Environmentally friendly water-based embossed ink and its preparation method and application

Abstract

The present invention relates to the technical field of premixed mortar, and in particular to an environmentally friendly water-based embossed effect ink and a preparation method and application thereof. The water-based embossed effect ink comprises: acrylic hard emulsion, acrylic soft emulsion, water-based solid acrylic resin, diethylene glycol monobutyl ether, large-particle polyethylene wax, normal-particle polyethylene wax, water-based surfactant, water-based silicone oil, monoethanolamine, water, photoinitiator, leveling agent, fumed silica, pigment, dispersant, thickener, carbon nanotube / silver complex and post-treatment agent. The water-based embossed effect ink designed by the present invention has excellent film-forming strength, toughness and light-resistant discoloration ability, further expands the application range of the water-based ink and optimizes the surface state after use, and is suitable for industrial promotion.

Description

Technical Field

[0001] The invention relates to the technical field of premixed mortar, and in particular to an environmentally friendly water-based embossed effect ink and a preparation method and application thereof. Background Art

[0002] Ink is mainly composed of pigments, binders, organic solvents and additives. It has a large VOC emission and serious environmental pollution. Water-based ink uses water as a solvent to replace organic solvents, which significantly reduces VOC emissions. It is suitable for packaging and printing products with high hygiene requirements such as food, beverages, medicines, and children's toys. This type of ink has the disadvantages of poor solvent resistance, slow drying, poor gloss, and easy paper shrinkage. UV ink mainly includes prepolymers, photoinitiators, pigments, active diluents and additives. Because of its fast curing rate, low environmental pollution, good performance of the cured product, and suitability for high-speed automated production, its application range is expanding. However, the addition of active diluents in UV inks has different degrees of irritation and toxicity to the human body, and it is not a completely environmentally friendly product.

[0003] Water-based UV ink combines the advantages of water-based ink and UV ink. It has developed rapidly in recent years and will be one of the main development directions of environmentally friendly ink in the future. Its advantages are mainly as follows: 1. It does not need to use active diluents to adjust the viscosity, which can solve the problems of VOC, toxicity and irritation; 2. The water-based system can more conveniently adjust the viscosity and rheology of the ink; 3. It is easy to obtain a non-sticky dry film before light curing, ensure the smoothness of the cured film, simplify the dust-proof operation, and the ink film can be touched before curing, can be stacked and repaired, and the mechanical scratches of the dry film are also easy to repair; 4. Ultra-thin to ultra-thin cured film; 5. It is suitable for general coating methods such as spraying, roller coating, and brushing, and the equipment is easy to clean; 6. It is flame retardant, which greatly reduces the risk of fire; 7. Because the viscosity of the water-based UV ink system is independent of the relative molecular mass of the prepolymer (only related to the solid content), and it is not necessary to add low-molecular active diluents, it solves the problem that traditional light-curing inks cannot take into account both hardness and flexibility. At present, the patents in this area mainly include CN101659785B, CN 101659809 A, CN102030884 A, CN 102241914 A and CN 102153914A, which disclose the use of hydrophilic monomers to introduce a large number of polar groups and unsaturated double bonds in the ink binder to obtain a water-based UV curing system. This system uses water as a solvent to replace the active diluent, which solves environmental problems while combining the advantages of water-based inks and UV inks. However, water-based UV inks still have the following shortcomings: 1. Water-based UV inks have good hydrophilicity and relatively poor water resistance; 2. The binders in water-based UV inks, such as polymers such as polyurethane acrylates or epoxy acrylates, are usually synthesized by a "one-step method", and the microscopic reaction process is difficult to control, resulting in poor stability of the ink. 3. The comprehensive properties such as gloss, hardness, adhesion, aging resistance, and wear resistance are still far behind those of solvent-based inks.

[0004] Therefore, based on material modification and preparation process improvement technology, this method proposes an environmentally friendly water-based embossed effect ink and its preparation method and application, which has a significant improvement effect on the film-forming strength, toughness, and light-resistant color change ability of the material, further expands the application range of the water-based ink and optimizes the surface state after use, and is suitable for industrial promotion. Summary of the invention

[0005] The present invention aims to provide an environmentally friendly water-based embossed effect ink and a preparation method and application thereof. By improving relevant processes and raw materials, the film-forming strength, toughness, light-resistant color change resistance and other effects of the water-based embossed effect ink are improved.

[0006] The key points of this method: In the preparation of water-based embossed effect ink:

[0007] 1. The added carbon nanotube / silver composite is connected by sericin. The role of sericin is mainly to help disperse the carbon nanotubes. Since sericin contains aromatic amino acid residues, such as tyrosine (4.3%), tryptophan (0.8%) and phenylalanine (0.7%), they have strong π-π interactions with the surface of carbon nanotubes. The coexistence of hydrophilic and hydrophobic groups in sericin makes it amphiphilic, thus giving it the ability to reduce surface energy and stabilize the dispersion of carbon nanotubes in water. In addition, these aromatic amino acid residues can be well combined with nanosilver (based on the hydrogen bonding between the functional groups in the amino acids and the oxygen-containing functional groups on the surface of nanosilver), so that the nanosilver can be well dispersed around the carbon nanotubes to form a composite material;

[0008] 2. It is necessary to ensure that all components can be mixed evenly, but the viscosity of the slurry system should not be increased to avoid affecting the wetting effect of the subsequent slurry. Therefore, planetary ball milling is used in the first step of mixing, and stirring mixing is used in the second step of mixing.

[0009] The specific implementation scheme of an environmentally friendly water-based embossed ink according to the present invention is as follows:

[0010] An environmentally friendly water-based embossed ink, comprising an acrylic hard emulsion (for example, a commercially available raw material, specifically a raw material of model AscentPoly F-1690), an acrylic soft emulsion (for example, a commercially available raw material, specifically a raw material of model AscentPoly F-1617), water-based solid acrylic resin (for example, it can be selected from commercially available raw materials, specifically, it can be a raw material with model number LZ-7002), diethylene glycol monobutyl ether, large particle size polyethylene wax (for example, it can be selected from commercially available raw materials, specifically, it can be a raw material with model number Mitsui W410), normal particle size polyethylene wax (for example, it can be selected from commercially available raw materials, specifically, it can be a raw material with model number Clariant wax powder 3620), water-based surfactant (for example, it can be selected from commercially available raw materials, specifically, it can be a raw material with model number A-102), water-based silicone oil (for example, it can be selected from commercially available raw materials, specifically, it can be a raw material with model number water-based silicone oil 204), monoethanolamine, water, photoinitiator, leveling agent, fumed silica, pigment, dispersant, thickener, carbon nanotube / silver composite, and post-treatment agent.

[0011] In terms of mass proportion, the ingredients include: 40-50 parts of acrylic hard emulsion, 10-20 parts of acrylic soft emulsion, 5-10 parts of water-based solid acrylic resin, 0.5-1 parts of diethylene glycol monobutyl ether, 1-2 parts of large-particle polyethylene wax, 5-10 parts of normal-particle polyethylene wax, 0.1-0.5 parts of water-based surfactant, 0.5-1 parts of water-based silicone oil, 0.1-0.2 parts of monoethanolamine, 1-5 parts of water, 2-10 parts of photoinitiator, 0.5-1 parts of leveling agent, 5-15 parts of fumed silica, 5-15 parts of pigment, 0.5-1.5 parts of dispersant, 0.2-0.5 parts of thickener, 1-3 parts of carbon nanotube / silver composite and 3-5 parts of post-treatment agent.

[0012] The photoinitiator is one of 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0013] The leveling agent is castor oil, polyoxyethylene ether, and hydrogenated castor oil polyoxyethylene ether.

[0014] The pigment is a mixture of one or more of water-based red pigment, water-based green pigment and water-based blue pigment.

[0015] The dispersant is polyether dispersant D156.

[0016] The thickener is ASE-60 alkali swelling thickener.

[0017] The post-treatment agent is a slurry of nano titanium dioxide, with a solid content of 30-40% and the rest being water.

[0018] Furthermore, the carbon nanotube / silver composite is prepared as follows:

[0019] Step 1: Cut the cocoons into small pieces, put them into a 1wt% K2CO3 aqueous solution and boil them at 90°C for 30 minutes, then cool them at room temperature and filter them, collect the filtrate and neutralize it with 1M hydrochloric acid, then remove the precipitate in the solution by centrifugation, and then dialyze with deionized water until chloride ions cannot be detected using a silver nitrate solution, and finally obtain sericin by freeze-drying the solution;

[0020] Adding sericin into deionized water to obtain a sericin solution, dispersing carbon nanotubes and nanosilver in the sericin solution, and then using a probe sonicator to sonicate the mixture for 30 minutes, the power of the sonicator is estimated to be 250 W; centrifuging the sonicated mixture twice at 2500 rpm, selecting solid materials, and obtaining a carbon nanotube / silver composite;

[0021] A method for preparing an environmentally friendly water-based embossed ink comprises the following steps:

[0022] Step 1: Planetary ball milling of acrylic hard emulsion, acrylic soft emulsion, water-based solid acrylic resin, diethylene glycol monobutyl ether, large-particle polyethylene wax, normal-particle polyethylene wax, water-based surfactant, water-based silicone oil, monoethanolamine, water, UV monomer, photoinitiator, leveling agent, fumed silica, pigment, dispersant, thickener, and carbon nanotube / silver composite at a ball milling speed of 200-400 rpm for 60-120 min;

[0023] Step 2: Add the post-treatment agent to the mixed slurry obtained in the first step, stir with a stirrer for 60-120 minutes at a stirring speed of 100-300 rpm to obtain an ink mixture;

[0024] Step 3: The ink mixture obtained in the second step is subjected to pressure filtration to obtain the water-based embossed ink; wherein the mesh size of the pressure filtration screen is 100-300 meshes.

[0025] Furthermore, the shape-preserving water-based embossed effect ink can be used in surface printing on paper, plastic, metal, and glass.

[0026] Beneficial effects of the present invention:

[0027] (1) The present invention adopts a water-based formula for the first time, which is more environmentally friendly and has lower printing costs;

[0028] (2) In the method designed by the present invention, adding a carbon nanotube / silver composite to the slurry can maintain the ink in its subsequent use and reduce pollution and dust; adding sericin to the composite can stabilize the dispersion of carbon nanotubes and nanosilver;

[0029] (3) In the method designed by the present invention, nano titanium dioxide is added to the water-based ink, which has a significant effect on improving the light-fastness and discoloration performance of the ink and is suitable for printing high value-added products. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 A flow chart for preparation. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0032] As an embodiment, the following content of the embodiments of the present invention provides several specific examples of the aforementioned environmentally friendly water-based embossed effect ink and its preparation method and application, such as Example 1, Example 2, Example 3 and Comparative Examples 1-5 for comparison and explanation.

[0033] Materials used in the present invention:

[0034] Acrylic hard emulsion AscentPoly F-1690;

[0035] Acrylic soft emulsion AscentPoly F-1617;

[0036] Water-based solid acrylic resin LZ-7002;

[0037] The normal particle size polyethylene wax is Clariant wax powder 3620, with an average particle size of 8.5 microns;

[0038] The large particle size polyethylene wax is Japan Mitsui W410, with an average particle size greater than 9.5 microns;

[0039] The water-based surfactant model is A-102;

[0040] The model of water-based silicone oil is water-based silicone oil 204.

[0041] The preparation process of carbon nanotube / silver composite is as follows:

[0042] 10 g of the original Bombyx mor i silkworm cocoons obtained from the market were cut into small pieces, put into 200 mL of a 1 wt% K2CO3 aqueous solution and boiled at 90°C for 30 minutes, then cooled and filtered at room temperature, the filtrate was collected and neutralized to pH 7 with 1 M hydrochloric acid, then the precipitate in the solution was removed by centrifugation, and then dialyzed with deionized water until chloride ions could not be detected using a silver nitrate solution, and finally, the sericin was obtained by freeze-drying the solution;

[0043] 100 mg of sericin was added to 20 mL of deionized water to obtain a sericin solution, 100 mg of carbon nanotubes (TMM1, Chengdu Organic Chemicals Co., Ltd., the diameter and length of the carbon nanotubes were 8 nm and 10-30 μm, respectively) and 30 mg of nanosilver (product model: ZH-Ag) were dispersed in the sericin solution, and then the mixture was sonicated for 30 minutes using a probe sonicator, and the power of the sonicator was estimated to be 250 W; the sonicated mixture was centrifuged twice at 2500 rpm, and the solid material was selected to obtain a carbon nanotube / silver composite.

[0044] Embodiment 1:

[0045] An environmentally friendly water-based embossed ink includes acrylic hard emulsion, acrylic soft emulsion, water-based solid acrylic resin, diethylene glycol monobutyl ether, large-particle polyethylene wax, normal-particle polyethylene wax, water-based surfactant, water-based silicone oil, monoethanolamine, water, photoinitiator, leveling agent, fumed silica, pigment, dispersant, thickener, carbon nanotube / silver composite, and post-treatment agent;

[0046] The components are as follows by mass: 40 parts of acrylic hard emulsion, 10 parts of acrylic soft emulsion, 5 parts of water-based solid acrylic resin, 0.5 parts of diethylene glycol monobutyl ether, 1 part of large-particle polyethylene wax, 5 parts of normal-particle polyethylene wax, 0.1 parts of water-based surfactant, 0.5 parts of water-based silicone oil, 0.1 parts of monoethanolamine, 1 part of water, 2 parts of photoinitiator, 0.5 parts of leveling agent, 5 parts of fumed silica, 5 parts of pigment, 0.5 parts of dispersant, 0.2 parts of thickener, 1 part of carbon nanotube / silver composite, and 3 parts of post-treatment agent;

[0047] The photoinitiator is 1-hydroxy-cyclohexyl-phenyl ketone;

[0048] The leveling agent is castor oil;

[0049] The pigment is BASF 3630WA water-based red pigment;

[0050] The dispersant is polyether dispersant D156;

[0051] The thickener is ASE-60 alkali swelling thickener;

[0052] The post-treatment agent is a slurry of nano titanium dioxide, with a solid content of 30% and the rest being water.

[0053] A method for preparing an environmentally friendly water-based embossed ink comprises the following steps:

[0054] Step 1: Planetary ball milling of acrylic hard emulsion, acrylic soft emulsion, water-based solid acrylic resin, diethylene glycol monobutyl ether, large-particle polyethylene wax, normal-particle polyethylene wax, water-based surfactant, water-based silicone oil, monoethanolamine, water, photoinitiator, leveling agent, fumed silica, pigment, dispersant, thickener, and carbon nanotube / silver composite at a ball milling speed of 200 rpm for 60 min;

[0055] Step 2: Add the nano titanium dioxide slurry into the mixed slurry obtained in the first step, stir with a stirrer for 60 minutes at a stirring speed of 100 rpm to obtain an ink mixture;

[0056] Step 3: The water-based embossed ink obtained in the second step is pressure filtered to obtain the desired water-based embossed ink, and the filter screen has a mesh number of 100 meshes.

[0057] Embodiment 2:

[0058] An environmentally friendly water-based embossed ink, comprising 45 parts of acrylic hard emulsion, 15 parts of acrylic soft emulsion, 7 parts of water-based solid acrylic resin, 0.7 parts of diethylene glycol monobutyl ether, 1.5 parts of large-particle polyethylene wax, 7 parts of normal-particle polyethylene wax, 0.3 parts of water-based surfactant, 0.7 parts of water-based silicone oil, 0.15 parts of monoethanolamine, 3 parts of water, 6 parts of photoinitiator, 0.7 parts of leveling agent, 10 parts of fumed silica, 10 parts of pigment, 1 part of dispersant, 0.4 parts of thickener, 2 parts of carbon nanotube / silver composite, and 4 parts of post-treatment agent;

[0059] Embodiment 3:

[0060] An environmentally friendly water-based embossed effect ink comprises 50 parts of acrylic hard emulsion, 20 parts of acrylic soft emulsion, 10 parts of water-based solid acrylic resin, 1 part of diethylene glycol monobutyl ether, 2 parts of large-particle polyethylene wax, 10 parts of normal-particle polyethylene wax, 0.5 parts of water-based surfactant, 1 part of water-based silicone oil, 0.2 parts of monoethanolamine, 5 parts of water, 10 parts of photoinitiator, 1 part of leveling agent, 15 parts of fumed silica, 15 parts of pigment, 1.5 parts of dispersant, 0.5 parts of thickener, 3 parts of carbon nanotube / silver composite and 5 parts of post-treatment agent.

[0061] Comparative Example 1:

[0062] The difference between this comparative example and Example 1 is that no carbon nanotube / silver composite is added, and the remaining steps and raw materials are the same as Example 1;

[0063] Comparative Example 2

[0064] The difference between this comparative example and Example 1 is that the carbon nanotube / silver composite is prepared by conventional mixing (i.e., no sericin is added during the mixing process), and the remaining steps and raw materials are the same as those of Example 1;

[0065] Comparative Example 3

[0066] The difference between this comparative example and Example 1 is that only carbon nanotubes are used, and the remaining steps and raw materials are the same as those of Example 1;

[0067] Comparative Example 4

[0068] The difference between this comparative example and Example 1 is that only carbon nanotubes and sericin are used, and nanosilver is not added. The remaining steps and raw materials are the same as those of Example 1;

[0069] Comparative Example 5:

[0070] The difference between this comparative example and Example 1 is that no post-treatment agent is added, and the remaining steps and raw materials are the same as Example 1.

[0071] Tensile strength is the resistance to the maximum uniform plastic deformation of the material. Before the tensile specimen is subjected to the maximum tensile stress, the deformation is uniform and consistent, but after exceeding the maximum tensile stress, the metal begins to shrink, that is, concentrated deformation occurs; for brittle materials with no (or very small) uniform plastic deformation, it reflects the fracture resistance of the material. The test standard can refer to the national standard GB / T228-1987), the unit is MPa;

[0072] Elongation after break:

[0073] It refers to the percentage of the elongated length of the specimen to the original length when the material breaks under the action of external force (tension). The test standard can refer to the national standard GB / T 528-2009.

[0074] Table 1: Effect test

[0075]

[0076] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the purpose and scope of the technical solution, which should be included in the scope of the claims of the present invention.

Claims

1. A method for preparing an environmentally friendly water-based embossed ink, characterized in that: The weight percentages of the components of the water-based embossed ink are as follows: 50 parts of acrylic hard emulsion AscentPolyF-1690, 20 parts of acrylic soft emulsion AscentPolyF-161, and 20 parts of water-based solid acrylic resin liquid LZ-7002. 10 parts, 1 part of diethylene glycol monobutyl ether, 2 parts of polyethylene wax with an average particle size greater than 9.5 microns, 10 parts of polyethylene wax with an average particle size of 8.5 microns, 0.5 parts of aqueous surfactant, 1 part of aqueous silicone oil, 0.2 parts of monoethanolamine, 5 parts of water, 10 parts of photoinitiator, 1 part of leveling agent, 15 parts of fumed silica, 15 parts of pigment, 1.5 parts of dispersant, 0.5 parts of thickener, 3 parts of carbon nanotube / silver composite, 5 parts of post-treatment agent; the photoinitiator is 1-hydroxy-cyclohexyl-phenyl ketone; the leveling agent is castor oil; the pigment is an aqueous red pigment; the dispersant is a polyether dispersant D156; the thickener is an ASE-60 alkali swelling thickener; the post-treatment agent is a slurry of nano titanium dioxide with a solid content of 30% and the rest being water; The carbon nanotube / silver composite preparation process comprises: cutting silkworm cocoons into small pieces, placing them in a K2CO3 aqueous solution containing a mass fraction of 1wt%, boiling them at 90°C for 30 minutes, cooling and filtering them at room temperature, collecting the filtrate and neutralizing it with 1M hydrochloric acid, then removing the precipitate in the solution by centrifugation, dialyzing them with deionized water until chloride ions cannot be detected using a silver nitrate solution, and finally obtaining sericin by freeze-drying the solution; adding sericin into deionized water to obtain a sericin solution, dispersing carbon nanotubes and nanosilver in the sericin solution, and then using a probe ultrasonic instrument to ultrasonically treat the mixture for 30 minutes, the power of the ultrasonic instrument being estimated to be 250W; centrifuging the ultrasonically treated mixture twice at 2500rpm to obtain a carbon nanotube / silver composite; the preparation method of the environmentally friendly water-based embossed ink comprises the following steps: the first step: mixing acrylic hard emulsion AscentPolyF-1690, acrylic soft emulsion Ascen tPolyF-1617, water-based solid acrylic resin liquid LZ-7002, diethylene glycol monobutyl ether, polyethylene wax with an average particle size greater than 9.5 microns, polyethylene wax with an average particle size of 8.5 microns, water-based surfactant, water-based silicone oil, monoethanolamine, water, photoinitiator, leveling agent, fumed silica, pigment, dispersant, thickener, carbon nanotube / silver composite are planetarily ball milled at a ball milling speed of 200 rpm for 60 min; the second step: adding the post-treatment agent to the mixed slurry obtained in the first step, stirring for 60 min with a vertical stirrer at a stirring speed of 100 rpm to obtain an ink mixture; the third step: pressurizing and filtering the ink mixture obtained in the second step to obtain the environmentally friendly water-based embossed effect ink; wherein the mesh size of the pressurized filtration is 100 meshes.

2. An application of the environmentally friendly water-based embossed ink prepared by the preparation method according to claim 1 in surface printing on paper, plastic, metal and glass.

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