A kind of green environmentally friendly high temperature resistant acrylic resin for ink and preparation method thereof

Abstract

The present invention relates to the technical field of acrylic resins, and discloses an acrylic resin for green, environmentally friendly, high temperature resistant ink and a preparation method thereof. The green, environmentally friendly, high temperature resistant ink acrylic resin comprises 100 parts by weight of vinyl monomer, 3-8 parts by weight of triazine-based styrene monomer, 0.7-0.8 parts by weight of initiator, and 0.5-3 parts by weight of zinc salt; the present invention introduces a styrene hard monomer structure and a triazine ring into the acrylic resin molecular chain, which is beneficial to improving the pencil hardness, mechanical properties and high temperature resistance of the paint film. The triazine-based styrene monomer contains an o-hydroxy Schiff base triazine structure, which has a strong coordination chelation effect with zinc ions, and can adsorb zinc ions in the acrylic resin molecular chain, which is not easy to wash and remove, and gives the paint film excellent antibacterial properties. The obtained acrylic resin has good practical applications in high temperature resistance and antibacterial inks.

Description

Technical Field

[0001] The invention relates to the technical field of acrylic resins, in particular to a green, environment-friendly, high-temperature-resistant acrylic resin for ink and a preparation method thereof. Background Art

[0002] Ink is widely used in the printing industry, electronics industry, food and drug packaging and other fields. Ink is mainly composed of binders, pigments, fillers, etc., among which the binder determines the performance of the ink. The preparation method of acrylic resin is simple, the film-forming property is good, and the weather resistance is excellent. It is widely used in ink binders. By adding different preparation monomers, acrylic resins with different properties can be obtained.

[0003] Antibacterial materials are functional materials with antibacterial and bactericidal properties, such as antibacterial inks, antibacterial plastics, antibacterial ceramics, etc. Common antibacterial agents include inorganic antibacterial agents such as zinc, silver, and titanium dioxide. Among them, zinc antibacterial agents are cheap and easy to obtain, green and pollution-free, and are widely used. The invention patent with announcement number CN101508863B discloses a nano-hydroxyapatite antibacterial coating and a preparation method thereof. Through the affinity between zinc oxide and zinc ions, and the complexation of zinc ions by hydroxyl groups on guar gum, the loss of zinc ions is reduced, and the sustained and stable antibacterial performance of acrylic emulsion coatings is significantly improved. Compared with the invention, the acrylic resin of the present invention has good antibacterial properties, and also has excellent mechanical properties and high temperature resistance. Summary of the invention

[0004] The invention solves the problem that the conventional acrylic resin for ink has poor high temperature resistance and no antibacterial property.

[0005] The technical solution of the present invention is: an acrylic resin for green, environmentally friendly, high temperature resistant ink, comprising 100 parts by weight of vinyl monomer, 3-8 parts by weight of triazine styrene monomer, 0.7-0.8 parts by weight of initiator, 1.8-2.5 parts by weight of neutralizer, 2-3 parts by weight of emulsifier, 0.5-3 parts by weight of zinc salt, 0.5-0.8 parts by weight of defoamer, and 0.3-0.5 parts by weight of leveling agent.

[0006] Preferably, the initiator is azobisisobutyronitrile.

[0007] Preferably, the preparation method of green, environmentally friendly, high temperature resistant acrylic resin for ink comprises: adding vinyl monomer, triazine styrene monomer, and emulsifier to water, heating to 70-80°C in a nitrogen atmosphere, adding initiator, stirring and reacting for 40-60 minutes, and then adding vinyl monomer, triazine styrene monomer, and initiator, stirring and reacting for 3-4 hours, and then adding zinc salt, stirring and reacting for 4-8 hours, and finally adding neutralizer, stirring and heating to evaporate, washing with ethanol, and dispersing the product in water after drying, adding defoaming agent and leveling agent, and stirring and mixing to obtain green, environmentally friendly, high temperature resistant acrylic resin for ink.

[0008] Preferably, the preparation method of triazine styrene monomer comprises:

[0009] (1) Add 2-chloro-4,6-diamino-1,3,5-triazine, 4-aminostyrene, sodium bicarbonate and water to ethanol, heat to 75-85°C, stir and react for 3-6 hours, condense and reflux during the reaction, heat and volatilize after the reaction, and cool and recrystallize in an ice water bath to obtain a styrene-based intermediate.

[0010] (2) Add styrene intermediate and salicylaldehyde to ethanol, heat to 45-60°C, stir and react for 6-10 hours, heat and volatilize after the reaction, and cool and recrystallize in an ice water bath to obtain triazine styrene monomer. The reaction formula is as follows:

[0011] .

[0012] Preferably, the vinyl monomer includes any one or a combination of methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, butyl acrylate, and butyl methacrylate.

[0013] Preferably, the neutralizing agent is triethylamine or N,N-dimethylethanolamine.

[0014] Preferably, the emulsifier is any one or a combination of OP-10, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.

[0015] Preferably, the zinc salt is any one or a combination of zinc nitrate and zinc chloride.

[0016] Preferably, the molar ratio of 2-chloro-4,6-diamino-1,3,5-triazine, 4-aminostyrene and sodium bicarbonate is 1:(1-1.2):(1-1.1).

[0017] Preferably, the molar ratio of the styryl intermediate to salicylaldehyde is 1:(2-2.2).

[0018] The technical effect of the present invention is as follows: the present invention polymerizes triazine-based styrene monomers with monomers such as acrylic acid and butyl methacrylate, thereby introducing a styrene hard monomer structure into the acrylic resin molecular chain, which is beneficial to improving the pencil hardness and mechanical properties of the acrylic resin paint film for ink, while introducing heat-resistant styrene and triazine ring structures, the thermal decomposition temperature of the paint film is significantly improved, and the high temperature resistance is enhanced.

[0019] The triazine-based styrene monomer of the present invention contains an o-hydroxy Schiff base triazine structure, has a strong coordination chelation effect with zinc ions, can adsorb zinc ions in the acrylic resin molecular chain, and is not easy to be washed off. The zinc ions give the paint film excellent antibacterial properties, and show a higher antibacterial rate against Escherichia coli and Staphylococcus aureus. The obtained acrylic resin uses water as a solvent, is green and environmentally friendly, has little pollution, and has good practical applications in high temperature resistance and antibacterial inks. DETAILED DESCRIPTION

[0020] In order to better understand the technical solution of the present invention, the above content of the present invention is further described in detail below through specific implementation methods in the form of embodiments, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above content of the present invention belong to the scope of the present invention.

[0021] Example 1

[0022] (1) Add 30 mmol 2-chloro-4,6-diamino-1,3,5-triazine, 36 mmol 4-aminostyrene, 33 mmol sodium bicarbonate and 200 mL water to 200 mL ethanol, heat to 85°C and stir to react for 3 h. Condensate reflux during the reaction. After the reaction, heat to evaporate. After the precipitate is precipitated, cool in an ice water bath for recrystallization to obtain a styrene-based intermediate.

[0023] (2) Add 20 mmol of styrene intermediate and 40 mmol of salicylaldehyde to 80 mL of ethanol, heat to 60°C, and stir to react for 10 hours. After the reaction, heat to evaporate the precipitate, cool in an ice water bath and recrystallize to obtain a triazine styrene monomer.

[0024] (3) Add 7.5g methyl acrylate, 1.8g acrylic acid, 20.7g butyl methacrylate, 0.5g triazine styrene monomer, 1g OP-10 and 2g sodium dodecylbenzene sulfonate to 800mL water, heat to 75°C in a nitrogen atmosphere, add 0.18g initiator azobisisobutyronitrile, stir and react for 60min, then add 18.2g methyl acrylate, 4.3g acrylic acid, 47.5g butyl methacrylate, 2.5g triazine styrene monomer, initiator 0.55g azobisisobutyronitrile, stir and react for 3h, then add 0.5g zinc chloride, stir and react for 4h, finally add 2.2g neutralizer N,N-dimethylethanolamine, stir and evaporate, wash with ethanol, and disperse the dried product in 150mL water, add 0.6g defoamer Surfynol 104E, 0.5g of leveling agent BYK-333, stir and mix to obtain green, environmentally friendly, high temperature resistant acrylic resin for ink.

[0025] Example 2

[0026] (1) Add 30 mmol 2-chloro-4,6-diamino-1,3,5-triazine, 30 mmol 4-aminostyrene, 30 mmol sodium bicarbonate and 150 mL water to 200 mL ethanol, heat to 75°C and stir to react for 6 h. Condensate reflux during the reaction. After the reaction, heat to evaporate. After the precipitate is precipitated, cool in an ice water bath and recrystallize to obtain a styrene-based intermediate.

[0027] (2) Add 20 mmol of styrene intermediate and 44 mmol of salicylaldehyde to 100 mL of ethanol, heat to 45°C, and stir to react for 6 hours. After the reaction, heat to evaporate the precipitate, cool in an ice water bath and recrystallize to obtain a triazine styrene monomer.

[0028] (3) Add 7.6 g methyl methacrylate, 1.8 g methacrylic acid, 20.6 g butyl acrylate, 0.8 g triazine styrene monomer, 0.7 g OP-10 and 1.3 g sodium dodecyl sulfate to 80 mL of water, heat to 80 °C in a nitrogen atmosphere, add 0.15 g initiator azobisisobutyronitrile, stir and react for 40 min, then add 17.9 g methyl methacrylate, 5.1 g methacrylic acid, 47 g butyl acrylate, 3.8 g triazine styrene monomer, and 0.55 g azobisisobutyronitrile as initiator, stir and react for 4 h, then add 1.5 g zinc chloride, stir and react for 5 h, finally add 1.8 g neutralizer triethylamine, stir and evaporate by heating, wash with ethanol, and disperse the dried product in 150 mL of water, add 0.8 g defoaming agent Surfynol 104E, 0.3g of leveling agent BYK-333, stir and mix to obtain green, environmentally friendly, high temperature resistant acrylic resin for ink.

[0029] Example 3

[0030] (1) Add 7.1 g methyl methacrylate, 1.6 g acrylic acid, 21.3 g butyl methacrylate, 1 g triazine styrene monomer (prepared in Example 1), 0.8 g OP-10 and 1.8 g sodium dodecylbenzene sulfonate to 800 mL of water, heat to 70°C in a nitrogen atmosphere, add 0.2 g azobisisobutyronitrile as initiator, stir and react for 60 min, then add 18.8 g methyl methacrylate, 4.5 g acrylic acid, 46.7 g butyl methacrylate, 5.7 g triazine styrene monomer, and 0.6 g azobisisobutyronitrile as initiator, stir and react for 4 h, then add 2.2 g zinc nitrate, stir and react for 8 h, finally add 2.5 g neutralizer triethylamine, stir and evaporate by heating, wash with ethanol, and disperse the dried product in 150 mL of water, add 0.5 g defoamer Surfynol 104E, 0.5g of leveling agent BYK-333, stir and mix to obtain green, environmentally friendly, high temperature resistant acrylic resin for ink.

[0031] Example 4

[0032] (1) Add 6.6 g of methyl methacrylate, 1.2 g of acrylic acid, 22.2 g of butyl methacrylate, 1 g of triazine styrene monomer (prepared in Example 1), and 1 g of OP-10 and 2g sodium dodecylbenzene sulfonate were heated to 75°C in a nitrogen atmosphere, 0.15g initiator azobisisobutyronitrile was added, and the mixture was stirred for 60 minutes. Then 18.2g methyl methacrylate, 4.7g acrylic acid, 47.1g butyl methacrylate, 7g triazine styrene monomer, and 0.58g azobisisobutyronitrile as initiator were added, and the mixture was stirred for 3 hours. Then 3g zinc nitrate was added, and the mixture was stirred for 8 hours. Finally, 1.8g neutralizer N,N-dimethylethanolamine was added, and the mixture was heated and evaporated after stirring. The mixture was washed with ethanol, and the dried product was dispersed in 150mL water. 0.8g defoamer Surfynol104E and 0.3g leveling agent BYK-333 were added, and the mixture was stirred to obtain a green, environmentally friendly, high temperature resistant acrylic resin for ink.

[0033] Comparative Example 1

[0034] (3) Add 7.5 g of methyl acrylate, 1.8 g of acrylic acid, 20.7 g of butyl methacrylate, 1 g of OP-10 and 2 g of sodium dodecylbenzene sulfonate to 800 mL of water, heat to 75 °C in a nitrogen atmosphere, add 0.18 g of initiator azobisisobutyronitrile, stir and react for 60 min, then add 18.2 g of methyl acrylate, 4.3 g of acrylic acid, 47.5 g of butyl methacrylate and 0.55 g of initiator azobisisobutyronitrile, stir and react for 3 h, finally add 2.2 g of neutralizer N,N-dimethylethanolamine, stir and evaporate by heating, wash with ethanol, and disperse the product into 150 mL of water after drying. Add 0.6 g of defoamer Surfynol 104E and 0.5 g of leveling agent BYK-333, stir and mix well to obtain green, environmentally friendly, high temperature resistant acrylic resin for ink.

[0035] Comparative Example 2

[0036] (3) Add 7.5 g of methyl acrylate, 1.8 g of acrylic acid, 20.7 g of butyl methacrylate, 0.5 g of triazine styrene monomer, 1 g of OP-10 and 2 g of sodium dodecylbenzene sulfonate to 800 mL of water, heat to 75 °C in a nitrogen atmosphere, add 0.18 g of initiator azobisisobutyronitrile, stir and react for 60 min, then add 18.2 g of methyl acrylate, 4.3 g of acrylic acid, 47.5 g of butyl methacrylate, 2.5 g of triazine styrene monomer and 0.55 g of initiator azobisisobutyronitrile, stir and react for 3 h, finally add 2.2 g of neutralizer N,N-dimethylethanolamine, stir and evaporate by heating, wash with ethanol, and disperse the product into 150 mL of water after drying. Add 0.6 g of defoamer Surfynol 104E and 0.5 g of leveling agent BYK-333, stir and mix well to obtain green, environmentally friendly, high temperature resistant acrylic resin for ink.

[0037] Comparative Example 3

[0038] (1) Add 7.5 g of methyl acrylate, 1.8 g of acrylic acid, 20.7 g of butyl methacrylate, 1 g of OP-10 and 2 g of sodium dodecylbenzene sulfonate to 800 mL of water, heat to 75 ° C in a nitrogen atmosphere, add 0.18 g of initiator azobisisobutyronitrile, stir and react for 60 min, then add 18.2 g of methyl acrylate, 4.3 g of acrylic acid, 47.5 g of butyl methacrylate and 0.55 g of initiator azobisisobutyronitrile, stir and react for 3 h, then add 0.5 g of zinc chloride, stir and react for 4 h, finally add 2.2 g of neutralizer N,N-dimethylethanolamine, stir and evaporate, wash with ethanol, and disperse the product into 150 mL of water after drying. Add 0.6 g of defoamer Surfynol 104E and 0.5 g of leveling agent BYK-333, stir and mix to obtain green, environmentally friendly, high temperature resistant acrylic resin for ink.

[0039] Comparative Example 4

[0040] (1) Add 7.5 g methyl acrylate, 1.8 g acrylic acid, 20.7 g butyl methacrylate, 0.5 g styrene intermediate (prepared in Example 1), 1 g OP-10 and 2 g sodium dodecylbenzene sulfonate to 800 mL of water, heat to 75°C in a nitrogen atmosphere, add 0.18 g initiator azobisisobutyronitrile, stir and react for 60 min, then add 18.2 g methyl acrylate, 4.3 g acrylic acid, 47.5 g butyl methacrylate, 2.5 g styrene intermediate, initiator 0.55 g azobisisobutyronitrile, stir and react for 3 h, then add 0.5 g zinc chloride, stir and react for 4 h, finally add 2.2 g neutralizer N,N-dimethylethanolamine, stir and evaporate by heating, wash with ethanol, and disperse the dried product in 150 mL of water, add 0.6 g defoamer Surfynol 104E, 0.5g of leveling agent BYK-333, stir and mix to obtain green, environmentally friendly, high temperature resistant acrylic resin for ink.

[0041] Pour the ink with acrylic resin on the mold surface and dry it at 80℃ for 12h to make a paint film. Test the pencil hardness of the paint film according to GB / T 6739-2022 method.

[0042] The paint film was placed in a thermogravimetric analyzer and subjected to thermogravimetric analysis in a nitrogen atmosphere at a heating rate of 10°C / min from room temperature to 700°C.

[0043] The test strains were cultured and activated to prepare a bacterial solution with a concentration of 10 6 cfu / mL bacterial suspension. Pipette 0.2mL of bacterial suspension and drop it on the surface of the paint film in the experimental group and the blank group respectively, and cover it with a sterilized polyethylene film. Incubate it at 37℃ for 24h in a constant temperature and humidity incubator. After incubation, wash the paint film and polyethylene film with a 0.8% sodium chloride solution. Take 0.2mL of washing solution and inoculate it in nutrient agar medium. Incubate it at 37℃ for 48h in a constant temperature and humidity incubator. After incubation, count the viable bacteria. Calculate the inhibition rate R. R=(BC) / B×100%.

[0044] B is the average number of recovered bacteria in the paint film samples of the blank group (cfu / piece). C is the average number of recovered bacteria in the paint film samples of the test group (cfu / piece).

[0045] The paint film of acrylic resin for ink in Comparative Example 1 is a blank group. The paint films of Examples 1-4 and Comparative Examples 2-4 are experimental groups. The test bacteria are Escherichia coli or Staphylococcus aureus. The test results are shown in Table 1.

[0046] Table 1: Test results

[0047]

[0048] Compared with Comparative Example 1, the acrylic resin for ink of Examples 1-4 adds triazine-based styrene monomers, and introduces the styrene hard monomer structure into the acrylic resin molecular chain, which is beneficial to improve the pencil hardness and mechanical properties of the paint film. At the same time, the heat-resistant styrene and triazine ring structures are introduced, and the thermal decomposition temperature of the paint film is significantly increased, and the high temperature resistance is enhanced. In addition, the triazine-based styrene monomer contains an o-hydroxy Schiff base triazine structure ( ), which has a strong coordination chelation effect with zinc ions, can adsorb zinc ions in the acrylic resin molecular chain, which is not easy to be washed off. Zinc ions give the paint film excellent antibacterial properties and show a higher antibacterial rate against Escherichia coli and Staphylococcus aureus.

[0049] Compared with Comparative Example 1, Comparative Example 2 also added triazine styrene monomer, the pencil hardness and thermal decomposition temperature of the acrylic resin paint film were also very high, and the mechanical properties and high temperature resistance were excellent, but no zinc ions were added, and the paint film had almost no antibacterial properties.

[0050] In Comparative Example 3, no triazine styrene monomer was added, and the pencil hardness and thermal decomposition temperature of the acrylic resin paint film were low, and the mechanical properties and high temperature resistance were poor. Although zinc ions were added, the acrylic resin had low coordination, chelating and adsorption effects on zinc ions. After washing, the zinc ions were easily washed away, resulting in a low antibacterial rate of the acrylic resin paint film.

[0051] Comparative Example 4 added a styrene-based intermediate ( ), the obtained acrylic resin does not contain o-hydroxy Schiff base structure, and has low coordination, chelation and adsorption effects with zinc ions. After washing, zinc ions are easily washed away, resulting in a low antibacterial rate of the acrylic resin paint film.

[0052] Although the above describes the specific implementation methods of the present invention, it does not limit the scope of protection of the present invention. Based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection of the present invention.

Claims

1. A green, environmentally friendly, high temperature resistant acrylic resin for ink, characterized in that: The green, environmentally friendly, high temperature resistant acrylic resin for ink comprises 100 parts by weight of vinyl monomer, 3-8 parts by weight of triazine styrene monomer, 0.7-0.8 parts by weight of initiator, 1.8-2.5 parts by weight of neutralizer, 2-3 parts by weight of emulsifier, 0.5-3 parts by weight of zinc salt, 0.5-0.8 parts by weight of defoamer, and 0.3-0.5 parts by weight of leveling agent; The triazine styrene monomer has the following structural formula (I): Formula (I).

2. The green, environmentally friendly, high temperature resistant acrylic resin for ink according to claim 1, characterized in that: The vinyl monomer includes any one or a combination of methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, butyl acrylate, and butyl methacrylate.

3. The green, environmentally friendly, high temperature resistant acrylic resin for ink according to claim 1, characterized in that: The initiator is azobisisobutyronitrile.

4. The green, environmentally friendly, high temperature resistant acrylic resin for ink according to claim 1, characterized in that: The neutralizing agent is triethylamine or N,N-dimethylethanolamine.

5. The green, environmentally friendly, high temperature resistant acrylic resin for ink according to claim 1, characterized in that: The emulsifier is any one or a combination of OP-10, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.

6. The green, environmentally friendly, high temperature resistant acrylic resin for ink according to claim 1, characterized in that: The zinc salt is any one or a combination of zinc nitrate and zinc chloride.

7. The green, environmentally friendly, high temperature resistant acrylic resin for ink according to claim 1, characterized in that: The preparation method of the triazine styrene monomer comprises: (1) Add 2-chloro-4,6-diamino-1,3,5-triazine, 4-aminostyrene, sodium bicarbonate and water to ethanol, heat to 75-85°C, stir and react for 3-6 hours, condense and reflux during the reaction, heat and volatilize after the reaction, cool and recrystallize to obtain a styrene-based intermediate; (2) Add styrene intermediate and salicylaldehyde to ethanol, heat to 45-60°C, stir and react for 6-10 hours, heat to volatilize after the reaction, cool and recrystallize to obtain triazine styrene monomer.

8. The green, environmentally friendly, high temperature resistant acrylic resin for ink according to claim 7, characterized in that: The molar ratio of 2-chloro-4,6-diamino-1,3,5-triazine, 4-aminostyrene and sodium bicarbonate is 1:(1-1.2):(1-1.1).

9. The green, environmentally friendly, high temperature resistant acrylic resin for ink according to claim 7, characterized in that: The molar ratio of styryl intermediate to salicylaldehyde is 1:(2-2.2).

10. A method for preparing the green, environmentally friendly, high temperature resistant acrylic resin for ink according to any one of claims 1 to 9, characterized in that: The preparation method comprises: adding vinyl monomer, triazine styrene monomer and emulsifier into water, heating to 70-80°C in a nitrogen atmosphere, adding initiator, stirring and reacting for 40-60 minutes, then adding vinyl monomer, triazine styrene monomer and initiator, stirring and reacting for 3-4 hours, then adding zinc salt, stirring and reacting for 4-8 hours, finally adding neutralizer, stirring and heating to evaporate, washing, drying and dispersing the product into water, adding defoamer and leveling agent, stirring and mixing, and obtaining green, environmentally friendly, high temperature resistant acrylic resin for ink.

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