Plant-based water-based ink and preparation method thereof

Abstract

The invention discloses plant-based water-based ink and a preparation method thereof, and relates to the field of water-based ink. When the plant-based water-based ink is prepared, microcrystalline cellulose is subjected to formylation, then is grafted with 2-mercaptoethylamine and then is bonded with nano-silver to prepare modified cellulose; the preparation method comprises the following steps: reacting octamethylcyclotetrasiloxane, 2-methyl ester ethyl dimethoxy methylsilane and pentamethyldisiloxane, and grafting hydrazine hydrate to prepare modified silicone oil; uniformly mixing poly (butylene adipate), castor oil, isophorone diisocyanate and the modified silicone oil to obtain a modified polyurethane emulsion; the preparation method comprises the following steps: reacting aminomalonic acid with 3, 5-di-tert-butyl-4-hydroxybenzaldehyde, and uniformly mixing with carbon black powder and 1, 5-dihydroxy-3-pentanone to obtain modified carbon black; uniformly mixing the modified polyurethane emulsion, the color paste, the flatting agent and the modified cellulose to obtain the plant-based water-based ink. The prepared plant-based water-based ink has excellent antistatic property, wear resistance and durability.

Description

Technical Field

[0001] The present invention relates to the field of water-based inks, and specifically to a plant-based water-based ink and a preparation method thereof. Background Art

[0002] With the rapid development of China's economy, the stationery market is becoming increasingly prosperous. As a stationery product widely used in daily life, the market demand for marker pens has been increasing year by year. Marker pens are mainly used for drawing, marking, signing, etc., and have high requirements for the performance of inks, such as quick drying, wear resistance, bright color, etc. Traditional marker pen inks mostly use solvent-based polyurethane inks. Although they have good performance, they have environmental problems and cause certain harm to the environment and human health. Therefore, the present invention prepares a plant-based water-based ink with excellent wear resistance. Summary of the Invention

[0003] The purpose of the present invention is to provide a plant-based water-based ink and a preparation method thereof to solve the problems existing in the prior art.

[0004] To solve the above technical problems, the present invention provides the following technical solutions:

[0005] A plant-based water-based ink, which is obtained by mixing a modified polyurethane emulsion, a color paste, a leveling agent and a modified cellulose evenly.

[0006] As an optimization, the leveling agent model is Tegovin 450, from Dongguan Hongrui Chemical Co., Ltd.

[0007] As an optimization, the color paste is obtained by reacting aminomalonic acid with 3,5-di-tert-butyl-4-hydroxybenzaldehyde, mixing with carbon black powder and 1,5-dihydroxy-3-pentanone, and then grinding and formulating.

[0008] As an optimization, the carbon black powder model is BC6190, from Tianjin Baochi Chemical Technology Co., Ltd.

[0009] As an optimization, the modified polyurethane emulsion is obtained by mixing polybutylene adipate, castor oil, isophorone diisocyanate and modified silicone oil evenly.

[0010] As an optimization, the polybutylene adipate model is PBA1000, from Xuzhou Yihuiyang New Materials Co., Ltd.

[0011] As an optimization, the castor oil is from Shandong Yunxin New Materials Technology Co., Ltd.

[0012] As an optimization, the modified cellulose is prepared by aldehyde group modification of microcrystalline cellulose, grafting 2-mercaptoethylamine and then bonding with nano silver.

[0013] As an optimization, the microcrystalline cellulose is of the CP2020 type and is from Shanxi Jinyang Pharmaceutical Excipients Co., Ltd.

[0014] As an optimization, the modified silicone oil is prepared by reacting octamethylcyclotetrasiloxane, 2-methoxycarbonylethyl dimethoxymethylsilane and pentamethyldisiloxane and then grafting hydrazine hydrate.

[0015] A preparation method of a plant-based water-based ink, comprising the following preparation steps:

[0016] (1) Mix microcrystalline cellulose and deionized water at a mass ratio of 1:(55 - 65), add

[0017] a hydrochloric acid solution with a concentration of 0.09 - 0.11 mol / L to adjust the pH to 2 - 4, stir in the dark at 25 - 35°C and 300 - 400 rpm for 10 - 20 min, add sodium periodate with a mass 0.9 - 1.1 times that of the microcrystalline cellulose, continue to stir in the dark for 7 - 9 h and then filter, wash with deionized water 3 - 5 times, freeze-dry for 11 - 13 h to obtain aldehyde-group cellulose; mix the aldehyde-group cellulose, 2-mercaptoethylamine and absolute ethanol at a mass ratio of 1:(2 - 4):(15 - 25), stir at 45 - 55°C and 300 - 400 rpm for 4 - 6 h, naturally cool to room temperature and then filter, wash with deionized water 3 - 5 times, dry at 55 - 65°C for 7 - 9 h to obtain pre-modified cellulose; mix the pre-modified cellulose and a nano-silver ethanol dispersion with a mass fraction of 35% - 45%, ultrasonically oscillate at 55 - 65°C for 25 - 35 min and then filter, wash with absolute ethanol 3 - 5 times, dry at 60 - 70°C for 8 - 10 h to obtain modified cellulose;

[0018] (2) Mix octamethylcyclotetrasiloxane, 2-methoxycarbonylethyl dimethoxymethylsilane and tetramethylammonium hydroxide silanolate at a mass ratio of 1:(1.3 - 1.5):(0.01 - 0.03), stir in a nitrogen atmosphere at 85 - 95°C and 100 - 200 rpm for 2 - 3 h, add pentamethyldisiloxane with a mass 0.1 - 0.3 times that of the octamethylcyclotetrasiloxane, raise the temperature to 95 - 105°C and continue to stir for 7 - 9 h, raise the temperature to 130 - 140°C at a rate of 10 - 20°C / min and continue to stir for 40 - 50 min, distill at 0.1 - 0.3 MPa for 1 - 2 h to obtain pre-modified silicone oil; mix the pre-modified silicone oil, hydrazine hydrate and ethanol at a mass ratio of 1:(1 - 2):(6 - 7), stir at 20 - 30°C and 300 - 400 rpm for 25 - 35 min, and carry out vacuum distillation to obtain modified silicone oil;

[0019] (3) Mix polybutylene adipate and castor oil in a mass ratio of 1:(0.4 - 0.5), add isophorone diisocyanate, and stir at 85 - 95 °C and 100 - 300 rpm for 2 - 4 h in a nitrogen atmosphere. Then add dimethylolpropionic acid in an amount of 0.07 - 0.08 times the mass of polybutylene adipate, cool down to 75 - 85 °C and continue stirring for 55 - 65 min. Next, add dibutyl dilaurate in an amount of 0.01 - 0.03 times the mass of polybutylene adipate, adjust the viscosity with acetone, cool down to 60 - 70 °C, add modified silicone oil in an amount of 0.01 - 0.05 times the mass of polybutylene adipate and chloroplatinic acid in an amount of 0.002 - 0.004 times the mass of polybutylene adipate, and continue stirring for 3 - 5 h. Then perform rotary evaporation at 35 - 45 °C for 30 - 50 min, add triethylamine in an amount of 0.056 - 0.058 times the mass of polybutylene adipate to neutralize for 30 - 40 min, add deionized water in an amount of 3 - 4 times the mass of polybutylene adipate, and stir at 600 - 800 rpm for 30 - 40 min to obtain a modified polyurethane emulsion;

[0020] (4) Mix aminomalonic acid, 3,5 - di - tert - butyl - 4 - hydroxybenzaldehyde and absolute ethanol in a mass ratio of 1:(1 - 3):(8 - 9), stir at 45 - 55 °C and 100 - 200 rpm for 4 - 6 h in a nitrogen atmosphere, and perform rotary evaporation to obtain an antioxidant; Mix carbon black powder, antioxidant, 1,5 - dihydroxy - 3 - pentanone and toluene in a mass ratio of 1:(1.1 - 1.3):(0.3 - 0.5):(9 - 11), stir at 75 - 85 °C and 200 - 400 rpm for 2 - 4 h, then filter, wash with absolute ethanol 3 - 5 times, and dry at 60 - 70 °C for 8 - 10 h to obtain modified carbon black;

[0021] (5) Grind the modified carbon black with a ball mill for 7 - 9 h, mix it with absolute ethanol in a mass ratio of 1:(8 - 10), and perform ultrasonic dispersion for 1 - 3 h to obtain a color paste; Mix the modified polyurethane emulsion, color paste, leveling agent and modified cellulose in a mass ratio of 1:(0.3 - 0.5):(0.04 - 0.06):(0.03 - 0.05), and disperse at 1500 - 2500 r / min for 25 - 35 min to obtain a plant - based water - based ink.

[0022] As an optimization, the reaction equation of the modified cellulose in step (1) is:

[0023]

[0024] As an optimization, the reaction equation of the modified silicone oil in step (2) is:

[0025]

[0026] As an optimization, the molar amount of isophorone diisocyanate added in step (3) is 0.49 times the sum of the molar amounts of hydroxyl groups contained in polybutylene adipate, castor oil and dimethylolpropionic acid.

[0027] As an optimization, the reaction equation of the modified polyurethane emulsion in step (3) is:

[0028]

[0029] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0030] When preparing the plant-based waterborne ink, the present invention aldehyde-modifies microcrystalline cellulose, grafts 2-mercaptoethylamine thereon and then bonds nano-silver to obtain modified cellulose; reacts octamethylcyclotetrasiloxane, 2-methoxyethyl dimethoxymethylsilane and pentamethyldisiloxane and then grafts hydrazine hydrate to obtain modified silicone oil; mixes polybutylene adipate, castor oil, isophorone diisocyanate and modified silicone oil to obtain a modified polyurethane emulsion; reacts aminomalonic acid and 3,5-di-tert-butyl-4-hydroxybenzaldehyde and then mixes with carbon black powder and 1,5-dihydroxy-3-pentanone to obtain modified carbon black; then formulates the modified carbon black into a color paste, and mixes it with the modified polyurethane emulsion, leveling agent and modified cellulose to obtain the plant-based waterborne ink.

[0031] First, aldehyde-modify microcrystalline cellulose, graft 2-mercaptoethylamine thereon and then bond nano-silver to obtain modified cellulose; react octamethylcyclotetrasiloxane, 2-methoxyethyl dimethoxymethylsilane and pentamethyldisiloxane and then graft hydrazine hydrate to obtain modified silicone oil; graft 2-mercaptoethylamine on microcrystalline cellulose through Schiff base reaction, utilize the strong bonding effect of S-Ag to generate chemical adsorption on the surface of nano-silver, form an electron transfer path, and improve the antistatic property of the plant-based waterborne ink; graft a flexible organosiloxane long chain on the polyurethane main chain through hydrosilylation, reduce the friction coefficient and improve the wear resistance of the plant-based waterborne ink; at the same time, form hydrazide groups on the siloxane long chain to form a cross-linked network with the carbonyl groups on the modified carbon black, further improving the wear resistance of the plant-based waterborne ink.

[0032] Secondly, mix polybutylene adipate, castor oil, isophorone diisocyanate and modified silicone oil to obtain a modified polyurethane emulsion; react aminomalonic acid with 3,5-di-tert-butyl-4-hydroxybenzaldehyde, then mix with carbon black powder and 1,5-dihydroxy-3-pentanone to obtain modified carbon black; further prepare a color paste from the modified carbon black, and mix it with the modified polyurethane emulsion, a leveling agent and modified cellulose to obtain a plant-based waterborne ink; introduce castor oil as a plant-based component into the polyurethane main chain to improve the environmental friendliness of the plant-based waterborne ink; introduce hydrophilic groups by grafting dimethylolpropionic acid during the polyurethane synthesis process, use volatile triethylamine as a neutralizing agent, and form a slightly acidic environment as the amine volatilizes, promoting the formation of covalent carbon-nitrogen crosslinks between the carbonyl groups on the modified carbon black and the hydrazide groups on the silicone-oxygen long chain to improve the abrasion resistance of the plant-based waterborne ink; at the same time, the tert-butylphenol grafted on the modified carbon black can capture free radicals and prevent the oxidation of the polyurethane main chain, improving the durability of the plant-based waterborne ink. Detailed implementation manners

[0033] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0034] The raw materials used in the following examples and comparative examples are all commercially available:

[0035] The leveling agent model is BYK 450, from Dongguan Hongrui Chemical Co., Ltd.;

[0036] The polybutylene adipate model is PBA1000, from Xuzhou Yihuiyang New Materials Co., Ltd.;

[0037] The castor oil is from Shandong Yunxin New Materials Technology Co., Ltd.;

[0038] The carbon black powder model is BC6190, from Tianjin Baochi Chemical Technology Co., Ltd.;

[0039] The microcrystalline cellulose model is CP2020, from Shanxi Jinyang Pharmaceutical Excipients Co., Ltd.

[0040] In the following examples and comparative examples, the molar amount of isophorone diisocyanate added is 0.49 times the sum of the molar amounts of hydroxyl groups contained in polybutylene adipate, castor oil and dimethylolpropionic acid.

[0041] Example 1:

[0042] A preparation method of a plant-based waterborne ink, the preparation method of the plant-based waterborne ink includes the following preparation steps:

[0043] (1) Mix microcrystalline cellulose and deionized water at a mass ratio of 1:55, add a 0.09 mol / L hydrochloric acid solution to adjust the pH to 2, stir in the dark at 25 °C and 300 rpm for 20 min, add sodium periodate 0.9 times the mass of the microcrystalline cellulose, continue to stir in the dark for 9 h, then filter, wash 3 times with deionized water, and freeze-dry for 11 h to obtain aldehyde-functionalized cellulose; Mix the aldehyde-functionalized cellulose, 2-mercaptoethylamine, and absolute ethanol at a mass ratio of 1:2:15, stir at 45 °C and 300 rpm for 6 h, naturally cool to room temperature, then filter, wash 3 times with deionized water, and dry at 55 °C for 9 h to obtain pre-modified cellulose; Mix the pre-modified cellulose and a 34% mass fraction of nano-silver ethanol dispersion, ultrasonically oscillate at 55 °C for 35 min, then filter, wash 3 times with absolute ethanol, and dry at 60 °C for 10 h to obtain modified cellulose;

[0044] (2) Mix octamethylcyclotetrasiloxane, 2-methoxycarbonylethyl dimethoxymethylsilane, and tetramethylammonium hydroxide silanolate at a mass ratio of 1:1.3:0.01, stir in a nitrogen atmosphere at 85 °C and 100 rpm for 3 h, add pentamethyldisiloxane 0.1 times the mass of the octamethylcyclotetrasiloxane, raise the temperature to 95 °C and continue stirring for 9 h, raise the temperature to 130 °C at a rate of 10 °C / min and continue stirring for 50 min, distill at 0.1 MPa for 2 h to obtain pre-modified silicone oil; Mix the pre-modified silicone oil, hydrazine hydrate, and ethanol at a mass ratio of 1:1:6, stir at 20 °C and 300 rpm for 35 min, and carry out vacuum distillation to obtain modified silicone oil;

[0045] (3) Mix polybutylene adipate and castor oil at a mass ratio of 1:0.4, add isophorone diisocyanate, stir in a nitrogen atmosphere at 85 °C and 100 rpm for 4 h, add dimethylolpropionic acid 0.07 times the mass of the polybutylene adipate, cool to 75 °C and continue stirring for 65 min, add dibutyltin dilaurate 0.01 times the mass of the polybutylene adipate, add acetone to adjust the viscosity, cool to 60 °C, add modified silicone oil 0.01 times the mass of the polybutylene adipate and chloroplatinic acid 0.002 times the mass of the polybutylene adipate, continue stirring for 5 h, carry out rotary evaporation at 35 °C for 50 min, add triethylamine 0.056 times the mass of the polybutylene adipate to neutralize for 40 min, add deionized water 3 times the mass of the polybutylene adipate, and stir at 600 rpm for 40 min to obtain a modified polyurethane emulsion;

[0046] (4) Mix aminomalonic acid, 3,5 - di - tert - butyl - 4 - hydroxybenzaldehyde, and absolute ethanol in a mass ratio of 1:1:8, stir at 45 °C and 100 rpm for 6 h in a nitrogen atmosphere, and obtain an antioxidant by rotary evaporation; mix carbon black powder, the antioxidant, 1,5 - dihydroxy - 3 - pentanone, and toluene in a mass ratio of 1:1.1:0.3:9, stir at 75 °C and 200 rpm for 4 h in a nitrogen atmosphere, then filter, wash 3 times with absolute ethanol, and dry at 60 °C for 10 h to obtain modified carbon black;

[0047] (5) Grind the modified carbon black with a ball mill for 7 h, mix it with absolute ethanol in a mass ratio of 1:8, and perform ultrasonic dispersion for 1 h to obtain a color paste; mix the modified polyurethane emulsion, the color paste, a leveling agent, and modified cellulose in a mass ratio of 1:0.3:0.04:0.03, and disperse at 1500 r / min for 35 min to obtain a plant - based water - based ink.

[0048] Example 2:

[0049] A preparation method of a plant - based water - based ink, the preparation method of the plant - based water - based ink includes the following preparation steps:

[0050] (1) Mix microcrystalline cellulose and deionized water in a mass ratio of 1:60, add a 0.11 mol / L hydrochloric acid solution to adjust the pH to 3, stir in the dark at 30 °C and 350 rpm for 15 min, add sodium periodate with a mass 1 time that of the microcrystalline cellulose, continue to stir in the dark for 8 h, then filter, wash 4 times with deionized water, and freeze - dry for 12 h to obtain aldehyde - functionalized cellulose; mix the aldehyde - functionalized cellulose, 2 - mercaptoethylamine, and absolute ethanol in a mass ratio of 1:3:20, stir at 50 °C and 350 rpm for 5 h, naturally cool to room temperature, then filter, wash 4 times with deionized water, and dry at 60 °C for 8 h to obtain pre - modified cellulose; mix the pre - modified cellulose and a 40% mass fraction of nano - silver ethanol dispersion, perform ultrasonic oscillation at 60 °C for 30 min, then filter, wash 4 times with absolute ethanol, and dry at 65 °C for 9 h to obtain modified cellulose;

[0051] (2) Mix octamethylcyclotetrasiloxane, 2 - methoxycarbonylethyl dimethoxymethylsilane, and tetramethylammonium hydroxide silanolate in a mass ratio of 1:1.4:0.02, stir at 90 °C and 150 rpm for 2.5 h in a nitrogen atmosphere, add pentamethyldisiloxane with a mass 0.2 times that of the octamethylcyclotetrasiloxane, raise the temperature to 100 °C and continue to stir for 8 h, raise the temperature to 135 °C at a rate of 15 °C / min and continue to stir for 45 min, distill at 0.2 MPa for 1.5 h to obtain pre - modified silicone oil; mix the pre - modified silicone oil, hydrazine hydrate, and ethanol in a mass ratio of 1:1.5:6.5, stir at 25 °C and 350 rpm for 30 min, and perform vacuum distillation to obtain modified silicone oil;

[0052] (3) Mix polybutylene adipate and castor oil in a mass ratio of 1:0.45, add isophorone diisocyanate, and stir at 90 °C and 200 rpm for 3 h in a nitrogen atmosphere. Add dimethylolpropionic acid in an amount 0.075 times the mass of polybutylene adipate, cool down to 80 °C and continue stirring for 60 min. Add dibutyl dilaurate in an amount 0.02 times the mass of polybutylene adipate, add acetone to adjust the viscosity, cool down to 65 °C, add modified silicone oil in an amount 0.03 times the mass of polybutylene adipate and chloroplatinic acid in an amount 0.003 times the mass of polybutylene adipate, continue stirring for 4 h, perform rotary evaporation at 40 °C for 40 min, add triethylamine in an amount 0.057 times the mass of polybutylene adipate to neutralize for 35 min, add deionized water in an amount 3.5 times the mass of polybutylene adipate, and stir at 700 rpm for 35 min to obtain a modified polyurethane emulsion;

[0053] (4) Mix aminomalonic acid, 3,5 - di - tert - butyl - 4 - hydroxybenzaldehyde and absolute ethanol in a mass ratio of 1:2:8.5, stir at 50 °C and 150 rpm for 5 h in a nitrogen atmosphere, and perform rotary evaporation to obtain an antioxidant; Mix carbon black powder, antioxidant, 1,5 - dihydroxy - 3 - pentanone and toluene in a mass ratio of 1:1.2:0.4:10, stir at 80 °C and 300 rpm for 3 h in a nitrogen atmosphere and then filter, wash 4 times with absolute ethanol, and dry at 65 °C for 9 h to obtain modified carbon black;

[0054] (5) Grind the modified carbon black with a ball mill for 8 h, mix it with absolute ethanol in a mass ratio of 1:9, and perform ultrasonic dispersion for 2 h to obtain a color paste; Mix the modified polyurethane emulsion, color paste, leveling agent and modified cellulose in a mass ratio of 1:0.4:0.05:0.04, and disperse at 2000 r / min for 30 min to obtain a plant - based water - borne ink.

[0055] Example 3:

[0056] A preparation method of a plant - based water - borne ink, the preparation method of the plant - based water - borne ink includes the following preparation steps:

[0057] (1) Mix microcrystalline cellulose and deionized water at a mass ratio of 1:65, add a 0.11 mol / L hydrochloric acid solution to adjust the pH to 4, stir in the dark at 35 °C and 400 rpm for 10 min, add sodium periodate 1.1 times the mass of the microcrystalline cellulose, continue to stir in the dark for 7 h, then filter, wash 5 times with deionized water, and freeze-dry for 13 h to obtain aldehyde-functionalized cellulose; Mix the aldehyde-functionalized cellulose, 2-mercaptoethylamine, and absolute ethanol at a mass ratio of 1:4:25, stir at 55 °C and 400 rpm for 4 h, naturally cool to room temperature, then filter, wash 5 times with deionized water, and dry at 65 °C for 7 h to obtain pre-modified cellulose; Mix the pre-modified cellulose and a 45% mass fraction of nano-silver ethanol dispersion, filter after ultrasonic oscillation at 65 °C for 25 min, wash 5 times with absolute ethanol, and dry at 70 °C for 8 h to obtain modified cellulose;

[0058] (2) Mix octamethylcyclotetrasiloxane, 2-methoxycarbonylethyl dimethoxymethylsilane, and tetramethylammonium hydroxide silanolate at a mass ratio of 1:1.5:0.03, stir in a nitrogen atmosphere at 95 °C and 200 rpm for 2 h, add pentamethyldisiloxane 0.3 times the mass of the octamethylcyclotetrasiloxane, raise the temperature to 105 °C and continue stirring for 7 h, raise the temperature to 140 °C at a rate of 20 °C / min and continue stirring for 40 min, distill at 0.3 MPa for 1 h to obtain pre-modified silicone oil; Mix the pre-modified silicone oil, hydrazine hydrate, and ethanol at a mass ratio of 1:2:7, stir at 30 °C and 400 rpm for 25 min, and perform vacuum distillation to obtain modified silicone oil;

[0059] (3) Mix polybutylene adipate and castor oil at a mass ratio of 1:0.5, add isophorone diisocyanate, stir in a nitrogen atmosphere at 95 °C and 300 rpm for 2 h, add dimethylolpropionic acid 0.08 times the mass of the polybutylene adipate, lower the temperature to 85 °C and continue stirring for 55 min, add dibutyltin dilaurate 0.03 times the mass of the polybutylene adipate, add acetone to adjust the viscosity, lower the temperature to 70 °C, add modified silicone oil 0.05 times the mass of the polybutylene adipate and chloroplatinic acid 0.004 times the mass of the polybutylene adipate, continue stirring for 3 h, perform rotary evaporation at 45 °C for 30 min, add triethylamine 0.058 times the mass of the polybutylene adipate to neutralize for 30 min, add deionized water 4 times the mass of the polybutylene adipate, and stir at 800 rpm for 30 min to obtain a modified polyurethane emulsion;

[0060] (4) Mix aminomalonic acid, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, and absolute ethanol in a mass ratio of 1:3:9, stir at 55 °C and 200 rpm for 4 h in a nitrogen atmosphere, and obtain an antioxidant by rotary evaporation; mix carbon black powder, antioxidant, 1,5-dihydroxy-3-pentanone, and toluene in a mass ratio of 1:1.3:0.5:11, stir at 85 °C and 400 rpm for 2 h in a nitrogen atmosphere, then filter, wash 5 times with absolute ethanol, and dry at 70 °C for 8 h to obtain modified carbon black;

[0061] (5) Grind the modified carbon black with a ball mill for 9 h, mix it with absolute ethanol in a mass ratio of 1:10, and ultrasonically disperse for 3 h to obtain a color paste; mix the modified polyurethane emulsion, color paste, leveling agent, and modified cellulose in a mass ratio of 1:0.5:0.06:0.05, and disperse at 2500 r / min for 25 min to obtain a plant-based waterborne ink.

[0062] Comparative Example 1:

[0063] The preparation method of the plant-based waterborne ink in Comparative Example 1 is only different from that in Example 2 in steps (1) and (5). Omit step (1). Modify step (3) to: Grind the modified carbon black with a ball mill for 8 h, mix it with absolute ethanol in a mass ratio of 1:9, and ultrasonically disperse for 2 h to obtain a color paste; mix the modified polyurethane emulsion, color paste, leveling agent, and microcrystalline cellulose in a mass ratio of 1:0.4:0.05:0.04, and disperse at 2000 r / min for 30 min to obtain a plant-based waterborne ink. The remaining steps are the same as those in Example 2.

[0064] Comparative Example 2:

[0065] The preparation method of the plant-based waterborne ink in Comparative Example 2 is only different from that in Example 2 in steps (2) and (3). Omit step (2). Modify step (3) to: Mix polybutylene adipate and castor oil in a mass ratio of 1:0.45, add isophorone diisocyanate, stir at 90 °C and 200 rpm for 3 h in a nitrogen atmosphere, add dimethylolpropionic acid in an amount of 0.075 times the mass of polybutylene adipate, cool to 80 °C and continue stirring for 60 min, add dibutyl dilaurate in an amount of 0.02 times the mass of polybutylene adipate, adjust the viscosity with acetone, cool to 65 °C and continue stirring for 4 h, rotary evaporate at 40 °C for 40 min, add triethylamine in an amount of 0.0165 times the mass of polybutylene adipate to neutralize for 35 min, add deionized water in an amount of 3.5 times the mass of polybutylene adipate, and stir at 700 rpm for 35 min to obtain a modified polyurethane emulsion. The remaining steps are the same as those in Example 2.

[0066] Comparative Example 3:

[0067] The preparation method of the plant-based waterborne ink of Comparative Example 3 is only different from that of Example 2 in steps (4) and (5). Step (4) is omitted. Step (5) is modified as follows: Grind carbon black powder with a ball mill for 8 h, mix it with absolute ethanol at a mass ratio of 1:9, and ultrasonically disperse for 2 h to obtain a color paste; Mix the modified polyurethane emulsion, color paste, leveling agent and modified cellulose at a mass ratio of 1:0.4:0.05:0.04, and disperse at 2000 r / min for 30 min to obtain a plant-based waterborne ink. The remaining steps are the same as those in Example 2.

[0068] Test Example

[0069] 1. Antistatic property

[0070] Test method: Coat the plant-based waterborne inks obtained in each example and comparative example on a PET substrate by screen printing according to GB / T 1410-2006, let it stand at 60 °C for 30 min, and measure the surface resistance with an SL-030 surface resistance tester.

[0071] 2. Abrasion resistance

[0072] Test method: Use the plant-based waterborne inks obtained in each example and comparative example to prepare an ink layer to be tested with a PET film as the test substrate according to GB / T 13217-2009, let it stand at 60 °C for 30 min, take it out and cool it to room temperature, wipe the surface of the printed sample forcefully with a cotton ball dipped in deionized water, and record the peeling situation of the ink layer.

[0073] 3. Durability

[0074] Test method: Use the plant-based waterborne inks obtained in each example and comparative example to prepare an ink layer to be tested with a PET film as the test substrate according to GB / T 13217-2009, let it stand at 60 °C for 30 min, take it out and cool it to room temperature, paste the tape on the surface of the ink layer and press it tightly, quickly tear off the tape while keeping the tape at a right angle to the ink layer, line a 2 mm wide grid paper under the ink layer, observe the number of grids of the remaining ink layer and the ink layer peeled off by the tape, and calculate the ink layer adhesion fastness A1 = number of grids of ink layer / (number of grids of ink layer + number of grids of peeled-off ink layer) * 100%; Use a PET film as the test substrate to prepare an ink layer to be tested, let it stand at 60 °C for 30 min, take it out and cool it to room temperature, age it under a xenon lamp for 24 h, calculate the ink layer adhesion fastness A2, and calculate the durability rate = A2 / A1 * 100%.

[0075] Table 1 below gives the analysis results of the antistatic, abrasion resistance and durability of the plant-based waterborne inks of Examples 1-3 and Comparative Examples 1-3 of the present invention.

[0076] Table 1

[0077]

[0078] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 1, it can be found that the plant-based waterborne ink prepared by the present invention has good antistatic, wear-resistant and durable properties.

[0079] Comparative Example 1: Unmodified microcrystalline cellulose; by comparison, the surface resistance of Examples 1, 2, and 3 is lower than that of Comparative Example 1, indicating that 2-mercaptoethylamine is grafted onto microcrystalline cellulose through a Schiff base reaction, and chemical adsorption occurs on the surface of nano-silver by the strong bonding effect of S-Ag, forming an electron transfer path to improve the antistatic property of the plant-based waterborne ink.

[0080] Comparative Example 2: Unmodified grafted silicone oil; by comparison, the ink layers of Examples 1, 2, and 3 do not peel off compared with Comparative Example 2, indicating that a flexible organosiloxane long chain is grafted onto the polyurethane main chain through hydrosilylation to reduce the friction coefficient and improve the wear resistance of the plant-based waterborne ink; at the same time, hydrazide groups are formed on the siloxane long chain to form a crosslinked network with the carbonyl groups on the modified carbon black, further improving the wear resistance of the plant-based waterborne ink.

[0081] Comparative Example 3: Unmodified carbon black powder; by comparison, the ink layers of Examples 1, 2, and 3 do not peel off and have a high durability rate compared with Comparative Example 3, indicating that hydrophilic groups are introduced by grafting dimethylolpropionic acid during the synthesis of polyurethane, and volatile triethylamine is used as a neutralizing agent. As the amine volatilizes, a slightly acidic environment is formed to promote the formation of covalent carbon-nitrogen crosslinks between the carbonyl groups on the modified carbon black and the hydrazide groups on the siloxane long chain, improving the wear resistance of the plant-based waterborne ink; at the same time, the tert-butylphenol grafted on the modified carbon black can capture free radicals and prevent the oxidation of the polyurethane main chain, improving the durability of the plant-based waterborne ink.

[0082] The specific embodiments described above further elaborate on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above description is only the specific embodiments of the present invention and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A plant-based water-based ink, characterized in that: The plant-based water-based ink is obtained by mixing modified polyurethane emulsion, color paste, leveling agent and modified cellulose; The color paste is prepared by mixing aminomalonic acid and 3,5-di-tert-butyl-4-hydroxybenzaldehyde with carbon black powder and 1,5-dihydroxy-3-pentanone, and then grinding. The modified polyurethane emulsion is obtained by uniformly mixing polybutylene adipate, castor oil, isophorone diisocyanate and modified silicone oil; The modified cellulose is prepared by aldehyde-forming microcrystalline cellulose, grafting 2-mercaptoethylamine and then bonding nanosilver; The modified silicone oil is prepared by reacting octamethylcyclotetrasiloxane, 2-methoxyethyldimethoxymethylsilane and pentamethyldisiloxane and then grafting hydrazine hydrate.

2. A method for preparing a plant-based water-based ink, characterized in that: The method comprises the following preparation steps: (1) mixing microcrystalline cellulose and deionized water, adding hydrochloric acid solution, stirring in the dark, adding sodium periodate, stirring, filtering, washing and drying to obtain aldehyded cellulose; mixing aldehyded cellulose, 2-mercaptoethylamine and anhydrous ethanol, stirring, cooling, filtering, washing and drying to obtain pre-modified cellulose; The pre-modified cellulose and the nano-silver ethanol dispersion are subjected to ultrasonic vibration, filtered, washed and dried to obtain modified cellulose; (2) octamethylcyclotetrasiloxane, 2-methoxyethyldimethoxymethylsilane and tetramethylammonium hydroxide siliconate are mixed and stirred, pentamethyldisiloxane is added, the temperature is raised and stirred, the temperature is raised and stirred, and distillation is performed to obtain pre-modified silicone oil; the pre-modified silicone oil, hydrazine hydrate and ethanol are mixed and stirred, and vacuum distillation is performed to obtain modified silicone oil; (3) polybutylene adipate and castor oil are mixed, isophorone diisocyanate is added, dimethylol propionic acid is added in a nitrogen atmosphere, the temperature is lowered and stirred, dibutyl dilaurate and acetone are added, the temperature is lowered, modified silicone oil and chloroplatinic acid are added, stirring is continued, rotary evaporation is performed, triethylamine is added, deionized water is added, and stirring is performed to obtain a modified polyurethane emulsion; (4) mixing aminomalonic acid, 3,5-di-tert-butyl-4-hydroxybenzaldehyde and anhydrous ethanol, stirring in a nitrogen atmosphere, and rotary evaporating to obtain an antioxidant; mixing carbon black powder, antioxidant, 1,5-dihydroxy-3-pentanone and toluene, stirring in a nitrogen atmosphere, filtering, washing and drying to obtain modified carbon black; (5) Grinding the modified carbon black with a ball mill, mixing with anhydrous ethanol, and ultrasonically dispersing to obtain a color paste; mixing the modified polyurethane emulsion, the color paste, the leveling agent, and the modified cellulose, and dispersing to obtain a plant-based water-based ink.

3. The method for preparing a plant-based water-based ink according to claim 2, characterized in that: The preparation process of the modified cellulose in step (1) is as follows: pre-modified cellulose and a nano-silver ethanol dispersion with a mass fraction of 35% to 45% are subjected to ultrasonic oscillation at 55 to 65° C. for 25 to 35 minutes, filtered, washed with anhydrous ethanol for 3 to 5 times, and dried at 60 to 70° C. for 8 to 10 hours to obtain modified cellulose; The preparation process of the pre-modified cellulose is as follows: aldehyded cellulose, 2-mercaptoethylamine and anhydrous ethanol are mixed in a mass ratio of 1:(2-4):(15-25), stirred at 45-55° C. and 300-400 rpm for 4-6 hours, naturally cooled to room temperature and then filtered, washed with deionized water for 3-5 times, and dried at 55-65° C. for 7-9 hours to obtain the pre-modified cellulose; The preparation process of the aldehyded cellulose is as follows: microcrystalline cellulose and deionized water are mixed at a mass ratio of 1:(55-65), 0.09-0.11 mol / L hydrochloric acid solution is added to adjust the pH to 2-4, stirring at 25-35° C. and 300-400 rpm in the dark for 10-20 min, adding sodium periodate 0.9-1.1 times the mass of the microcrystalline cellulose, stirring in the dark for 7-9 h, filtering, washing with deionized water for 3-5 times, and freeze-drying for 11-13 h to obtain the aldehyded cellulose.

4. The method for preparing a plant-based water-based ink according to claim 2, characterized in that: The preparation process of the modified silicone oil in step (2) is as follows: pre-modified silicone oil, hydrazine hydrate and ethanol are mixed in a mass ratio of 1:(1-2):(6-7), stirred at 20-30° C. and 300-400 rpm for 25-35 min, and distilled under reduced pressure to obtain modified silicone oil; The preparation process of the pre-modified silicone oil is as follows: octamethylcyclotetrasiloxane, 2-methoxyethyldimethoxymethylsilane and tetramethylammonium hydroxide silicon alkoxide are mixed in a mass ratio of 1:(1.3-1.5):(0.01-0.03), stirred for 2-3 hours at 85-95° C. and 100-200 rpm in a nitrogen atmosphere, pentamethyldisiloxane with a mass of 0.1-0.3 times that of octamethylcyclotetrasiloxane is added, the temperature is raised to 95-105° C. and stirring is continued for 7-9 hours, the temperature is raised to 130-140° C. at a speed of 10-20° C. / min and stirring is continued for 40-50 minutes, and distilled at 0.1-0.3 MPa for 1-2 hours to obtain the pre-modified silicone oil.

5. The method for preparing a plant-based water-based ink according to claim 2, characterized in that: The preparation process of the modified polyurethane emulsion in step (3) is as follows: polybutylene adipate and castor oil are mixed in a mass ratio of 1:(0.4-0.5), isophorone diisocyanate is added, and the mixture is stirred for 2-4 hours at 85-95° C. and 100-300 rpm in a nitrogen atmosphere, dimethylol propionic acid is added in an amount of 0.07-0.08 times the mass of polybutylene adipate, the mixture is cooled to 75-85° C. and stirred for 55-65 minutes, dibutyl dilaurate is added in an amount of 0.01-0.03 times the mass of polybutylene adipate, and acetone is added to adjust the viscosity. Cooling to 60-70° C., adding modified silicone oil in an amount of 0.01-0.05 times the mass of polybutylene adipate and chloroplatinic acid in an amount of 0.002-0.004 times the mass of polybutylene adipate, continuing stirring for 3-5 hours, rotary evaporation at 35-45° C. for 30-50 minutes, adding triethylamine in an amount of 0.056-0.058 times the mass of polybutylene adipate for neutralization for 30-40 minutes, adding deionized water in an amount of 3-4 times the mass of polybutylene adipate, stirring at 600-800 rpm for 30-40 minutes, and obtaining a modified polyurethane emulsion; The molar amount of the added isophorone diisocyanate is 0.49 times the sum of the molar amounts of hydroxyl groups contained in polybutylene adipate, castor oil and dimethylol propionic acid.

6. The method for preparing a plant-based water-based ink according to claim 2, characterized in that: The preparation process of the modified carbon black in step (4) is as follows: carbon black powder, antioxidant, 1,5-dihydroxy-3-pentanone and toluene are mixed in a mass ratio of 1:(1.1-1.3):(0.3-0.5):(9-11), stirred for 2-4 hours at 75-85° C. and 200-400 rpm in a nitrogen atmosphere, filtered, washed with anhydrous ethanol for 3-5 times, and dried at 60-70° C. for 8-10 hours to obtain modified carbon black; The preparation process of the antioxidant is as follows: aminomalonic acid, 3,5-di-tert-butyl-4-hydroxybenzaldehyde and anhydrous ethanol are mixed in a mass ratio of 1:(1-3):(8-9), stirred in a nitrogen atmosphere at 45-55° C. and 100-200 rpm for 4-6 hours, and rotary evaporated to obtain the antioxidant.

7. The method for preparing a plant-based water-based ink according to claim 2, characterized in that: The preparation process of the plant-based water-based ink in step (5) is as follows: the modified polyurethane emulsion, the color paste, the leveling agent and the modified cellulose are mixed in a mass ratio of 1: (0.3-0.5): (0.04-0.06): (0.03-0.05), and dispersed at 1500-2500 r / min for 25-35 min to obtain the plant-based water-based ink; The preparation process of the color paste is as follows: grinding the modified carbon black with a ball mill for 7 to 9 hours, mixing with anhydrous ethanol at a mass ratio of 1:(8 to 10), and ultrasonically dispersing for 1 to 3 hours to obtain the color paste.

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