Modified filler environment-friendly ink and preparation method thereof

Abstract

The invention relates to the technical field of ink, in particular to modified filler environment-friendly ink and a preparation method thereof. The modified filler environment-friendly printing ink is prepared from the following raw materials in parts by mass: 20 to 40 parts of waterborne acrylic emulsion, 10 to 20 parts of polyurethane acrylate prepolymer, 1 to 5 parts of bis (trimethylolpropane) tetraacrylate, 10 to 20 parts of pentaerythritol tetraacrylate, 5 to 10 parts of mica powder, 1 to 2 parts of 3-aminopropyltriethoxysilane, 0.1 to 1 part of epoxy chloropropane and 5 to 10 parts of amino-terminated polyamidoamine. The coating is prepared from the following components in parts by weight: 1-2 parts of a photoinitiator, 1-3 parts of a dispersing agent, 1-2 parts of a reactive diluent, 1-2 parts of an organic silicon defoaming agent, 0.5-1.5 parts of a mildew preventive, 0.1-1 part of a thixotropic agent, 5-15 parts of pigment, 1-5 parts of kaolin, 5-10 parts of polyethylene wax and 1-5 parts of water. The obtained ink is good in dispersion stability, good in flexibility after being cured and excellent in adhesive force.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ink, in particular to a modified filler environment-friendly ink and a preparation method thereof. BACKGROUND

[0002] With the continuous improvement of people's living standards, the demand for the quality of commodity packaging is increasing. As the core container of commodity packaging, the packaging box not only needs to ensure the safety of transportation, but also needs to have the functions of beautifying commodities and promoting sales. Therefore, the market demand is rising, and the application scenarios are becoming more and more widely. This requires the packaging box to have sufficient structural strength and excellent surface printing quality to meet the expectations of consumers for beauty and practicality.

[0003] Traditional oil-based ink is cured by oxidation film or solvent volatilization, and the printed matter needs to be placed for one to two days or even longer to completely dry. In this process, the penetration of the ink into the substrate can easily cause problems such as color layer settlement, printing dot expansion, and color saturation decrease, affecting the printing effect. With the rapid development of modern economy, environmental protection and safety awareness are increasing, and water-based ink is widely used due to its environmental characteristics and low VOCs emission. However, water-based ink is prone to friction during the packaging box transportation process, and the lack of wear resistance leads to frequent discoloration, which becomes a key problem restricting its application.

[0004] In order to improve the wear resistance, mica filler is often added, which can significantly enhance the wear resistance of the ink, but can easily cause delamination in the water-based ink system, which not only destroys the stability of the ink, leading to poor leveling and uneven spreading of the printed surface, but also significantly reduces the adhesion strength, making the printed matter prone to falling off during subsequent processing or use. These problems limit the application of water-based ink in high-end packaging field and need to be solved urgently. SUMMARY

[0005] The present application aims to solve the problems existing in the prior art and provides a modified filler environment-friendly ink and a preparation method thereof.

[0006] A modified filler environment-friendly ink, the raw materials of which include, by mass fraction: water-based acrylic emulsion 20-40 parts, polyurethane acrylate prepolymer 10-20 parts, bistrishydroxymethylpropane tetraacrylate 1-5 parts, pentaerythritol tetraacrylate 10-20 parts, mica powder 5-10 parts, 3-aminopropyl triethoxysilane 1-2 parts, epichlorohydrin 0.1-1 part, amino-terminated polyamide amine 5-10 parts, photoinitiator 1-2 parts, dispersant 1-3 parts, active diluent 1-2 parts, silicone defoamer 1-2 parts, mildewcide 0.5-1.5 parts, thixotropic agent 0.1-1 parts, pigment 5-15 parts, kaolin 1-5 parts, polyethylene wax 5-10 parts, and water 1-5 parts.

[0007] Preferably, the photoinitiator is at least one of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone.

[0008] Preferably, the dispersant is sodium polyacrylate.

[0009] Preferably, the reactive diluent is trimethylolpropane triacrylate.

[0010] Preferably, the mildewcide is sodium dehydroacetate.

[0011] Preferably, the thixotropic agent is sodium carboxymethyl cellulose.

[0012] Preferably, the pigment is at least one of carbon black, phthalocyanine blue, iron oxide red.

[0013] The preparation method of the modified filler environment-friendly ink comprises the following steps: S1, mica powder is added to a sodium hydroxide solution, stirred at 40-50℃ for 1-2h, filtered, washed, vacuum dried, added to an ethanol aqueous solution, 3-aminopropyl triethoxysilane is added, the pH of the system is adjusted to 8-10 using triethylamine, reflux stirring is carried out at 60-70℃ for 1-2h, epichlorohydrin is added and stirred for 10-30min, amino-terminated polyamide amine is added and stirred for 2-5h, filtered, washed, vacuum dried to obtain a functionalized mica filler; S2, the water-based acrylic emulsion, polyurethane acrylate prepolymer, functionalized mica filler, and bistrimethylolpropane tetraacrylate are uniformly mixed, and photoinitiator, dispersant, reactive diluent, silicone antifoaming agent, mildewcide, and thixotropic agent are added and uniformly mixed to obtain a premix; S3, pigments, kaolin, polyethylene wax, and water are added to pentaerythritol tetraacrylate (a multifunctional acrylate crosslinking monomer) and uniformly mixed, ground, and the premix is added and uniformly mixed.

[0014] Preferably, in S1, the mass fraction of the sodium hydroxide solution is 20-30%, and the mass fraction of the ethanol aqueous solution is 70-80%.

[0015] Preferably, in S3, the grinding is performed to a fineness of <20μm.

[0016] Beneficial effects: The silane group of 3-aminopropyl triethoxysilane is combined on the surface of mica, the amino-terminated polyamide amine dendrimer is grafted under the cooperation of epichlorohydrin, a three-dimensional network structure is formed, the functionalized mica filler not only has a flexible segment, but also has a large steric hindrance, the stability of the mica filler is significantly improved, and the settlement and agglomeration are effectively inhibited.

[0017] The application utilizes functional mica and pentaerythritol tetraacrylate to be compounded, which can not only ensure the flexibility of the ink, effectively adjust the viscosity of the ink, but also make the system more easily form a continuous network structure in the process of ultraviolet curing, effectively enhance the stability and adhesion strength.

[0018] The application uniformly disperses the functional mica in the system, which can effectively avoid the agglomeration and stratification phenomenon caused by traditional physical mixing, so that the ink realizes uniform flow during coating process, the functional mica filler is compatible with the water-based acrylic emulsion and polyurethane acrylate prepolymer, the interface bonding force between the filler and the resin matrix is significantly enhanced, thereby improving the adhesion strength of the printed film layer.

[0019] The obtained ink has good dispersion stability, good flexibility and excellent adhesion after curing, and the preparation method is simple, so that it has excellent application prospect in printing ink. DETAILED DESCRIPTION

[0020] The application will be further described below in combination with specific examples.

[0021] Example 1

[0022] An environmental-friendly ink of modified filler, raw materials of which include: 20g of water-based acrylic emulsion, 10g of polyurethane acrylate prepolymer, 1g of ditrimethylolpropane tetraacrylate, 10g of pentaerythritol tetraacrylate, 5g of mica powder, 1g of 3-aminopropyl triethoxysilane, 0.1g of epichlorohydrin, 5g of amino-terminated polyamide amine, 1g of photoinitiator 369, 1g of polyacrylic acid sodium salt, 1g of trimethylolpropane triacrylate, 1g of defoaming agent BYK-024, 0.5g of sodium dehydroacetate, 0.1g of sodium carboxymethyl cellulose, 5g of pigment, 1g of kaolin, 5g of polyethylene wax, and 1g of water.

[0023] The preparation method of the above-mentioned environmental-friendly ink of modified filler includes the following steps: S1, the mica powder is added into 1g of 20% mass fraction sodium hydroxide solution, stirred at 40℃ for 1h, filtered, washed, vacuum dried, added into 40g of 70% mass fraction ethanol aqueous solution, 3-aminopropyl triethoxysilane is added, the pH of the system is adjusted to 8-10 by using triethylamine, stirred at 60℃ for 1h, epichlorohydrin is added and stirred for 10min, amino-terminated polyamide amine is added and stirred for 2h, filtered, washed, vacuum dried to obtain the functional mica filler; S2, the water-based acrylic emulsion, the polyurethane acrylate prepolymer, the functional mica filler and the ditrimethylolpropane tetraacrylate are uniformly mixed, the photoinitiator 369, the polyacrylic acid sodium salt, the trimethylolpropane triacrylate, the defoaming agent BYK-024, the sodium dehydroacetate and the sodium carboxymethyl cellulose are added and uniformly mixed to obtain a premix; S3, add pigments, kaolin, polyethylene wax, and water to the pentaerythritol tetraacrylate, mix uniformly, and grind on a three-roll mill to a fineness of <20 μm, add the premix and mix uniformly.

[0024] Example 2

[0025] An environmentally-friendly ink modified filler, raw materials of which include: 40 g of water-based acrylic emulsion, 20 g of polyurethane acrylate prepolymer, 5 g of ditrimethylolpropane tetraacrylate, 20 g of pentaerythritol tetraacrylate, 10 g of mica powder, 2 g of 3-aminopropyl triethoxysilane, 1 g of epichlorohydrin, 10 g of amino-terminated polyamide amine, 2 g of photoinitiator 369, 3 g of polyacrylic acid sodium salt, 2 g of trimethylolpropane triacrylate, 2 g of defoamer BYK-024, 1.5 g of sodium dehydroacetate, 1 g of sodium carboxymethyl cellulose, 15 g of pigments, 5 g of kaolin, 10 g of polyethylene wax, and 5 g of water.

[0026] A preparation method of the above-mentioned environmentally-friendly ink modified filler, comprising the following steps: S1, add mica powder to 3 g of 30% sodium hydroxide solution, stir at a temperature of 50°C for 2 h, filter, wash, and vacuum dry, add to 60 g of 80% ethanol aqueous solution, add 3-aminopropyl triethoxysilane, adjust the pH of the system to 8-10 using triethylamine, reflux and stir at a temperature of 70°C for 2 h, add epichlorohydrin and stir for 30 min, add amino-terminated polyamide amine and stir for 5 h, filter, wash, and vacuum dry to obtain functionalized mica filler; S2, mix the water-based acrylic emulsion, polyurethane acrylate prepolymer, and functionalized mica filler uniformly, add photoinitiator 369, polyacrylic acid sodium salt, trimethylolpropane triacrylate, defoamer BYK-024, sodium dehydroacetate, and sodium carboxymethyl cellulose under light protection to obtain a premix; S3, add pigments, kaolin, polyethylene wax, and water to the pentaerythritol tetraacrylate, mix uniformly, and grind on a three-roll mill to a fineness of <20 μm, add the premix and mix uniformly.

[0027] Example 3

[0028] A modified filler environment-friendly ink, raw materials of which include: water-based acrylic emulsion 25g, polyurethane acrylate prepolymer 18g, ditrimethylolpropane tetraacrylate 2g, pentaerythritol tetraacrylate 18g, mica powder 7g, 3-aminopropyl triethoxysilane 1.8g, epichlorohydrin 0.3g, amino-terminated polyamide 9g, photoinitiator 369 1.2g, polyacrylic acid sodium salt 2.5g, trimethylolpropane triacrylate 1.2g, defoamer BYK-024 1.8g, sodium dehydroacetate 0.8g, sodium carboxymethyl cellulose 0.7g, pigment 8g, kaolin 4g, polyethylene wax 7g, water 4g.

[0029] The preparation method of the modified filler environment-friendly ink, comprising the following steps: S1, add mica powder to 1.5g of 28% sodium hydroxide solution, stir at 42℃ for 100min, filter, wash, vacuum dry, add to 45g of 77% ethanol aqueous solution, add 3-aminopropyl triethoxysilane, adjust the system pH to 8-10 with triethylamine, reflux and stir at 62℃ for 100min, add epichlorohydrin and stir for 15min, add amino-terminated polyamide and stir for 4h, filter, wash, vacuum dry to obtain functionalized mica filler; S2, mix water-based acrylic emulsion, polyurethane acrylate prepolymer, functionalized mica filler, ditrimethylolpropane tetraacrylate uniformly, add photoinitiator 369, polyacrylic acid sodium salt, trimethylolpropane triacrylate, defoamer BYK-024, sodium dehydroacetate, sodium carboxymethyl cellulose uniformly in the dark to obtain a premix; S3, add pigment, kaolin, polyethylene wax, water to pentaerythritol tetraacrylate and mix uniformly, grind on a three-roll mill to a fineness of <20μm, add the premix and mix uniformly.

[0030] Example 4

[0031] A modified filler environment-friendly ink, raw materials of which include: water-based acrylic emulsion 35g, polyurethane acrylate prepolymer 12g, ditrimethylolpropane tetraacrylate 4g, pentaerythritol tetraacrylate 12g, mica powder 9g, 3-aminopropyl triethoxysilane 1.2g, epichlorohydrin 0.7g, amino-terminated polyamide 7g, 2-methyl-1-(4-methylthio phenyl)-2-morpholino-1-propanone 1.8g, polyacrylic acid sodium salt 1.5g, trimethylolpropane triacrylate 1.8g, defoamer BYK-024 1.2g, sodium dehydroacetate 1.2g, sodium carboxymethyl cellulose 0.3g, pigment 12g, kaolin 2g, polyethylene wax 9g, water 2g.

[0032] The preparation method of the modified filler environment-friendly ink, comprising the following steps: S1, mica powder is added to 2.5g of 22% sodium hydroxide solution, stirred at 48℃ for 80min, filtered, washed, vacuum dried, added to 55g of 73% ethanol aqueous solution, 3-aminopropyl triethoxysilane is added, the system pH is adjusted to 8-10 with triethylamine, stirred at 68℃ for 80min, epoxy chloropropane is added and stirred for 25min, amino-terminated polyamide amine is added and stirred for 3h, filtered, washed, vacuum dried to obtain functionalized mica filler; S2, the water-based acrylic emulsion, polyurethane acrylate prepolymer, functionalized mica filler, double trimethylolpropane tetraacrylate are mixed uniformly, 2-methyl-1-(4-methylthio phenyl)-2-morpholinyl-1-propanone, polyacrylic acid sodium salt, trimethylolpropane triacrylate, defoamer BYK-024, sodium dehydroacetate, sodium carboxymethyl cellulose are added uniformly to obtain a premix under light protection; S3, pigment, kaolin, polyethylene wax, water are added to the pentaerythritol tetraacrylate and mixed uniformly, ground on a three-roll mill to a fineness of <20μm, and the premix is added and mixed uniformly.

[0033] Example 5

[0034] An environmentally friendly ink modified filler, which raw materials include: water-based acrylic emulsion 30g, polyurethane acrylate prepolymer 15g, double trimethylolpropane tetraacrylate 3g, pentaerythritol tetraacrylate 15g, mica powder 8g, 3-aminopropyl triethoxysilane 1.5g, epoxy chloropropane 0.5g, amino-terminated polyamide amine 8g, 2-methyl-1-(4-methylthio phenyl)-2-morpholinyl-1-propanone 1.5g, polyacrylic acid sodium salt 2g, trimethylolpropane triacrylate 1.5g, defoamer BYK-024 1.5g, sodium dehydroacetate 1g, sodium carboxymethyl cellulose 0.5g, pigment 10g, kaolin 3g, polyethylene wax 8g, water 3g.

[0035] The preparation method of the above-mentioned modified filler environmentally friendly ink, comprising the following steps: S1, mica powder is added to 2g of 25% sodium hydroxide solution, stirred at 45℃ for 90min, filtered, washed, vacuum dried, added to 50g of 75% ethanol aqueous solution, 3-aminopropyl triethoxysilane is added, the system pH is adjusted to 8-10 with triethylamine, stirred at 65℃ for 90min, epoxy chloropropane is added and stirred for 20min, amino-terminated polyamide amine is added and stirred for 3.5h, filtered, washed, vacuum dried to obtain functionalized mica filler; S2, the aqueous acrylic emulsion, polyurethane acrylate prepolymer, functional mica filler, double trimethylolpropane tetraacrylate is mixed uniformly, 2-methyl-1-(4-methylthio phenyl)-2-morpholinyl-1-propanone, polyacrylic acid sodium salt, trimethylolpropane triacrylate, defoamer BYK-024, sodium dehydroacetic acid, sodium carboxymethyl cellulose is mixed uniformly to get premix; S3, the pigment, kaolin, polyethylene wax, water is added to pentaerythritol tetraacrylate and mixed uniformly, and is ground on a three-roll mill to a fineness of <20 μm, and is mixed uniformly with the premix.

[0036] Comparative Example 1

[0037] A modified filler environment-friendly ink, raw materials of which include: 30g of aqueous acrylic emulsion, 15g of polyurethane acrylate prepolymer, 3g of double trimethylolpropane tetraacrylate, 15g of pentaerythritol tetraacrylate, 18g of mica powder, 1.5g of 2-methyl-1-(4-methylthio phenyl)-2-morpholinyl-1-propanone, 2g of polyacrylic acid sodium salt, 1.5g of trimethylolpropane triacrylate, 1.5g of defoamer BYK-024, 1g of sodium dehydroacetic acid, 0.5g of sodium carboxymethyl cellulose, 10g of pigment, 3g of kaolin, 8g of polyethylene wax, and 3g of water.

[0038] The preparation method of the modified filler environment-friendly ink, comprising the following steps: S1, the aqueous acrylic emulsion, polyurethane acrylate prepolymer, functional mica filler, double trimethylolpropane tetraacrylate is mixed uniformly, 2-methyl-1-(4-methylthio phenyl)-2-morpholinyl-1-propanone, polyacrylic acid sodium salt, trimethylolpropane triacrylate, defoamer BYK-024, sodium dehydroacetic acid, sodium carboxymethyl cellulose is mixed uniformly to get premix; S2, the pigment, kaolin, polyethylene wax, water is added to pentaerythritol tetraacrylate and mixed uniformly, and is ground on a three-roll mill to a fineness of <20 μm, and is mixed uniformly with the premix.

[0039] Comparative Example 2

[0040] A modified filler environment-friendly ink, raw materials of which include: 30g of aqueous acrylic emulsion, 15g of polyurethane acrylate prepolymer, 3g of double trimethylolpropane tetraacrylate, 15g of pentaerythritol tetraacrylate, 10g of mica powder, 8g of amino-terminated polyamide amine, 1.5g of 2-methyl-1-(4-methylthio phenyl)-2-morpholinyl-1-propanone, 2g of polyacrylic acid sodium salt, 1.5g of trimethylolpropane triacrylate, 1.5g of defoamer BYK-024, 1g of sodium dehydroacetic acid, 0.5g of sodium carboxymethyl cellulose, 10g of pigment, 3g of kaolin, 8g of polyethylene wax, and 3g of water.

[0041] The preparation method of the modified filler environment-friendly ink comprises the following steps: S1, mica powder is added into 2g of 25% sodium hydroxide solution, stirred at 45℃ for 90min, filtered, washed, vacuum dried, added into 50g of 75% ethanol aqueous solution, filtered, washed, vacuum dried to obtain functionalized mica filler; S2, the water-based acrylic emulsion, polyurethane acrylate prepolymer, functionalized mica filler, double-trihydroxymethyl propane tetraacrylate, and amino-terminated polyamide amine are uniformly mixed, 2-methyl-1-(4-methylthio phenyl)-2-morpholino-1-propanone, sodium polyacrylate, trimethylolpropane triacrylate, defoaming agent BYK-024, sodium dehydroacetate, and sodium carboxymethyl cellulose are uniformly mixed to obtain a premix; S3, the pigment, kaolin, polyethylene wax, and water are uniformly mixed in the pentaerythritol tetraacrylate, and the mixture is ground on a three-roll mill to a fineness of <20μm, and then the premix is uniformly mixed.

[0042] The environment-friendly inks obtained in Example 5 and Comparative Examples 1-2 are placed in a centrifuge at a rotation speed of 2000r / min, and after centrifugation at 25℃ and 50℃ for 30min and 60min respectively, whether stratification occurs is observed. If no change in appearance is observed, it is recorded as 0, and if turbidity, precipitate, or stratification is observed, it is recorded as ×. The results are shown in Table 1.

[0043] Table 1 Stability of environment-friendly inks of various groups

[0044] As shown in Table 1 above, the environment-friendly inks obtained in the present application are excellent in stability and thermal stability.

[0045] The environment-friendly inks obtained in Example 5 and Comparative Examples 1-2 are uniformly sprayed on the surface of aluminum foil paper (thickness 30μm) at room temperature, and completely cured using a photocuring machine (80W / cm 2 , 10cm from the light source).

[0046] The leveling property of the aluminum foil paper sample after complete curing and drying of the above surface ink is evaluated. The evaluation standard for leveling property is: the surface is flat, no water streaks, no sagging, and no fisheye, recorded as 0; any one or more of the following conditions occurs: uneven surface, water streaks, sagging, and fisheye, recorded as ×.

[0047] A 60mm long adhesive tape is adhered to the surface of the aluminum foil paper sample after complete curing and drying of the above surface ink, and the adhesive tape has no wrinkles. After the adhesive tape is pulled up vertically and uniformly for about 15s with a finger, the adhesion is evaluated by checking whether the sample is discolored after being pulled. If the sample is not discolored, it is recorded as 0; if the sample is discolored, it is recorded as ×.

[0048] The aluminum foil paper sample after complete curing and drying of the surface ink is folded at 180° to evaluate the flexibility, and after 50 times, whether the paper test surface is warped, peeled off or other phenomena are observed, if not, it is recorded as 0; if it appears, it is recorded as ×.

[0049] The results are shown in Table 2.

[0050] Table 2: The leveling property, adhesion and flexibility of the environmental protection ink after curing of each group

[0051] As shown in the above Table 2, the environmental protection ink obtained by the present application has high adhesion strength and good flexibility.

[0052] The reason for the above results is that the silane group of 3-aminopropyl triethoxysilane is combined on the surface of mica, and the grafted end amino polyamide amine dendrimer is combined under the cooperation of epichlorohydrin, forming a three-dimensional network structure, so that the functionalized mica filler not only has a flexible segment, but also has a large steric hindrance, which significantly improves the stability of the mica filler, effectively inhibits the sedimentation and agglomeration. The present application uses functionalized mica and pentaerythritol tetraacrylate to compound, which not only ensures the flexibility of the ink, effectively adjusts the viscosity of the ink, but also makes the system more easily form a continuous network structure during ultraviolet curing process, effectively enhances the stability and adhesion strength. The present application uniformly disperses the functionalized mica in the system, which can effectively avoid the agglomeration and stratification phenomenon caused by traditional physical mixing, so that the ink realizes uniform leveling during coating process. The functionalized mica filler has good compatibility with water-based acrylic emulsion and polyurethane acrylate prepolymer, which significantly enhances the interfacial bonding force between the filler and the resin matrix, thereby improving the adhesion strength of the printed film layer.

[0053] The above is only the preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto, any person skilled in the art can make equivalent replacement or change according to the technical solution and the inventive concept of the present application within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A modified filler environmentally friendly ink, characterized in that, The raw materials, by weight, include: 20-40 parts of water-based acrylic emulsion, 10-20 parts of polyurethane acrylate prepolymer, 1-5 parts of bis(trimethylolpropane)tetraacrylate, 10-20 parts of pentaerythritol tetraacrylate, 5-10 parts of mica powder, 1-2 parts of 3-aminopropyltriethoxysilane, 0.1-1 part of epichlorohydrin, 5-10 parts of amino-terminated polyamide amine, 1-2 parts of photoinitiator, 1-3 parts of dispersant, 1-2 parts of reactive diluent, 1-2 parts of silicone defoamer, 0.5-1.5 parts of mildew inhibitor, 0.1-1 part of thixotropic agent, 5-15 parts of pigment, 1-5 parts of kaolin, 5-10 parts of polyethylene wax, and 1-5 parts of water.

2. The modified filler environmentally friendly ink according to claim 1, characterized in that, The photoinitiator is at least one of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone and 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone.

3. The modified filler environmentally friendly ink according to claim 1, characterized in that, The dispersant is sodium polyacrylate.

4. The modified filler environmentally friendly ink according to claim 1, characterized in that, The reactive diluent is trimethylolpropane triacrylate.

5. The modified filler environmentally friendly ink according to claim 1, characterized in that, The antifungal agent is sodium dehydroacetate.

6. The modified filler environmentally friendly ink according to claim 1, characterized in that, The thixotropic agent is sodium carboxymethyl cellulose.

7. The modified filler environmentally friendly ink according to claim 1, characterized in that, The pigment is at least one of carbon black, phthalocyanine blue, and iron oxide red.

8. A method for preparing a modified filler-based environmentally friendly ink as described in any one of claims 1-7, characterized in that, Includes the following steps: S1. Add mica powder to sodium hydroxide solution, stir at 40-50℃ for 1-2 hours, filter, wash, vacuum dry, add to ethanol aqueous solution, add 3-aminopropyltriethoxysilane, adjust the pH of the system to 8-10 with triethylamine, reflux and stir at 60-70℃ for 1-2 hours, add epichlorohydrin and stir for 10-30 minutes, add terminal amino polyamide amine and stir for 2-5 hours, filter, wash, vacuum dry to obtain functionalized mica filler; S2. Mix the water-based acrylic emulsion, polyurethane acrylate prepolymer, functionalized mica filler, and bis(trimethylolpropane)tetraacrylate evenly, and add the photoinitiator, dispersant, reactive diluent, silicone defoamer, mildew inhibitor, and thixotropic agent in the dark and mix evenly to obtain a premix. S3. Add pigment, kaolin, polyethylene wax and water to pentaerythritol tetraacrylate (a polyfunctional acrylate crosslinking monomer), mix well, grind, and then add premix and mix well.

9. The method for preparing the modified filler environmentally friendly ink according to claim 8, characterized in that, In S1, the mass fraction of sodium hydroxide solution is 20-30%, and the mass fraction of ethanol aqueous solution is 70-80%.

10. The method for preparing the modified filler environmentally friendly ink according to claim 8, characterized in that, In S3, grind to a fineness of <20μm.

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