A heat-resistant, non-sticky and low-brittle water-based matte ink and its preparation method

Abstract

The present application discloses a heat-resistant and non-tacky low-brittle water-based matte ink and a preparation method thereof. The heat-resistant and non-tacky low-brittle water-based matte ink comprises the following raw materials in parts by mass: 20-30 parts of a waterborne polyurethane-acrylate polymer, 10-15 parts of a waterborne acrylate emulsion, 1-4 parts of ammonia water, 8-14 parts of a pigment, 4-8 parts of a polyethylene glycol toughening agent, 2-6 parts of a dispersant, 3-9 parts of an auxiliary agent, 2-6 parts of a matting powder, 5-10 parts of ethanol, and 15-25 parts of deionized water; the polyethylene glycol toughening agent molecule contains a benzene ring and a flexible carbon chain. The addition of a small molecule toughening agent can improve the crosslinking density and rigidity of the water-based matte ink, and solve the problems that the water-based matte ink is prone to back tackiness at high temperatures and becomes brittle at low temperatures.

Description

Technical Field

[0001] This application relates to the field of water-based inks, and in particular to a heat-resistant tacky and low-brittle water-based matte ink and a preparation method thereof. Background Art

[0002] Water-based inks use water as the main solvent and water-based resins as binders. Water-based resins have good solubility in water and can be stably dispersed. Compared with oil-based inks, water-based inks have almost no emissions of volatile organic compounds and have the green characteristics of being environmentally friendly and non-toxic, which exactly meet the higher requirements of consumers for packaging inks. As a kind of water-based ink, water-based matte ink not only has the excellent performance characteristics of water-based ink, but also forms a paint film with a soft luster, which can bring a fresh and comfortable feeling, and is widely used in the printing and decoration industries.

[0003] However, as a kind of water-based ink, water-based matte ink also has the common defects of water-based inks. In particular, the film layer will show a certain degree of reverse tackiness at high temperatures and is prone to embrittlement at low temperatures. Summary of the Invention

[0004] To solve the problems that water-based matte ink is prone to reverse tackiness at high temperatures and embrittlement at low temperatures, this application provides a heat-resistant tacky and low-brittle water-based matte ink and a preparation method thereof.

[0005] In the first aspect, this application provides a heat-resistant tacky and low-brittle water-based matte ink, which includes the following raw materials in parts by mass: 20 - 30 parts of waterborne polyurethane-acrylate polymer, 10 - 15 parts of waterborne acrylate emulsion, 1 - 4 parts of ammonia water, 8 - 14 parts of pigment, 4 - 8 parts of polyethylene glycol toughening agent, 2 - 6 parts of dispersant, 3 - 9 parts of auxiliary agent, 2 - 6 parts of matting powder, 5 - 10 parts of ethanol, and 15 - 25 parts of deionized water; the polyethylene glycol toughening agent molecule contains a benzene ring and a flexible carbon chain.

[0006] Preferably, the pigment is one or more of phthalocyanine blue, iron oxide yellow, permanent red, benzidine yellow, and titanium dioxide.

[0007] Preferably, the dispersant is a combination of one or more of polyoxyethylene alkylphenol ether, polycarboxylate, and sodium lignosulfonate.

[0008] Preferably, the auxiliary agent is a leveling agent and an antifoaming agent.

[0009] Preferably, the leveling agent is one of polyether-modified silicone and organosilicon acrylate.

[0010] Preferably, the antifoaming agent is one of emulsion-type polysiloxane and polyether-modified organosilicon defoaming agent.

[0011] The polyethylene glycol toughening agent contains a benzene ring and a flexible carbon chain. On the one hand, the benzene ring can adjust the rigidity of the water-based matte ink and improve the reverse sticking phenomenon of the water-based matte ink. On the other hand, the flexible carbon chain of the polyethylene glycol toughening agent can be inserted between the molecular chains of the water-based polyurethane-acrylate polymer and the acrylate, reducing the force between the molecular chains, thereby enhancing the impact strength of the water-based matte ink at low temperature, improving the low-temperature performance of the water-based matte ink, and not being prone to embrittlement at low temperature.

[0012] Preferably, the raw materials of the polyethylene glycol toughening agent include polyethylene glycol and 3-phenylpropionic acid with a molar ratio of (9-12):(5-8), and the polyethylene glycol toughening agent is prepared by an esterification reaction of the polyethylene glycol and 3-phenylpropionic acid.

[0013] More preferably, the molar ratio of polyethylene glycol to 3-phenylpropionic acid is 10:6.7.

[0014] Preferably, the molecular weight of the polyethylene glycol is 400-800.

[0015] Preferably, the preparation steps of the polyethylene glycol toughening agent are as follows: heat the aqueous solution to 60-80 °C, add polyethylene glycol and 3-phenylpropionic acid, and add a catalyst. Keep the solution temperature at 60-80 °C, stir and mix. After reacting for 1-2 h, filter, wash, dry, and grind to obtain the polyethylene glycol toughening agent.

[0016] Preferably, the catalyst is concentrated sulfuric acid with a mass fraction of 98%.

[0017] By adopting the above technical solution, 3-phenylpropionic acid is bonded to polyethylene glycol through an esterification reaction, so that the benzene ring is grafted onto the polyethylene glycol molecular chain, adjusting the rigidity of the water-based matte ink while reducing the force between the molecular chains. The molecular weight of polyethylene glycol is selected to be 400-800. On the one hand, when the molecular weight of polyethylene glycol is too small, the flexible chain segment of the prepared polyethylene glycol toughening agent is too short to reduce the force between the polymer molecular chains. On the other hand, when the molecular weight of polyethylene glycol is greater than 800, the prepared polyethylene glycol toughening agent is difficult to enter between the polymer molecular chains, and the effect of reducing the force between the molecular chains cannot be achieved. Polyethylene glycol with a molecular weight between 400 and 800 can effectively interpenetrate between the molecular chains of the water-based polyurethane-acrylate polymer and the acrylate, improving both the high-temperature reverse sticking phenomenon of the water-based matte ink and the low-temperature performance of the water-based matte ink, and not being prone to embrittlement at low temperature.

[0018] Preferably, the water-based polyurethane-acrylate polymer is an interpenetrating network polymer of a polyurethane emulsion and a polyacrylate emulsion. The water-based polyurethane-acrylate polymer includes the following raw materials in parts by mass: 18-22 parts of diisocyanate, 11-16 parts of diol, and 20-30 parts of acrylate monomer.

[0019] Preferably, the preparation steps of the aqueous polyurethane-acrylate polymer are as follows:

[0020] Synthesis of aqueous polyurethane: Under the protection of inert gas, a chain extender and a catalyst are added to a mixed solution of diisocyanate and diol, and a reaction premix is obtained through a chain extension reaction; a crosslinking agent is added to the reaction premix, mixed evenly, and a polyurethane solution is obtained through reaction; the polyurethane solution is added to an aqueous solution and an aqueous polyurethane emulsion is obtained through an emulsification reaction;

[0021] Synthesis of aqueous polyurethane-acrylate interpenetrating network: An acrylate monomer and an emulsifier are added to the aqueous polyurethane emulsion, mixed evenly, and a swelling reaction is carried out to obtain a reaction crude mixture; an initiator is added to the reaction crude mixture, stirred and mixed, and the aqueous polyurethane-acrylate polymer is obtained through reaction.

[0022] Preferably, the diisocyanate includes one or a combination of several of hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane dimethylene diisocyanate, and tetramethyl dimethylene diisocyanate.

[0023] Preferably, the diol includes one or a combination of several of polyethylene adipate glycol, polytetrahydrofuran glycol, and polyethylene oxide glycol.

[0024] Preferably, the chain extender includes one or a combination of several of ethylene glycol, 1,2-propanediol, 1,4-butanediol, and trimethylolpropane.

[0025] Preferably, the catalyst includes one of dibutyltin dilaurate, triethylamine, ethylenediamine, and triethylenediamine.

[0026] Preferably, the crosslinking agent includes one of trimethylolpropane, diethylenetriamine, and triethylenetetramine.

[0027] Preferably, the acrylate monomer includes an acrylate hard monomer and an acrylate soft monomer; the acrylate hard monomer includes one or a combination of several of methyl methacrylate, methyl acrylate, and ethyl methacrylate; the acrylate soft monomer includes one or a combination of several of acrylic acid, butyl acrylate, isooctyl acrylate, n-butyl methacrylate, and tert-butyl acrylate.

[0028] Preferably, the emulsifier includes one or a combination of several of sodium dodecyl sulfate, polyoxyethylene lauryl phenol ether, sodium dodecylbenzenesulfonate, ethoxylated alkylphenol sulfate amine, and disodium alkyl oxy diphenyl sulfonate.

[0029] Preferably, the initiator includes one of azobisisobutyronitrile, potassium persulfate, ammonium persulfate, and sodium bisulfite.

[0030] By adopting the above technical solution, an interpenetrating network polymer of polyurethane emulsion and polyacrylate emulsion is obtained. On the one hand, the interpenetrating network structure can enable the polyurethane-acrylate polymer to better exert the advantages of polyurethane emulsion and polyacrylate emulsion. At the same time, it also increases the crosslinking density and the adhesion to pigments and substrates, thereby improving the reverse sticking phenomenon of the water-based matte ink. On the other hand, the interpenetrating network structure of polyurethane emulsion and polyacrylate emulsion is beneficial to the insertion of polyethylene glycol toughening agent. The small molecular weight polyethylene glycol toughening agent can be evenly dispersed in the network structure of the water-based polyurethane-acrylate polymer, which can effectively reduce the intermolecular force between the molecular chains of the water-based polyurethane-acrylate polymer, achieving the improvement of the low-temperature performance of the water-based matte ink and not being brittle at low temperatures.

[0031] Preferably, the solid content of the water-based acrylate emulsion is 40-45%.

[0032] By adopting the above technical solution, controlling the solid content of the water-based acrylate emulsion can regulate the crosslinking density of the water-based acrylate emulsion and prevent insufficient crosslinking density. When the crosslinking density is too small, the viscosity of the ink decreases, the pigment ions are easy to precipitate, it is not easy to disperse in the ink, the stability of the system decreases, and the water-based matte ink is easy to reverse stick at high temperatures; when the crosslinking density is too large, the hardness of the ink is high, the film-forming performance decreases, and the film is prone to cracking.

[0033] Preferably, the matting powder is wax-treated silica, and the D50 particle size of the silica is 6 μm.

[0034] By adopting the above technical solution, the silica is micron-sized silica and is treated with wax, and no hard precipitation will occur after long-term placement, and the film formed by the water-based matte ink is evenly coated.

[0035] In the second aspect, the present application provides a preparation method of a heat-resistant and non-sticky low-brittle water-based matte ink, which includes the following steps: Premixing: Mix the deionized water, pigment and dispersant evenly to obtain a premixed liquid A; Mix the water-based polyurethane-acrylate polymer, water-based acrylate emulsion and ethanol evenly to obtain a premixed liquid B;

[0036] Mixing: Stir the premixed liquid A and the premixed liquid B evenly to obtain a mixed liquid A; Add matting powder, polyethylene glycol toughening agent and additives to the mixed liquid A, stir evenly to obtain a mixed liquid B; Add ammonia water to the mixed liquid B, stir evenly, and filter to obtain a heat-resistant and non-sticky low-brittle water-based matte ink.

[0037] In summary, the present application has the following beneficial effects:

[0038] 1. The polyethylene glycol toughening agent contains a benzene ring and a flexible carbon chain in its molecule. The benzene ring can increase the rigidity of the water-based matte ink and improve the high-temperature back tack phenomenon of the water-based matte ink; the flexible carbon chain can be inserted between the molecular chains of the polyurethane-acrylate polymer and the acrylate, reducing the interaction force between the molecular chains, improving the softness and elasticity of the polymer, thereby enhancing the impact strength of the water-based matte ink at low temperature, improving the low-temperature performance of the water-based matte ink, and not being brittle easily at low temperature.

[0039] 2. The polyurethane-acrylate polymer is an interpenetrating network polymer of a polyurethane emulsion and a polyacrylate emulsion. The interpenetrating network structure can better exert the performance advantages of the polyurethane emulsion and the polyacrylate emulsion, improve the crosslinking density of the water-based matte ink, thereby increasing the adhesion between the water-based matte ink and the substrate, and thus improving the high-temperature back tack phenomenon of the water-based matte ink. At the same time, the polyethylene glycol toughening agent is a small molecule toughening agent, which can penetrate into the network structure and play a more effective role, improving the low-temperature performance of the water-based matte ink. Specific embodiments

[0040] Preparation examples of polyethylene glycol toughening agent

[0041] Preparation example 1-1, a polyethylene glycol toughening agent, is prepared by the following method:

[0042] 800 g of deionized water is heated in a water bath to 70 °C. 400 g of polyethylene glycol with a molecular weight of 420 ± 20 and 100 g of 3-phenylpropionic acid are added to the deionized water, stirred and mixed to fully dissolve the polyethylene glycol and 3-phenylpropionic acid. 12 g of 98 wt% concentrated sulfuric acid is added dropwise to the mixed solution, and stirring is continued while maintaining the solution temperature at 70 °C for 2 h. Then, it is subjected to suction filtration, washing, drying and grinding to obtain the polyethylene glycol toughening agent.

[0043] Preparation example 1-2, a polyethylene glycol toughening agent, the difference from preparation example 1-1 is only that the addition amount of polyethylene glycol is 600 g, the addition amount of deionized water is 1000 g, and the addition amount of concentrated sulfuric acid is 18 g.

[0044] Preparation example 1-3, a polyethylene glycol toughening agent, the difference from preparation example 1-1 is only that the addition amount of 3-phenylpropionic acid is 200 g.

[0045] Preparation example 1-4, a polyethylene glycol toughening agent, the difference from preparation example 1-1 is only that the polyethylene glycol with a molecular weight of 420 ± 20 is replaced with an equal amount of polyethylene glycol with a molecular weight of 560 ± 20.

[0046] Preparation example 1-5, a polyethylene glycol toughening agent, the difference from preparation example 1-1 is only that the polyethylene glycol with a molecular weight of 420 ± 20 is replaced with an equal amount of polyethylene glycol with a molecular weight of 1000 ± 20.

[0047] Preparation Example of Polyurethane-Acrylate Polymer

[0048] Preparation Example 2-1, a polyurethane-acrylate polymer, was prepared according to the following method:

[0049] Synthesis of aqueous polyurethane: Take 5.4 kg of dimethylformamide. Under a nitrogen atmosphere, add 4 kg of isophorone diisocyanate and 2.6 kg of polytetrahydrofuran diol to the dimethylformamide, stir and mix to fully dissolve the isophorone diisocyanate and polytetrahydrofuran diol.

[0050] Raise the temperature of the mixed solution to 80 °C, add 0.12 kg of 1,5-butanediol and 0.012 kg of dibutyltin dilaurate to the solution, stir evenly, keep the temperature at 80 °C, after reacting for 1 h, add 0.24 kg of trimethylolpropane to the solution, continue to react for 1 h, after the reaction, lower the temperature to 40 °C, add 0.8 kg of acetone and 0.12 kg of triethylamine, and continue to stir for 20 min.

[0051] Then lower the temperature of the solution to room temperature, add 4.8 kg of deionized water to the solution for emulsification, and stir for 30 min to obtain an aqueous polyurethane emulsion.

[0052] Synthesis of aqueous polyurethane-acrylate interpenetrating network: At room temperature, take 4 kg of the prepared aqueous polyurethane emulsion, add 1 kg of methyl methacrylate and 1.5 kg of butyl acrylate to the polyurethane emulsion, stir evenly, then add 0.15 kg of sodium dodecyl sulfate and continue to stir. After 20 h, raise the temperature of the solution to 75 °C, add 0.12 kg of azobisisobutyronitrile, continue to stir, and after reacting for 6 h, obtain an aqueous polyurethane-acrylate polymer.

[0053] Preparation Example 2-2, a polyurethane-acrylate polymer, is different from Preparation Example 2-1 only in that the addition amount of isophorone diisocyanate is 3.6 kg, the addition amount of polytetrahydrofuran diol is 2.2 kg, the addition amount of methyl methacrylate is 0.8 kg, and the addition amount of butyl acrylate is 1.2 kg.

[0054] Preparation Example 2-3, a polyurethane-acrylate polymer, is different from Preparation Example 2-1 only in that the addition amount of isophorone diisocyanate is 4.4 kg, the addition amount of polytetrahydrofuran diol is 3.2 kg, the addition amount of methyl methacrylate is 1.2 kg, and the addition amount of butyl acrylate is 1.8 kg.

[0055] Preparation Example 2-4, a polyurethane-acrylate polymer, is different from Preparation Example 2-1 only in that the addition amount of methyl methacrylate is 1.5 kg and the addition amount of butyl acrylate is 2.0 kg.

[0056] Example

[0057] Example 1, a heat-resistant and non-sticky low-brittle water-based matte ink, the preparation steps are as follows:

[0058] Premixing: Add 1.2 kg of phthalocyanine blue and 0.4 kg of sodium lignosulfonate to 2 kg of deionized water, stir and mix for 15 min to obtain premixed liquid A. Take 2.6 kg of the waterborne polyurethane-acrylate polymer prepared in Preparation Example 2-1, 1.2 kg of a waterborne acrylate emulsion with a solid content of 43% ± 0.5% (model: Joncryl LV 7601), and 0.8 kg of ethanol for mixing, stir for 20 min to obtain premixed liquid B.

[0059] Mixing: Mix premixed liquid A and premixed liquid B, stir for 20 min to obtain mixed liquid A. Add 0.4 kg of matting powder (model: OK520), 0.6 kg of the polyethylene glycol toughening agent prepared in Preparation Example 1-1, 0.2 kg of polyether-modified silicone (model: BYK-333), and 0.3 kg of emulsion-type polysiloxane (model: Dehydran 1293) to mixed liquid A, stir and mix for 1 h to obtain mixed liquid B. Add 0.3 kg of an ammonia water solution containing 25 wt% - 28 wt% ammonia to mixed liquid B, stir and mix for 20 min, and then filter to obtain the heat-resistant and non-sticky low-brittle water-based matte ink.

[0060] Example 2, a heat-resistant and non-sticky low-brittle water-based matte ink, the preparation steps are as follows:

[0061] Premixing: Add 1.2 kg of phthalocyanine blue and 0.4 kg of sodium lignosulfonate to 1.8 kg of deionized water, stir and mix for 15 min to obtain premixed liquid A. Take 2.3 kg of the waterborne polyurethane-acrylate polymer prepared in Preparation Example 2-1, 1.5 kg of a waterborne acrylate emulsion with a solid content of 43% ± 0.5% (model: Joncryl LV 7601), and 1 kg of ethanol for mixing, stir for 20 min to obtain premixed liquid B.

[0062] Mixing: Mix premixed liquid A and premixed liquid B, stir for 20 min to obtain mixed liquid A. Add 0.4 kg of matting powder (model: OK520), 0.6 kg of the polyethylene glycol toughening agent prepared in Preparation Example 1-1, 0.2 kg of polyether-modified silicone (model: BYK-333), and 0.3 kg of emulsion-type polysiloxane (model: Dehydran 1293) to mixed liquid A, stir and mix for 1 h to obtain mixed liquid B. Add 0.3 kg of an ammonia water solution containing 25 wt% - 28 wt% ammonia to mixed liquid B, stir and mix for 20 min, and then filter to obtain the heat-resistant and non-sticky low-brittle water-based matte ink.

[0063] Example 3. An anti-thermal adhesion and low-brittle water-based matte ink is prepared as follows:

[0064] Premixing: Add 1.2 kg of phthalocyanine blue and 0.4 kg of sodium lignosulfonate to 2 kg of deionized water, stir and mix for 15 min to obtain premixed liquid A. Take 2.6 kg of the waterborne polyurethane-acrylate polymer prepared in Preparation Example 2-2, 1.2 kg of a waterborne acrylate emulsion with a solid content of 43% ± 0.5% (model: Joncryl LV 7601), and 0.8 kg of ethanol, mix them, and stir for 20 min to obtain premixed liquid B.

[0065] Mixing: Mix premixed liquid A and premixed liquid B, stir for 20 min to obtain mixed liquid A. Add 0.4 kg of matting powder (model: OK520), 0.4 kg of the polyethylene glycol toughening agent prepared in Preparation Example 1-1, 0.2 kg of polyether-modified silicone (model: BYK-333), and 0.3 kg of emulsion-type polysiloxane (model: Dehydran 1293) to mixed liquid A, stir and mix for 1 h to obtain mixed liquid B. Add 0.3 kg of an aqueous ammonia solution containing 25 wt% - 28 wt% ammonia to mixed liquid B, stir and mix for 20 min, and then filter to obtain the anti-thermal adhesion and low-brittle water-based matte ink.

[0066] Example 4. An anti-thermal adhesion and low-brittle water-based matte ink is prepared as follows:

[0067] Premixing: Add 1 kg of phthalocyanine blue and 0.3 kg of sodium lignosulfonate to 2 kg of deionized water, stir and mix for 15 min to obtain premixed liquid A. Take 2.6 kg of the waterborne polyurethane-acrylate polymer prepared in Preparation Example 2-3, 1.2 kg of a waterborne acrylate emulsion with a solid content of 43% ± 0.5% (model: Joncryl LV 7601), and 0.8 kg of ethanol, mix them, and stir for 20 min to obtain premixed liquid B.

[0068] Mixing: Mix premixed liquid A and premixed liquid B, stir for 20 min to obtain mixed liquid A. Add 0.5 kg of matting powder (model: OK520), 0.6 kg of the polyethylene glycol toughening agent prepared in Preparation Example 1-2, 0.3 kg of polyether-modified silicone (model: BYK-333), and 0.5 kg of emulsion-type polysiloxane (model: Dehydran 1293) to mixed liquid A, stir and mix for 1 h to obtain mixed liquid B. Add 0.2 kg of an aqueous ammonia solution containing 25 wt% - 28 wt% ammonia to mixed liquid B, stir and mix for 20 min, and then filter to obtain the anti-thermal adhesion and low-brittle water-based matte ink.

[0069] Example 5. An anti-thermal adhesion and low-brittle water-based matte ink, which is different from Example 1 only in that the waterborne polyurethane-acrylate polymer prepared in Preparation Example 2-1 is replaced with the waterborne polyurethane-acrylate polymers prepared in Preparation Examples 2-4 in equal amounts.

[0070] Example 6. An anti-thermal adhesion and low-brittle water-based matte ink, which is different from Example 1 only in that the addition amount of the waterborne polyurethane-acrylate polymer prepared in Preparation Example 2-1 is 1.5 kg, and the addition amount of the waterborne acrylate emulsion with the model number (Joncryl LV 7601) is 2.3 kg.

[0071] Example 7. An anti-thermal adhesion and low-brittle water-based matte ink, which is different from Example 1 only in that the polyethylene glycol toughening agent prepared in Preparation Example 1-3 is used to replace the polyethylene glycol toughening agent prepared in Preparation Example 1-1 in equal amounts.

[0072] Example 8. An anti-thermal adhesion and low-brittle water-based matte ink, which is different from Example 1 only in that the polyethylene glycol toughening agent prepared in Preparation Example 1-4 is used to replace the polyethylene glycol toughening agent prepared in Preparation Example 1-1 in equal amounts.

[0073] Example 9. An anti-thermal adhesion and low-brittle water-based matte ink, which is different from Example 1 only in that the polyethylene glycol toughening agent prepared in Preparation Example 1-5 is used to replace the polyethylene glycol toughening agent prepared in Preparation Example 1-1 in equal amounts.

[0074] Example 10. An anti-thermal adhesion and low-brittle water-based matte ink, which is different from Example 1 only in that the waterborne polyurethane grafted acrylate emulsion (model number: SC-21) is used to replace the waterborne polyurethane-acrylate polymer prepared in Preparation Example 2-1 in equal amounts.

[0075] Comparative Example

[0076] Comparative Example 1. An anti-thermal adhesion and low-brittle water-based matte ink, which is different from Example 1 only in that the polyethylene glycol toughening agent prepared in Preparation Example 1-1 is replaced with polyethylene glycol with a molecular weight of 420 ± 20 in equal amounts.

[0077] Comparative Example 2. An anti-thermal adhesion and low-brittle water-based matte ink, which is different from Example 1 only in that the polyethylene glycol toughening agent prepared in Preparation Example 1-1 is replaced with 3-phenylpropionic acid in equal amounts.

[0078] Comparative Example 3. An anti-thermal adhesion and low-brittle water-based matte ink, which is different from Example 1 only in that no polyethylene glycol toughening agent is added.

[0079] Performance Detection Test

[0080] 1. High-temperature anti-sticking performance test: The test was carried out in accordance with GB / T 13217.7-2009 "Test Methods for Adhesion Fastness of Liquid Ink". The adhesion fastness grade was defined as 0-5 levels. Level 0 indicated the best adhesion fastness, that is, the ink imprint on the printed substrate film was not adhered by the tape; Level 2.5 meant that 50% of the ink imprint on the printed substrate film was adhered by the tape; Level 5 meant that 100% of the ink imprint on the printed substrate film was adhered by the tape. Compare the adhesion fastness of the ink on the ink sample at room temperature and after being placed in a forced-air drying oven at 50°C for 1 h.

[0081] 2. High-temperature anti-sticking performance test: The water-based matte ink was placed in a forced-air drying oven at 50°C for 48 h, and the changes in viscosity and fineness before and after were compared. Among them, the viscosity test was carried out in accordance with GB / T 13217.4-2008 "Test Methods for Viscosity of Liquid Ink", and the fineness test was carried out in accordance with GB / T 13217.3-2008 "Test Methods for Fineness of Liquid Ink".

[0082] 3. Low-temperature embrittlement resistance performance test: After the ink was cured, it was placed in a constant-temperature oven at -20°C, and the time when cracks appeared in the ink was compared.

[0083] The test results are shown in Table 1:

[0084] Table 1 Test Results of High-temperature Anti-sticking and Low-temperature Embrittlement Resistance Performance

[0085]

[0086] Analysis of test results:

[0087] According to Table 1, combined with Example 1 and Comparative Example 1, it can be seen that the adhesion fastness of Comparative Example 1 decreased significantly compared with Example 1 after being placed at 50°C, and the changes in viscosity and fineness before and after were obvious. Cracks appeared in the ink after 2 h at -20°C, indicating that the thermal stability of Comparative Example 1 was poor compared with Example 1, and the high-temperature anti-sticking and low-temperature embrittlement resistance performance decreased significantly. The reason may be that the polyethylene glycol used in Comparative Example 1 did not undergo a bonding reaction with 3-phenylpropionic acid, and there was no benzene ring on the polyethylene glycol molecular chain to adjust the rigidity of the ink, resulting in poor adhesion of the ink and being more prone to anti-sticking at high temperatures. At the same time, the polyethylene glycol molecular chain had a large flexibility and a too high degree of cross-linking with the system, resulting in embrittlement at low temperatures.

[0088] Combined with Example 1 and Comparative Example 2, it can be seen that after being placed at 50 °C, the adhesion fastness of Comparative Example 2 decreased significantly compared with that of Example 1. The viscosity and fineness changed significantly before and after. After 1 h at -20 °C, cracks appeared in the ink, indicating that Comparative Example 2 had poor thermal stability compared with Example 1, and the low-temperature embrittlement performance decreased significantly. The reason may be that polyethylene glycol was not added in Comparative Example 2, and the system lost the support of the flexible chain segment of polyethylene glycol. The benzene ring structure in 3-phenylpropionic acid could only increase the rigidity of the ink to a certain extent, slightly improving the anti-blocking property, but it could not weaken the interaction between the molecular chains of the water-based resin, resulting in the ink being prone to embrittlement at low temperatures. At the same time, the benzene ring density in the system was large, which could not meet the requirements of structural bonding, resulting in a significant decrease in the adhesion fastness of the ink.

[0089] Combined with Example 1 and Comparative Example 3, it can be seen that after being placed at 50 °C, the adhesion fastness of Comparative Example 3 decreased significantly compared with that of Example 1. The viscosity and fineness changed significantly before and after. After 0.5 h at -20 °C, cracks appeared in the ink, indicating that Comparative Example 3 had poor thermal stability compared with Example 1, and the high-temperature anti-blocking and low-temperature embrittlement performances decreased significantly. It can be seen that the polyethylene glycol toughener can effectively improve the low-temperature performance of the water-based matte ink, effectively avoiding the embrittlement of the ink at low temperatures, and at the same time, to a certain extent, curbing the phenomenon of high-temperature anti-blocking of the ink. The reason may be that the polyethylene glycol toughener was not added in Comparative Example 3. Without the support of the rigid benzene ring structure and without small molecule compounds to weaken the interaction between the molecular chains of the water-based resin, the ink was prone to embrittlement at low temperatures and anti-blocking at high temperatures.

[0090] Combined with Example 1 and Example 10, it can be seen that after being placed at 50 °C, the adhesion fastness of Example 10 decreased compared with that of Example 1. The viscosity and fineness changed significantly before and after. After 3 h at -20 °C, cracks appeared in the ink, indicating that Example 10 had poor thermal stability compared with Example 1, and the high-temperature anti-blocking and low-temperature embrittlement performances decreased. The reason may be that the polyurethane-grafted polyacrylate emulsion was used in Example 10. Compared with the interpenetrating network structure of polyurethane and polyacrylate, the small molecule polyethylene glycol toughener could penetrate into the network. The effect of the polyethylene glycol toughener on the grafted compound was not as significant as that of the network structure, resulting in the ink using the polyurethane-grafted polyacrylate emulsion having inferior high-temperature anti-blocking and low-temperature embrittlement performances compared with the interpenetrating network structure of polyurethane and polyacrylate.

[0091] Combining Example 1, Example 8 and Example 9, it can be seen that the thermal stability, high-temperature anti-blocking and low-temperature embrittlement resistance of Example 8 do not change significantly compared with Example 1. However, after being placed at 50°C, the adhesion fastness of Example 9 decreases compared with Example 1, and the viscosity and fineness change significantly before and after. After 3 hours at -20°C, cracks appear in the ink, indicating that the thermal stability of Example 9 is poor compared with Example 1, and the high-temperature anti-blocking and low-temperature embrittlement resistance decrease. The reason may be that the polyethylene glycol toughening agent used in Example 8 is polyethylene glycol with a molecular weight of 560±20, within the required range of the polyethylene glycol molecular weight, while the polyethylene glycol toughening agent used in Example 9 is polyethylene glycol with a molecular weight of 1000±20, exceeding the required range. The molecular weight of polyethylene glycol in Example 9 increases significantly, resulting in difficulty for the polyethylene glycol toughening agent to enter the polyurethane-acrylate polymer, unable to effectively act between the molecular chains, and unable to exert the effect of the polyethylene glycol toughening agent, resulting in poor final thermal stability and decreased high-temperature anti-blocking and low-temperature embrittlement resistance.

[0092] Combining Example 1 and Example 7, it can be seen that after being placed at 50°C, the adhesion fastness of Example 7 decreases slightly compared with Example 1, and the viscosity and fineness change before and after. After 3.5 hours at -20°C, cracks appear in the ink, indicating that the thermal stability of Example 7 is slightly worse than that of Example 1, and the high-temperature anti-blocking and low-temperature embrittlement resistance also decrease. The reason may be that an excessive amount of 3-phenylpropionic acid is added to the polyethylene glycol in Example 7. A large number of rigid groups are connected to the polyethylene glycol molecular chain, increasing the rigidity of the toughening agent and decreasing the flexibility of the molecular chain, unable to meet the requirements of structural bonding, resulting in a significant change in the fineness of the ink and a decrease in the high-temperature anti-blocking and low-temperature embrittlement resistance.

[0093] Combining Example 1 and Example 6, it can be seen that after being placed at 50°C, the adhesion fastness of Example 6 decreases slightly compared with Example 1, and the viscosity and fineness change before and after. After 3.5 hours at -20°C, cracks appear in the ink, indicating that the thermal stability of Example 6 is slightly worse than that of Example 1, and the high-temperature anti-blocking and low-temperature embrittlement resistance also decrease. The reason may be that the addition amount of the polyurethane-acrylate polymer is reduced in Example 6, the water-based resin in the network structure of the ink decreases, the crosslinking density decreases, and the high-temperature anti-blocking performance of the ink decreases. At the same time, the reduction of the network structure reduces the action space of the small-molecule polyethylene glycol toughening agent, and the low-temperature embrittlement resistance of the ink also decreases.

[0094] Combining Example 1 and Example 5, it can be seen that after being placed at 50°C, the adhesion fastness of Example 5 slightly decreases compared to Example 1, the viscosity and fineness change before and after, and cracks appear in the ink after 3.5 h at -20°C, indicating that the thermal stability of Example 5 is slightly worse than that of Example 1, and the anti-high-temperature back tack and anti-low-temperature embrittlement properties also decrease. The reason may be that in Example 5, the content of acrylate in the polyurethane-acrylate polymer increases, and the polyurethane-acrylate polymer cannot effectively exert the interaction after the polymerization of polyurethane and acrylate. The water-based resin with a network structure in the ink also decreases, and the anti-high-temperature back tack performance of the ink decreases. At the same time, the reduction of the network structure reduces the action space of the small molecule polyethylene glycol toughening agent, and the anti-low-temperature embrittlement performance of the ink also decreases.

[0095] Combining Example 1 and Examples 2 to 4, it can be seen that there are no obvious changes in the thermal stability, anti-high-temperature back tack performance, and anti-low-temperature embrittlement performance of Examples 2 to 4 compared to Example 1. The reason may be that in Example 2, the addition amounts of the resin and the solvent are adjusted within a given range, in Example 3, the addition amount of the polyethylene glycol toughening agent is adjusted within a given range, and in Example 4, the addition amounts of various additives are adjusted within a given range, indicating that within the required range, adjusting the addition amounts of each component has no obvious effect on the anti-high-temperature back tack and anti-low-temperature embrittlement properties of the ink.

[0096] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A heat-resistant, non-sticky and low-brittle water-based matte ink, characterized in that, It includes raw materials in the following parts by mass: 20 - 30 parts of waterborne polyurethane - acrylate polymer, 10 - 15 parts of waterborne acrylate emulsion, 1 - 4 parts of ammonia water, 8 - 14 parts of pigment, 4 - 8 parts of polyethylene glycol toughening agent, 2 - 6 parts of dispersant, 3 - 9 parts of auxiliary agent, 2 - 6 parts of matting powder, 5 - 10 parts of ethanol, and 15 - 25 parts of deionized water; The polyethylene glycol toughening agent is prepared by the catalytic esterification reaction of polyethylene glycol and 3 - phenylpropionic acid. The molecular weight of polyethylene glycol is 400 - 800, and the molar ratio of polyethylene glycol to 3 - phenylpropionic acid is (9 - 12):(5 - 8); The waterborne polyurethane - acrylate polymer is an interpenetrating network polymer of polyurethane emulsion and polyacrylate emulsion, and contains a monomer combination of methyl methacrylate and butyl acrylate.

2. The water-based matte ink with heat resistance to adhesion and low brittleness according to claim 1, characterized in that The preparation steps of the polyethylene glycol toughening agent are as follows: Heat the aqueous solution to 60 - 80 °C, add polyethylene glycol and 3 - phenylpropionic acid, and add a catalyst. Keep the solution temperature at 60 - 80 °C, stir and mix. After reacting for 1 - 2 h, filter, wash, dry, and grind to obtain the polyethylene glycol toughening agent.

3. An anti-thermal adhesion and low-brittle water-based matte ink according to claim 1, characterized in that, The waterborne polyurethane - acrylate polymer includes raw materials in the following parts by mass: 18 - 22 parts of diisocyanate, 11 - 16 parts of diol, and 20 - 30 parts of acrylate monomer.

4. The water-based matte ink with heat resistance to sticking and low brittleness according to claim 3, characterized in that The preparation steps of the waterborne polyurethane - acrylate polymer are as follows: Synthesis of waterborne polyurethane: Under the protection of inert gas, add a chain extender and a catalyst to the mixed solution of diisocyanate and diol, and obtain a reaction premix through a chain extension reaction; add a cross - linker to the reaction premix, mix evenly, and react to obtain a polyurethane solution; add the polyurethane solution to an aqueous solution and obtain a waterborne polyurethane emulsion through an emulsification reaction; Synthesis of waterborne polyurethane - acrylate interpenetrating network: Add an acrylate monomer to the waterborne polyurethane emulsion, mix evenly, and carry out a swelling reaction to obtain a reaction crude mixture; add an initiator to the reaction crude mixture, stir and mix, and react to obtain the waterborne polyurethane - acrylate polymer.

5. An anti-thermal adhesion and low-brittle water-based matte ink according to claim 4, characterized in that The acrylate monomer includes acrylate hard monomer and acrylate soft monomer; the acrylate hard monomer includes one or a combination of several of methyl methacrylate, methyl acrylate, and ethyl methacrylate; the acrylate soft monomer includes one or a combination of several of butyl acrylate, isooctyl acrylate, n - butyl methacrylate, and tert - butyl acrylate.

6. The water-based matte ink with heat resistance to adhesion and low brittleness according to claim 1, characterized in that The solid content of the waterborne acrylate emulsion is 40 - 45%.

7. An anti-thermal adhesion and low-brittle water-based matte ink according to claim 1, characterized in that, The matting powder is silica treated with wax, and the D50 particle size of the silica is 6 μm.

8. The preparation method of a heat-resistant, non-sticky and low-brittle water-based matte ink according to any one of claims 1 to 7, characterized in that, It includes the following steps: Premixing: Mix the deionized water, pigment, and dispersant evenly to obtain premixed liquid A; mix the waterborne polyurethane - acrylate polymer, waterborne acrylate emulsion, and ethanol evenly to obtain premixed liquid B; Mixing: Stir premixed liquid A and premixed liquid B evenly to obtain mixed liquid A; Add matting powder, polyethylene glycol toughening agent, and auxiliary agent to mixed liquid A, stir evenly to obtain mixed liquid B; add ammonia water to mixed liquid B, stir evenly, and filter to obtain a heat - resistant, low - brittle, water - based matte ink.

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