Anti-oxidation and anti-corrosion water-based printing ink and preparation method thereof

Abstract

The invention relates to the technical field of ink, in particular to antioxidant and anticorrosive water-based printing ink and a preparation method thereof. The antioxidant and anticorrosive water-based printing ink is prepared from the following raw materials in parts by weight: 50-80 parts of water-based acrylic resin, 40-60 parts of deionized water, 30-50 parts of pigment, 8-10 parts of an antioxidant material, 5-7 parts of an anticorrosive material, 4-6 parts of a dispersing agent and 3-5 parts of a defoaming agent. According to the water-based printing ink, when the first additive and the phosphite ester in the ink exist at the same time, the phosphite ester can decompose hydroperoxide generated in the oxidation process of the water-based printing ink and hydroperoxide generated in the free radical capturing process of the hindered phenol antioxidant at the same time, and the hydroperoxide is reduced into a relatively stable alcohol compound; the hydroperoxide is prevented from being decomposed to generate new free radicals, so that the oxidation of the ink is further inhibited, and the oxidation resistance of the water-based printing ink is effectively improved.

Description

Technical Field

[0001] The invention relates to the technical field of inks, in particular to an anti-oxidation and anti-corrosion water-based printing ink and a preparation method thereof. Background Art

[0002] Water-based printing ink is an ink with water as the main solvent. It is mainly composed of water-based resin, pigment, additives and water. It is mainly used to transfer images and texts from the printing plate to substrates, such as paper, plastic film, etc., to achieve information display and decoration purposes.

[0003] In the prior art, water-based printing inks are easily and inevitably exposed to light during use and storage. High-energy light such as ultraviolet rays in the light can excite molecules in the ink to produce free radicals. For example, after absorbing light energy, the pigment particles in the ink will transfer energy to the surrounding resin and solvent molecules, causing them to undergo photochemical reactions and produce free radicals. These free radicals will accelerate the oxidation process of the ink, and the existing antioxidant system may not be able to remove these light-induced free radicals in time, resulting in a decrease in the antioxidant performance of the ink. Based on this, the present invention provides an antioxidant and anti-corrosion water-based printing ink and a preparation method thereof. Summary of the invention

[0004] The purpose of the present invention is to provide an antioxidant and anti-corrosion water-based printing ink and a preparation method thereof. The antioxidant and anti-corrosion water-based printing ink prepared by the present invention not only has good antioxidant properties, but also has excellent anti-corrosion properties, thereby effectively improving the use performance of the water-based printing ink.

[0005] To achieve the above object, the present invention provides the following technical solutions: An anti-oxidation and anti-corrosion water-based printing ink comprises the following raw materials in parts by weight: 50-80 parts of water-based acrylic resin, 40-60 parts of deionized water, 30-50 parts of pigment, 8-10 parts of antioxidant, 5-7 parts of antiseptic, 4-6 parts of dispersant and 3-5 parts of defoamer.

[0006] Furthermore, the pigment is selected from at least one of titanium dioxide pigment, carbon black pigment and phthalocyanine blue pigment.

[0007] Furthermore, the dispersant is selected from at least one of polyacrylic acid sodium salt, polycarboxylic acid sodium salt and sodium chloride.

[0008] Furthermore, the defoaming agent is selected from at least one of dimethyl polysiloxane, siloxane polymer, and fluorinated silicone.

[0009] Furthermore, the antioxidant material is prepared by the following method: adding the first additive and phosphite in a mass ratio of (2-3):1 into a mixing tank, stirring at 300-500r / min for 30-60min to prepare the antioxidant material.

[0010] Furthermore, the first additive is prepared by the following method: recovering soybean oil residue fertilizer from a vegetable oil factory as a raw material, adding it into a dryer, drying it at 50-80°C for 2-4 hours, then transferring it to a crusher to crush the raw material, then transferring it to a grinder, grinding it to obtain a powder with a particle size of 100-200 μm, mixing the powder with ethanol to obtain an ethanol mixed solution containing phenolic compounds, wherein the mass ratio of the ethanol to the powder is (4-6):1, then transferring it to a centrifuge for centrifugal filtration, and then transferring it to a distillation kettle, adjusting the pressure to 10-15 MPa, and performing reduced pressure distillation at 50-70°C to obtain the first additive.

[0011] Furthermore, the preservative is prepared by the following method: weigh chitosan additive and brown algae extract in a mass ratio of 1:1, crush them and add them into a grinder to grind them into 100-200 μm powder, then transfer them to a stirring tank, set the speed to 300-500 r / min, stir for 30-60 minutes, and obtain the preservative additive.

[0012] Furthermore, the chitosan additive is prepared by the following method: collecting crab shell waste as raw material in a fresh food factory, washing and removing impurities, and then transferring to an oven to dry at 30-50°C, then crushing and grinding to obtain shell powder, and then mixing with a hydrochloric acid solution with a concentration of 1-3 mol / L, the mass ratio of the hydrochloric acid solution to the shell powder is (10-20): 1, stirring and reacting at room temperature to obtain a soluble salt solution, and then filtering, removing residues, washing, and obtaining residues, adding a sodium hydroxide solution with a concentration of 2-5 mol / L, the mass ratio of sodium hydroxide to the residue is (8-10): 1, transferring to a mixing tank, heating to 90-100°C, and stirring for 3-6 hours to allow the protein components in the shell to undergo a hydrolysis reaction under alkaline conditions and dissolve, and then centrifuging to obtain the chitosan additive, and then rinsing with a large amount of clean water until neutral to remove residual alkali solution and hydrolyzed protein products.

[0013] Furthermore, the brown algae extract is prepared by the following method: selecting kelp as a raw material, washing, removing impurities, draining, adding a grinder to grind to obtain kelp particles, then adding the kelp particles to a sodium hydroxide solution with a concentration of 1-3 mol / L and mixing, the mass ratio of the sodium hydroxide solution to the crushed material is (4-6): 1, and then transferring to a stirring kettle, setting the temperature to 60-80°C, the speed to 300-500r / min, and keeping warm and stirring for 3-5h. During the process, the alkaline environment will destroy the cell structure of the kelp, so that the active ingredients such as multi-enzymes in the brown algae are released into the solution to obtain an extract, and then filtering through a Buchner funnel, and then adding hydrochloric acid solution under stirring conditions to adjust the pH value of the extract to 7 to complete neutralization. During the process, components such as brown algae polyphenols will precipitate due to the change in pH value, and then standing for precipitation for 4-6h, removing the supernatant to obtain a precipitate, and washing the precipitate with deionized water to remove impurities such as salts remaining on the surface of the precipitate to obtain a brown algae extract.

[0014] On the other hand, the method for preparing an antioxidant and anti-corrosion water-based printing ink comprises the following steps: weighing water-based acrylic resin, deionized water, pigment, antioxidant, preservative, dispersant and defoaming agent as needed and putting them into a dispersion tank, setting the speed to 700-800r / min, the time to 5-10min, completing the mixing of all raw materials, and obtaining an antioxidant and anti-corrosion water-based printing ink.

[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. In the present invention, in the prepared antioxidant, the hindered phenol antioxidant structure of the first additive is mainly used to capture free radicals and improve the antioxidant effect of water-based ink. A small amount of hydroperoxide compounds will be generated in the process, and the phosphite is mainly used to decompose the hydroperoxides. When the first additive and the phosphite exist in the ink at the same time, the phosphite can simultaneously decompose the hydroperoxides generated in the oxidation process of the water-based printing ink and the hydroperoxides generated in the process of the hindered phenol antioxidant capturing free radicals, reduce the hydroperoxides to relatively stable alcohol compounds, prevent the decomposition of the hydroperoxides to generate new free radicals, thereby further inhibiting the oxidation of the ink and effectively improving the antioxidant performance of the water-based printing ink.

[0016] 2. In the present invention, chitosan additive extracted from crab shells is added to the ink system. Chitosan can be adsorbed on the surface of microbial cells and further react with components in the cell wall. For bacteria, it can combine with peptidoglycan in the cell wall, destroy the structural integrity of peptidoglycan, increase the permeability of the cell wall, and leak substances in the cell, eventually killing the bacteria. For mold, chitosan may interfere with the synthesis or structural stability of chitin in its cell wall, inhibit the growth and reproduction of mold, and thus improve the antiseptic properties of water-based printing ink.

[0017] 3. In the present invention, the brown algae extract prepared from kelp raw material contains brown algae polyphenols and other ingredients, which have antibacterial activity. It mainly inhibits microorganisms by interacting with components such as proteins and lipids on the cell membrane of microorganisms, destroying the integrity of the cell membrane, and causing leakage of intracellular substances. For molds, brown algae polyphenols may also interfere with the synthesis of their cell walls or destroy the enzyme system in their cells.

[0018] 4. In the present invention, when the chitosan additive in the preservative and the brown algae extract are used together in the ink, the antibacterial mechanisms of the two cooperate with each other and complement each other. Chitosan first quickly locates and attaches to the surface of microbial cells through electrostatic adsorption, and initially destroys the external structure of the microorganism, causing loopholes in the microbial defense system, so that the brown algae extract ingredients such as brown algae polyphenols can more smoothly pass through the damaged cell membrane or cell wall, penetrate deep into the cell, and accurately strike the key targets in the cell. This synergistic mode greatly enhances the inhibition and killing effect on microorganisms, thereby significantly improving the anti-corrosion performance of the ink and extending the service life of the ink. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The invention proposes a flow chart of an antioxidant and anti-corrosion water-based printing ink and a preparation method thereof. DETAILED DESCRIPTION

[0020] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0021] In order to enable those skilled in the art to better understand the solution of the present application, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the accompanying drawings.

[0022] An anti-oxidation and anti-corrosion water-based printing ink comprises the following raw materials in parts by weight: 50-80 parts of water-based acrylic resin, 40-60 parts of deionized water, 30-50 parts of pigment, 8-10 parts of antioxidant, 5-7 parts of antiseptic, 4-6 parts of dispersant and 3-5 parts of defoamer.

[0023] In some embodiments, the pigment is at least one of titanium dioxide pigment, carbon black pigment and phthalocyanine blue pigment.

[0024] In some embodiments, the dispersant is selected from at least one of polyacrylic acid sodium salt, polycarboxylic acid sodium salt and sodium chloride.

[0025] In some embodiments, the defoaming agent is at least one of dimethyl polysiloxane, siloxane polymer, and fluorinated silicone.

[0026] In some embodiments, the antioxidant material is prepared by the following method: adding the first additive material and phosphite in a mass ratio of (2-3):1 into a mixing tank, stirring at 300-500 r / min for 30-60 min to prepare the antioxidant material.

[0027] In this embodiment, the hindered phenol antioxidant structure of the first additive is mainly used to capture free radicals and improve the antioxidant effect of water-based ink. A small amount of hydroperoxide compounds will be generated in the process, and the phosphite is mainly used to decompose hydroperoxides. When both exist in the ink at the same time, the phosphite can simultaneously decompose the hydroperoxides generated in the oxidation process of the water-based printing ink and the hydroperoxides generated in the process of the hindered phenol antioxidant capturing free radicals, and reduce the hydroperoxides to relatively stable alcohol compounds, preventing the decomposition of hydroperoxides to produce new free radicals, thereby further inhibiting the oxidation of the ink and effectively improving the antioxidant properties of the water-based printing ink.

[0028] In some embodiments, the first additive is prepared by the following method: recovering soybean oil residue fertilizer from a vegetable oil factory as a raw material, adding it to a dryer, drying it at 50-80°C for 2-4 hours, then transferring it to a crusher to crush the raw material, and then transferring it to a grinder to grind it to obtain a powder with a particle size of 100-200 μm, mixing the powder with ethanol to obtain an ethanol mixture containing phenolic compounds, the mass ratio of ethanol to powder is (4-6): 1, and then transferring it to a centrifuge for centrifugal filtration, and then transferring it to a distillation kettle, adjusting the pressure to 10-15 MPa, and performing reduced pressure distillation at 50-70°C to obtain the first additive.

[0029] In this embodiment, the first additive prepared from soybean oil residue is mainly tocopherol, which is a common hindered phenol antioxidant structure. When an alkyl free radical is generated in the ink system, the hindered phenol reacts with it to generate a phenoloxy free radical. The substituent on the benzene ring makes it relatively stable and cannot continue to trigger a chain oxidation reaction like an alkyl free radical, thereby interrupting the free radical chain reaction of ink oxidation, effectively delaying the oxidation process of the ink, and improving the antioxidant performance.

[0030] In some embodiments, the preservative is prepared by the following method: weigh chitosan additive and brown algae extract in a mass ratio of 1:1, crush them and add them into a grinder to grind them into 100-200 μm powder, then transfer them to a stirring tank, set the speed to 300-500 r / min, stir for 30-60 minutes, and obtain the preservative additive.

[0031] In this embodiment, when chitosan additives and brown algae extracts are used together in ink, the antibacterial mechanisms of the two cooperate with each other and complement each other. Chitosan first quickly locates and attaches to the surface of microbial cells through electrostatic adsorption, and initially destroys the external structure of the microorganisms, causing loopholes in the microbial defense system, thereby allowing brown algae extract ingredients such as brown algae polyphenols to more smoothly pass through the damaged cell membrane or cell wall, penetrate deep into the cells, and accurately strike key targets within the cells. This synergistic mode greatly enhances the inhibition and killing effect on microorganisms, thereby significantly improving the anti-corrosion properties of the ink and extending the service life of the ink.

[0032] In some embodiments, the chitosan additive is prepared by the following method: collecting crab shell waste as raw material in a fresh food factory, washing and removing impurities, and then transferring to an oven to dry at 30-50°C, and then crushing and grinding to obtain shell powder, and then mixing with a 1-3 mol / L hydrochloric acid solution, the mass ratio of hydrochloric acid solution to shell powder is (10-20): 1, stirring and reacting at room temperature to obtain a soluble salt solution, and then filtering, removing residues, and washing to obtain residues, adding a 2-5 mol / L sodium hydroxide solution, the mass ratio of sodium hydroxide to residue is (8-10): 1, transferring to a mixing tank, heating to 90-100°C, and stirring for 3-6 hours to allow the protein components in the shell to undergo a hydrolysis reaction under alkaline conditions and dissolve, and then centrifuging to obtain chitosan additives, and then rinsing with a large amount of clean water until neutral to remove residual alkali solution and hydrolyzed protein products.

[0033] In this embodiment, chitosan additives extracted from crab shells are added to the ink system. Chitosan can be adsorbed on the surface of microbial cells and further react with components in the cell wall. For bacteria, it can combine with peptidoglycan in the cell wall, destroy the structural integrity of peptidoglycan, increase the permeability of the cell wall, leak substances in the cell, and ultimately kill the bacteria. For mold, chitosan may interfere with the synthesis or structural stability of chitin in its cell wall, inhibit the growth and reproduction of mold, and thus improve the anti-corrosion properties of water-based printing inks.

[0034] In some embodiments, the brown algae extract is prepared by the following method: kelp is selected as a raw material, washed, impurities removed, and drained, and then added to a grinder to obtain kelp particles, and then the kelp particles are added to a sodium hydroxide solution with a concentration of 1-3 mol / L and mixed, and the mass ratio of the sodium hydroxide solution to the crushed material is (4-6): 1, and then transferred to a stirring kettle, set the temperature to 60-80°C, the speed to 300-500r / min, and keep stirring for 3-5h. During the process, the alkaline environment will destroy the cell structure of the kelp, so that the active ingredients such as multi-enzymes in the brown algae are released into the solution to obtain an extract, and then filtered through a Buchner funnel, and then under stirring conditions, hydrochloric acid solution is added dropwise to adjust the pH value of the extract to 7 to complete neutralization. During the process, components such as brown algae polyphenols will precipitate due to the change in pH value, and then stand for precipitation for 4-6h. After removing the supernatant, a precipitate is obtained, and the precipitate is washed with deionized water to remove impurities such as salts remaining on the surface of the precipitate to obtain a brown algae extract.

[0035] In this embodiment, the brown algae extract prepared from kelp raw materials contains ingredients such as brown algae polyphenols, which have antibacterial activity. They mainly inhibit microorganisms by interacting with components such as proteins and lipids on the cell membrane of microorganisms, destroying the integrity of the cell membrane, and causing leakage of intracellular substances. For molds, brown algae polyphenols may also interfere with the synthesis of their cell walls or destroy the enzyme system in their cells.

[0036] In some embodiments, a method for preparing an antioxidant and anti-corrosion water-based printing ink comprises the following steps: weighing water-based acrylic resin, deionized water, pigment, antioxidant, preservative, dispersant and defoaming agent as needed and putting them into a dispersion tank, setting the speed to 700-800r / min, the time to 5-10min, completing the mixing of all raw materials, and obtaining an antioxidant and anti-corrosion water-based printing ink.

[0037] Based on the above embodiments, the inventors also conducted the following experiments: It should be noted that the raw materials used in the following experiments are all commercially available raw materials.

[0038] Experiment 1: Preparation of the first additive: Soybean oil residue fertilizer is recovered from a vegetable oil plant as a raw material, added to a dryer, dried at 50°C for 2 hours, then transferred to a pulverizer to pulverize the raw material, then transferred to a grinder, ground to obtain a powder with a particle size of 100 μm, mixed and stirred the powder with ethanol to obtain an ethanol mixed solution containing phenolic compounds, the mass ratio of ethanol to powder being 4:1, then transferred to a centrifuge for centrifugal filtration, then transferred to a distillation kettle, the pressure was adjusted to 10 MPa, and vacuum distillation was performed at 50°C; Preparation of antioxidant material: Add the first additive and phosphite in a mass ratio of 2:1 into a mixing tank and stir at 300 r / min for 30 min; Preparation of chitosan additive: crab shell waste is collected from the fresh food factory as raw material, washed and impurities are removed, and then transferred to an oven to dry at 30°C, and then crushed and ground to obtain shell powder, which is then mixed with a 1 mol / L hydrochloric acid solution, and the mass ratio of the hydrochloric acid solution to the shell powder is 10:1. Stirring reaction at room temperature to obtain a soluble salt solution, and then filtering, removing residues, washing, and obtaining residues, adding a 2 mol / L sodium hydroxide solution, and the mass ratio of sodium hydroxide to the residue is 8:1, and transferring to a mixing tank, heating to 90°C, and stirring for 3 hours to allow the protein components in the shell to undergo a hydrolysis reaction under alkaline conditions and dissolve, and then centrifugation filtration, and then rinse with a large amount of clean water until neutral, to remove residual alkali solution and hydrolyzed protein products; Preparation of brown algae extract: kelp is selected as raw material, washed, impurities removed, drained, added to a grinder and crushed to obtain kelp particles, then the kelp particles are added to a sodium hydroxide solution with a concentration of 1 mol / L and mixed, the mass ratio of sodium hydroxide solution to crushed material is 4:1, and then transferred to a stirring kettle, the temperature is set to 60°C, the speed is 300r / min, and the heat preservation and stirring treatment is carried out for 3 hours. During the process, the alkaline environment will destroy the cell structure of the kelp, so that the multi-enzyme and other active ingredients in the brown algae are released into the solution to obtain an extract, which is then filtered through a Buchner funnel, and then hydrochloric acid solution is added dropwise under stirring conditions to adjust the pH value of the extract to 7 to complete neutralization. During the process, components such as brown algae polyphenols will precipitate due to changes in pH value, and then the solution is allowed to stand for 4 hours. After removing the supernatant, a precipitate is obtained, and the precipitate is washed with deionized water to remove impurities such as salts remaining on the surface of the precipitate; Preparation of preservatives: weigh chitosan additive and brown algae extract in a mass ratio of 1:1, crush them and add them into a grinder to grind them into 100 μm powder, then transfer them to a stirring tank, set the speed to 300 r / min, and stir for 30 minutes; Raw material preparation: 50 parts of water-based acrylic resin, 40 parts of deionized water, 30 parts of pigment, 8 parts of antioxidant, 5 parts of preservative, 4 parts of dispersant and 3 parts of defoamer, among which the pigment is titanium dioxide pigment, the dispersant is sodium polyacrylate, and the defoamer is dimethyl polysiloxane; Preparation of antioxidant and anti-corrosion water-based printing ink: weigh water-based acrylic resin, deionized water, pigment, antioxidant, anti-corrosion material, dispersant and defoamer as needed and put them into the dispersion tank, set the speed to 700r / min, the time to 5-10min, complete the mixing of all raw materials, and obtain antioxidant and anti-corrosion water-based printing ink.

[0039] Experiment 2: Preparation of the first additive: Soybean oil residue fertilizer is recovered from a vegetable oil plant as a raw material, added to a dryer, dried at 70°C for 3 hours, then transferred to a pulverizer to pulverize the raw material, then transferred to a grinder, ground to obtain a powder with a particle size of 150 μm, mixed and stirred the powder with ethanol to obtain an ethanol mixed solution containing phenolic compounds, the mass ratio of ethanol to powder being 5:1, then transferred to a centrifuge for centrifugal filtration, then transferred to a distillation kettle, the pressure was adjusted to 13 MPa, and vacuum distilled at 60°C; Preparation of antioxidant material: Add the first additive and phosphite in a mass ratio of 2.5:1 into a mixing tank and stir at 400 r / min for 45 min; Preparation of chitosan additive: crab shell waste is collected from fresh food factories as raw materials, washed and impurities are removed, and then transferred to an oven to dry at 40°C, then crushed and ground to obtain shell powder, and then mixed with a 2mol / L hydrochloric acid solution, the mass ratio of hydrochloric acid solution to shell powder is 15:1, stirred and reacted at room temperature to obtain a soluble salt solution, and then filtered, removed and washed to obtain a residue, added with a 3mol / L sodium hydroxide solution, the mass ratio of sodium hydroxide to residue is 9:1, transferred to a mixing tank, heated to 95°C, and stirred for 5 hours to allow the protein components in the shell to undergo a hydrolysis reaction under alkaline conditions and dissolve, and then centrifuged and filtered, and then rinsed with a large amount of clean water until neutral to remove residual alkali solution and hydrolyzed protein products; Preparation of brown algae extract: kelp is selected as raw material, washed, impurities removed, drained, added to a grinder and crushed to obtain kelp particles, then the kelp particles are added to a sodium hydroxide solution with a concentration of 2 mol / L and mixed, the mass ratio of sodium hydroxide solution to crushed material is 5:1, and then transferred to a stirring kettle, the temperature is set to 70°C, the speed is 400r / min, and the stirring treatment is carried out for 4 hours. During the process, the alkaline environment will destroy the cell structure of the kelp, so that the active ingredients such as multi-enzymes in the brown algae are released into the solution to obtain an extract, which is then filtered through a Buchner funnel, and then hydrochloric acid solution is added dropwise under stirring to adjust the pH value of the extract to 7 to complete neutralization. During the process, components such as brown algae polyphenols will precipitate due to changes in pH value, and then the solution is allowed to stand for 5 hours. After removing the supernatant, a precipitate is obtained, and the precipitate is washed with deionized water to remove impurities such as salts remaining on the surface of the precipitate; Preparation of preservatives: weigh chitosan additive and brown algae extract in a mass ratio of 1:1, crush them and add them into a grinder to grind them into 150 μm powder, then transfer them to a stirring tank, set the speed to 400 r / min, and stir for 45 minutes; Raw materials: 65 parts of water-based acrylic resin, 50 parts of deionized water, 40 parts of pigment, 9 parts of antioxidant, 6 parts of preservative, 5 parts of dispersant and 4 parts of defoamer, wherein the pigment is carbon black pigment, the dispersant is sodium polycarboxylate, and the defoamer is siloxane polymer; Preparation of antioxidant and anti-corrosion water-based printing ink: weigh water-based acrylic resin, deionized water, pigment, antioxidant, preservative, dispersant and defoamer as needed and put them into the dispersion tank, set the speed to 750r / min, the time to 8min, complete the mixing of all raw materials, and obtain antioxidant and anti-corrosion water-based printing ink.

[0040] Experiment 3: Preparation of the first additive: Soybean oil residue fertilizer is recovered from a vegetable oil plant as a raw material, added to a dryer, dried at 80°C for 4 hours, then transferred to a pulverizer to pulverize the raw material, then transferred to a grinder, ground to obtain a powder with a particle size of 200 μm, mixed and stirred the powder with ethanol to obtain an ethanol mixed solution containing phenolic compounds, the mass ratio of ethanol to powder being 6:1, then transferred to a centrifuge for centrifugal filtration, then transferred to a distillation kettle, the pressure was adjusted to 15 MPa, and vacuum distillation was performed at 70°C; Preparation of antioxidant material: Add the first additive and phosphite in a mass ratio of 3:1 into a mixing tank and stir at 500 r / min for 60 min; Preparation of chitosan additive: crab shell waste is collected from fresh food factories as raw materials, washed and impurities are removed, and then transferred to an oven to dry at 50°C, then crushed and ground to obtain shell powder, and then mixed with a 3 mol / L hydrochloric acid solution, the mass ratio of hydrochloric acid solution to shell powder is 20:1, stirred and reacted at room temperature to obtain a soluble salt solution, and then filtered, slag removed, and washed to obtain a residue, and a 5 mol / L sodium hydroxide solution is added, the mass ratio of sodium hydroxide to residue is 10:1, and transferred to a mixing tank, heated to 100°C, and stirred for 6 hours to allow the protein components in the shell to undergo a hydrolysis reaction under alkaline conditions and dissolve, and then centrifuged and filtered, and then rinsed with a large amount of clean water until neutral, to remove residual alkali solution and hydrolyzed protein products; Preparation of brown algae extract: kelp is selected as raw material, washed, impurities removed, drained, added to a grinder and crushed to obtain kelp particles, then the kelp particles are added to a sodium hydroxide solution with a concentration of 3 mol / L and mixed, the mass ratio of sodium hydroxide solution to crushed material is 6:1, and then transferred to a stirring kettle, the temperature is set to 80°C, the speed is 500r / min, and the heat preservation and stirring treatment is carried out for 5 hours. During the process, the alkaline environment will destroy the cell structure of the kelp, so that the multi-enzyme and other active ingredients in the brown algae are released into the solution to obtain an extract, which is then filtered through a Buchner funnel, and then hydrochloric acid solution is added dropwise under stirring conditions to adjust the pH value of the extract to 7 to complete neutralization. During the process, components such as brown algae polyphenols will precipitate due to changes in pH value, and then the solution is allowed to stand for 6 hours. After removing the supernatant, a precipitate is obtained, and the precipitate is washed with deionized water to remove impurities such as salts remaining on the surface of the precipitate; Preparation of preservatives: weigh chitosan additive and brown algae extract in a mass ratio of 1:1, crush them and add them into a grinder to grind them into 200 μm powder, then transfer them to a stirring tank, set the speed to 500 r / min, and stir for 60 min; Raw materials: 80 parts of water-based acrylic resin, 60 parts of deionized water, 50 parts of pigment, 10 parts of antioxidant, 7 parts of preservative, 6 parts of dispersant and 5 parts of defoamer, among which phthalocyanine blue pigment is used as pigment, sodium chloride is used as dispersant, and fluorinated silicone is used as defoamer; Preparation of antioxidant and anti-corrosion water-based printing ink: weigh water-based acrylic resin, deionized water, pigment, antioxidant, preservative, dispersant and defoamer as needed and put them into the dispersion tank, set the speed to 800r / min, the time to 10min, complete the mixing of all raw materials, and obtain antioxidant and anti-corrosion water-based printing ink.

[0041] Comparative Example 1: The difference between this comparative example and Experiment 1 is that the antioxidant material in this comparative example does not contain the first additive.

[0042] Comparative Example 2: The difference between this comparative example and Experiment 1 is that this comparative example does not contain antioxidant.

[0043] Comparative Example 3: The difference between this comparative example and Experiment 1 is that the preservative material in this comparative example does not contain chitosan additive.

[0044] Comparative Example 4: The difference between this comparative example and Experiment 1 is that this comparative example does not contain preservatives.

[0045] Performance test: The performance test was carried out on the antioxidant and anti-corrosion water-based printing inks prepared in Experiment 1, Experiment 2, Experiment 3, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4.

[0046] In the antioxidant performance test, accelerated aging and chemical reagent methods were used for testing.

[0047] Accelerated aging test method: under extreme conditions of high temperature 80℃, high humidity 80%RH, strong light 5000Lx, simulate a long-term natural oxidation process, the test time is 72 hours, after the test, score according to the oxidation condition of the ink (such as color change, structural stability, etc.), 10 points means the best, 0 points means the worst; Chemical reagent test method: Use 30% hydrogen peroxide solution as an oxidizing chemical reagent. After contacting the ink sample for 30 minutes, observe and record the oxidation reaction speed and degree of the ink. The test results are divided into 0-10 points, with 10 points being the best and 0 being the worst.

[0048] In the anti-corrosion performance test, salt spray test method and acid-base test method are used respectively.

[0049] Salt spray test method: In a salt spray test chamber, use 5% sodium chloride solution for spraying, the spray pressure is 0.1MPa, the test time is continuous spraying for 96 hours, simulate the corrosion situation in the marine environment, observe and record the corrosion situation of the ink, and the test results are divided into 0-10 points, where 10 points is the best and 0 points is the worst; Acid-base test method: Place the ink sample in 10% hydrogen chloride solution and 10% sodium hydroxide solution respectively, soak for 24 hours each, observe and record the corrosion resistance of the ink in acidic and alkaline solutions. Similarly, score the ink according to its anti-corrosion performance, observe and record the acid-base corrosion resistance of the ink, and the test results are divided into 0-10 points, with 10 points being the best and 0 points being the worst.

[0050] Record the test results of each item, add them up to get the final test results, and record them in the following table:

[0051] It can be seen from the above table that the antioxidant and anti-corrosion properties of the antioxidant and anti-corrosion water-based printing inks prepared in comparative examples 1, 2, 3 and 4 are lower than those in experiments 1, 2 and 3; this shows that by adding antioxidants and preservatives during the preparation of the antioxidant and anti-corrosion water-based printing inks, the antioxidant and anti-corrosion properties of the antioxidant and anti-corrosion water-based printing inks can be effectively improved.

[0052] By comparing and analyzing the relevant data in the table, it can be seen that the antioxidant and anti-corrosion water-based printing ink prepared by the present invention not only has good antioxidant performance, but also has excellent anti-corrosion performance. This shows that the antioxidant and anti-corrosion water-based printing ink and the preparation method thereof provided by the present invention have a broader market prospect and are more suitable for promotion.

[0053] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0054] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An anti-oxidation and anti-corrosion water-based printing ink, characterized in that: The invention comprises the following raw materials in parts by weight: 50-80 parts of water-based acrylic resin, 40-60 parts of deionized water, 30-50 parts of pigment, 8-10 parts of antioxidant, 5-7 parts of preservative, 4-6 parts of dispersant and 3-5 parts of defoaming agent.

2. The anti-oxidation and anti-corrosion water-based printing ink according to claim 1, characterized in that: The pigment is selected from at least one of titanium dioxide pigment, carbon black pigment and phthalocyanine blue pigment.

3. The anti-oxidation and anti-corrosion water-based printing ink according to claim 1, characterized in that: The dispersant is selected from at least one of polyacrylic acid sodium salt, polycarboxylic acid sodium salt and sodium chloride.

4. The anti-oxidation and anti-corrosion water-based printing ink according to claim 1, characterized in that: The defoaming agent is selected from at least one of dimethyl polysiloxane, siloxane polymer and fluorinated silicone.

5. The anti-oxidation and anti-corrosion water-based printing ink according to claim 1, characterized in that: The antioxidant material is prepared by the following method: adding the first additive material and phosphite in a mass ratio of (2-3):1 into a mixing tank, stirring at 300-500r / min for 30-60min to prepare the antioxidant material.

6. The anti-oxidation and anti-corrosion water-based printing ink according to claim 5, characterized in that: The first additive is prepared by the following method: recovering soybean oil residue as raw material from a vegetable oil factory, drying, crushing and grinding the raw material to obtain a powder with a particle size of 100-200 μm, mixing the powder with ethanol and stirring to obtain a mixed liquid, wherein the mass ratio of the ethanol to the powder is (4-6):1, centrifuging and filtering the mixed liquid, and then transferring it to a distillation kettle, adjusting the pressure to 10-15 MPa, and performing reduced pressure distillation at 50-70°C to obtain the first additive.

7. The anti-oxidation and anti-corrosion water-based printing ink according to claim 1, characterized in that: The antiseptic material is prepared by the following method: weighing chitosan additive and brown algae extract in a mass ratio of 1:1, crushing and grinding them, transferring them to a stirring tank, setting the speed to 300-500r / min, stirring for 30-60min, and preparing the antiseptic additive.

8. The anti-oxidation and anti-corrosion water-based printing ink according to claim 7, characterized in that: The chitosan additive is prepared by the following method: collecting crab shells as raw materials, washing and removing impurities, and then transferring to an oven to dry at 30-50°C, then crushing and grinding to obtain shell powder, mixing the shell powder with a hydrochloric acid solution with a concentration of 1-3 mol / L, the mass ratio of the hydrochloric acid solution to the shell powder is (10-20):1, stirring to react, obtaining a solution, filtering, removing residues, washing, obtaining residues, adding a sodium hydroxide solution with a concentration of 2-5 mol / L, the mass ratio of sodium hydroxide to the residue is (8-10):1, transferring to a mixing tank, heating to 90-100°C, keeping warm and stirring for 3-6 hours, and then centrifugally filtering to obtain the chitosan additive.

9. The anti-oxidation and anti-corrosion water-based printing ink according to claim 7, characterized in that: The brown algae extract is prepared by the following method: selecting kelp as a raw material, washing, removing impurities, draining, adding a grinder to grind to obtain kelp particles, then adding the kelp particles to a sodium hydroxide solution with a concentration of 1-3 mol / L and mixing, wherein the mass ratio of the sodium hydroxide solution to the crushed material is (4-6):1, and then transferring to a stirring kettle, setting the temperature to 60-80°C, the speed to 300-500r / min, and stirring for 3-5h to obtain an extract, filtering the extract, and then adding a hydrochloric acid solution dropwise under stirring conditions to adjust the pH value of the extract to 7, completing neutralization, standing and settling for 4-6h, removing the supernatant to obtain a precipitate, and washing the precipitate with deionized water to obtain the brown algae extract.

10. A method for preparing an anti-oxidation and anti-corrosion water-based printing ink as claimed in any one of claims 1 to 9, characterized in that: The method comprises the following steps: weighing water-based acrylic resin, deionized water, pigment, antioxidant, preservative, dispersant and defoamer as required and putting them into a dispersion tank, setting the rotation speed to 700-800r / min and the time to 5-10min, completing the mixing of all raw materials, and preparing an antioxidant and anti-corrosion water-based printing ink.

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