Environment-friendly hydrophobic ink and preparation method thereof

Abstract

The invention relates to environment-friendly hydrophobic ink and a preparation method thereof, and belongs to the technical field of water-based ink. A copolymerization modifier capable of being combined in a water-based polyacrylate emulsion in an initiation polymerization mode in the stage of preparing the modified water-based polyacrylate emulsion is prepared, and an o-hydroxy aromatic ketone structure in the copolymerization modifier can endow water-based ink with lasting ultraviolet absorption performance; the trifluoromethyl structure can reduce the surface energy of the water-based ink, and the benzimidazole ring structure can form stable coordinate bonds with metal ions, so that the bonding performance of the water-based ink and a metal substrate is enhanced; when the copolymerization modifier is used for modifying the water-based polyacrylate emulsion, the long-term performance, the hydrophobic and oil-resistant performance and the adhesion performance on the surface of a metal base material of the finished water-based ink can be effectively improved.

Description

Technical Field

[0001] This invention belongs to the field of water-based ink technology, specifically, it relates to an environmentally friendly hydrophobic ink and its preparation method. Background Technology

[0002] Water-based inks, due to their extremely low volatile organic compound (VOC) content, offer significant advantages such as being non-toxic, odorless, safe, and environmentally friendly, and are gradually replacing traditional solvent-based inks. Among them, polyacrylate resins have become the most important matrix resins for water-based inks due to their excellent film-forming properties, transparency, aging resistance, and formulation flexibility.

[0003] The main drawback of polyacrylate resins is their sensitivity to ultraviolet light. Under prolonged outdoor sunlight, they are prone to photo-oxidation, leading to yellowing and peeling of the paint film. Although the weather resistance of polyacrylates can be improved by adding ultraviolet absorbers, small molecule additives have poor compatibility and binding force with the polyacrylate resin matrix, and are prone to migration and failure during storage and use. Secondly, water-based systems are inherently hydrophilic, and their paint films typically have poor water and oil resistance, which also accelerates the migration of ultraviolet absorbers. To address these technical shortcomings, this invention provides an environmentally friendly hydrophobic ink and its preparation method. Summary of the Invention

[0004] The purpose of this invention is to provide an environmentally friendly hydrophobic ink and its preparation method, so as to solve the problems mentioned in the background art.

[0005] The objective of this invention can be achieved through the following technical solutions: A method for preparing an environmentally friendly hydrophobic ink includes the following steps: Step 1: Acrylic acid is esterified with 2,3-diaminophenol to obtain a comonomer; The reaction process is as follows: Acrylic acid, 2,3-diaminophenol, p-toluenesulfonic acid and toluene are mixed in a reaction vessel and reacted at a temperature of 60-80℃ for 16-32 hours. After the reaction is completed, the reaction solution is cooled to room temperature and the solvent is removed by rotary evaporation. The remaining solid is washed with deionized water and dried to obtain the comonomer.

[0006]

[0007] The second step involves reacting the comonomer with trifluoroacetic acid via a benzimidazole reaction to obtain an intermediate. The reaction process is as follows: the comonomer, trifluoroacetic acid, and N,N-dimethylacetamide are mixed in a reaction vessel and reacted at 110-150℃ for 3-6 hours. After the reaction is completed, the reaction solution is cooled to room temperature and poured into deionized water to precipitate. After filtering to separate the solid, the obtained solid is washed with deionized water and dried to obtain the intermediate.

[0008]

[0009] The third step is to perform a Fourier rearrangement on the intermediate to obtain the copolymerized modified monomer; The reaction process is as follows: The intermediate, aluminum chloride, and N,N-dimethylacetamide are mixed in a reaction vessel and reacted at 120-140℃ for 6-14 hours. After the reaction is completed, the reaction solution is poured into deionized water to precipitate. After filtering to separate the solid, the obtained solid is washed with deionized water and dried to obtain the copolymerized modified monomer.

[0010]

[0011] Step 4: Polymerize the polymerizing monomer, comonomer, emulsifier, initiator, and molecular weight regulator in deionized water to obtain a modified waterborne polyacrylate emulsion; Step 5: Mix and grind the modified water-based polyacrylate emulsion, nano silica, functional additives, and pigments evenly to obtain environmentally friendly hydrophobic ink.

[0012] Further, the polymerizing monomer is at least one selected from methyl methacrylate, styrene, acrylonitrile, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, acrylic acid, and methacrylic acid.

[0013] Furthermore, the emulsifier is at least one of sodium dodecyl sulfate and sodium dodecylbenzene sulfonate.

[0014] Furthermore, the initiator is at least one of ammonium persulfate and potassium persulfate.

[0015] Furthermore, the molecular weight regulator is an α-methylstyrene linear dimer.

[0016] Furthermore, the functional additive is at least one of wetting and dispersing agents, leveling agents, defoamers, and film-forming aids.

[0017] Furthermore, the method for modifying polyacrylate emulsion polymerization is as follows: S1. Dissolve the initiator in deionized water to prepare an initiator aqueous solution with a mass fraction of 5-10%. Then mix the polymerizing monomer, comonomer, emulsifier, molecular weight regulator and deionized water to obtain a pre-emulsion for later use. S2. Mix 20-30% of the pre-emulsion and 30-40% of the initiator aqueous solution and react at 75-83℃ for 20-30 min to obtain a seed emulsion. Then, keep the temperature constant and add the remaining pre-emulsion and the remaining initiator aqueous solution dropwise to the system over a period of 3-4 h. After the addition is complete, raise the temperature to 86-92℃ and keep it at that temperature for 40-60 min. Finally, cool the reaction solution and adjust the pH of the system to 7-8 to obtain a modified polyacrylate emulsion.

[0018] Furthermore, the mass ratio of the initiator to the monomer used is 1–1.8:100–120; the mass ratio of the monomer, copolymerizing modifier, emulsifier, molecular weight regulator, and deionized water used in the preparation of the preemulsion is 100–120:5–9:1–3:0.6–1.2:120–180.

[0019] Furthermore, the mass ratio of the modified waterborne polyacrylate emulsion, nano silica, functional additives, and pigments used is 150–180:10–12:2–5:10–30.

[0020] The present invention also provides an environmentally friendly hydrophobic ink prepared by the above steps.

[0021] In summary, the present invention has at least the following beneficial effects: 1) This invention prepares a copolymer modifier with ultraviolet absorption capability. The copolymer modifier has polymerizable double bonds, trifluoromethyl structure and benzimidazole ring structure in its structure. It can form stable covalent bonds in the modified waterborne polyacrylate emulsion by initiating polymerization during the preparation stage. The ortho-hydroxy aromatic ketone structure in the copolymer modifier can endow the waterborne ink with durable ultraviolet absorption performance, the trifluoromethyl structure can reduce the surface energy of the waterborne ink, and the benzimidazole ring structure can form stable coordination bonds with metal ions, thereby enhancing the bonding performance between the waterborne ink and the metal substrate. By using the copolymer modifier of this invention to modify the waterborne polyacrylate emulsion, the long-term performance, hydrophobic and oil-resistant properties of the finished waterborne ink and its adhesion performance on the surface of the metal substrate can be effectively improved.

[0022] 2) The UV absorption mechanism of the o-hydroxy aromatic ketone structure UV absorber is that the phenolic hydroxyl group in the molecule can form a stable intramolecular hydrogen bond with the adjacent carbonyl group. After absorbing the energy of ultraviolet light, the hydroxyl group will transfer a proton to the carbonyl group through the intramolecular hydrogen bond network, transitioning from the ground state to the excited state. After the molecule returns from the excited state to the ground state, the energy of the ultraviolet light is dissipated as heat through vibrational relaxation. The copolymer modifier structure prepared in this invention not only contains an o-hydroxy aromatic ketone structure, but also an imidazole ring connected to the ortho position of the phenolic hydroxyl group. The imidazole ring structure can not only coordinate with metal ions, but the NH structure can also become an additional hydrogen bond site adjacent to the phenolic hydroxyl group, enhancing the intramolecular hydrogen bond network, thereby stabilizing the radiative transition channel of the hydroxyl proton and reducing the activation energy barrier of hydroxyl proton transfer. This gives the o-hydroxy aromatic ketone structure stronger UV absorption capacity and photostability, thereby further improving the weather resistance of water-based inks. Detailed Implementation

[0023] This invention provides an environmentally friendly hydrophobic ink and its preparation method. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired result. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and fall within the scope of protection of this invention. The method and application of this invention have been described through preferred embodiments. Those skilled in the art can clearly modify or appropriately change and combine the method and application described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0024] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.

[0025] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.

[0026] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0027] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items.

[0028] It should be understood that the order of the steps or the order in which certain actions are performed is not important as long as the invention remains operational. Furthermore, two or more steps or actions can be performed simultaneously.

[0029] The use of any and all instances or exemplary language such as “e.g.” or “including” in this document is merely intended to better illustrate the invention and is not intended to limit the scope of the invention unless the claims are made. No language in this specification should be construed as indicating that any unclaimed element is essential to the practice of the invention.

[0030] Furthermore, the numerical ranges and parameters used to define the present invention are approximate values, and the relevant values ​​in the specific embodiments have been presented as precisely as possible. However, any value inevitably contains standard deviations due to individual test methods. Therefore, unless explicitly stated otherwise, it should be understood that all ranges, quantities, values, and percentages used in this disclosure are modified with the word "approximately". Here, "approximately" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a specific value or range.

[0031] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0032] The embodiments and comparative examples of this invention describe some examples, in which the embodiments illustrate certain implementations of the invention. However, this does not mean that the effects of the invention can only be achieved in these examples.

[0033] To further illustrate the present invention, the following describes in detail an environmentally friendly hydrophobic ink and its preparation method provided by the present invention, in conjunction with embodiments.

[0034] Example 1 A method for preparing an environmentally friendly hydrophobic ink includes the following steps: Step 1: Mix 6 parts by mass of acrylic acid, 10 parts by mass of 2,3-diaminophenol, 4 parts by mass of p-toluenesulfonic acid, and 80 parts by mass of toluene in a reaction vessel and react at 60°C for 32 hours. After the reaction is completed, cool the reaction solution to room temperature and remove the solvent by rotary evaporation. Wash the remaining solid with deionized water and dry to obtain the comonomer.

[0035] Step 2: Mix 10 parts by mass of comonomer, 8 parts by mass of trifluoroacetic acid, and 72 parts by mass of N,N-dimethylacetamide in a reaction vessel and react at 110°C for 6 hours. After the reaction is completed, cool the reaction solution to room temperature and pour it into deionized water to precipitate. After filtering to separate the solid, wash the obtained solid with deionized water and dry it to obtain the intermediate.

[0036] Third step: Mix 10 parts by mass of intermediate, 6 parts by mass of aluminum chloride and 96 parts by mass of N,N-dimethylacetamide in a reaction vessel and react at 120℃ for 14 hours. After the reaction is completed, pour the reaction solution into deionized water to precipitate. After filtering to separate the solid, wash the obtained solid with deionized water and dry it to obtain the copolymerized modified monomer.

[0037] Step 4: Dissolve 1 part by mass of ammonium persulfate in deionized water to prepare an aqueous solution of 5% by mass. Then mix 100 parts by mass of polymerizing monomer, 5 parts by mass of copolymerizing modified monomer, 1 part by mass of sodium dodecyl sulfate, 0.6 parts by mass of α-methylstyrene linear dimer, and 120 parts by mass of deionized water to obtain a pre-emulsion for later use. Step 5: Mix 20% of the pre-emulsion and 30% of the ammonium persulfate aqueous solution and react at 75℃ for 30 min to obtain the seed emulsion. Then, keep the temperature constant and add the remaining pre-emulsion and the remaining ammonium persulfate aqueous solution dropwise over 4 h. After the addition is complete, raise the temperature to 86℃ and keep it at that temperature for 60 min. Finally, cool the reaction solution and adjust the pH of the system to 7 to obtain the modified polyacrylate emulsion. Step 6: Mix and grind 150 parts by weight of modified waterborne polyacrylic emulsion, 10 parts by weight of nano silica, 2 parts by weight of functional additives, and 10 parts by weight of pigment to obtain environmentally friendly hydrophobic ink.

[0038] In this embodiment, the polymer monomers used include 35 parts by weight of methyl methacrylate, 10 parts by weight of styrene, 25 parts by weight of butyl acrylate, 15 parts by weight of ethyl acrylate, 5 parts by weight of 2-ethylhexyl acrylate, 4 parts by weight of acrylic acid, and 6 parts by weight of methacrylic acid, totaling 100 parts by weight. The functional additives used include 0.8 parts by weight of wetting and dispersing agent BYK-167 TF, 0.4 parts by weight of leveling agent BYK-361 N, 0.5 parts by weight of defoamer BYK-065, and 0.3 parts by weight of film-forming aid propylene glycol methyl ether acetate.

[0039] The environmentally friendly hydrophobic ink is prepared by the above steps.

[0040] Example 2 A method for preparing an environmentally friendly hydrophobic ink includes the following steps: Step 1: Mix 9 parts by mass of acrylic acid, 15 parts by mass of 2,3-diaminophenol, 6 parts by mass of p-toluenesulfonic acid, and 100 parts by mass of toluene in a reaction vessel and react at 70°C for 24 hours. After the reaction is completed, cool the reaction solution to room temperature and remove the solvent by rotary evaporation. Wash the remaining solid with deionized water and dry to obtain the comonomer.

[0041] Step 2: Mix 15 parts by mass of comonomer, 12 parts by mass of trifluoroacetic acid, and 90 parts by mass of N,N-dimethylacetamide in a reaction vessel and react at 130°C for 4.5 h. After the reaction is complete, cool the reaction solution to room temperature and pour it into deionized water to precipitate. After filtering to separate the solid, wash the obtained solid with deionized water and dry it to obtain the intermediate.

[0042] Third step: Mix 15 parts by mass of intermediate, 9 parts by mass of aluminum chloride and 80 parts by mass of N,N-dimethylacetamide in a reaction vessel and react at 130℃ for 10 hours. After the reaction is completed, pour the reaction solution into deionized water to precipitate. After filtering to separate the solid, wash the obtained solid with deionized water and dry it to obtain the copolymerized modified monomer.

[0043] Step 4: Dissolve 1.4 parts by mass of potassium persulfate in deionized water to prepare a 7.5% potassium persulfate aqueous solution. Then mix 110 parts by mass of polymerizing monomer, 7 parts by mass of copolymerizing modified monomer, 2 parts by mass of sodium dodecylbenzenesulfonate, 0.9 parts by mass of α-methylstyrene linear dimer, and 150 parts by mass of deionized water to obtain a pre-emulsion for later use. Step 5: Mix 25% of the pre-emulsion and 35% of the potassium persulfate aqueous solution and react at 79℃ for 25 min to obtain the seed emulsion. Then, keep the temperature constant and add the remaining pre-emulsion and the remaining potassium persulfate aqueous solution dropwise over 3.5 h. After the addition is complete, raise the temperature to 89℃ and keep it at that temperature for 50 min. Finally, cool the reaction solution and adjust the pH of the system to 7.5 to obtain the modified polyacrylate emulsion. Step 6: Mix and grind 165 parts by weight of modified waterborne polyacrylate emulsion, 11 parts by weight of nano silica, 3.5 parts by weight of functional additives, and 20 parts by weight of pigment to obtain environmentally friendly hydrophobic ink.

[0044] In this embodiment, the polymer monomers used include 35 parts by weight of methyl methacrylate, 20 parts by weight of styrene, 10 parts by weight of acrylonitrile, 25 parts by weight of butyl acrylate, 15 parts by weight of 2-ethylhexyl acrylate, and 5 parts by weight of methacrylic acid, totaling 110 parts by weight. The functional additives used include 1.5 parts by weight of wetting and dispersing agent BYK-167 TF, 0.7 parts by weight of leveling agent BYK-300 N, 0.8 parts by weight of defoamer BYK-024, and 0.5 parts by weight of film-forming aid propylene glycol methyl ether acetate.

[0045] The environmentally friendly hydrophobic ink is prepared by the above steps.

[0046] Example 3 A method for preparing an environmentally friendly hydrophobic ink includes the following steps: Step 1: Mix 12 parts by mass of acrylic acid, 20 parts by mass of 2,3-diaminophenol, 8 parts by mass of p-toluenesulfonic acid, and 120 parts by mass of toluene in a reaction vessel and react at 80°C for 16 hours. After the reaction is completed, cool the reaction solution to room temperature and remove the solvent by rotary evaporation. Wash the remaining solid with deionized water and dry to obtain the comonomer.

[0047] Step 2: Mix 20 parts by mass of comonomer, 16 parts by mass of trifluoroacetic acid, and 108 parts by mass of N,N-dimethylacetamide in a reaction vessel and react at 150°C for 3 hours. After the reaction is completed, cool the reaction solution to room temperature and pour it into deionized water to precipitate. After filtering to separate the solid, wash the obtained solid with deionized water and dry it to obtain the intermediate.

[0048] Third step: Mix 20 parts by mass of intermediate, 12 parts by mass of aluminum chloride and 96 parts by mass of N,N-dimethylacetamide in a reaction vessel and react at 140℃ for 6 hours. After the reaction is completed, pour the reaction solution into deionized water to precipitate. After filtering to separate the solid, wash the obtained solid with deionized water and dry it to obtain the copolymerized modified monomer.

[0049] Step 4: Dissolve 1.8 parts by mass of ammonium persulfate in deionized water to prepare a 10% ammonium persulfate aqueous solution. Then, mix 120 parts by mass of polymerizing monomer, 9 parts by mass of copolymerizing modified monomer, 3 parts by mass of sodium dodecylbenzenesulfonate, 1.2 parts by mass of α-methylstyrene linear dimer, and 180 parts by mass of deionized water to obtain a pre-emulsion for later use. Step 5: Mix 30% of the pre-emulsion and 40% of the ammonium persulfate aqueous solution and react at 83℃ for 20 min to obtain the seed emulsion. Then, keep the temperature constant and add the remaining pre-emulsion and the remaining ammonium persulfate aqueous solution dropwise over 3 h. After the addition is complete, raise the temperature to 92℃ and keep it at that temperature for 40 min. Finally, cool the reaction solution and adjust the pH of the system to 8 to obtain the modified polyacrylate emulsion. Step 6: Mix and grind 180 parts by weight of modified waterborne polyacrylic emulsion, 12 parts by weight of nano silica, 5 parts by weight of functional additives, and 30 parts by weight of pigment to obtain environmentally friendly hydrophobic ink.

[0050] In this embodiment, the polymer monomers used include 40 parts by mass of methyl methacrylate, 15 parts by mass of styrene, 10 parts by mass of acrylonitrile, 30 parts by mass of butyl acrylate, 15 parts by mass of ethyl acrylate, 5 parts by mass of 2-ethylhexyl acrylate, and 5 parts by mass of acrylic acid, totaling 120 parts by mass. The functional additives used include 2 parts by mass of wetting and dispersing agent BYK-163 TF, 1 part by mass of leveling agent BYK-380 N, 1 part by mass of defoamer BYK-024, and 1 part by mass of film-forming aid ethylene glycol butyl ether.

[0051] The environmentally friendly hydrophobic ink is prepared by the above steps.

[0052] Comparative Example 1 The difference between this comparative example and Example 1 is that no copolymer-modifying monomer is prepared, and no copolymer-modifying monomer is added when preparing the polyacrylate emulsion. Instead, 1 part by weight of UV absorber UV-0 and 2 parts by weight of benzimidazole are added when preparing the environmentally friendly hydrophobic ink.

[0053] A method for preparing an environmentally friendly hydrophobic ink includes the following steps: Step 1: Dissolve 1 part by mass of ammonium persulfate in deionized water to prepare an aqueous solution of 5% by mass. Then mix 100 parts by mass of polymeric monomer, 1 part by mass of sodium dodecyl sulfate, 0.6 parts by mass of α-methylstyrene linear dimer, and 120 parts by mass of deionized water to obtain a pre-emulsion for later use. The second step involves mixing 20% ​​of the pre-emulsion and 30% of the ammonium persulfate aqueous solution and reacting them at 75°C for 30 minutes to obtain a seed emulsion. Then, while maintaining the temperature, the remaining pre-emulsion and the remaining ammonium persulfate aqueous solution are added dropwise to the system over a period of 4 hours. After the addition is complete, the temperature is raised to 86°C and maintained for 60 minutes. Finally, the reaction solution is cooled and the pH of the system is adjusted to 7 to obtain a modified polyacrylate emulsion. The third step involves mixing and grinding 147 parts by weight of modified waterborne polyacrylate emulsion, 1 part by weight of UV absorber UV-0, 2 parts by weight of benzimidazole, 10 parts by weight of nano silica, 2 parts by weight of functional additives, and 10 parts by weight of pigment until uniform, thus obtaining an environmentally friendly hydrophobic ink.

[0054] The monomers used in this comparative example comprise 35 parts by weight of methyl methacrylate, 10 parts by weight of styrene, 25 parts by weight of butyl acrylate, 15 parts by weight of ethyl acrylate, 5 parts by weight of 2-ethylhexyl acrylate, 4 parts by weight of acrylic acid, and 6 parts by weight of methacrylic acid, totaling 100 parts by weight. The functional additives used include 0.8 parts by weight of wetting and dispersing agent BYK-167 TF, 0.4 parts by weight of leveling agent BYK-361 N, 0.5 parts by weight of defoamer BYK-065, and 0.3 parts by weight of film-forming aid propylene glycol methyl ether acetate.

[0055] Comparative Example 2 The difference between this comparative example and Example 1 is that no copolymer-modifying monomer is prepared, and no copolymer-modifying monomer is added when preparing the polyacrylate emulsion. Instead, 3 parts by weight of UV-0 ultraviolet absorber is added when preparing the environmentally friendly hydrophobic ink.

[0056] A method for preparing an environmentally friendly hydrophobic ink includes the following steps: Step 1: Dissolve 1 part by mass of ammonium persulfate in deionized water to prepare an aqueous solution of 5% by mass. Then mix 100 parts by mass of polymeric monomer, 1 part by mass of sodium dodecyl sulfate, 0.6 parts by mass of α-methylstyrene linear dimer, and 120 parts by mass of deionized water to obtain a pre-emulsion for later use. The second step involves mixing 20% ​​of the pre-emulsion and 30% of the ammonium persulfate aqueous solution and reacting them at 75°C for 30 minutes to obtain a seed emulsion. Then, while maintaining the temperature, the remaining pre-emulsion and the remaining ammonium persulfate aqueous solution are added dropwise to the system over a period of 4 hours. After the addition is complete, the temperature is raised to 86°C and maintained for 60 minutes. Finally, the reaction solution is cooled and the pH of the system is adjusted to 7 to obtain a modified polyacrylate emulsion. The third step involves mixing and grinding 147 parts by weight of modified waterborne polyacrylate emulsion, 3 parts by weight of UV absorber UV-0, 10 parts by weight of nano silica, 2 parts by weight of functional additives, and 10 parts by weight of pigment until homogeneous to obtain environmentally friendly hydrophobic ink.

[0057] The monomers used in this comparative example comprise 35 parts by weight of methyl methacrylate, 10 parts by weight of styrene, 25 parts by weight of butyl acrylate, 15 parts by weight of ethyl acrylate, 5 parts by weight of 2-ethylhexyl acrylate, 4 parts by weight of acrylic acid, and 6 parts by weight of methacrylic acid, totaling 100 parts by weight. The functional additives used include 0.8 parts by weight of wetting and dispersing agent BYK-167 TF, 0.4 parts by weight of leveling agent BYK-361 N, 0.5 parts by weight of defoamer BYK-065, and 0.3 parts by weight of film-forming aid propylene glycol methyl ether acetate.

[0058] Experimental Example 1 The environmentally friendly hydrophobic inks obtained in Examples 1-3 and Comparative Examples 1-2 were subjected to performance tests. The water contact angle of each component sample after complete drying and curing was measured using a water contact angle tester. The oil resistance of each component ink was tested according to the national standard GB / T 9274-1988 "Determination of Resistance to Liquid Media for Paints and Varnishes". The adhesion level of each component ink on tinplate surfaces was tested according to the national standard GB / T 9286-2021 "Cross-cut Test for Paints and Varnishes". After the samples underwent a 600-hour accelerated UV aging test according to the national standard GB / T16422.3 "Laboratory Light Exposure Test Methods for Plastics - Part 3: Fluorescent UV Lamp", the tests were repeated. The test results are shown in Table 1. Table 1

[0059] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing an environmentally friendly hydrophobic ink, characterized in that, Includes the following steps: Step 1: Acrylic acid is esterified with 2,3-diaminophenol to obtain a comonomer; The second step involves reacting the comonomer with trifluoroacetic acid via a benzimidazole reaction to obtain an intermediate. The third step is to perform a Fourier rearrangement on the intermediate to obtain the copolymerized modified monomer; Step 4: Polymerize the polymerizing monomer, comonomer, emulsifier, initiator, and molecular weight regulator in deionized water to obtain a modified waterborne polyacrylate emulsion; Step 5: Mix and grind the modified water-based polyacrylate emulsion, nano silica, functional additives, and pigments evenly to obtain environmentally friendly hydrophobic ink.

2. The method for preparing an environmentally friendly hydrophobic ink according to claim 1, characterized in that, The polymer monomer is at least one selected from methyl methacrylate, styrene, acrylonitrile, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, acrylic acid, and methacrylic acid.

3. The method for preparing an environmentally friendly hydrophobic ink according to claim 1, characterized in that, The emulsifier is at least one of sodium dodecyl sulfate and sodium dodecylbenzene sulfonate.

4. The method for preparing an environmentally friendly hydrophobic ink according to claim 1, characterized in that, The initiator is at least one of ammonium persulfate and potassium persulfate.

5. The method for preparing an environmentally friendly hydrophobic ink according to claim 1, characterized in that, The molecular weight regulator is α-methylstyrene linear dimer.

6. The method for preparing an environmentally friendly hydrophobic ink according to claim 1, characterized in that, The functional additive is at least one of wetting and dispersing agents, leveling agents, defoamers, and film-forming aids.

7. The method for preparing an environmentally friendly hydrophobic ink according to claim 1, characterized in that, The method for modifying polyacrylate emulsion polymerization is as follows: S1. Dissolve the initiator in deionized water to prepare an initiator aqueous solution with a mass fraction of 5-10%. Then mix the polymerizing monomer, comonomer, emulsifier, molecular weight regulator and deionized water to obtain a pre-emulsion for later use. S2. Mix 20-30% of the pre-emulsion and 30-40% of the initiator aqueous solution and react at 75-83℃ for 20-30 min to obtain a seed emulsion. Then, keep the temperature constant and add the remaining pre-emulsion and the remaining initiator aqueous solution dropwise to the system over a period of 3-4 h. After the addition is complete, raise the temperature to 86-92℃ and keep it at that temperature for 40-60 min. Finally, cool the reaction solution and adjust the pH of the system to 7-8 to obtain a modified polyacrylate emulsion.

8. The method for preparing an environmentally friendly hydrophobic ink according to claim 1, characterized in that, The mass ratio of the modified waterborne polyacrylate emulsion, nano silica, functional additives, and pigments used is 150–180:10–12:2–5:10–30.

9. The method for preparing an environmentally friendly hydrophobic ink according to claim 7, characterized in that, The mass ratio of the initiator to the monomer used is 1-1.8:100-120; the mass ratio of the monomer, copolymer modifier, emulsifier, molecular weight regulator and deionized water used in the preparation of the preemulsion is 100-120:5-9:1-3:0.6-1.2:120-180.

10. The environmentally friendly hydrophobic ink obtained by the preparation method according to claim 1.

Images