CN111978789A

CN111978789A - Environment-friendly printing ink and preparation method thereof

Info

Publication number: CN111978789A
Application number: CN202011065619.2A
Authority: CN
Inventors: 付正谋
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-09-30
Filing date: 2020-09-30
Publication date: 2020-11-24

Abstract

The invention discloses an environment-friendly printing ink which comprises the following raw materials in parts by weight: 40-60 parts of modified water-based acrylic resin, 5-10 parts of nano composite filler, 3-5 parts of functional assistant, 10-20 parts of soybean oil fatty acid ethyl ester, 3-5 parts of anti-skinning agent, 25-30 parts of connecting agent, 1-3 parts of defoaming agent and 5-10 parts of slipping agent; the invention also discloses a preparation method of the printing ink, the printing ink is prepared by taking the modified water-based acrylic resin, the soybean oil fatty acid ethyl ester and the connecting agent as main materials and adding the nano composite filler, the functional auxiliary agent, the anti-skinning agent, the defoaming agent and the slipping agent.

Description

Environment-friendly printing ink and preparation method thereof

Technical Field

The invention belongs to the field of ink manufacturing, and particularly relates to environment-friendly printing ink and a preparation method thereof.

Background

The ink is a uniform mixture composed of a connecting material, a filling material, an additive and the like of a color body (such as pigment, fuel and the like); can be printed and dried on the printed matter, and is a colored paste-like adhesive body with a certain fluidity. Thus, color (hue), body (rheology such as consistency, fluidity, etc.) and drying properties are three important properties of the ink. The ink has a great weight, different physical properties, thick and sticky properties, vegetable oil as a binder, and resin, solvent or water as a binder. These are determined according to the object to be printed, i.e., the substrate, the printing method, the type of printing plate, and the drying method.

In the prior art, the ink has large pungent odor, and still has defects in the aspects of printing data such as density, fixation speed, ink gloss and the like. Currently, there are two types of printing inks used in publishing printing: a water-soluble stamp-pad ink using polyamide resin as main raw material is a composite ink using organic solvent as main solvent and polyurethane resin as raw material, for example, a two-component polyurethane composite ink, the main component is polyurethane oil containing hydroxyl group, the curing agent is polyurethane oligomer containing isocyanate group, because the main component reacts with the curing agent, the main component usually uses benzene and ketone solvents, and the isocyanate group in the curing agent has great toxicity. The two kinds of ink have pungent smell and are toxic, great influence is caused to the environment, residues are easy to be left, and the human health is damaged.

Disclosure of Invention

The invention aims to provide environment-friendly printing ink and a preparation method thereof.

The technical problems to be solved by the invention are as follows:

there are two types of printing inks in the prior art: a water-soluble stamp-pad ink using polyamide resin as main raw material is a composite ink using organic solvent as main solvent and polyurethane resin as raw material, for example, a two-component polyurethane composite ink, the main component is polyurethane oil containing hydroxyl group, the curing agent is polyurethane oligomer containing isocyanate group, because the main component reacts with the curing agent, the main component usually uses benzene and ketone solvents, and the isocyanate group in the curing agent has great toxicity. The two kinds of ink have pungent smell and are toxic, great influence is caused to the environment, residues are easy to be left, and the human health is damaged.

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

an environment-friendly printing ink comprises the following raw materials in parts by weight: 40-60 parts of modified water-based acrylic resin, 5-10 parts of nano composite filler, 3-5 parts of functional assistant, 10-20 parts of soybean oil fatty acid ethyl ester, 3-5 parts of anti-skinning agent, 25-30 parts of connecting agent, 1-3 parts of defoaming agent and 5-10 parts of slipping agent;

the preparation method of the environment-friendly printing ink specifically comprises the following steps:

firstly, adding a nano composite filler and a functional assistant into a reaction kettle, then sequentially adding a connecting agent and soybean oil fatty acid ethyl ester, and stirring at the rotation speed of 200-;

secondly, adding the modified waterborne acrylic resin into the mixture A, heating to 60-70 ℃, stirring for 20-25min at the rotation speed of 500-;

and thirdly, adding an anti-skinning agent, a defoaming agent and a slip agent into the mixture B, stirring at the rotating speed of 300-500r/min for 30-40min at room temperature, standing for 20-25min, and grinding to obtain slurry with the fineness of below 15 mu m by a three-roller machine, namely the environment-friendly printing ink.

Further, the anti-skinning agent is formed by mixing 2, 6-di-tert-butyl-4-methylphenol, soybean oil, mineral oil and hydroquinone, wherein the mass ratio of the 2, 6-di-tert-butyl-4-methylphenol to the soybean oil to the mineral oil to the hydroquinone is 2-4:1-3:2: 1.

Further, the preparation method of the modified waterborne acrylic resin specifically comprises the following steps:

step S1, adding 3-8 parts by weight of nano titanium dioxide, 55-65 parts by weight of ethanol, 20-30 parts by weight of deionized water and 1-8 parts by weight of gamma-methyl acrylamide oxypropyltrimethylsilane into a water bath reflux reaction kettle, carrying out reflux reaction for 5-6h, then cooling to room temperature, and carrying out centrifugal separation and washing on the product to obtain modified inorganic nano titanium dioxide;

step S2, adding 5-10 parts by weight of methyl methacrylate, 2-4 parts by weight of butyl acrylate, 1-3 parts by weight of acrylic acid and 3-5 parts by weight of propyl acrylate into a reaction kettle, and stirring at the rotation speed of 200-300r/min for 30-50min to obtain a mixed monomer;

and S3, adding the modified inorganic nano titanium dioxide obtained in the step S1 and the mixed monomer obtained in the step S2 into an emulsifying kettle, adding 5-12 parts by weight of ammonium persulfate and 3-5 parts by weight of sodium bicarbonate, heating to 75-80 ℃, stirring at the rotation speed of 500 plus one year for 30-60min, preserving heat for 1.5h, then cooling to 40 ℃, adding ammonia water with the mass fraction of 40%, adjusting the pH value of the solution to 8-9, and filtering through 300-mesh gauze to obtain the modified waterborne acrylic resin.

Further, the preparation method of the nano composite filler comprises the following steps:

s11, weighing 40g of shrimp shell fragments, placing the shrimp shell fragments in a crusher, rotating for 5-10min to obtain shrimp shell powder, adding the shrimp shell powder into 100mL of 1mol/L hydrochloric acid solution, mechanically stirring for 2-4h at the rotation speed of 200-;

step S12, soaking the acid-leached shrimp shell powder in 50mL of 1mol/L sodium hydroxide solution, heating in an oil bath at the temperature of 80-90 ℃, mechanically stirring at the rotating speed of 50-100r/min for 30-60min, then filtering, washing filter residues with deionized water until the washing liquid is neutral, and obtaining basic chitin;

s13, putting the basic chitin into 50mL of sodium chlorite solution with the mass fraction of 0.3% for bleaching for 1-2h, filtering to obtain filter residue, and washing the bleached basic chitin with deionized water for 5-8 times to obtain purified chitin;

step S14, drying the purified chitin in an oven at 80-85 ℃ for 1-2 hours to obtain dried chitin, then immersing the dried chitin into 40-60mL of 33% sodium hydroxide solution by mass fraction, then adding 5-10mL of 33% sodium borohydride solution by mass fraction, then placing the mixture in an oil bath kettle at 90-95 ℃, mechanically stirring for 1-3 hours at the rotation speed of 100-.

Further, the preparation method of the soybean oil fatty acid ethyl ester comprises the following steps:

adding soybean oil into a reaction kettle provided with a condensing tube for preheating at the temperature of 60-70 ℃ for 15-30min, and then dissolving sodium hydroxide into ethanol to obtain a mixed alcohol solution, wherein the solid-to-liquid ratio of the sodium hydroxide to the ethanol is 1 g: 3-5mL, adding the obtained mixed alcohol solution into preheated soybean oil, wherein the volume ratio of the mixed alcohol solution to the preheated soybean oil is 1:1, stirring at the rotating speed of 300-.

Further, the preparation method of the functional auxiliary agent comprises the following steps:

dissolving 5-10 parts by weight of beta-cyclodextrin in 20-30 parts by weight of 40-50 ℃ deionized water, stirring at the rotation speed of 200-300r/min for 20-40min to obtain a beta-cyclodextrin solution, dissolving 40-60 parts by weight of tea polyphenol powder in 50-80 parts by weight of deionized water at the rotation speed of 50-100r/min, stirring for 20-40min to form a tea polyphenol solution, mixing the beta-cyclodextrin solution and the tea polyphenol solution, carrying out ultrasonic treatment for 2-4h, standing for 5-10h, filtering, washing filter residues with deionized water for 3 times, then putting the filter residues into a refrigerator for freezing for 24h, and finally putting the refrigerator into a freeze dryer for treatment at the temperature of-50 ℃ for 12h to obtain the functional auxiliary agent.

Further, the connecting agent is one or a mixture of more of tricresyl phosphate, hydrogenated rosin glyceride, ethyl acetate, epoxy resin, ethanol and dibutyltin dilaurate which are mixed in any proportion.

Further, the defoaming agent is one of polyoxypropylene glycerol ether and polyoxypropylene ethylene oxide glycerol ether.

Further, the slip agent is a high density polyethylene wax.

Further, the preparation method of the environment-friendly printing ink specifically comprises the following steps:

The invention has the beneficial effects that:

1. the environment-friendly printing ink is prepared by taking modified water-based acrylic resin, soybean oil fatty acid ethyl ester and a connecting agent as main materials, adding nano composite filler, a functional assistant, an anti-skinning agent, a defoaming agent and a slip agent, adding modified nano titanium dioxide by adopting a mixed monomer with high water resistance, improving the copolymerization effect of an acrylic monomer, changing the surface activity of the nano titanium dioxide by utilizing a silane coupling agent under an alcohol solution, grafting organic molecules on the surface of the titanium dioxide, and neutralizing the characteristic of good hydrophilicity of the traditional acrylic resin, so that the prepared modified water-based acrylic resin has the advantages of good water resistance, uniform texture and good film forming effect; dissolving minerals in shrimp shell by acid leaching method, removing protein in shrimp shell by alkaline leaching method, the color impurities in the shrimp shell are removed by bleaching with sodium chlorite solution, the nano chitin dispersant with positive charges is prepared to be used as nano composite filler, the nano chitin has a unique fiber structure with high length-diameter ratio, when the modified polyurethane is used in printing ink, the toughness and the scratch resistance of an ink film can be improved, simultaneously, the surface tension of an ink system can be reduced to a certain extent, the ink is matched with a substrate with smaller surface tension by reducing the surface tension of the ink system, and further, the potential energy of the surface of the base material is obviously improved during the adhesion, so that the printing ink is easier to wet and spread on the surface of the base material, the adhesion of the printing ink is improved, by adding the tea polyphenol/beta-cyclodextrin inclusion compound, the antibacterial property of the printing ink is improved, and the use value of the environment-friendly ink is increased.

2. The printing ink prepared by the invention has no heavy metal additive and no harmful organic additive, is environment-friendly and pollution-free, and has the characteristics of high heat resistance, good adsorptivity and high antibacterial performance.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.

Example 1

An environment-friendly printing ink comprises the following raw materials in parts by weight: 40 parts of modified water-based acrylic resin, 5 parts of nano composite filler, 3 parts of functional assistant, 10 parts of soybean oil fatty acid ethyl ester, 3 parts of anti-skinning agent, 25 parts of connecting agent, 1 part of defoaming agent and 5 parts of slipping agent;

firstly, adding a nano composite filler and a functional assistant into a reaction kettle, then sequentially adding a connecting agent and soybean oil fatty acid ethyl ester, and stirring at a rotating speed of 200r/min for 20min to obtain a mixture A;

secondly, adding the modified waterborne acrylic resin into the mixture A, heating to 60 ℃, stirring for 20min at the rotating speed of 500r/min, then heating to 80 ℃, and continuously stirring for 30min under the condition of unchanged rotating speed to obtain a mixture B;

and thirdly, adding an anti-skinning agent, a defoaming agent and a slip agent into the mixture B, stirring at the rotating speed of 300r/min for 30min at room temperature, standing for 20min, and grinding by a three-roll machine to obtain slurry with the fineness of below 15 microns, namely the environment-friendly printing ink.

The anti-skinning agent is prepared by mixing 2, 6-di-tert-butyl-4-methylphenol, soybean oil, mineral oil and hydroquinone, wherein the mass ratio of the 2, 6-di-tert-butyl-4-methylphenol to the soybean oil to the mineral oil to the hydroquinone is 2:1:2: 1.

The preparation method of the modified water-based acrylic resin specifically comprises the following steps:

step S1, adding 3 parts by weight of nano titanium dioxide, 55 parts by weight of ethanol, 20 parts by weight of deionized water and 1 part by weight of gamma-methyl acrylamide oxypropyltrimethylsilane into a water bath reflux reaction kettle, carrying out reflux reaction for 5 hours, then cooling to room temperature, and carrying out centrifugal separation and washing on a product to obtain modified inorganic nano titanium dioxide;

step S2, adding 5 parts by weight of methyl methacrylate, 2 parts by weight of butyl acrylate, 1 part by weight of acrylic acid and 3 parts by weight of propyl acrylate into a reaction kettle, and stirring for 30min at a rotating speed of 200r/min to obtain a mixed monomer;

and S3, adding the modified inorganic nano titanium dioxide obtained in the step S1 and the mixed monomer obtained in the step S2 into an emulsifying kettle, adding 5 parts by weight of ammonium persulfate and 3 parts by weight of sodium bicarbonate, heating to 75 ℃, stirring at the rotating speed of 500r/min for 30min, preserving heat for 1.5h, then cooling to 40 ℃, adding ammonia water with the mass fraction of 40%, adjusting the pH value of the solution to 8, and filtering through 300-mesh gauze to obtain the modified waterborne acrylic resin.

The preparation method of the nano composite filler comprises the following steps:

s11, weighing 40g of shrimp shell fragments, placing the shrimp shell fragments in a crusher, rotating for 5min to obtain shrimp shell powder, adding the shrimp shell powder into 100mL of 1mol/L hydrochloric acid solution, mechanically stirring for 2h at a rotating speed of 200r/min, filtering, washing filter residues with deionized water until the washing liquid is neutral, and obtaining acid-leaching shrimp shell powder;

step S12, soaking the acid-leached shrimp shell powder in 50mL of 1mol/L sodium hydroxide solution, heating in an oil bath at the temperature of 80 ℃, mechanically stirring at the rotating speed of 50r/min for 30min, filtering, and washing filter residues with deionized water until the washing liquid is neutral to obtain basic chitin;

s13, putting the basic chitin into 50mL of sodium chlorite solution with the mass fraction of 0.3% for bleaching for 1h, filtering to obtain filter residue, and washing the bleached basic chitin with deionized water for 5 times to obtain purified chitin;

step S14, drying the purified chitin in an oven at 80 ℃ for 1 hour to obtain dried chitin, then immersing the dried chitin into 40mL of 33 mass percent sodium hydroxide solution, then adding 5mL of 33 mass percent sodium borohydride solution, then placing the mixture in an oil bath pan at 90 ℃, mechanically stirring for 1 hour at the rotating speed of 100r/min, then adding 1mol/L acetic acid to adjust the pH value of the solution to 3, homogenizing in a high-pressure homogenizer, and obtaining the nano composite filler after the homogenization is finished.

The preparation method of the soybean oil fatty acid ethyl ester comprises the following steps:

adding soybean oil into a reaction kettle provided with a condensing tube for preheating at 60 ℃ for 15min, and then dissolving sodium hydroxide into ethanol to obtain a mixed alcohol solution, wherein the solid-to-liquid ratio of the sodium hydroxide to the ethanol is 1 g: and 3mL, adding the obtained mixed alcohol solution into preheated soybean oil, wherein the volume ratio of the mixed alcohol solution to the preheated soybean oil is 1:1, stirring at the rotating speed of 300r/min for 1h, then distilling to recover excessive ethanol, adding deionized water with the mass of 20% of that of the soybean oil, stirring at the rotating speed of 500r/min for 30min to obtain a mixed solution, then transferring the mixed solution into a separating funnel for separation, and washing and drying to obtain the required soybean fatty acid ethyl ester.

The preparation method of the functional auxiliary agent comprises the following steps:

dissolving 5 parts by weight of beta-cyclodextrin in 20 parts by weight of 40 ℃ deionized water, stirring for 20min at a rotation speed of 200r/min to obtain a beta-cyclodextrin solution, dissolving 40 parts by weight of tea polyphenol powder in 50 parts by weight of deionized water, stirring for 20min at a rotation speed of 50r/min to form a tea polyphenol solution, mixing the beta-cyclodextrin solution and the tea polyphenol solution, carrying out ultrasonic treatment for 2h, standing for 5h, filtering, washing filter residues with deionized water for 3 times, then putting the filter residues into a refrigerator for freezing for 24h, and finally putting the refrigerator into a freeze dryer for treating for 12h at-50 ℃ to obtain the functional auxiliary agent.

The connecting agent is a mixture of tricresyl phosphate and hydrogenated rosin glyceride in any proportion.

The defoaming agent is one of polyoxypropylene glycerol ether and polyoxypropylene ethylene oxide glycerol ether.

The slip agent is high-density polyethylene wax.

Example 2

An environment-friendly printing ink comprises the following raw materials in parts by weight: 50 parts of modified water-based acrylic resin, 8 parts of nano composite filler, 4 parts of functional assistant, 15 parts of soybean oil fatty acid ethyl ester, 4 parts of anti-skinning agent, 28 parts of connecting agent, 2 parts of defoaming agent and 8 parts of slipping agent;

firstly, adding a nano composite filler and a functional assistant into a reaction kettle, then sequentially adding a connecting agent and soybean oil fatty acid ethyl ester, and stirring at a rotating speed of 250r/min for 23min to obtain a mixture A;

secondly, adding the modified water-based acrylic resin into the mixture A, heating to 65 ℃, stirring for 23min at the rotation speed of 700r/min, then heating to 83 ℃, and continuously stirring for 34min under the condition of unchanged rotation speed to obtain a mixture B;

and thirdly, adding an anti-skinning agent, a defoaming agent and a slip agent into the mixture B, stirring at the rotating speed of 400r/min for 35min at room temperature, standing for 23min, and grinding by a three-roll machine to obtain slurry with the fineness of below 15 microns, namely the environment-friendly printing ink.

The anti-skinning agent is prepared by mixing 2, 6-di-tert-butyl-4-methylphenol, soybean oil, mineral oil and hydroquinone, wherein the mass ratio of the 2, 6-di-tert-butyl-4-methylphenol to the soybean oil to the mineral oil to the hydroquinone is 3:2:2: 1.

step S1, adding 5 parts by weight of nano titanium dioxide, 60 parts by weight of ethanol, 25 parts by weight of deionized water and 6 parts by weight of gamma-methyl acrylamide oxypropyltrimethylsilane into a water bath reflux reaction kettle, carrying out reflux reaction for 5.5 hours, then cooling to room temperature, and carrying out centrifugal separation and washing on a product to obtain modified inorganic nano titanium dioxide;

step S2, adding 8 parts by weight of methyl methacrylate, 3 parts by weight of butyl acrylate, 2 parts by weight of acrylic acid and 4 parts by weight of propyl acrylate into a reaction kettle, and stirring at the rotating speed of 250r/min for 40 to obtain a mixed monomer;

and S3, adding the modified inorganic nano titanium dioxide obtained in the step S1 and the mixed monomer obtained in the step S2 into an emulsifying kettle, adding 10 parts by weight of ammonium persulfate and 4 parts by weight of sodium bicarbonate, heating to 78 ℃, stirring at the rotating speed of 800r/min for 40min, preserving heat for 1.5h, then cooling to 40 ℃, adding ammonia water with the mass fraction of 40%, adjusting the pH value of the solution to 8.5, and filtering through 300-mesh gauze to obtain the modified waterborne acrylic resin.

s11, weighing 40g of shrimp shell fragments, placing the shrimp shell fragments in a crusher, rotating for 8min to obtain shrimp shell powder, adding the shrimp shell powder into 100mL of 1mol/L hydrochloric acid solution, mechanically stirring for 3h at the rotating speed of 250r/min, filtering, washing filter residues with deionized water until the washing liquid is neutral, and obtaining acid-leaching shrimp shell powder;

step S12, soaking the acid-leached shrimp shell powder in 50mL of 1mol/L sodium hydroxide solution, heating in an oil bath at 85 ℃, mechanically stirring at a rotating speed of 80r/min for 40min, filtering, and washing filter residues with deionized water until the washing solution is neutral to obtain basic chitin;

s13, putting the basic chitin into 50mL of sodium chlorite solution with the mass fraction of 0.3% for bleaching for 1.5h, filtering to obtain filter residue, and washing the bleached basic chitin with deionized water for 7 times to obtain purified chitin;

step S14, drying the purified chitin in an oven at 83 ℃ for 1.5h to obtain dried chitin, then immersing the dried chitin into 50mL of 33% sodium hydroxide solution by mass fraction, then adding 8mL of 33% sodium borohydride solution by mass fraction, then placing the mixture in an oil bath pan at 93 ℃, mechanically stirring the mixture for 2h at the rotating speed of 150r/min, then adding 1mol/L acetic acid to adjust the pH value of the solution to be 3.3, homogenizing the mixture in a high-pressure homogenizer, and obtaining the nano composite filler after the homogenization is finished.

adding soybean oil into a reaction kettle provided with a condensing tube for preheating at 65 ℃ for 20min, and then dissolving sodium hydroxide into ethanol to obtain a mixed alcohol solution, wherein the solid-to-liquid ratio of the sodium hydroxide to the ethanol is 1 g: 4mL, adding the obtained mixed alcohol solution into preheated soybean oil, wherein the volume ratio of the mixed alcohol solution to the preheated soybean oil is 1:1, stirring at the rotating speed of 400r/min for 2h, then distilling to recover excessive ethanol, adding deionized water with the mass of 20% of that of the soybean oil, stirring at the rotating speed of 600r/min for 40min to obtain a mixed solution, then transferring the mixed solution into a separating funnel for separation, and washing and drying to obtain the required soybean fatty acid ethyl ester.

dissolving 8 parts by weight of beta-cyclodextrin in 25 parts by weight of deionized water at 43 ℃, stirring for 30min at the rotating speed of 250r/min to obtain a beta-cyclodextrin solution, dissolving 50 parts by weight of tea polyphenol powder in 70 parts by weight of deionized water at the rotating speed of 80r/min, stirring for 30min to form a tea polyphenol solution, mixing the beta-cyclodextrin solution and the tea polyphenol solution, carrying out ultrasonic treatment for 3h, standing for 8h, filtering, washing filter residues with deionized water for 3 times, then putting the filter residues into a refrigerator for freezing for 24h, and finally putting the refrigerator into a freeze dryer for treating for 12h at-50 ℃ to obtain the functional auxiliary agent.

The connecting agent is tricresyl phosphate.

The slip agent is high-density polyethylene wax.

Example 3

An environment-friendly printing ink comprises the following raw materials in parts by weight: 60 parts of modified water-based acrylic resin, 10 parts of nano composite filler, 5 parts of functional assistant, 20 parts of soybean oil fatty acid ethyl ester, 5 parts of anti-skinning agent, 30 parts of connecting agent, 3 parts of defoaming agent and 10 parts of slipping agent;

firstly, adding a nano composite filler and a functional assistant into a reaction kettle, then sequentially adding a connecting agent and soybean oil fatty acid ethyl ester, and stirring at a rotating speed of 300r/min for 25min to obtain a mixture A;

secondly, adding the modified waterborne acrylic resin into the mixture A, heating to 70 ℃, stirring for 25min at the rotating speed of 800r/min, then heating to 85 ℃, and continuously stirring for 35min under the condition of unchanged rotating speed to obtain a mixture B;

and thirdly, adding an anti-skinning agent, a defoaming agent and a slip agent into the mixture B, stirring at the rotating speed of 500r/min for 40min at room temperature, standing for 25min, and grinding by a three-roll machine to obtain slurry with the fineness of below 15 microns, namely the environment-friendly printing ink.

The anti-skinning agent is prepared by mixing 2, 6-di-tert-butyl-4-methylphenol, soybean oil, mineral oil and hydroquinone, wherein the mass ratio of the 2, 6-di-tert-butyl-4-methylphenol to the soybean oil to the mineral oil to the hydroquinone is 4:3:2: 1.

step S1, adding 8 parts by weight of nano titanium dioxide, 65 parts by weight of ethanol, 30 parts by weight of deionized water and 8 parts by weight of gamma-methyl acrylamide oxypropyltrimethylsilane into a water bath reflux reaction kettle, carrying out reflux reaction for 6 hours, then cooling to room temperature, and carrying out centrifugal separation and washing on a product to obtain modified inorganic nano titanium dioxide;

step S2, adding 10 parts by weight of methyl methacrylate, 4 parts by weight of butyl acrylate, 3 parts by weight of acrylic acid and 5 parts by weight of propyl acrylate into a reaction kettle, and stirring at the rotating speed of 300r/min for 50min to obtain a mixed monomer;

and S3, adding the modified inorganic nano titanium dioxide obtained in the step S1 and the mixed monomer obtained in the step S2 into an emulsifying kettle, adding 12 parts by weight of ammonium persulfate and 5 parts by weight of sodium bicarbonate, heating to 80 ℃, stirring at the rotating speed of 1000r/min for 60min, preserving heat for 1.5h, then cooling to 40 ℃, adding ammonia water with the mass fraction of 40%, adjusting the pH value of the solution to 9, and filtering through 300-mesh gauze to obtain the modified waterborne acrylic resin.

s11, weighing 40g of shrimp shell fragments, placing the shrimp shell fragments in a crusher, rotating for 10min to obtain shrimp shell powder, adding the shrimp shell powder into 100mL of 1mol/L hydrochloric acid solution, mechanically stirring for 4h at the rotating speed of 300r/min, filtering, washing filter residues with deionized water until the washing liquid is neutral, and obtaining acid-leaching shrimp shell powder;

step S12, soaking the acid-leached shrimp shell powder in 50mL of 1mol/L sodium hydroxide solution, heating in an oil bath at 90 ℃, mechanically stirring at the rotating speed of 100r/min for 60min, filtering, and washing filter residues with deionized water until the washing solution is neutral to obtain basic chitin;

s13, putting the basic chitin into 50mL of sodium chlorite solution with the mass fraction of 0.3% for bleaching for 2 hours, filtering to obtain filter residue, and washing the bleached basic chitin with deionized water for 8 times to obtain purified chitin;

step S14, drying the purified chitin in an oven at 85 ℃ for 2 hours to obtain dried chitin, then immersing the dried chitin in 60mL of 33 mass percent sodium hydroxide solution, then adding 10mL of 33 mass percent sodium borohydride solution, then placing the mixture in an oil bath kettle at 95 ℃, mechanically stirring the mixture for 3 hours at the rotating speed of 200r/min, then adding 1mol/L acetic acid to adjust the pH value of the solution to 3.5, homogenizing the mixture in a high-pressure homogenizer, and obtaining the nano composite filler after the homogenization is finished.

adding soybean oil into a reaction kettle provided with a condensing tube for preheating at 70 ℃ for 30min, and then dissolving sodium hydroxide into ethanol to obtain a mixed alcohol solution, wherein the solid-to-liquid ratio of the sodium hydroxide to the ethanol is 1 g: and 5mL, adding the obtained mixed alcohol solution into preheated soybean oil, wherein the volume ratio of the mixed alcohol solution to the preheated soybean oil is 1:1, stirring at the rotating speed of 500r/min for 3h, then distilling to recover excessive ethanol, adding deionized water with the mass of 20% of that of the soybean oil, stirring at the rotating speed of 800r/min for 60min to obtain a mixed solution, then transferring the mixed solution into a separating funnel for separation, and washing and drying to obtain the required soybean fatty acid ethyl ester.

dissolving 10 parts by weight of beta-cyclodextrin in 30 parts by weight of deionized water at 50 ℃, stirring for 40min at a rotating speed of 300r/min to obtain a beta-cyclodextrin solution, dissolving 60 parts by weight of tea polyphenol powder in 80 parts by weight of deionized water at a rotating speed of 100r/min, stirring for 40min to form a tea polyphenol solution, mixing the beta-cyclodextrin solution and the tea polyphenol solution, carrying out ultrasonic treatment for 4h, standing for 10h, filtering, washing filter residues with deionized water for 3 times, then putting the filter residues into a refrigerator for freezing for 24h, and finally putting the refrigerator into a freeze dryer for treating for 12h at-50 ℃ to obtain the functional auxiliary agent.

The slip agent is high-density polyethylene wax.

Comparative example 1

The modified waterborne acrylic resin in the raw materials of the embodiment 1 is replaced by the waterborne acrylic resin, and the rest raw materials and the preparation process are unchanged.

Comparative example 2

The nano composite filler in the raw materials of the embodiment 2 is removed, and the rest raw materials and the preparation process are not changed.

Comparative example 3

The functional assistant in the raw materials of the example 3 is removed, and the rest raw materials and the preparation process are not changed.

Comparative example 4

This comparative example is one of the printing inks commonly found in the market.

And (3) performance testing: the printing inks prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to a performance test, an initial drying test, according to the following criteria: reference GB/T13217.5-2008; and (3) testing the adhesive force: reference is made to GB/T13217.7-2009; antibacterial property: reference GB/T21866-2008; printing adaptability test: reference QBT 1058-1998; surface tension test: testing the surface tension of the ink at room temperature regulation by using a KRUSS surface tension meter; the water resistance test method comprises the following steps: the dry ink scratch sample is soaked in water for 3-5h, the scratch sample is taken out and graded according to the change condition of the scratch sample, the standard is used as the water resistance performance of the ink, wherein the scratch sample changes color seriously to 1 grade, the scratch sample changes color obviously to 2 grade, the scratch sample changes color slightly to 3 grade, the scratch sample does not change color to 4 grade, and the test result is shown in the following table:

as can be seen from the above table, the ink coatings of examples 1-3 have better effects than comparative examples 1-4 in the tests of initial drying, adhesion, printing adaptability, surface tension, water resistance and escherichia coli bacteriostasis rate, and the printing inks prepared by the invention have the characteristics of antibiosis, water resistance, strong printing adaptability and the like.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims

1. The environment-friendly printing ink is characterized by comprising the following raw materials in parts by weight: 40-60 parts of modified water-based acrylic resin, 5-10 parts of nano composite filler, 3-5 parts of functional assistant, 10-20 parts of soybean oil fatty acid ethyl ester, 3-5 parts of anti-skinning agent, 25-30 parts of connecting agent, 1-3 parts of defoaming agent and 5-10 parts of slipping agent;

the environment-friendly printing ink is prepared by the following steps:

firstly, adding a nano composite filler and a functional assistant into a reaction kettle, then sequentially adding a connecting agent and soybean oil fatty acid ethyl ester, and stirring for 20-25min under the condition of a rotation speed of 200-;

2. The environment-friendly printing ink as claimed in claim 1, wherein the anti-skinning agent is formed by mixing 2, 6-di-tert-butyl-4-methylphenol, soybean oil, mineral oil and hydroquinone, and the mass ratio of the 2, 6-di-tert-butyl-4-methylphenol, the soybean oil, the mineral oil and the hydroquinone is 2-4:1-3:2: 1.

3. The environment-friendly printing ink as claimed in claim 1, wherein the preparation method of the modified water-based acrylic resin specifically comprises the following steps:

4. The environment-friendly printing ink as claimed in claim 1, wherein the preparation method of the nano composite filler comprises the following steps:

step S14, drying the purified chitin in an oven at 80-85 ℃ for 1-2 hours to obtain dried chitin, then soaking the dried chitin into 40-60mL of 33% sodium hydroxide solution by mass fraction, then adding 5-10mL of 33% sodium borohydride solution by mass fraction, placing the mixture in an oil bath kettle at 90-95 ℃, mechanically stirring for 1-3 hours at the rotation speed of 100-.

5. The environment-friendly printing ink as claimed in claim 1, wherein the preparation method of the soybean oil fatty acid ethyl ester comprises the following steps:

6. The environment-friendly printing ink as claimed in claim 1, wherein the preparation method of the functional additive comprises the following steps:

7. The environment-friendly printing ink as claimed in claim 1, wherein the linking agent is one or more of tricresyl phosphate, hydrogenated rosin glycerol ester, ethyl acetate, epoxy resin, ethanol and dibutyltin dilaurate mixed in any proportion; the defoaming agent is one of polyoxypropylene glycerol ether and polyoxypropylene ethylene oxide glycerol ether; the slip agent is high-density polyethylene wax.

8. The method for preparing the environment-friendly printing ink as claimed in claim 1, wherein the method for preparing the environment-friendly printing ink specifically comprises the following steps: