Environmentally friendly inks and their preparation methods

Abstract

This invention discloses an environmentally friendly ink and its preparation method, belonging to the field of printing ink technology. The invention adds aminomethylphenylboronic acid and its derivatives as modifiers to a compound of epoxidized vegetable oil acrylate and glyceryl carbonate acrylate. This facilitates the formation of a highly cross-linked network structure and further improves the cross-linking density, effectively solving the problem of insufficient strength of epoxidized vegetable oil acrylate as the main chain segment. Thus, the biomass ink possesses high bio-based content while maintaining properties such as hardness and weather resistance comparable to conventional inks. The ink exhibits good adhesion to substrates such as plastics. The use of glyceryl carbonate acrylate, while acting as the main reactant, also provides a diluent, reducing solvent usage. Combined with low-volatile solvents, this maintains the overall flash point of the ink at a high level, resulting in a high safety factor and significant market application value.

Description

Technical Field

[0001] This invention relates to the field of ink technology, and in particular to an environmentally friendly ink and its preparation method. Background Technology

[0002] With increasingly stringent global environmental regulations and growing consumer demand for sustainable products, the ink industry is accelerating its transformation towards low-carbon, environmentally friendly, low-VOC, and even zero-VOC solutions. Biomass inks, due to their renewable, biodegradable, and widely available characteristics, have become an important research direction for replacing traditional petroleum-based inks. However, traditional biomass inks often use vegetable oil-modified resins as the matrix material. Their adhesion to plastic substrates, as well as the hardness and scratch resistance of the cured coating, are significantly weaker than traditional petroleum-based ink systems, and also weaker than highly volatile polyurethane acrylate or epoxy acrylate systems. Furthermore, some biomass ink formulations use excessive amounts of highly volatile organic solvents to achieve quick-drying effects, posing safety hazards such as volatile pollution, flammability, and explosion. Therefore, it is necessary to develop a safer and more environmentally friendly ink formulation. Summary of the Invention

[0003] The main objective of this invention is to develop a biomass ink with good stability, low volatile content, and strong ink layer adhesion. This ink has a high safety factor and is not prone to combustion or explosion during production, storage, and transportation.

[0004] To achieve the above objectives, the present invention proposes an environmentally friendly ink, wherein the base material of the environmentally friendly ink is prepared by reacting epoxidized vegetable oil acrylate and glyceryl carbonate acrylate under the action of a modifier; the modifier includes aminomethylphenylboronic acid and its derivatives.

[0005] In one embodiment, the aminomethylphenylboronic acid and its derivatives include at least one of aminomethylphenylboronic acid and aminomethylphenylboronic acid salt.

[0006] In one embodiment, the environmentally friendly ink comprises the following raw materials in parts by weight: Epoxidized vegetable oil acrylate: 35-45 parts; Glyceryl carbonate acrylate: 10-20 parts; Modifier: 4-8 parts; Pigment: 3-5 parts; Filler: 10-15 parts; Photoinitiator: 3-5 parts; Additives: 1-3 parts; Solvent: 20-30 parts.

[0007] In one embodiment, the epoxidized vegetable oil acrylate includes at least one of epoxidized soybean oil acrylate, epoxidized linseed oil acrylate, epoxidized castor oil acrylate, and epoxidized rapeseed oil acrylate.

[0008] In one embodiment, the glyceryl carbonate acrylate is prepared by esterification of acrylic acid and its derivatives with glyceryl carbonate.

[0009] In one embodiment, the glyceryl carbonate acrylate is prepared by esterification of methacrylic acid and its derivatives with glyceryl carbonate.

[0010] In one embodiment, the method for preparing the glyceryl carbonate acrylate includes the following steps: Glyceryl carbonate, acrylate monomer, catalyst, and p-hydroxyanisole are added to a reaction vessel and heated to 80°C~90°C. The reaction is carried out under a protective atmosphere for 4h~8h, with byproducts being discharged during the reaction. After the reaction is completed, the mixture is cooled, a desiccant is added, and then the desiccant and catalyst are removed by filtration. The corresponding fraction of product is collected to complete the preparation of the glyceryl carbonate acrylate. The molar ratio of glyceryl carbonate to acrylate monomer is 0.8~1.1:2. The catalyst includes zirconium acetylacetonate.

[0011] In one embodiment, the filler comprises barium sulfate and talc in a weight ratio of 8-11:2-4.

[0012] This invention also proposes a method for preparing the environmentally friendly ink, comprising the following steps: S1. Dissolve the modifier in a solvent to obtain a modifier solution; add a portion of glyceryl carbonate acrylate to the modifier solution, stir, and obtain a first dispersion; S2. Heat the epoxidized vegetable oil acrylate to 40℃~50℃ and keep it at that temperature for 20min~30min. Then add the remaining glyceryl carbonate acrylate, stir and disperse. Then add the pigment and filler, stir and disperse. Then add the first dispersion prepared in step S1, stir and disperse to obtain a semi-finished slurry. S3. Grind the semi-finished slurry obtained in step S2 on a three-roll mill, filter it, and then add photoinitiator and additives while stirring under light-protected conditions. Stir and disperse, and degas under vacuum to complete the preparation of the environmentally friendly ink.

[0013] In one embodiment, in step S1, the amount of glyceryl carbonate acrylate in the first dispersion is one-third to one-half of the total weight of the glyceryl carbonate acrylate.

[0014] In one embodiment, in step S3, the filtration fineness is 300 mesh to 500 mesh.

[0015] The environmentally friendly ink of this invention uses aminomethylphenylboronic acid and its derivatives as modifiers in its base material, which is a compound of epoxidized vegetable oil acrylate and glyceryl carbonate acrylate. This facilitates the formation of a highly cross-linked network structure and further improves the cross-linking density, effectively solving the problem of insufficient strength of the main chain segments of epoxidized vegetable oil acrylate. Thus, the biomass ink possesses high bio-based content while maintaining properties such as hardness and weather resistance comparable to conventional inks. Furthermore, some unreacted modifier components in the ink can react and bond with active groups on the surface of plastic substrates, resulting in excellent adhesion to plastic substrates and other substrates. It should also be noted that the ink of this invention uses glyceryl carbonate acrylate, which acts as the main reactant and also has a diluting effect, thereby reducing the amount of solvent used. The combination of glyceryl carbonate acrylate and low-volatility solvents maintains the overall flash point of the ink at a high level, resulting in a high safety factor. It is less prone to combustion or explosion during production, storage, and transportation, and has high market application value. Detailed Implementation

[0016] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0017] It should be noted that if the embodiments of the present invention involve directional indicators (such as up, down, left, right, front, back, etc.), the directional indicators are only used to explain the relative positional relationship and movement of the components in a specific posture. If the specific posture changes, the directional indicators will also change accordingly.

[0018] Furthermore, if the embodiments of this invention involve descriptions such as "first" or "second," these descriptions are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined with "first" or "second" may explicitly or implicitly include at least one of those features. Additionally, the use of "and / or" or "and / or" throughout the text includes three parallel solutions. For example, "A and / or B" includes solution A, solution B, or a solution where both A and B are satisfied simultaneously. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or impossible to implement, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by this invention.

[0019] The technical problem addressed by this invention is that, with increasingly stringent global environmental regulations and growing consumer demand for sustainable products, the ink industry is accelerating its transformation towards low-carbon, environmentally friendly, low-VOC, and even zero-VOC directions. Biomass inks, due to their renewable, biodegradable, and widely available characteristics, have become an important research direction for replacing traditional petroleum-based inks. However, traditional biomass inks often use vegetable oil-modified resins as the matrix material, resulting in significantly weaker adhesion to plastic substrates and weaker hardness and scratch resistance of the cured coating compared to traditional petroleum-based ink systems, as well as weaker performance compared to highly volatile polyurethane acrylate or epoxy acrylate systems. Furthermore, some biomass ink formulations, in pursuit of quick-drying effects, incorporate excessive amounts of highly volatile organic solvents, posing safety hazards such as volatile pollution, flammability, and explosion. Therefore, it is necessary to develop a safer and more environmentally friendly ink formulation.

[0020] To address the aforementioned technical problems, this invention proposes an environmentally friendly ink, the base material of which is prepared by reacting epoxidized vegetable oil acrylate and glyceryl carbonate acrylate under the action of a modifier; the modifier includes aminomethylphenylboronic acid and its derivatives.

[0021] Specifically, epoxidized vegetable oil acrylates serve as the main film-forming substance. The inks in the vegetable oil system have low shrinkage after drying, and the molecular structure contains both long-chain fatty acid carbon chains derived from vegetable oils and acrylate groups. The long-chain structure endows the ink coating with a certain degree of flexibility and wettability to the substrate, while the acrylate groups provide reaction sites for subsequent curing and crosslinking. Glyceryl carbonate acrylates can act as a reactive diluent to reduce the viscosity of the system, thereby reducing or even replacing volatile and flammable organic solvents in traditional formulations, thus solving VOC emissions and safety hazards. On the other hand, the carbonate groups and polar groups such as hydroxyl groups can react to form bonds, thereby significantly enhancing the intermolecular forces between the ink and the plastic substrate, thus greatly improving the adhesion of the ink.

[0022] Furthermore, the compounding of epoxidized vegetable oil acrylates and glyceryl carbonate acrylates effectively addresses the shortcomings of traditional biomass inks in terms of adhesion, hardness, and scratch resistance. It should also be noted that using aminomethylphenylboronic acid and its derivatives as modifiers allows the amino groups to react with the carbonyl groups on the epoxy groups or glyceryl carbonate rings, forming chemical bonds and increasing the crosslinking density. Introducing boric acid groups into the polymer network further enhances thermal stability and also forms borate ester bonds, hydrogen bonds, and a certain degree of coordination within the coating, thus providing a toughening effect. The benzene ring structure increases the rigidity of the polymer chain, which also contributes to improving the hardness of the ink coating.

[0023] In one specific embodiment, the aminomethylphenylboronic acid and its derivatives include at least one of aminomethylphenylboronic acid and aminomethylphenylboronic acid salt.

[0024] It should be noted that aminomethylphenyl borate salts have better water solubility or polar solvent solubility. In aminomethylphenyl borate salts, the amino group is protected by protonation, which can effectively delay the reaction between the amino group and epoxy groups in the ink system, thereby preventing the ink viscosity from increasing during storage and helping to maintain the rheological properties of the ink product.

[0025] In one embodiment, the environmentally friendly ink comprises the following raw materials in parts by weight: epoxidized vegetable oil acrylate: 35-45 parts; glyceryl carbonate acrylate: 10-20 parts; modifier: 4-8 parts; pigment: 3-5 parts; filler: 10-15 parts; photoinitiator: 3-5 parts; additives: 1-3 parts; solvent: 20-30 parts.

[0026] Specifically, epoxidized vegetable oil acrylate, used as the main film-forming resin in inks, is produced by the epoxidative addition of vegetable oils such as soybean oil, rapeseed oil, and castor oil with peroxy acids to generate epoxidized vegetable oil. This epoxidized vegetable oil is then esterified by ring-opening addition of acrylic acid to produce epoxidized vegetable oil acrylate. However, using epoxidized vegetable oil acrylate alone as a film-forming resin in inks suffers from low crosslinking density, insufficient hardness, and poor scratch resistance. Therefore, the addition of typical bio-based reactive monomers, such as glyceryl carbonate acrylate, improves the overall curing rate and crosslinking density, serving as both a reactive monomer and a diluent. Modifiers further enhance the crosslinking density and improve film strength and weather resistance.

[0027] It should also be noted that by precisely controlling the above ratios, the epoxidized vegetable oil acrylate, glyceryl carbonate acrylate, and modifier can work synergistically to give the ink film a balance of hardness, toughness, and adhesion. An excess of epoxidized vegetable oil acrylate will result in insufficient ink film hardness and poor scratch resistance; a deficiency will affect the continuity of the ink film formation; a deficiency of glyceryl carbonate acrylate will prevent it from increasing the crosslinking density of the film and replacing some of the solvent; an excess of glyceryl carbonate acrylate will lead to increased film shrinkage and reduced adhesion; and an excess of modifier will negatively impact storage and the transparency of the ink film.

[0028] In one embodiment, the solvent is selected from at least one of turpentine, propylene glycol methyl ether acetate, and dipropylene glycol dimethyl ether. Preferably, the solvent has a boiling point of not less than 120°C, thereby reducing the overall volatility of the ink and enabling rapid leveling after printing.

[0029] In one embodiment, the epoxidized vegetable oil acrylate includes at least one of epoxidized soybean oil acrylate, epoxidized linseed oil acrylate, epoxidized castor oil acrylate, and epoxidized rapeseed oil acrylate.

[0030] In a preferred embodiment, the epoxidized vegetable oil acrylate comprises 20wt% to 30wt% epoxidized castor oil acrylate. It is understood that using a small amount of epoxidized castor oil acrylate in combination with other lower-cost epoxidized vegetable oil acrylates as raw materials can further improve the weather resistance of the ink film, extend the ink's lifespan in outdoor applications, and also ensure that the cost of the ink raw materials remains at a low level.

[0031] In a more preferred embodiment, the epoxidized vegetable oil acrylate further includes 6wt% to 10wt% of modified epoxidized vegetable oil acrylate. Specifically, the modified epoxidized vegetable oil acrylate can be maleic anhydride-modified epoxidized vegetable oil acrylate, which can further increase the crosslinking density and enhance the film hardness and weather resistance; or it can be hydroxylated modified epoxidized vegetable oil acrylate, which can improve the dispersibility with pigments and fillers and reduce the amount of additives.

[0032] In one embodiment, the glyceryl carbonate acrylate is prepared by esterification of acrylic acid and its derivatives with glyceryl carbonate. In another embodiment, the glyceryl carbonate acrylate is prepared by esterification of methacrylic acid and its derivatives with glyceryl carbonate.

[0033] In one specific embodiment, the method for preparing the glyceryl carbonate acrylate includes the following steps: Glyceryl carbonate, acrylate monomer, catalyst, and p-hydroxyanisole are added to a reaction vessel and heated to 80°C~90°C. The reaction is carried out under a protective atmosphere for 4h~8h, with byproducts being discharged during the reaction. After the reaction is completed, the mixture is cooled, a desiccant is added, and then the desiccant and catalyst are removed by filtration. The corresponding fraction of product is collected to complete the preparation of the glyceryl carbonate acrylate. The molar ratio of glyceryl carbonate to acrylate monomer is 0.8~1.1:2. The catalyst includes zirconium acetylacetonate.

[0034] It should be noted that in the above preparation process, sufficient amounts of p-hydroxyanisole, acting as a polymerization inhibitor, must be added to prevent the acrylate from self-polymerizing under heating. Zirconium acetylacetonate is sensitive to moisture; therefore, the reaction vessel and reactants must be an anhydrous system. Since the acrylate and byproducts need to be discharged at 80℃~90℃, a low-boiling-point acrylate must be selected and used in conjunction with a distillation column to prevent excessive acrylate distillation.

[0035] In one specific embodiment, the method for preparing the glyceryl carbonate acrylate includes the following steps: Glyceryl carbonate, methyl acrylate, zirconium acetylacetonate, and p-hydroxyanisole are added to a reaction vessel and heated to 80°C~90°C. The reaction is carried out under a protective atmosphere for 4h~8h, with byproducts being discharged during the reaction. After the reaction is completed, the mixture is cooled, and anhydrous magnesium sulfate is added as a desiccant. The desiccant and catalyst are then removed by filtration, and the product is collected to complete the preparation of the glyceryl carbonate acrylate. The molar ratio of glyceryl carbonate to acrylate monomers is 0.8~1.1:2; the amount of zirconium acetylacetonate is 1% of the total mass of the materials, and the amount of p-hydroxyanisole is 0.5% of the mass of the acrylate.

[0036] In one embodiment, the filler comprises barium sulfate and talc in a weight ratio of 8-11:2-4. It is understood that barium sulfate, as the main filler, primarily provides gloss and abrasion resistance, has low oil absorption, and even at higher addition levels, it does not significantly affect the viscosity and rheological properties of the ink system. The combination of talc and barium sulfate helps promote uniform dispersion of the filler system.

[0037] In one embodiment, the environmentally friendly ink further includes 0.5 to 2 parts by weight of ultraviolet absorber, including but not limited to UV-P, UV-327, etc., which work synergistically with antioxidants to inhibit the aging effect of ultraviolet rays on the film layer and improve the sun resistance and rain resistance of the ink film layer.

[0038] In a preferred embodiment, the environmentally friendly ink further includes 1 to 2 parts by weight of a phosphate ester coupling agent. The combined effect of the ink matrix components and the coupling agent results in better adhesion of the ink to the metal substrate, which is beneficial for meeting the printing requirements of metal containers in packaging printing.

[0039] In a preferred embodiment, the environmentally friendly ink further includes 1 to 2 parts by weight of a silane coupling agent. Under the combined action of the ink matrix components and the coupling agent, the binding force between the ink and the hydroxyl groups on the glass surface is enhanced, achieving long-lasting printing on the glass surface and making it suitable for glass packaging, glassware, and other applications.

[0040] In one embodiment, when the ink is used for screen printing, the ink viscosity at room temperature is controlled at 1000 mPa·s to 3000 mPa·s; when used for gravure printing, the ink viscosity at room temperature is controlled at 500 mPa·s to 1500 mPa·s.

[0041] This invention also proposes a method for preparing the environmentally friendly ink, comprising the following steps: S1. Dissolve the modifier in a solvent to obtain a modifier solution; add a portion of glyceryl carbonate acrylate to the modifier solution, stir, and obtain a first dispersion; S2. Heat the epoxidized vegetable oil acrylate to 40℃~50℃ and keep it at that temperature for 20min~30min. Then add the remaining glyceryl carbonate acrylate, stir and disperse. Then add the pigment and filler, stir and disperse. Then add the first dispersion prepared in step S1, stir and disperse to obtain a semi-finished slurry. S3. Grind the semi-finished slurry obtained in step S2 on a three-roll mill, filter it, and then add photoinitiator and additives while stirring under light-protected conditions. Stir and disperse, and degas under vacuum to complete the preparation of the biomass environmentally friendly ink.

[0042] In one embodiment, in step S1, the amount of glyceryl carbonate acrylate in the first dispersion is one-third to one-half of the total weight of the glyceryl carbonate acrylate.

[0043] In one embodiment, in step S3, the filtration fineness is 300 mesh to 500 mesh.

[0044] The present invention further illustrates the technical solution through specific embodiments.

[0045] Example 1 The environmentally friendly ink of Example 1 comprises the following raw materials in parts by weight: Epoxidized castor oil acrylate: 10 parts; Epoxidized soybean oil acrylate: 35 parts; Glyceryl carbonate acrylate: 15 parts; Aminomethyl phenyl borate salt: 6 parts; Pigment: 4 parts; Barium sulfate filler: 9 parts; Talc filler: 3 parts; Photoinitiator (OXE-01): 4 parts; Defoamer and leveling agent: 1 part each; Dipropylene glycol dimethyl ether: 20 parts; Ultraviolet absorber: 1 part.

[0046] The preparation method of glyceryl carbonate acrylate includes the following steps: Glyceryl carbonate, methyl acrylate, zirconium acetylacetonate, and p-hydroxyanisole were added to a reaction vessel and heated to 80°C-90°C. The reaction was carried out for 5 hours under a protective atmosphere, with byproducts being discharged during the reaction. Methanol was distilled off while methyl acrylate was refluxed. After the reaction was completed, the vessel was cooled, and anhydrous magnesium sulfate was added. The desiccant and catalyst were then removed by filtration. The product at the bottom of the vessel was collected to complete the preparation.

[0047] The molar ratio of glyceryl carbonate to methyl acrylate is 1:2; the amount of zirconium acetylacetonate is 1% of the total material mass; and the amount of p-hydroxyanisole is 0.5% of the acrylate mass.

[0048] The ink preparation method in Example 1 includes the following steps: S1. Dissolve the modifier in a solvent to obtain a modifier solution; add half of the glyceryl carbonate acrylate to the modifier solution, stir, and obtain a first dispersion; S2. Heat the epoxidized vegetable oil acrylate to 40°C and keep it warm for 20 minutes. Then add the remaining glyceryl carbonate acrylate, stir and disperse. Then add the pigment and filler, stir and disperse. Then add the first dispersion prepared in step S1, stir and disperse to obtain a semi-finished slurry. S3. Grind the semi-finished slurry obtained in step S2 on a three-roll mill, filter to obtain a slurry with a fineness of less than 300 mesh, and then add photoinitiator and additives while stirring under light-protected conditions, stir and disperse, and vacuum degas to complete the preparation of environmentally friendly ink.

[0049] Example 2 Example 2 is based on Example 1, except that the raw material ratio is different. The environmentally friendly ink of Example 2 includes the following raw materials in parts by weight: Epoxidized soybean oil acrylate: 33 parts; Hydroxylated modified epoxidized rapeseed oil acrylate: 3 parts; Glyceryl carbonate acrylate: 10 parts; Aminomethyl phenyl borate salt: 5 parts; Pigment: 3 parts; Barium sulfate filler: 10 parts; Talc filler: 3 parts; Photoinitiator: 3 parts; Defoamer and leveling agent: 1 part each; Propylene glycol methyl ether acetate: 10 parts; Dipropylene glycol dimethyl ether: 15 parts; Ultraviolet absorber: 1 part; Phosphate ester coupling agent: 1.5 parts.

[0050] Example 3 Example 3 is based on Example 1, except that the raw material ratio is different. The environmentally friendly ink of Example 3 includes the following raw materials in parts by weight: Epoxidized soybean oil acrylate: 30 parts; Epoxidized castor oil acrylate: 10 parts; Glyceryl carbonate acrylate: 20 parts; Aminomethylphenylboronic acid: 8 parts; Pigment: 3 parts; Barium sulfate filler: 10 parts; Talc filler: 3 parts; Photoinitiator: 3 parts; Defoamer and leveling agent: 1 part each; Turpentine oil: 10 parts; Dipropylene glycol dimethyl ether: 15 parts; Ultraviolet absorber: 1 part; Silane coupling agent: 1.5 parts.

[0051] Comparative Example 1 Comparative Example 1 is based on Example 1, except that the raw material ratio is different and no modifier, aminomethylphenyl borate salt, is added in Comparative Example 1.

[0052] Comparative Example 2 Comparative Example 2 is based on Example 2, except that the raw material ratio is different. In Comparative Example 2, glyceryl carbonate acrylate is replaced with an equal amount of 2-ethylhexyl acrylate.

[0053] Comparative Example 3 Comparative Example 3 is based on Example 1, except that the raw material ratios are different. The environmentally friendly ink of Comparative Example 3 includes the following raw materials in parts by weight: Epoxidized castor oil acrylate: 10 parts; Epoxidized soybean oil acrylate: 35 parts; Glyceryl carbonate acrylate: 30 parts; Aminomethyl phenyl borate salt: 10 parts; Pigment: 4 parts; Barium sulfate filler: 9 parts; Talc filler: 3 parts; Photoinitiator: 4 parts; Defoamer and leveling agent: 1 part each; Ethylene glycol butyl ether acetate: 15 parts; Ultraviolet absorber: 1 part.

[0054] Comparative Example 4 Comparative Example 4 is based on Example 1, except that the raw material ratios are different. The environmentally friendly ink of Comparative Example 4 includes the following raw materials in parts by weight: Epoxidized castor oil acrylate: 10 parts; Epoxidized soybean oil acrylate: 35 parts; Glyceryl carbonate acrylate: 15 parts; Aminomethyl phenyl borate salt: 16 parts; Pigment: 4 parts; Barium sulfate filler: 9 parts; Talc filler: 3 parts; Photoinitiator: 4 parts; Defoamer and leveling agent: 1 part each; Ethylene glycol butyl ether acetate: 15 parts; Ultraviolet absorber: 1 part.

[0055] Performance testing: The inks prepared in the above examples and comparative examples were coated onto the surface of polycarbonate sheets to form a film layer with a thickness of about 0.3 mm. An LED-UV curing lamp (power about 120W) was used, with a curing distance of 10~15cm and a curing speed of 3m / min~8m / min. The curing was first pre-cured at low temperature (45℃, 1min) and then fully cured at high temperature (60℃, 2min) to ensure complete curing without surface stickiness or internal uncured phenomena.

[0056] (1) The flash point of the inks prepared in the examples and comparative examples was determined using a Setta closed flash point tester; (2) The hardness of the film layer was determined according to standard GB / T 6739-1996; the water absorption rate of the film layer was determined according to standard GB / T1733–93; and the ink adhesion was determined according to the method of standard GB / T9286–1998. (3) The gloss of the ink film was determined according to the method of standard GB / T 13217.2-2009.

[0057] The measurement results are shown in Table 1.

[0058] Table 1

[0059] Analysis of the data in Table 1 shows that in Comparative Example 2, replacing glyceryl carbonate acrylate with conventional acrylate monomers in the ink formulation resulted in a lower crosslinking density of the matrix material, which in turn reduced the mechanical strength and hardness to a certain extent. In Comparative Example 3, the glyceryl carbonate acrylate was relatively excessive, which led to a decrease in the adhesion and gloss of the film. In Comparative Example 4, the excessive modifier significantly reduced the gloss of the ink film.

[0060] The above description is merely an exemplary embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention under the technical concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. An environmentally friendly ink, characterized in that, The base material of the environmentally friendly ink is prepared by reacting epoxidized vegetable oil acrylate and glyceryl carbonate acrylate under the action of a modifier. The modifiers include aminomethylphenylboronic acid and its derivatives.

2. The environmentally friendly ink as described in claim 1, characterized in that, The aminomethylphenylboronic acid and its derivatives include at least one of aminomethylphenylboronic acid and aminomethylphenylboronic acid salt.

3. The environmentally friendly ink as described in claim 1, characterized in that, The environmentally friendly ink comprises the following raw materials in parts by weight: Epoxidized vegetable oil acrylate: 35-45 parts; Glyceryl carbonate acrylate: 10 to 20 parts; Modifier: 4 to 8 parts; Pigment: 3 to 5 parts; Filler: 10 to 15 parts; Photoinitiator: 3 to 5 parts; Additives: 1 to 3 parts; Solvent: 20 to 30 parts.

4. The environmentally friendly ink as described in claim 1, characterized in that, The epoxidized vegetable oil acrylates include at least one of epoxidized soybean oil acrylates, epoxidized linseed oil acrylates, epoxidized castor oil acrylates, and epoxidized rapeseed oil acrylates.

5. The environmentally friendly ink as described in claim 1, characterized in that, The glyceryl carbonate acrylate is prepared by esterification of acrylic acid and its derivatives with glyceryl carbonate; and / or, the glyceryl carbonate acrylate is prepared by esterification of methacrylic acid and its derivatives with glyceryl carbonate.

6. The environmentally friendly ink as described in claim 1, characterized in that, The preparation method of the glyceryl carbonate acrylate includes the following steps: Add glyceryl carbonate, acrylate monomer, catalyst and p-hydroxyanisole to the reaction vessel, heat to 80℃~90℃, react for 4h~8h under a protective atmosphere, and discharge by-products while reacting. After the reaction is completed, cool, add desiccant, then filter to remove desiccant and catalyst, collect the product of the corresponding fraction, and complete the preparation of the glyceryl carbonate acrylate. The molar ratio of the glycerol carbonate to the acrylate monomer is 0.8~1.1:2; the catalyst includes zirconium acetylacetonate.

7. The environmentally friendly ink as described in claim 1, characterized in that, The filler comprises barium sulfate and talc in a weight ratio of 8~11:2~4.

8. A method for preparing an environmentally friendly ink as described in any one of claims 1 to 7, characterized in that, Includes the following steps: S1. Dissolve the modifier in a solvent to obtain a modifier solution; add a portion of glyceryl carbonate acrylate to the modifier solution, stir, and obtain a first dispersion; S2. Heat the epoxidized vegetable oil acrylate to 40℃~50℃ and keep it at that temperature for 20min~30min. Then add the remaining glyceryl carbonate acrylate, stir and disperse. Then add the pigment and filler, stir and disperse. Then add the first dispersion prepared in step S1, stir and disperse to obtain a semi-finished slurry. S3. Grind the semi-finished slurry obtained in step S2 on a three-roll mill, filter it, and then add photoinitiator and additives while stirring under light-protected conditions. Stir and disperse, and degas under vacuum to complete the preparation of the environmentally friendly ink.

9. The method for preparing the environmentally friendly ink as described in claim 8, characterized in that, In step S1, the amount of glyceryl carbonate acrylate in the first dispersion is one-third to one-half of the total weight of glyceryl carbonate acrylate.

10. The method for preparing the environmentally friendly ink as described in claim 8, characterized in that, In step S3, the filtration fineness is 300 mesh to 500 mesh.

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