Highly water-resistant water-based ink and process for its preparation

Abstract

The application relates to a high-water-resistance water-based ink and a preparation process thereof, wherein the water-based ink comprises the following raw materials in parts by mass: 100-140 parts of an acrylic emulsion; 120-160 parts of titanium white powder; 5-15 parts of a thickening agent; 0-5 parts of a functional additive; 80-100 parts of an organic pigment; 10-20 parts of a pigment dispersant; 20-60 parts of ethylene glycol; 400-600 parts of deionized water; a water-resistance additive, the added mass being 0.1-0.2 times the sum of the mass of the acrylic emulsion and the mass of the titanium white powder; the water-resistance additive is regenerated cellulose with embedded zirconium oxide particles; the regenerated cellulose is a microporous structure; the zirconium oxide particles are embedded in the microporous structure of the regenerated cellulose; and the mass ratio of the zirconium oxide particles to the regenerated cellulose is 1:10-20. The water-based ink has good water resistance and anti-settling performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of water-based ink, in particular to a high water-resistant water-based ink and a preparation process thereof. BACKGROUND

[0002] With the continuous progress of printing technology and the enhancement of environmental awareness, traditional solvent-based ink has gradually failed to meet the requirements of modern society for environmental protection and sustainable development due to its containing a large amount of volatile organic compounds (VOCs), which pose potential threats to the environment and human health. Therefore, the development of environmentally friendly ink has become an important development direction for the printing industry.

[0003] Water-based ink greatly reduces the emission of VOCs due to the absence of volatile organic solvents, thereby reducing air pollution, improving the environment for printing operators, and benefiting the health of workers. It can completely eliminate certain toxic and harmful substances in solvent-based ink, eliminate harm to the human body and pollution to packaged goods, improve overall environmental quality, and is particularly suitable for packaging and printing products such as cigarettes, alcohol, food, beverages, medicines, and children's toys that require strict hygiene conditions. In addition, it not only reduces the risk of fire and hidden dangers caused by static electricity and flammable solvents, but also reduces the toxicity of residual printing surfaces and facilitates the cleaning of printing equipment.

[0004] As an environmentally friendly ink, water-based ink has gradually gained market attention due to its low VOCs emission, good printing adaptability, and color reproduction. Water-based ink is mainly composed of water-soluble resin, pigment, water, and additives. During printing, water is used as a solvent or diluent, effectively reducing environmental pollution.

[0005] However, water-based ink still faces some technical challenges in practical applications. For example, water-based ink often uses water or small-molecule alcohol aqueous solution as a solvent or dispersion medium. Although its water resistance is significantly improved through appropriate modification and treatment, it is still significantly worse than solvent-based ink. How to obtain a water-based ink with high water resistance is a difficult technical problem that needs to be solved. SUMMARY

[0006] In order to improve the poor water resistance of water-based ink on the market, the present application provides a high water-resistant water-based ink and a preparation process thereof.

[0007] In a first aspect, the present application provides a high water-resistant water-based ink, which adopts the following technical solution:

[0008] A high water-resistant water-based ink, comprising at least the following mass parts of raw materials:

[0009] Acrylic emulsion 100-140 parts;

[0010] Titanium white 120-160 parts;

[0011] Thickening agent 5-15 parts;

[0012] Functional auxiliary agent 0-5 parts;

[0013] Organic pigment 80-100 parts;

[0014] Pigment dispersant 10-20 parts;

[0015] Ethylene glycol 20-60 parts;

[0016] Deionized water 400-600 parts;

[0017] The ink further comprises a water-resistant additive, the water-resistant additive being regenerated cellulose with zirconium oxide particles embedded therein, the regenerated cellulose being of a multi-microporous structure, the zirconium oxide particles being embedded in the microporous structure of the regenerated cellulose, the mass ratio of the zirconium oxide particles to the regenerated cellulose being 1:10-20, and the added mass of the water-resistant additive being 0.1-0.2 times the sum of the mass of the acrylic emulsion and the mass of the titanium white.

[0018] By adopting the technical solution, the water-resistant additive is added in the present application, and the water-resistant additive is a special regenerated cellulose material with zirconium oxide particles embedded therein (it should be noted that it is not a cellulose derivative such as CMC, but regenerated cellulose). Cellulose has very good hydrophilicity due to a large number of hydroxyl groups, so it is generally believed that adding cellulose into the ink should lead to an increase in the hydrophilicity of the ink, and naturally, it will also lead to a decrease in the water resistance of the ink, so if the water resistance of the paint film is to be improved, adding cellulose is often not the preferred solution.

[0019] However, the inventors of the present application unexpectedly found that when the added cellulose has a multi-microporous structure and zirconium oxide particles are embedded in the multi-microporous structure, and the added amount is controlled to be not more than 0.2 times and not less than 0.1 times the sum of the mass of the acrylic emulsion and the mass of the titanium white, the paint film can obtain better water resistance by adding hydrophilic cellulose.

[0020] This is probably due to the fact that the large number of hydroxyl groups on the surface of regenerated cellulose does indeed impart good hydrophilicity, which allows it to be well and evenly dispersed, and the evenly dispersed regenerated cellulose can form a large number of hydrogen bonds with the water-based resin (acrylic emulsion) and titanium dioxide filler in the ink, and an addition amount of no less than 0.1 times means that a large number of introduced hydrogen bonds can form a relatively complete hydrogen bond network, thereby improving the water resistance of the paint film. In addition, compared with natural cellulose in nature, a large number of microporous structures are introduced during the phase separation regeneration of regenerated cellulose, and these microporous structures will produce obvious capillary phenomenon, so that a large number of water-based resins and other components will be embedded into the microporous structure of regenerated cellulose to form physical embedding in addition to the hydrogen bond network, which greatly improves the compatibility and connection tightness of the materials in the paint film, thereby obtaining better water resistance.

[0021] Of course, the addition amount of regenerated cellulose should not be higher than 0.2 times, so as to prevent the excessive introduction of hydroxyl groups from significantly improving the hydrophilicity of the paint film, thereby causing the water resistance of the paint film to decrease as expected. In addition, the microporous structure of regenerated cellulose not only produces capillary adsorption of the materials in the paint film, but also causes capillary water absorption. Therefore, if the regenerated cellulose is too large, in addition to the excessive introduction of hydroxyl groups, the capillary water absorption caused by the excessive microporous structure will also cause the water resistance of the paint film to decrease.

[0022] On the basis of the foregoing, the zirconium oxide embedded in the microporous structure of regenerated cellulose cooperates with the regenerated cellulose to enable the paint film to have better water resistance.

[0023] This is probably due to the fact that, on the one hand, as mentioned above, regenerated cellulose exhibits significantly stronger capillary water absorption than natural cellulose, and the zirconium oxide filled in the microporous structure can alleviate this phenomenon to some extent; on the other hand, cellulose is relatively soft, and the embedded zirconium oxide particles can significantly improve the strength of the cellulose, so that the dispersed cellulose in the paint film plays a good pinning role. Overall, the embedded zirconium oxide particles can reduce capillary water absorption, and more exhibit the positive effect of hydrogen bonding formed by cellulose itself on water resistance.

[0024] Of course, zirconium oxide should not be added in excess (for example, the ratio of zirconium oxide to cellulose is less than 1:10), on the one hand, zirconium oxide itself has relatively good hydrophilicity and can form hydrogen bonds with the hydroxyl groups on the regenerated cellulose, thereby reducing the free hydroxyl groups that can form a hydrogen bond network in the paint film, and whether the decrease in the integrity of the hydrogen bond network or the high hydrophilicity caused by zirconium oxide itself will cause the water resistance of the paint film to decrease. In addition, excessive zirconium oxide will cause the microporous structure of cellulose to be excessively blocked, and the acrylic emulsion and titanium dioxide and other materials will have difficulty producing sufficient physical embedding with the microporous structure of regenerated cellulose, and the mutual combination tightness will decrease, thereby causing the strength and water resistance of the paint film to decrease.

[0025] It is also worth noting that the production process of water-based ink is difficult to avoid a certain degree of heating, and the acrylic emulsion is an alkali-soluble resin, so the whole system is alkaline and the temperature is relatively high, under this condition, regenerated cellulose is prone to uncontrollable degradation behavior, and zirconium oxide has good heat insulation performance, which is coated on the fiber of regenerated cellulose, which can greatly reduce the possibility of degradation of regenerated cellulose in the production process of ink, thereby ensuring the formation of hydrogen bond network and physical embedding effect. Of course, the good heat insulation performance of zirconium oxide also means that if the amount of zirconium oxide is excessive, it will cause the thermal conductivity of water-based ink to decrease excessively, and the drying speed is too low to cause the adhesion of the paint film to decrease.

[0026] Optionally, the thickening agent is a mixture of sodium alginate and sodium carboxymethyl cellulose in a mass ratio of 1-2:1.

[0027] By adopting the above technical scheme, sodium alginate and sodium carboxymethyl cellulose are both common thickening agents for water-based ink, and their combination can play a good thickening and stabilizing effect. Among them, sodium carboxymethyl cellulose is a natural high molecular compound soluble in water, which has good thickening performance. Sodium alginate is a polysaccharide extracted from brown algae, which has excellent gelling ability and stability. The combination of these two functional substances further improves the comprehensive performance of sodium carboxymethyl cellulose and sodium alginate. Stability is also one of the key performances of many products. Sodium carboxymethyl cellulose and sodium alginate can effectively prevent the sedimentation and aggregation of solid particles or gas bubbles in liquid and gel systems. Its excellent stability makes the product maintain long-term stability during storage and use, and is not easy to separate and precipitate. This is very important for water-based ink systems containing titanium dioxide inorganic particles.

[0028] It is worth noting that when sodium alginate is present in the thickening agent, whether the regenerated cellulose in the water-resistant additive has zirconium oxide particles embedded therein has a significant impact on the anti-settling and anti-layering performance of the water-based ink.

[0029] Specifically, the inventors of the present application found that, in the contrast experiment, if there is only regenerated cellulose in the water-resistant additive without zirconium oxide, the anti-delamination performance of the water-based ink is significantly reduced, which is quite unexpected. It is generally believed that the zirconium oxide embedded in the cellulose does not affect the anti-delamination performance of the water-based ink. This may be due to the fact that although sodium alginate can be used to adjust the viscosity of the system, the molecular chain of sodium alginate is unstable and prone to degradation during the production process at slightly high temperature or during high-temperature storage, thereby causing unexpected changes in the viscosity of the water-based ink and reducing the anti-delamination performance of the water-based ink. The zirconium oxide embedded in the regenerated cellulose has good heat insulation effect, which not only avoids the alkaline hydrolysis of the regenerated cellulose at high temperature, but also significantly reduces the degradation process of sodium alginate, thereby alleviating the problem.

[0030] Optionally, the pigment dispersant is at least one of sodium dodecyl benzene sulfonate, polyethylene glycol diglycidyl ether, bromotetradecylpyridine, and cashew phenol.

[0031] Optionally, the pigment dispersant is a mixture of cashew phenol and polyethylene glycol diglycidyl ether in a mass ratio of 1:2-3.

[0032] By adopting the above technical solution, cashew phenol is a green industrial raw material refined from natural cashew nut shell oil and has a wide range of applications. As a surface active agent, cashew phenol can significantly improve the dispersion performance of pigments in water-based ink, and therefore has good dispersibility and stability in coatings and ink, which can improve the color and durability of the paint film.

[0033] Polyethylene glycol diglycidyl ether is a polymer compound obtained by the reaction of ethylene glycol and glycidyl ether, which has the main characteristics of high water solubility, surface active agent property, ionic property, biological compatibility, and chemical modifier property, and is widely used in water-based system surface active agent applications. It can also improve the dispersibility and stability of pigments, thereby improving the color and durability of the paint film.

[0034] In addition, the inventors of the present application found that, compared with the use of cashew phenol or polyethylene glycol diglycidyl ether alone, the use of both can improve the water resistance of the paint film. This may be due to the fact that, as mentioned above, polyethylene glycol diglycidyl ether not only has surface active agent property, but also has chemical modifier property, which may act as a crosslinking agent. The two side end epoxy groups are ring-opened and react with the phenolic hydroxyl group on the cashew phenol, the alcoholic hydroxyl group on the regenerated cellulose, and the active group on the water-based resin, respectively, thereby forming a three-dimensional crosslinking network-like morphology to improve the water resistance of the paint film.

[0035] Optionally, the water-resistant additive is prepared by the following process:

[0036] A1, dispersing zirconium oxide, placing zirconium oxide in a solvent and ultrasonic dispersion to obtain a dispersion liquid, the solvent being at least one of acetone, dioxane, dimethylacetamide, N-methyl pyrrolidone;

[0037] A2, dissolving, adding cellulose diacetate into the dispersion liquid and dissolving to obtain a blending liquid, the addition concentration of cellulose diacetate being 8-12wt%; the mass ratio of the addition of zirconium oxide and cellulose diacetate being 1:10-20;

[0038] A3, phase separation solidification, placing the blending liquid in a phase separation bath, making cellulose diacetate phase separate into a microporous structure and making zirconium oxide adhere to the fiber structure, and filtering out to obtain a semi-finished product, the phase separation bath being an aqueous solution of a small molecule alcohol, the surface tension of the phase separation bath being not greater than 40mN / m, and the small molecule alcohol being at least one of ethanol, propanol, and isopropanol;

[0039] A4, hydrolysis regeneration, blending the semi-finished product with a sodium hydroxide solution to hydrolyze cellulose diacetate to regenerate cellulose, and filtering out and washing to obtain regenerated cellulose with zirconium oxide particles embedded therein.

[0040] By adopting the above technical solution, in step A3, the phase separation bath with low surface tension can improve its penetration ability, so as to exchange with the solvent in the blending liquid more quickly to form micropores with smaller pore size, and the lower concentration of cellulose diacetate makes the micropores have a larger number although the pore size is smaller. Therefore, the phase separation bath with low surface tension can make the finally prepared regenerated cellulose have a large number of microporous structures with small size, so that better physical embedding effect can be formed after adding the water-based ink, and it is easier to form a hydrogen bond network through more uniform dispersion and exposed hydroxyl groups, thereby improving water resistance and improving anti-delamination performance.

[0041] Optionally, in step A3, the blending liquid is injected into the stirring phase separation bath in a spraying manner, the spraying speed of the blending liquid being 2-10L / min, and the stirring speed of the phase separation bath being 50-100r / min.

[0042] By adopting the above technical solution, the special spraying phase separation method can make the blending liquid be injected into the phase separation bath in a continuous manner, but during the phase separation process, the cellulose diacetate is more likely to form irregular granular structures rather than forming continuous structures such as film-shaped or strip-shaped, sheet-shaped, etc., which greatly reduces the contact area of the finally prepared regenerated cellulose with each material, thereby forming a larger amount of hydrogen bonds to obtain good anti-delamination performance and water resistance.

[0043] Optionally, step A4 specifically includes the following steps:

[0044] A41, cold mixing, blending the semi-finished product with a sodium hydroxide solution, and controlling the system temperature to be no more than 20℃, to obtain a cold mixing system;

[0045] A42, heating hydrolysis, heating the cold mixing system to 60-80℃ to hydrolyze the cellulose diacetate under alkaline conditions to regenerate regenerated cellulose;

[0046] A43, filtration and washing, filtering and washing the regenerated cellulose in the hydrolysis system and the zirconium oxide embedded in the pores of the regenerated cellulose to neutral, to obtain a water-resistant additive.

[0047] By adopting the above technical solution, compared with directly blending and hydrolyzing the semi-finished product with a sodium hydroxide solution under high temperature conditions to regenerate, the method of first cold mixing and then heating hydrolysis can ensure that the sodium hydroxide is first uniformly attached to the fiber and then hydrolyzed, thereby improving the uniformity of hydrolysis of cellulose diacetate, and accordingly, the defect resistance of water-based ink can be improved.

[0048] Optionally, the concentration of the sodium hydroxide solution is 0.2-1g / L, and the mass ratio of sodium hydroxide in the sodium hydroxide solution to the added mass of cellulose diacetate in step A2 is 1:2-3.

[0049] By adopting the above technical solution, by controlling the amount of sodium hydroxide added during blending, and combining the special process of first cold mixing and then heating hydrolysis, during the cold mixing stage, the sodium hydroxide is first uniformly attached to the surface of the cellulose diacetate, and during the heating hydrolysis stage, the surface of the cellulose diacetate is hydrolyzed to regenerated cellulose, while the inside is still cellulose diacetate due to insufficient amount of sodium hydroxide. This treatment makes the finally prepared water-resistant additive have a special skin-core structure, in which the surface is fully hydrolyzed regenerated cellulose, and the inner core is not fully hydrolyzed cellulose diacetate; the introduction of regenerated cellulose with a large number of hydroxyl groups on the surface can ensure that the water-resistant additive forms a hydrogen bond network with the remaining materials, and the cellulose diacetate in the inner core has higher mechanical strength, which, combined with the embedded zirconium oxide, makes the water-resistant additive have higher strength and is not easy to break during the preparation of water-based ink, and better plays the role of water resistance improvement and pinning strength improvement.

[0050] In a second aspect, the present application provides a preparation process of water-based ink, which adopts the following technical solution:

[0051] A preparation process of water-based ink, the following process steps:

[0052] S1, stirring and initial mixing, blending and stirring all raw materials except acrylic emulsion and water-resistant additive to be uniform, then adding acrylic emulsion and stirring to be uniform, to obtain an initial mixture;

[0053] S2, sand grinding, transferring the primary mixture into a sand grinder for one-stage sand grinding, adding water-resistant additive for two-stage sand grinding, and filtering the material after sand grinding is completed;

[0054] S3, packaging, storage and transportation.

[0055] Optionally, in the step S2, the one-stage grinding is indirectly cooled by cooling water to control the grinding temperature to 25-35℃, and the grinding is completed when the fineness is not greater than 15μm; then the cooling water is cut off and the water-resistant additive is added, and the grinding state is maintained until the temperature in the grinder reaches 50-60℃, and the two-stage grinding is completed.

[0056] By adopting the above technical solution, the special two-stage grinding method can ensure good grinding effect by first performing one-stage grinding with high viscosity at low temperature, and further adding water-resistant additive and performing low-viscosity grinding at high temperature, which can avoid the problems of difficult discharge and blockage of the sand grinder caused by high viscosity, and can avoid the soft regenerated cellulose from being excessively ground and broken, so as to play the role of local pinning and physical interlocking. BRIEF DESCRIPTION OF DRAWINGS

[0057] Figure 1 is the SEM diagram of the water-resistant additive prepared in the application. DETAILED DESCRIPTION

[0058] The application will be further described below.

[0059] The following is a preparation example of the water-resistant additive disclosed in the application:

[0060] Preparation Example 1

[0061] The water-resistant additive in the preparation example is prepared by the following process steps:

[0062] A1, zirconium oxide dispersion, placing zirconium oxide in a solvent and ultrasonic dispersion to obtain a dispersion liquid, the solvent is N-methyl pyrrolidone, and the addition concentration of zirconium oxide is controlled to be 0.67wt%; wherein, the ultrasonic dispersion process only needs to ensure that the zirconium oxide is fully dispersed, and can be adjusted conventionally, in the preparation example, the ultrasonic power is 50W, the ultrasonic time is 15min, the zirconium oxide is purchased from Japan DKK Company (the first rare element chemical industry Co., Ltd.), the specific model is UEP-50, the D 50 50-60m 2 / g.

[0063] A2, dissolving, adding cellulose diacetate into the dispersion and dissolving to obtain a blending liquid, the adding concentration of cellulose diacetate is 10wt%; in the blending liquid, the adding mass ratio of zirconium oxide and cellulose diacetate is 1:14.9; cellulose diacetate is purchased from Daiso Corporation, the specific model is CAFBLO® Flake L-50, and the esterification rate (acetic acid combination rate) is 54%-56%.

[0064] A3, phase separation and solidification, injecting the blending liquid into the stirring phase separation bath by the way of jetting through the nozzle, making cellulose diacetate phase separation into microporous structure and making zirconium oxide adhere to the fiber structure, filtering to obtain a semi-finished product, the phase separation bath is an aqueous solution of small molecule alcohol. In this preparation example, the phase separation bath is an aqueous solution of ethanol, and by controlling the concentration of ethanol, the surface tension of the phase separation bath is about 35 mN / m; the jetting speed of the blending liquid is 6 L / min, and the stirring speed of the phase separation bath is 75 r / min.

[0065] A4, hydrolysis and regeneration, blending the semi-finished product with sodium hydroxide solution to hydrolyze and regenerate cellulose diacetate into cellulose by removing acetate, filtering and washing to obtain regenerated cellulose with zirconium oxide particles embedded; specifically, this step adopts the process of cold mixing first and then hydrolysis in hot water, and the specific steps are as follows:

[0066] A41, cold mixing, blending the semi-finished product with sodium hydroxide solution, and controlling the system temperature to be not more than 20℃, specifically, in this preparation example, the system temperature is controlled to be 15℃, to obtain a cold mixing system; the concentration of sodium hydroxide solution is controlled to be 0.5g / L, in step A2 of this preparation example, 50g of cellulose diacetate is used, therefore, the total amount of sodium hydroxide to be added in this step is controlled to be 20g, since the concentration of sodium hydroxide solution is controlled to be 0.5g / L, therefore, 40L of sodium hydroxide solution is needed in total to ensure that the mass ratio of sodium hydroxide in the sodium hydroxide solution to the adding mass of cellulose diacetate in step A2 is 1:2.5.

[0067] A42, heating and hydrolysis, heating the cold mixing system to 70℃ to hydrolyze and regenerate cellulose diacetate into regenerated cellulose under alkaline conditions;

[0068] A43, filtering and washing, filtering and washing the regenerated cellulose in the hydrolysis system and the zirconium oxide embedded in the micropores of the regenerated cellulose to neutral, to obtain a water-resistant additive; the scanning electron microscope image of the obtained water-resistant additive is shown in Figure 1

[0069] Preparation Example 2-7

[0070] Preparation Example 2-7 is mainly different from Preparation Example 1 in that each preparation process step is properly adjusted, and the specific details are shown in the following table:

[0071] ​

[0072] It should be noted that the preparation example 6 of the present application does not use the process of cold mixing and then hydrolysis, but directly blends the semi-finished product with the sodium hydroxide solution with a temperature of 80℃. In the preparation example 8, zirconium oxide particles are not added, so that the water-resistant additive prepared is only of cellulose material.

[0073] The following is an embodiment of the water-based ink disclosed in the present application:

[0074] In the embodiment of the present application, a high water-resistant water-based ink is disclosed, which specifically comprises the following raw materials in mass parts:

[0075] Acrylic emulsion 120 parts;

[0076] Titanium white 140 parts;

[0077] Thickening agent 10 parts;

[0078] Functional additives 3 parts;

[0079] Organic pigment 90 parts;

[0080] Pigment dispersant 15 parts;

[0081] Ethylene glycol 40 parts;

[0082] Deionized water 500 parts;

[0083] Water-resistant additive 39 parts, which is 0.15 times the sum of the added mass of acrylic emulsion and titanium white.

[0084] Specifically, the acrylic emulsion in the embodiment is purchased from Dow Chemical's RESIN HF-05A water-based self-crosslinking thermosetting acrylic resin, with a solid content of about 40%; the titanium white is specifically the anatase titanium white DHA-100 of Bluestar Dahua, the thickening agent is a mixture of sodium alginate and sodium carboxymethyl cellulose in a mass ratio of 1.5:1; the functional additives are specifically 1 part of defoaming agent and 2 parts of leveling agent, the defoaming agent is specifically Dow Chemical's DC65 silicone defoaming agent, and the leveling agent is specifically BYK-333 silicone leveling agent of BYK; the organic pigment can be selected conventionally, and in the embodiment, phthalocyanine blue BGS is selected as the organic pigment; the pigment dispersant is a mixture of cardanol and polyethylene glycol diglycidyl ether in a mass ratio of 1:2.5.

[0085] The high water-resistant water-based ink in the embodiment is prepared by the following process steps:

[0086] S1, stirring and primary mixing, blending and stirring all the raw materials except acrylic emulsion and water-resistant additive to be uniform, then adding acrylic emulsion and stirring to be uniform to obtain a primary mixed material;

[0087] S2, sand grinding, the primary mixture is transferred to a sand grinder for one-stage sand grinding, then water-resistant additive is added for two-stage sand grinding, and the sand grinding is completed and the material is filtered out; specifically, the grinding temperature is controlled to 30°C by indirect cooling through cooling water during one-stage grinding, and the grinding is completed when the fineness is no more than 15 μm; then the cooling water is cut off and the water-resistant additive is added, and the grinding state is maintained until the temperature in the grinder reaches 55°C, and the two-stage grinding is completed.

[0088] S3, packaging and storage.

[0089] Example 2-7 differs from Example 1 mainly in that the raw material composition and the process steps are adjusted, and the specific details are shown in the following table.

[0090] Specifically,

[0091] The main difference between Example 2 and Example 1 is that the thickening agent is adjusted to 15 parts, but it is still a mixture of sodium alginate and sodium alginate and sodium carboxymethyl cellulose in a mass ratio of 1.5:1, the functional aid is specifically 0.5 parts of defoaming agent and 0.5 parts of leveling agent, and the pigment dispersant is adjusted to 10 parts, but it is still a mixture of cardanol and polyethylene glycol diglycidyl ether in a mass ratio of 1:2.5.

[0092] Similar to Example 2, the main difference between Example 3 and Example 1 is that the type and ratio of the thickening agent, the type of the functional aid, and the type and ratio of the pigment dispersant are not changed, and only the amount is adjusted.

[0093] The main difference between Example 4 and Example 1 is that although the amount of thickening agent is still 10 parts, the thickening agent is only sodium alginate, and CMC-Na is not added.

[0094] The main difference between Example 5 and Example 6 and Example 1 is that although the amount of pigment dispersant is still 15 parts, the pigment dispersant in Example 5 is only polyethylene glycol diglycidyl ether, and the pigment dispersant in Example 6 is only cardanol.

[0095] The main difference between Example 7 and Example 1 is that although the amount of pigment dispersant is still 15 parts, the pigment dispersant in Example 7 is only sodium dodecyl benzene sulfonate, and the water-resistant additive added is prepared in Preparation Example 2.

[0096] Example 8 - Example 12 differ from Example 1 mainly in that the water-resistant additive added in Example 8 is prepared in Preparation Example 3, the water-resistant additive added in Example 9 is prepared in Preparation Example 4, the water-resistant additive added in Example 10 is prepared in Preparation Example 5, the water-resistant additive added in Example 11 is prepared in Preparation Example 6, and the water-resistant additive added in Example 12 is prepared in Preparation Example 7.

[0097] Comparative Example

[0098] Comparative Example 1

[0099] Comparative Example 1 differs from Example 1 only in that the water-resistant additive used in Comparative Example 1 is not the water-resistant additive prepared in the respective preparation examples of the present application, but a conventional commercially available microcrystalline cellulose, specifically Toncellus® TC105 from Dongchen Pharmaceutical, with a D 50 of 20 μm and a bulk density of about 0.25 g / cm 3 .

[0100] Comparative Example 2

[0101] Comparative Example 2 differs from Example 1 only in that the water-resistant additive added in Comparative Example 2 is prepared in Preparation Example 8.

[0102] Comparative Example 3

[0103] Comparative Example 3 differs from Example 1 only in that an excess of water-resistant additive is added in Comparative Example 3, with an addition amount of 78 parts, which is 0.3 times the sum of the added mass of the acrylic emulsion and titanium dioxide.

[0104] Comparative Example 4

[0105] Comparative Example 4 differs from Comparative Example 3 and Example 1 only in that not enough water-resistant additive is added in Comparative Example 4, with an addition amount of 78 parts, which is 0.3 times the sum of the added mass of the acrylic emulsion and titanium dioxide.

[0106]

[0107] Performance testing and data

[0108] Water resistance, alcohol resistance

[0109] The water resistance of the water-based inks prepared in each embodiment and comparative example of the present application was tested according to the standard QB568-1983 water resistance, alcohol resistance test. Specifically, according to QB568, 10 sheets of qualitative filter paper soaked with aqueous solution or anhydrous ethanol were covered on 1 / 2 of the ink film, and a weight was added and left for 24 h. The grade was evaluated according to the changes of the paint film. The evaluation was made in 5 grades, and the higher the grade, the better the water resistance and alcohol resistance. It should be noted that although this scheme has been abolished, it is still a good test method for indicating the water resistance and alcohol resistance of the paint film, and the performance detection process is simple, and the result is intuitive and has strong observation.

[0110] Anti-settling property

[0111] The water-based inks prepared in each embodiment and comparative example were placed in a transparent airtight container, first centrifuged in a low-speed centrifuge at a speed of 200 rpm for 12 h, then placed in an oven at 60°C and left for 7 days. After taking out, whether there was delamination was observed. By observing the flocculation and sedimentation degree at the bottom, the evaluation was made in 5 grades, and the higher the grade, the better the anti-settling property.

[0112] The performance parameters of the paint film prepared in each embodiment and comparative example are shown in the following table:

[0113]

[0114] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, and the modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A highly water-resistant water-based ink, characterized by: At least the following raw materials are included by mass parts: Acrylic emulsion 100-140 parts; Titanium white 120-160 parts; Thickening agent 5-15 parts; Functional additives 0-5 parts; Organic pigments 80-100 parts; Pigment dispersant 10-20 parts; Ethylene glycol 20-60 parts; Deionized water 400-600 parts; The ink further comprises a water-resistant additive, which is regenerated cellulose with zirconium oxide particles embedded therein, the regenerated cellulose has a microporous structure, the zirconium oxide particles are embedded in the microporous structure of the regenerated cellulose, the mass ratio of the zirconium oxide particles to the regenerated cellulose is 1:10-20, and the added mass of the water-resistant additive is 0.1-0.2 times the sum of the mass of the acrylic emulsion and the titanium white.

2. The high water-resistant water-based ink according to claim 1, characterized by: The thickening agent is a mixture of sodium alginate and sodium carboxymethyl cellulose in a mass ratio of 1-2:

1.

3. The high water-resistant water-based ink according to claim 1, characterized in that: The pigment dispersant is at least one of sodium dodecyl benzene sulfonate, polyethylene glycol diglycidyl ether, bromotetradecyl pyridine, and cardanol.

4. The high water-resistant water-based ink according to claim 3, characterized in that: The pigment dispersant is a mixture of cardanol and polyethylene glycol diglycidyl ether in a mass ratio of 1:2-3.

5. A highly water-resistant water-based ink according to any one of claims 1-4, characterized in that: The water-resistant additive is prepared by the following process: A1, zirconium oxide dispersion, zirconium oxide is placed in a solvent and ultrasonically dispersed to obtain a dispersion liquid, the solvent is at least one of acetone, dioxane, dimethylacetamide, and N-methyl pyrrolidone; A2, dissolving, adding cellulose diacetate to the dispersion liquid and dissolving to obtain a blended liquid, the added concentration of cellulose diacetate is 8-12wt%, and the mass ratio of the added zirconium oxide and cellulose diacetate is 1:10-20; A3, phase separation and solidification, placing the blended liquid in a phase separation bath, allowing the cellulose diacetate to phase separate into a microporous structure and the zirconium oxide to adhere to the fiber structure, filtering out to obtain a semi-finished product, the phase separation bath is an aqueous solution of a small molecule alcohol, the surface tension of the phase separation bath is not greater than 40mN / m, and the small molecule alcohol is at least one of ethanol, propanol, and isopropanol; A4, hydrolysis and regeneration, blending the semi-finished product with a sodium hydroxide solution to hydrolyze and regenerate the cellulose diacetate into cellulose by removing acetate, filtering out and washing to obtain regenerated cellulose with zirconium oxide particles embedded therein.

6. The high water-resistant water-based ink according to claim 5, characterized in that: In step A3, the blended liquid is injected into the stirring phase separation bath by spraying, the spraying speed of the blended liquid is 2-10L / min, and the stirring speed of the phase separation bath is 50-100r / min.

7. The high water-resistant water-based ink according to claim 5, characterized in that: Step A4 specifically includes the following steps: A41, cold mixing, blending the semi-finished product with a sodium hydroxide solution, and controlling the system temperature to be not greater than 20℃ to obtain a cold mixing system; A42, heating and hydrolysis, heating the cold mixing system to 60-80℃ to hydrolyze and regenerate the cellulose diacetate into regenerated cellulose under alkaline conditions; A43, filtering and washing, filtering and washing the regenerated cellulose and the zirconium oxide embedded in the micropores of the regenerated cellulose in the hydrolysis system to neutral, thereby obtaining the water-resistant additive.

8. The high water-resistant water-based ink according to claim 7, characterized by: The concentration of the sodium hydroxide solution is 0.2-1 g / L, and the ratio of the mass of sodium hydroxide in the sodium hydroxide solution to the added mass of cellulose diacetate in step A2 is 1:2-3.

9. The process for the production of water-based inks according to any one of claims 1-8, characterized by the fact that: The process comprises the following steps: S1, stirring and primary mixing, blending and stirring all raw materials except for the acrylic emulsion and water-resistant additive, then adding the acrylic emulsion and stirring uniformly to obtain a primary mixture; S2, sanding, transferring the primary mixture into a sanding machine for one-stage sanding, then adding the water-resistant additive for two-stage sanding, and filtering the sanding mixture after sanding; S3, packaging, storage and transportation.

10. The process for producing an aqueous ink according to claim 9, characterized by: In the step S2, the one-stage grinding is indirectly cooled by cooling water to control the grinding temperature to 25-35℃, and the grinding is completed when the fineness is not greater than 15 μm; Then the cooling water is cut off and the water-resistant additive is added, and the grinding state is maintained until the temperature in the grinding machine reaches 50-60℃, and the two-stage grinding is completed.

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