A kind of water-based acrylic resin-based ink and preparation method thereof

Abstract

The invention discloses a water-based acrylic resin-based ink and a preparation method thereof, and belongs to the technical field of water-based ink. The invention comprises the following raw materials in parts by weight: 20-30 parts of acrylic acid, 18-26 parts of butyl acrylate, 15-24 parts of ethyl acrylate, 5-15 parts of multi-effect antibacterial agent, 6-9 parts of emulsifier, 200-250 parts of deionized water, 0.1-0.3 parts of initiator, 6-12 parts of pigment, and 8-12 parts of anhydrous ethanol. The ink obtained is a water-based ink, with low VOC emission and low environmental pollution; the connecting material selects a soft monomer, which gives the ink better flexibility; wherein the multi-effect antibacterial agent can cross-link with the matrix, improve the heat resistance, oxidation resistance and antibacterial properties of the ink, and the performance is long-term stable and not easy to fall off; therefore, the ink obtained by the invention is a water-based ink, which is environmentally friendly, and also has stable and efficient heat resistance, oxidation resistance and antibacterial properties, and good flexibility.

Description

Technical Field

[0001] The invention belongs to the technical field of water-based inks, and in particular relates to a water-based acrylic resin-based ink and a preparation method thereof. Background Art

[0002] With the continuous development of modern industry, the printing industry has become increasingly important in production and life. The rapid development of the printing industry has led to an increasing demand for printing inks. Commonly used solvent-based inks are quite dangerous during the production process and printing. Organic solvents and solvent-based inks are flammable liquids and are volatile. They will form explosive mixed gases in the air, which are highly dangerous and cause great harm to the environment and human body. Therefore, solvent-based inks are being gradually eliminated. At the same time, the research and application scope of water-based inks are steadily increasing. Water-based inks are inks that use water as a solvent or dispersant, and have environmental and safety advantages such as no pollution to the atmospheric environment. They are widely used in food packaging, tobacco and alcohol packaging, children's toy packaging, etc.

[0003] Water-based ink mainly includes pigment, binder and water. The binder is the fluid part of the ink as the continuous phase of the ink. It is a key factor affecting the printing performance of the ink. The quality of the binder directly affects the performance of the ink. Commonly used binders are divided into two categories: water-based polyacrylic resin (PA) and water-based polyurethane (WPU). Among them, water-based acrylic resin not only has the advantages of organic solvent-based resins such as excellent gloss, acid and alkali resistance and good pollution resistance, but also has the characteristics of low price, safe use, energy saving, and reduced environmental pollution and public hazards. It is a low-VOC green and environmentally friendly material. However, when the ink is used outdoors for a long time, such as outdoor advertising, it will be damaged by adverse factors such as ultraviolet rays, acid and alkali, and high temperature weather for a long time. Generally, it cannot exceed one year, and more serious yellowing and discoloration will occur, and the antioxidant and heat resistance are poor; in addition, when the ink is printed on the packaging material, the ink layer provides a habitat for the growth and reproduction of microorganisms. When people come into contact with food packaging, they are easily infected with bacteria or microorganisms, thereby affecting people's health. Therefore, it is urgent to invent a water-based ink that can solve the above problems to meet the higher demands in the field of water-based ink technology. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a water-based acrylic resin-based ink and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A method for preparing a water-based acrylic resin-based ink comprises the following steps:

[0007] A1. Acrylic acid, butyl acrylate, ethyl acrylate, a multi-effect antibacterial agent and an emulsifier are mixed and stirred evenly, added into deionized water, and dispersed at high speed to obtain an emulsion; then an initiator is added to initiate a polymerization reaction, and the reaction is completed to obtain a connecting material;

[0008] A2. After preliminarily stirring and mixing the connecting material, pigment, anhydrous ethanol and deionized water prepared in step A1, add them into a single-tank planetary high-energy ball mill and grind them for 2-5 hours (ball milling speed is 600-1200 r / min) with high-speed stirring to obtain a water-based acrylic resin-based ink.

[0009] Furthermore, the raw materials are calculated in parts by weight as follows: 20-30 parts of acrylic acid, 18-26 parts of butyl acrylate, 15-24 parts of ethyl acrylate, 5-15 parts of multi-effect antibacterial agent, 6-9 parts of emulsifier, 200-250 parts of deionized water, 0.1-0.3 parts of initiator, 6-12 parts of pigment, and 8-12 parts of anhydrous ethanol.

[0010] Furthermore, the mass ratio of deionized water in step A1 to that in step A2 is 4:1.

[0011] Furthermore, the initiator is a water-soluble initiator.

[0012] Furthermore, the emulsifier is prepared by compounding alkylphenol polyoxyethylene ether and sodium lauryl sulfate in a mass ratio of 2:1.

[0013] The prepared acrylic resin linker selects butyl acrylate and ethyl acrylate, two soft monomers, to make the prepared ink more flexible; the emulsifier is an anionic and non-ionic compound emulsifier, which has a better emulsification effect; the prepared ink is a water-based ink with low VOC emissions and low environmental pollution.

[0014] Furthermore, the multi-effect antibacterial agent is prepared by the following steps:

[0015] S1. Mix 3,5-di-tert-butyl-4-hydroxybenzaldehyde, piperidine (condensing agent) and toluene in a three-necked flask equipped with a stirring device, heat to 30°C, stir until the solid is completely dissolved, add 3,4-diaminopyridine, control the reaction temperature to 55°C, keep the reaction for 4 hours, and after the reaction is completed, cool naturally and distill under reduced pressure to obtain intermediate 1; the ratio of 3,5-di-tert-butyl-4-hydroxybenzaldehyde, piperidine, toluene and 3,4-diaminopyridine is 23.4g:15mL:100mL:11.7g;

[0016] Under the action of the condensing agent, the amino group on 3,4-diaminopyridine condenses with the aldehyde group on 3,5-di-tert-butyl-4-hydroxybenzaldehyde to form an imine group (C=N Schiff base structure), and by controlling the molar ratio of the two to be close to 1:1 and a slight excess of 3,4-diaminopyridine, only one amino group on 3,4-diaminopyridine participates in the reaction to obtain intermediate 1; the specific reaction process is as follows:

[0017]

[0018] S2. Add intermediate 1, 3-mercaptopropionic acid, dicyclohexylcarbodiimide (DCC, dehydrating agent) and N,N-dimethylformamide (DMF) to a three-necked flask equipped with a stirring device, stir and mix well, place in a 50°C water bath, and heat in a water bath for 8 hours. After the reaction is completed, filter, remove the solvent by vacuum distillation, and then purify by column chromatography (the eluent is a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two is 1:2), and remove the eluent by rotary evaporation to obtain intermediate 2; the ratio of the amount of intermediate 1, 3-mercaptopropionic acid, dicyclohexylcarbodiimide and toluene is 32.5g:10.6g:20.6g:150mL;

[0019] Under the action of dicyclohexylcarbodiimide, intermediate 1 undergoes an amidation reaction with 3-mercaptopropionic acid to obtain intermediate 2. The specific reaction process is as follows:

[0020]

[0021] S3, in a three-necked flask equipped with a stirring device, add intermediate 2 and N, N-dimethylformamide and stir and mix them evenly, then add 4-bromo-1-butene dropwise, control the reaction temperature to 70 ° C, keep the reaction for 8 hours, the reaction is completed, and part of the solvent is removed by distillation under reduced pressure, and then purified by column chromatography (eluent using a mixed solvent of benzene / ethyl acetate, the volume ratio of the two is 4:3), and the eluent is removed by rotary evaporation to obtain intermediate 3; the ratio of the amount of intermediate 2, N, N-dimethylformamide, and 4-bromo-1-butene is 41.3g:150mL:13.5g;

[0022] Intermediate 2 undergoes quaternization reaction with 4-bromo-1-butene to obtain intermediate 3; the specific reaction process is as follows:

[0023]

[0024] S4. Add intermediate 3, AIBN (azobisisobutyronitrile) and N,N-dimethylformamide to a three-necked flask equipped with a stirring device, stir and mix evenly, then drop tetramethyltetravinylcyclotetrasiloxane, maintain the temperature of the system at 80°C, react for 4 hours, and after the reaction is completed, first remove part of the solvent by rotary evaporation, and then purify by column chromatography (the eluent is a mixed solvent of ethyl acetate / benzene, and the volume ratio of the two is 2:5), and remove the eluent by rotary evaporation to obtain a multi-effect antibacterial agent; the ratio of the amount of intermediate 3, AIBN, N,N-dimethylformamide, and tetramethyltetravinylcyclotetrasiloxane is 187.2g:5.2g:300mL:34.4g;

[0025] Under the action of AIBN, the unsaturated carbon-carbon double bond on the tetramethyltetravinylcyclotetrasiloxane molecule undergoes a thiol-ene click reaction with the -SH on the intermediate 3. By controlling the molar ratio of the two to be close to 1:4, a multi-effect antibacterial agent is obtained; the specific reaction process is as follows:

[0026]

[0027] The prepared multi-effect antibacterial agent has a cyclic siloxane as the core, and the cyclic siloxane structure contains multiple Si-O bonds with high bond energy, which can improve the heat resistance of the acrylic resin matrix; molecular chains containing carbon-carbon double bonds in a dendritic structure are distributed on the peripheral side, so that the multi-effect antibacterial agent can form a cross-linked acrylic ester network structure during the polymerization of acrylic acid, greatly improving the heat resistance and mechanical strength of the matrix, and also improving the migration resistance and exudation resistance of the multi-effect antibacterial agent, and improving the stability of the performance; in addition, the multi-effect antibacterial agent molecule also contains pyridinium quaternary ammonium salt, Schiff base and hindered phenol structure, among which pyridinium quaternary ammonium salt is A new type of quaternary ammonium salt has a more concentrated positive charge and stronger bactericidal ability, which avoids the problem of bacterial resistance caused by the long-term use of quaternary ammonium antibacterial agents, and can greatly enhance the antibacterial properties of the matrix; in addition, the C=N Schiff base structure can interact with bacterial proteins and enzymes, hindering the synthesis of bacterial nucleotides and amino acids, and synergistically acting with pyridine quaternary ammonium salts to further improve the antibacterial properties of the matrix; finally, the hindered phenol structure has excellent antioxidant properties, which can not only improve the antioxidant properties of the matrix, but also act as an antioxidant in the production process, avoiding the addition of additional antioxidants and affecting the homogeneity of the ink.

[0028] Beneficial effects of the present invention:

[0029] 1. The ink prepared by the present invention is a water-based ink with low VOC emission and low environmental pollution; the connection material is a soft monomer, which gives the ink better flexibility;

[0030] 2. Compared with inorganic antibacterial agents, the prepared multi-effect antibacterial agent has better compatibility with the substrate and can also cross-link with the substrate to improve the heat resistance, oxidation resistance and antibacterial properties of the ink, and the performance is long-lasting and stable and not easy to fall off;

[0031] Therefore, the ink prepared by the present invention is a water-based ink, which is environmentally friendly, has stable and efficient heat resistance, antioxidant and antibacterial properties, and good flexibility, and has important application value in the field of water-based ink technology. DETAILED DESCRIPTION

[0032] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] Example 1

[0034] Preparation of multi-effect antibacterial agent:

[0035] S1. In a three-necked flask equipped with a stirring device, 23.4 g of 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 15 mL of piperidine and 100 mL of toluene were mixed, the temperature was raised to 30°C, and the mixture was stirred until the solid was completely dissolved. Then, 11.7 g of 3,4-diaminopyridine was added, the reaction temperature was controlled to 55°C, and the reaction was kept warm for 4 hours. After the reaction was completed, the mixture was naturally cooled and distilled under reduced pressure to obtain intermediate 1.

[0036] S2, in a three-necked flask equipped with a stirring device, add 32.5g of intermediate 1, 10.6g of 3-mercaptopropionic acid, 20.6g of dicyclohexylcarbodiimide and 150mL of N,N-dimethylformamide, stir and mix well, place in a 50°C water bath, heat in a water bath for 8h, filter after the reaction, remove the solvent by vacuum distillation, and purify by column chromatography (the eluent is a mixed solvent of benzene / ethyl acetate, the volume ratio of the two is 1:2), and remove the eluent by rotary evaporation to obtain intermediate 2;

[0037] S3, in a three-necked flask equipped with a stirring device, 41.3g of intermediate 2 and 150mL of N,N-dimethylformamide were added and stirred and mixed uniformly, and then 13.5g of 4-bromo-1-butene was added dropwise, and the reaction temperature was controlled to 70°C. The reaction was kept warm for 8h. After the reaction was completed, part of the solvent was removed by distillation under reduced pressure, and then purified by column chromatography (the eluent was a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two was 4:3), and the eluent was removed by rotary evaporation to obtain intermediate 3;

[0038] S4. Add 187.2 g of intermediate 3, 5.2 g of AIBN and 300 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirring device, stir and mix well, then drop 34.4 g of tetramethyltetravinylcyclotetrasiloxane, maintain the temperature of the system at 80°C, and react for 4 hours. After the reaction is completed, first remove part of the solvent by rotary evaporation, and then purify by column chromatography (the eluent is a mixed solvent of ethyl acetate / benzene in a volume ratio of 2:5), and remove the eluent by rotary evaporation to obtain a multi-effect antibacterial agent.

[0039] Example 2

[0040] Preparation of multi-effect antibacterial agent:

[0041] S1. In a three-necked flask equipped with a stirring device, 46.8 g of 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 30 mL of piperidine and 200 mL of toluene were mixed, the temperature was raised to 30°C, and the mixture was stirred until the solid was completely dissolved. 23.4 g of 3,4-diaminopyridine was added, the reaction temperature was controlled to 55°C, and the reaction was kept warm for 4 hours. After the reaction was completed, the mixture was naturally cooled and distilled under reduced pressure to obtain intermediate 1.

[0042] S2, in a three-necked flask equipped with a stirring device, add 65g of intermediate 1, 21.2g of 3-mercaptopropionic acid, 41.2g of dicyclohexylcarbodiimide and 300mL of N,N-dimethylformamide, stir and mix well, place in a 50°C water bath, heat in a water bath for 8h, filter after the reaction, remove the solvent by vacuum distillation, and purify by column chromatography (the eluent is a mixed solvent of benzene / ethyl acetate, the volume ratio of the two is 1:2), and remove the eluent by rotary evaporation to obtain intermediate 2;

[0043] S3, in a three-necked flask equipped with a stirring device, 82.6g of intermediate 2 and 300mL of N,N-dimethylformamide were added and stirred and mixed uniformly, and then 27g of 4-bromo-1-butene was added dropwise, and the reaction temperature was controlled to 70°C. The reaction was kept warm for 8h. After the reaction was completed, part of the solvent was removed by distillation under reduced pressure, and then purified by column chromatography (the eluent was a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two was 4:3), and the eluent was removed by rotary evaporation to obtain intermediate 3;

[0044] S4. Add 374.4 g of intermediate 3, 10.4 g of AIBN and 600 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirring device, stir and mix well, then drop 68.8 g of tetramethyltetravinylcyclotetrasiloxane, maintain the temperature of the system at 80°C, and react for 4 hours. After the reaction is completed, first remove part of the solvent by rotary evaporation, and then purify by column chromatography (the eluent is a mixed solvent of ethyl acetate / benzene in a volume ratio of 2:5), and remove the eluent by rotary evaporation to obtain a multi-effect antibacterial agent.

[0045] Example 3

[0046] A1, 20g acrylic acid, 18g butyl acrylate, 15g ethyl acrylate, 5g of the multi-effect antibacterial agent prepared in Example 1 and 6g of emulsifier (prepared by compounding 4g alkylphenol polyoxyethylene ether and 2g sodium lauryl sulfate) were mixed and stirred evenly, added into 160g deionized water, and dispersed at high speed to obtain an emulsion; then 0.1g of azodiisopropylimidazoline was added to initiate polymerization reaction, and the reaction was completed to obtain a connecting material;

[0047] A2. Preliminarily stir and mix the connecting material prepared in step A1, 6 g of phthalocyanine blue, 8 g of anhydrous ethanol and 40 g of deionized water, add them into a single-tank planetary high-energy ball mill and grind them for 2 h (ball milling speed is 600 r / min), and stir at high speed to obtain a water-based acrylic resin-based ink.

[0048] Example 4

[0049] A1, 25g acrylic acid, 22g butyl acrylate, 20g ethyl acrylate, 10g of the multi-effect antibacterial agent prepared in Example 2 and 9g of emulsifier (prepared by 6g alkylphenol polyoxyethylene ether and 3g sodium lauryl sulfate) were mixed and stirred evenly, added into 160g deionized water, and dispersed at high speed to obtain an emulsion; then 0.2g of azodiisopropylimidazoline was added to initiate polymerization reaction, and the reaction was completed to obtain a connecting material;

[0050] A2. Preliminarily stir and mix the connecting material prepared in step A1, 9 g of permanent yellow, 10 g of anhydrous ethanol and 40 g of deionized water, add them into a single-tank planetary high-energy ball mill and grind them for 3.5 h (ball milling speed is 900 r / min), and stir at high speed to obtain a water-based acrylic resin-based ink.

[0051] Example 5

[0052] A1, 30g acrylic acid, 26g butyl acrylate, 24g ethyl acrylate, 15g of the multi-effect antibacterial agent prepared in Example 2 and 9g of emulsifier (prepared by 6g alkylphenol polyoxyethylene ether and 3g sodium lauryl sulfate) were mixed and stirred evenly, added into 160g deionized water, and dispersed at high speed to obtain an emulsion; then 0.3g of azodiisopropylimidazoline was added to initiate polymerization reaction, and the reaction was completed to obtain a connecting material;

[0053] A2. Preliminarily stir and mix the connecting material prepared in step A1, 12 g of phthalocyanine green, 12 g of anhydrous ethanol and 40 g of deionized water, add them into a single-tank planetary high-energy ball mill and grind them for 5 hours (ball milling speed is 1200 r / min) with high-speed stirring to obtain a water-based acrylic resin-based ink.

[0054] Comparative Example 1

[0055] The multi-effect antibacterial agent in Example 5 was replaced by a commercially available antibacterial agent of equal quality, and the remaining steps were the same as those in Example 5 to prepare ink.

[0056] Comparative Example 2

[0057] A commercially available water-based acrylic resin was used as a binder and preliminarily stirred and mixed with 12 g of phthalocyanine green, 12 g of anhydrous ethanol and 40 g of deionized water. The mixture was added into a single-tank planetary high-energy ball mill and ground for 5 h (the ball milling speed was 1200 r / min) with high-speed stirring to obtain ink.

[0058] The following performance tests were performed on Examples 3-5 and Comparative Examples 1-2 using different test methods according to different standards:

[0059] The flexibility is measured using the national standard GB / T 1731-1993 "Determination of paint film flexibility";

[0060] The national standard GB / T 21866-2008 "Determination of antibacterial properties and antibacterial effects of antibacterial coatings (paint films)" was used to determine the antibacterial performance and antibacterial durability;

[0061] The samples were placed in a 150°C environment for 48 hours to measure the antibacterial properties before and after heat aging (using the national standard GB / T21866-2008);

[0062] According to the national standard GB / T 1865-2009 "Artificial weathering and artificial radiation exposure of paints and varnishes to filtered xenon arc radiation", the samples were aged and observed for powdering, shedding and fading.

[0063] The measured results are shown in the following table:

[0064]

[0065] It can be seen from the above table that the heat resistance, oxidation resistance and antibacterial properties of the product prepared in the embodiment of the present invention are higher than those of the control example, and the product has good flexibility, and has important application value in the field of water-based ink technology.

[0066] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0067] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A water-based acrylic resin-based ink, characterized in that: The invention comprises the following raw materials in parts by weight: 20-30 parts of acrylic acid, 18-26 parts of butyl acrylate, 15-24 parts of ethyl acrylate, 5-15 parts of multi-effect antibacterial agent, 6-9 parts of emulsifier, 200-250 parts of deionized water, 0.1-0.3 parts of initiator, 6-12 parts of pigment and 8-12 parts of anhydrous ethanol; Wherein, the multi-effect antibacterial agent is prepared by the following steps: S1. Mix 3,5-di-tert-butyl-4-hydroxybenzaldehyde, piperidine and toluene, heat to 30°C, stir until the solid is completely dissolved, add 3,4-diaminopyridine, react at 55°C for 4h, and after the reaction is completed, cool and distill under reduced pressure to obtain intermediate 1; the ratio of 3,5-di-tert-butyl-4-hydroxybenzaldehyde, piperidine, toluene and 3,4-diaminopyridine is 23.4g:15mL:100mL:11.7g; S2, after mixing the intermediate 1, 3-mercaptopropionic acid, dicyclohexylcarbodiimide and N,N-dimethylformamide, heating at 50°C for 8h, the reaction was completed, filtering, vacuum distillation, column chromatography purification, rotary evaporation to obtain intermediate 2; the ratio of the amount of intermediate 1, 3-mercaptopropionic acid, dicyclohexylcarbodiimide and toluene was 32.5g:10.6g:20.6g:150mL; S3, after mixing intermediate 2 and N, N-dimethylformamide evenly, add 4-bromo-1-butene dropwise, react at 70°C for 8h, complete the reaction, perform vacuum distillation, purify by column chromatography, and rotary evaporation to obtain intermediate 3; the ratio of intermediate 2, N, N-dimethylformamide, and 4-bromo-1-butene is 41.3g:150mL:13.5g; S4. Add intermediate 3, AIBN and N,N-dimethylformamide into a flask, stir to mix evenly, then add tetramethyltetravinylcyclotetrasiloxane dropwise, react at 80°C for 4 hours, and after the reaction is completed, perform rotary evaporation, purify by column chromatography, and obtain a multi-effect antibacterial agent by rotary evaporation; the dosage ratio of intermediate 3, AIBN, N,N-dimethylformamide and tetramethyltetravinylcyclotetrasiloxane is 187.2g:5.2g:300mL:34.4g.

2. A water-based acrylic resin-based ink according to claim 1, characterized in that: The initiator is a water-soluble initiator.

3. A water-based acrylic resin-based ink according to claim 1, characterized in that: The emulsifier is prepared by compounding alkylphenol polyoxyethylene ether and sodium lauryl sulfate in a mass ratio of 2:

1.

4. The method for preparing a water-based acrylic resin-based ink according to claim 1, characterized in that: The following steps are involved: A1. Acrylic acid, butyl acrylate, ethyl acrylate, a multi-effect antibacterial agent and an emulsifier are mixed and stirred evenly, added into deionized water, and dispersed at high speed to obtain an emulsion; then an initiator is added to initiate a polymerization reaction, and the reaction is completed to obtain a connecting material; A2. After preliminarily stirring and mixing the connecting material, pigment, anhydrous ethanol and deionized water prepared in step A1, add them into a single-tank planetary high-energy ball mill and grind them for 2-5 hours with high-speed stirring to obtain a water-based acrylic resin-based ink.

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