodities, and as compared with the traditional packaging materials, plastic packaging has the advantages of lightness, transparency, stable chemical performance, moisture resistance, oxidation resistance and strong air tightness, flexible packaging printing mainly based on plastic films plays an increasingly important role in packaging printing. It is estimated that plastic packaging has accounted for 32% to 44% of the total printed packaging in advanced countries of the world since 1980.

Generally, since the contents of a single plastic packaging material are poor in protection and it is difficult to satisfy the packaging requirements of heat resistance, moisture resistance, air permeability and heat sealing, a multi-purpose composite material, i.e., a base film is printed and then laminated with a heat-seal film to form a bag-like shape, and the contents are sealed and sealed by a heat-seal method, is generally known.

The existing composite ink adopts benzenes, ketones and the like as solvents, is easy to cause pollution in packaging, printing and production, and can cause great harm to the health of operators; and the odor is large, the residue of harmful solvent is difficult to reach the standard, and the method is particularly not suitable for food packaging printing. In addition, many products have poor universality, can only be used on one or a few base materials, mostly concentrate on the low-end O-print market, have limited functions, and are often only suitable for composite packaging. In addition, the existing composite ink adopts ester-soluble polyurethane resin and vinyl chloride-vinyl acetate matched as an ink connecting material, and is dispersed and ground with organic pigment, so that the requirement on later-stage composite strength is met. However, the vinyl chloride-vinyl acetate copolymer is difficult to dissolve, and the prepared composite ink has poor redissolution performance and low printing transfer rate.

Disclosure of Invention

The invention aims to provide improved printing ink and a preparation method thereof, wherein modified water-based epoxy resin is used as a high polymer binder, the resin can be dissolved in water and can improve the scratch resistance, wear resistance and water resistance of a printing ink coating, absolute ethyl alcohol is used as a resin diluent, and water is used as a solvent, so that organic matters can not be volatilized, the printing ink is safe and environment-friendly, meanwhile, the composite filler is used for replacing the traditional rutile titanium dioxide, the effect of titanium dioxide can be better exerted, the reinforcing, anti-aging, anti-ultraviolet and other capabilities of the titanium dioxide on the printing ink coating are improved, and the prepared composite printing ink is the improved printing ink which is environment-friendly, stable and strong in comprehensive performance.

The purpose of the invention can be realized by the following technical scheme:

an improved composite printing ink is prepared from the following raw materials in parts by weight: 20-30 parts of modified waterborne epoxy resin, 12-15 parts of composite filler, 3-4 parts of polyethylene wax emulsion, 1-2 parts of defoaming agent, 15-20 parts of absolute ethyl alcohol and 20-25 parts of deionized water;

the improved plate composite ink is prepared by the following steps:

firstly, mixing modified waterborne epoxy resin, absolute ethyl alcohol and deionized water, stirring for 10min at the temperature of 15-25 ℃ and at the speed of 150r/min, adding a defoaming agent, and continuously stirring for 15min to obtain a premix;

and step two, simultaneously adding the composite filler and the polyethylene wax emulsion into the premix, increasing the rotating speed to 200r/min, stirring for 30-40min, and performing ultrasonic dispersion treatment at the temperature of 15-25 ℃ for 150-160min to obtain the improved plate composite ink.

Further, the modified waterborne epoxy resin is prepared by the following method:

(1) preparing modified kaolinite, namely preparing mixed acid by using 98% concentrated sulfuric acid and 70% concentrated nitric acid according to the mass ratio of 1: 1, putting the kaolinite into the mixed acid according to the solid-liquid ratio of 1 g: 8m L, stirring and reacting for 120min in a 80 ℃ water bath, repeatedly centrifuging and washing by using deionized water until the pH value of washing liquor is 6.6-7, drying for 24h in a 60 ℃ drying box, crushing and sieving by using a 120-mesh sieve to obtain the modified kaolinite;

(2) adding waterborne epoxy resin and hydroquinone under a nitrogen seal piece in a four-neck flask provided with a dropping funnel, a stirrer and a reflux condenser, slowly heating to 96 ℃, adding triphenylphosphine after the epoxy resin is fully melted, slowly dropwise adding metered acrylic acid, and fully reacting for 6-7 hours after dropwise adding is finished to obtain pretreated waterborne epoxy resin; wherein the mass ratio of the water-based epoxy resin to the acrylic acid is 1: 2;

(3) uniformly mixing the pretreated waterborne epoxy resin with metered methyl methacrylate, butyl acrylate, hydroxymethyl acrylamide, modified kaolin and 4/5 ammonium persulfate to obtain a reaction mixture;

(4) adding a small amount of absolute ethyl alcohol into a four-neck flask provided with a dropping funnel, a stirrer and a reflux condenser, stirring and heating to the reflux temperature of 78 ℃, slowly dripping 1/4 reaction mixture after the reflux is stable, reacting for 15min, dripping the rest reaction mixture, heating the system to 80 ℃ after the dripping is finished, adding the rest 1/5 ammonium persulfate, carrying out heat preservation reaction for 2h, then adding n-butyl alcohol, stirring for about 10min until the mixture is uniform, cooling to 50-60 ℃, then dripping 50 ℃ of deionized water under uniform stirring at 1000r/min, carrying out heat preservation stirring for 10min, and discharging to obtain the modified waterborne epoxy resin.

Further, the mass ratio of the pretreated aqueous epoxy resin, the monomer, the modified kaolin, the ammonium persulfate, the n-butanol and the deionized water at 50 ℃ is 4: 1: 0.1: 0.15: 0.05: 0.1, and the mass ratio of the methyl methacrylate, the butyl acrylate and the methacrylamide is 4: 7: 1.

Further, the composite filler is prepared by the following method:

adding calcium carbonate, hydroxypropyl cellulose and water into a sand mill according to a corresponding proportion, grinding the mixture at a high speed for 2 hours, adding titanium dioxide into the mixture, increasing the rotating speed, continuously grinding the mixture for 2 hours, and finally dehydrating, filtering and drying the mixture to obtain the composite filler.

Further, the mass ratio of the calcium carbonate, the hydroxypropyl cellulose, the water and the titanium dioxide is 2: 0.3-0.4: 2-3: 1.

A preparation method of improved composite printing ink comprises the following steps:

firstly, mixing modified waterborne epoxy resin, absolute ethyl alcohol and deionized water, stirring for 10min at the temperature of 15-25 ℃ and at the speed of 150r/min, adding a defoaming agent, and continuously stirring for 15min to obtain a premix;

and step two, simultaneously adding the composite filler and the polyethylene wax emulsion into the premix, increasing the rotating speed to 200r/min, stirring for 30-40min, and performing ultrasonic dispersion treatment at the temperature of 15-25 ℃ for 150-160min to obtain the improved plate composite ink.

The invention has the beneficial effects that:

the composite ink adopts modified waterborne epoxy resin as an ink binder, utilizes the epoxy functional groups on the molecular chains of acrylic acid and epoxy resin to perform ring-opening esterification reaction to introduce double bonds to obtain pretreated epoxy resin, introduces methyl methacrylate, butyl acrylate and methacrylamide into the epoxy resin molecules according to a certain proportion through free radical polymerization, and simultaneously dopes modified kaolin to perform in-situ polymerization in the free radical polymerization process; certain interaction exists between the modified kaolin and the high polymer, so that the cross-linking points of the high polymer are increased, the free chain segment of the high polymer is difficult to move, the flexibility is reduced, the Tg is increased, and the prepared ink is favorable for obtaining excellent hardness and scratch resistance in application; during film forming, the uncoated free kaolin particles are solidified and transferred to the surface of the adhesive film along with the adhesive film, and the adhesive force of the free kaolin particles is improved by the hydroxyl groups on the surface of the adhesive film, so that the scratch resistance and the wear resistance of the ink during production and use are improved; the modified kaolin particles are uniformly dispersed in a polymer matrix through in-situ polymerization, and have strong interaction with the polymer; secondly, part of kaolin migrated on the surface can form a compact Si-O-Si network structure on the surface of the film, and a micro-nano structure similar to a lotus leaf is formed during film forming, so that ethanol molecules and water molecules can be effectively prevented from diffusing into the ink coating, and the water resistance and the alcohol resistance of the ink are improved;

the composite ink of the invention adopts the composite filler to replace the conventional rutile type titanium dioxide, the particle size of calcium carbonate can be effectively reduced by firstly grinding the calcium carbonate, and the specific surface area can be effectively increased, in addition, the calcium carbonate particles can absorb a large amount of energy after being extruded due to the impact and the repeated action of friction of the grinding medium, and further the surface of the calcium carbonate particles can be activated; meanwhile, the surface of the calcium carbonate contains hydroxyl, the hydroxyl on the hydroxypropyl cellulose can form hydrogen bonds with the hydroxyl on the surface of the calcium carbonate, so that the hydroxypropyl cellulose is adsorbed on the surface of calcium carbonate particles, at the moment, titanium dioxide is added into the calcium carbonate, the surfaces of titanium dioxide particles can be coated by the calcium carbonate particles, the material characteristics of the titanium dioxide and the calcium carbonate are absorbed by the titanium dioxide coated with the calcium carbonate particles, the effect of the titanium dioxide (as a coloring agent, the titanium dioxide has the functions of reinforcement, aging resistance and filling, and simultaneously has excellent ozone resistance and ultraviolet resistance) can be better played, and the quality of the prepared ink is ensured; the hydroxypropyl cellulose is easy to dissolve in water, so that the dispersibility of the composite filler in an aqueous medium is improved to a large extent, and the composite filler coated with the calcium carbonate has weather resistance, temperature resistance and corrosion resistance;

the composite ink of the invention adopts the modified waterborne epoxy resin as the high polymer binder, the resin can be dissolved in water and can improve the scratch resistance, the wear resistance and the water resistance of an ink coating, the absolute ethyl alcohol is used as a resin diluent, the water is used as a solvent, and organic matters can not be volatilized, so that the ink is safe and environment-friendly, meanwhile, the composite filler is adopted to replace the traditional rutile titanium dioxide, the function of the titanium dioxide can be better exerted, the reinforcing, anti-aging, anti-ultraviolet and other capabilities of the titanium dioxide to the ink coating are improved, and the prepared composite ink is an improved printing ink with environmental protection, stability and strong comprehensive performance.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

An improved composite printing ink is prepared from the following raw materials in parts by weight: 20-30 parts of modified waterborne epoxy resin, 12-15 parts of composite filler, 3-4 parts of polyethylene wax emulsion, 1-2 parts of defoaming agent, 15-20 parts of absolute ethyl alcohol and 20-25 parts of deionized water;

the defoaming agent is P1-40, specifically, water-white hydrogenated petroleum resin P1-40;

the modified waterborne epoxy resin is prepared by the following method:

(1) preparing modified kaolinite, namely preparing mixed acid by using 98% concentrated sulfuric acid and 70% concentrated nitric acid according to the mass ratio of 1: 1, putting the kaolinite into the mixed acid according to the solid-liquid ratio of 1 g: 8m L, stirring and reacting for 120min in a 80 ℃ water bath, repeatedly centrifuging and washing by using deionized water until the pH value of washing liquor is 6.6-7, drying for 24h in a 60 ℃ drying box, crushing and sieving by using a 120-mesh sieve to obtain the modified kaolinite;

(2) adding waterborne epoxy resin and hydroquinone (accounting for 0.3 percent of the total mass) into a four-neck flask provided with a dropping funnel, a stirrer and a reflux condenser under a nitrogen seal condition, slowly heating to 96 ℃, adding triphenylphosphine (accounting for 0.35 percent of the total mass) after the epoxy resin is fully melted, slowly dropwise adding metered acrylic acid, and fully reacting for 6-7 hours after dropwise adding is finished to obtain pretreated waterborne epoxy resin; wherein the mass ratio of the water-based epoxy resin to the acrylic acid is 1: 2;

(3) uniformly mixing the pretreated waterborne epoxy resin with metered methyl methacrylate, butyl acrylate, hydroxymethyl acrylamide, modified kaolin and 4/5 ammonium persulfate to obtain a reaction mixture;

(4) adding a small amount of absolute ethyl alcohol into a four-neck flask provided with a dropping funnel, a stirrer and a reflux condenser, stirring and heating to the reflux temperature of 78 ℃, slowly dripping 1/4 reaction mixture after the reflux is stable, reacting for 15min, dripping the rest reaction mixture, heating the system to 80 ℃ after the dripping is finished, adding the rest 1/5 ammonium persulfate, carrying out heat preservation reaction for 2h, then adding n-butyl alcohol, stirring for about 10min until the mixture is uniform, cooling to 50-60 ℃, then dripping 50 ℃ of deionized water under uniform stirring at 1000r/min, carrying out heat preservation stirring for 10min, and discharging to obtain the modified waterborne epoxy resin;

wherein the mass ratio of the pretreated waterborne epoxy resin, the monomers (methyl methacrylate, butyl acrylate and methacrylamide), the modified kaolin, the ammonium persulfate, the n-butanol and the deionized water at 50 ℃ is 4: 1: 0.1: 0.15: 0.05: 0.1, and the mass ratio of the methyl methacrylate, the butyl acrylate and the methacrylamide is 4: 7: 1;

introducing double bonds by utilizing the ring-opening esterification reaction of epoxy functional groups on the molecular chains of acrylic acid and epoxy resin to obtain pretreated epoxy resin, introducing methyl methacrylate, butyl acrylate and methacrylamide into the epoxy resin molecules according to a certain proportion through free radical polymerization, and simultaneously, doping modified kaolin in the free radical polymerization process to carry out in-situ polymerization;

after the kaolin is modified by concentrated acid, the surface of the kaolin contains a large number of active groups such as hydroxyl groups and the like, and the kaolin has strong interaction force with an initiator (ammonium persulfate), so that the initiator is attached to the particle surface, a monomer is initiated to polymerize, and composite latex particles taking a high molecular chain as a shell and kaolin particles as a core are formed, so that the latex particle size is increased, the viscosity of the system is reduced along with the increase of the latex particle size, the leveling property of the ink is improved, and the ink is easier to be uniformly coated during printing production; certain interaction exists between the modified kaolin and the high polymer, so that the cross-linking points of the high polymer are increased, the free chain segment of the high polymer is difficult to move, the flexibility is reduced, the Tg is increased, and the prepared ink is favorable for obtaining excellent hardness and scratch resistance in application; during film forming, the uncoated free kaolin particles are solidified and transferred to the surface of the adhesive film along with the adhesive film, and the adhesive force of the free kaolin particles is improved by the hydroxyl groups on the surface of the adhesive film, so that the scratch resistance and the wear resistance of the ink during production and use are improved; the modified kaolin particles are uniformly dispersed in a polymer matrix through in-situ polymerization, and have strong interaction with the polymer; secondly, part of kaolin migrated on the surface can form a compact Si-O-Si network structure on the surface of the film, and a micro-nano structure similar to a lotus leaf is formed during film forming, so that ethanol molecules and water molecules can be effectively prevented from diffusing into the ink coating, and the water resistance and the alcohol resistance of the ink are improved;

the composite filler is prepared by the following method:

adding calcium carbonate, hydroxypropyl cellulose and water into a sand mill according to a corresponding proportion, carrying out high-speed grinding for 2 hours, then adding titanium dioxide into the sand mill, increasing the rotating speed, continuing grinding for 2 hours, and finally carrying out dehydration, filtration and drying to obtain the composite filler, wherein the mass ratio of the calcium carbonate to the hydroxypropyl cellulose to the water to the titanium dioxide is 2: 0.3-0.4: 2-3: 1;

the calcium carbonate is ground firstly, so that the particle size of the calcium carbonate can be effectively reduced, the specific surface area can be effectively increased, and in addition, the calcium carbonate particles can absorb a large amount of energy after being extruded due to the multiple actions of impact and friction of the grinding medium, so that the surface of the calcium carbonate particles can be activated; meanwhile, the surface of the calcium carbonate contains hydroxyl, the hydroxyl on the hydroxypropyl cellulose can form hydrogen bonds with the hydroxyl on the surface of the calcium carbonate, so that the hydroxypropyl cellulose is adsorbed on the surface of calcium carbonate particles, at the moment, titanium dioxide is added into the calcium carbonate, the surfaces of titanium dioxide particles can be coated by the calcium carbonate particles, the material characteristics of the titanium dioxide and the calcium carbonate are absorbed by the titanium dioxide coated with the calcium carbonate particles, the effect of the titanium dioxide (as a coloring agent, the titanium dioxide has the functions of reinforcement, aging resistance and filling, and simultaneously has excellent ozone resistance and ultraviolet resistance) can be better played, and the quality of the prepared ink is ensured; the hydroxypropyl cellulose is easy to dissolve in water, so that the dispersibility of the composite filler in an aqueous medium is improved to a large extent, and the composite filler coated with the calcium carbonate has weather resistance, temperature resistance and corrosion resistance;

the preparation method of the improved composite ink comprises the following steps:

firstly, mixing modified waterborne epoxy resin, absolute ethyl alcohol and deionized water, stirring for 10min at the temperature of 15-25 ℃ and at the speed of 150r/min, adding a defoaming agent, and continuously stirring for 15min to obtain a premix;

and step two, simultaneously adding the composite filler and the polyethylene wax emulsion into the premix, increasing the rotating speed to 200r/min, stirring for 30-40min, and performing ultrasonic dispersion treatment at the temperature of 15-25 ℃ for 150-160min to obtain the improved plate composite ink.