Waterproof ink and preparation method thereof

Abstract

The invention relates to waterproof ink and a preparation method thereof, and belongs to the technical field of ink preparation. Comprising the following raw materials in parts by weight: 5-10 parts of acrylic resin, 1-3 parts of a surfactant, 15-20 parts of pigment, 5-10 parts of glycerol, 50-60 parts of deionized water, 0.5-2 parts of a defoaming agent, 1-3 parts of a film-forming agent, 5-8 parts of modified carbon nanotubes and 3-5 parts of modified zein, modified carbon nanotubes are added in ink components, the water resistance of the ink is improved through the hydrophobic effect of water-soluble polymerized cyclodextrin and methyltriethoxysilane, the modified zein is mixed with the pigment, the waterproof and color fixing effects of the pigment are improved, and the modified zein and other components act together, so that the color fastness of the ink is improved, and the color fastness of the ink is improved. The ink with an excellent waterproof effect is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of ink preparation and relates to waterproof ink and a preparation method thereof. Background Art

[0002] The application field of marker pen ink is very wide. It is widely used in express delivery, office, artistic creation and other fields, which improves efficiency and increases the convenience and fun of life.

[0003] As a type of marker ink, waterproof ink has significant technical characteristics. It usually uses special oil-based or water-based ink formulas, which can ensure that the ink dries quickly after writing or printing and forms a tough film to effectively prevent water penetration and diffusion. Therefore, the words or patterns written by markers with waterproof ink can remain clear and durable in humid or rainy environments and will not be easily smudged or wiped off.

[0004] In order to further expand the application, it is necessary to develop an ink with excellent waterproof effect to meet the needs of different fields. Summary of the invention

[0005] The object of the present invention is to provide a waterproof ink and a preparation method thereof, wherein the prepared ink has an excellent waterproof effect.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A waterproof ink, comprising the following raw materials in parts by weight: 5 to 10 parts of acrylic resin, 1 to 3 parts of surfactant, 15 to 20 parts of pigment, 5 to 10 parts of glycerol, 50 to 60 parts of deionized water, 0.5 to 2 parts of defoaming agent, 1 to 3 parts of film-forming agent, 5 to 8 parts of modified carbon nanotubes and 3 to 5 parts of modified zein;

[0008] The preparation process of modified carbon nanotubes is as follows:

[0009] S1.1, adding carbon nanotubes to a mixed acid solution of sulfuric acid and nitric acid in a volume ratio of 3:1, heating to 70-80°C and reflux for 5-6 hours, washing until the solution pH is 6.5-7.5, and drying at 80°C for 12 hours to obtain acidified carbon nanotubes;

[0010] S1.2. Dissolve water-soluble polymerized cyclodextrin in deionized water, add methyltriethoxysilane and anhydrous ethanol, stir and disperse for 2 hours, adjust the pH of the solution to 6-7 to obtain a mixed solution A, continue to add acidified carbon nanotubes at 40°C, stir at 450 r / min for 5 hours to obtain modified carbon nanotubes, wherein the solid-liquid ratio of the acidified carbon nanotubes and the mixed solution A is 1g:20mL.

[0011] As a preferred technical solution of the present invention, the preparation method of the modified zein is as follows:

[0012] Zein and ethanol aqueous solution in a mass ratio of 1:5 are mixed, and stirred at a speed of 400 r / min for 1 hour to obtain a mixed solution B. 3-5% of the mass of the mixed solution B is added to the mixed solution B, and the stirring and mixing are continued for 60-90 minutes while maintaining the speed to obtain modified zein.

[0013] As a preferred technical solution of the present invention, the surfactant is one of sodium lauryl sulfate, polyoxyethylene lauryl ether, fatty alcohol polyoxyethylene ether, sodium carboxymethyl cellulose and sodium stearate.

[0014] As a preferred technical solution of the present invention, the defoaming agent is one of BYK-410, DAPRO AP7015 and Sago-1551.

[0015] As a preferred technical solution of the present invention, the film-forming agent is one of sorbitan monostearate and glyceryl monostearate.

[0016] As a preferred technical solution of the present invention, the pigment is one of natural red, blue or black plant pigment and carbon black.

[0017] As a preferred technical solution of the present invention, in step S1.1, the usage ratio of the carbon nanotubes to the mixed acid solution is 0.3-0.5 mg / mL.

[0018] As a preferred technical solution of the present invention, in step S1.2, the mass ratio of the water-soluble polymerized cyclodextrin, deionized water, methyltriethoxysilane and anhydrous ethanol is (15-20): (80-100): (5-10): (80-100).

[0019] As a preferred technical solution of the present invention, the mass fraction of ethanol in the ethanol aqueous solution is 80%.

[0020] A method for preparing waterproof ink, comprising the following steps:

[0021] S1. Add surfactant and deionized water into the reaction kettle at room temperature according to weight, stir at 500r / min for 60-90min, then add pigment, and continue stirring for 60-90min;

[0022] S2, adding modified carbon nanotubes in sequence while maintaining stirring, stirring again at room temperature for 60 to 120 minutes to obtain a mixed slurry, and letting it stand for 2 hours to obtain slurry A;

[0023] S3, mixing the pigment and the modified zein at room temperature, stirring at a speed of 500 r / min for 60 to 90 min, to obtain slurry B;

[0024] S4. Keep stirring, mix slurry A and slurry B, add acrylic resin, glycerin, defoaming agent and film-forming agent, and continue stirring at room temperature for 1 to 2 hours to prepare the waterproof ink.

[0025] Acidification can improve the surface properties of carbon nanotubes, making them easier to disperse in the solution. The acidified carbon nanotubes are mixed with water-soluble polymerized cyclodextrin and methyltriethoxysilane. The network structure of the water-soluble polymerized cyclodextrin helps to bind the acidified carbon nanotube molecules, enhance the dispersibility and stability of the acidified carbon nanotubes in the dispersion medium, and prevent them from agglomerating. And through inclusion complexation, the water-soluble polymerized cyclodextrin can improve the interfacial compatibility of the acidified carbon nanotubes with other components in the ink.

[0026] Due to the inclusion complex of water-soluble polymerized cyclodextrin, its special structure and properties can form a protective layer on the surface of ink to prevent water molecules from penetrating into the interior of the ink, thereby improving the waterproof performance of the ink. At the same time, methyltriethoxysilane contains hydrophobic methyl groups, which make the surface of carbon nanotubes hydrophobic after modification, which helps to maintain the integrity of ink droplets in waterproof ink and further improve the waterproof performance of ink.

[0027] In the present invention, zein is added to the ink, zein is used as a hydrophobic protein, and is soluble in an alcoholic aqueous solution. Zein can be closely combined with a pigment to ensure the stability and dispersibility of the pigment in the ink. Cocamidopropyl betaine is added for modification, and cocamidopropyl betaine is a zwitterionic surfactant with excellent emulsification, dispersion and wetting properties. Modified zein is mixed with the pigment during the preparation process, and it can effectively prevent the agglomeration and precipitation of the pigment or dye, thereby improving the uniformity and stability of the ink. Cocamidopropyl betaine is utilized to reduce the surface tension of the ink, thereby improving its wettability and permeability.

[0028] Modified zein can enhance the film-forming property of ink and its ability to bind pigments. Zein has excellent film-forming property, which is due to its rich content of sulfur-containing amino acids and hydrophobic amino acids, which can form a stable and dense network structure during the film-forming process. This film not only has good mechanical properties, but also has excellent barrier properties, which can effectively prevent the penetration of moisture, oxygen and ultraviolet rays. In marker pen ink, the film-forming property of zein allows the ink to dry quickly on paper and form a solid film, thereby fixing the pigment in the ink and preventing it from fading or diffusing, further achieving the waterproof and color-fixing effect of the ink.

[0029] Beneficial effects of the present invention:

[0030] In the present invention, modified carbon nanotubes are added to the ink components, the water-soluble polymerized cyclodextrin and the hydrophobic effect of methyltriethoxysilane are used to improve the water resistance of the ink, and the modified zein is mixed with the pigment to improve the water-resistant and color-fixing effect of the pigment. The ink is obtained by working together with other components to obtain an ink with excellent water-resistant effect. DETAILED DESCRIPTION

[0031] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0032] Acrylic resin: water-based acrylic resin, purchased from Guangdong Keding Functional Materials Co., Ltd.; fatty alcohol polyoxyethylene ether: purchased from Shandong Xinheng Chemical Co., Ltd.; carbon black: purchased from Wuhan Jiyesheng Chemical Co., Ltd.; glycerol: purchased from Wuhan Jixinyibang Biotechnology Co., Ltd.; BYK-410: purchased from Yuchuan (Shanghai) Chemical Co., Ltd.; sorbitan oleate: purchased from Shanghai MacLean Biochemical Technology Co., Ltd., product number: S798904; zein: purchased from Shanghai Xige Biotechnology Co., Ltd.; carbon nanotubes: purchased from Shanghai Liantian Materials Technology Co., Ltd.; cocamidopropyl betaine: purchased from Shanghai Jiader Chemical Technology Co., Ltd.; water-soluble polymerized cyclodextrin: purchased from Shanghai MacLean Biochemical Technology Co., Ltd., product number: S871829.

[0033] Example 1

[0034] The invention comprises the following raw materials in parts by weight: 5 parts of acrylic resin, 1 part of fatty alcohol polyoxyethylene ether, 15 parts of carbon black, 5 parts of glycerol, 50 parts of deionized water, 0.5 parts of BYK-410, 1 part of sorbitan oleate, 5 parts of modified carbon nanotubes and 3 parts of modified zein.

[0035] Preparation of modified carbon nanotubes:

[0036] S1.1, adding carbon nanotubes to a mixed acid solution of sulfuric acid and nitric acid in a volume ratio of 3:1, heating to 70°C and reflux for 5 hours, washing until the solution pH is 6.5-7.5, and drying at 80°C for 12 hours to obtain acidified carbon nanotubes, wherein the amount ratio of the carbon nanotubes to the mixed acid solution is 0.3 mg / mL;

[0037] S1.2. Dissolve water-soluble polymerized cyclodextrin in deionized water, add methyltriethoxysilane and anhydrous ethanol, stir and disperse for 2 hours, adjust the pH of the solution to 6-7 to obtain a mixed solution A, continue to add acidified carbon nanotubes at 40°C, and stir at a speed of 450 r / min for 5 hours to obtain modified carbon nanotubes, wherein the solid-liquid ratio of the acidified carbon nanotubes and the mixed solution A is 1 g:20 mL, and the mass ratio of the water-soluble polymerized cyclodextrin, deionized water, methyltriethoxysilane and anhydrous ethanol is 15:80:5:80.

[0038] Preparation of modified zein:

[0039] Zein with a mass ratio of 1:5 was mixed with an ethanol aqueous solution with a mass fraction of 80%, and stirred at a speed of 400 r / min for 1 hour to obtain a mixed solution B. 3% of the mass of the mixed solution B was added to the mixed solution B, and the stirring and mixing were continued for 60 minutes while maintaining the speed to obtain modified zein.

[0040] Preparation of waterproof ink:

[0041] S1. Add surfactant and deionized water into the reaction kettle at room temperature according to weight, stir at 500r / min for 60min, then add pigment and continue stirring for 60min;

[0042] S2, adding modified carbon nanotubes in sequence while maintaining stirring, stirring again at room temperature for 60 min to obtain a mixed slurry, and letting it stand for 2 h to obtain slurry A;

[0043] S3, mixing the pigment and the modified zein at room temperature, and stirring at a speed of 500 r / min for 60 min to obtain slurry B;

[0044] S4. Keep stirring, mix slurry A and slurry B, add acrylic resin, glycerin, defoaming agent and film-forming agent, and continue stirring at room temperature for 1 hour to prepare the waterproof ink.

[0045] Example 2

[0046] The invention comprises the following raw materials in parts by weight: 8 parts of acrylic resin, 2 parts of fatty alcohol polyoxyethylene ether, 18 parts of carbon black, 8 parts of glycerol, 55 parts of deionized water, 1 part of BYK-410, 2 parts of sorbitan oleate, 6 parts of modified carbon nanotubes and 4 parts of modified zein.

[0047] Preparation of modified carbon nanotubes:

[0048] S1.1, adding carbon nanotubes to a mixed acid solution of sulfuric acid and nitric acid in a volume ratio of 3:1, heating to 75°C and reflux for 5.5h, washing until the solution pH is 6.5-7.5, and drying at 80°C for 12h to obtain acidified carbon nanotubes, wherein the amount ratio of the carbon nanotubes to the mixed acid solution is 0.4mg / mL;

[0049] S1.2. Dissolve water-soluble polymerized cyclodextrin in deionized water, add methyltriethoxysilane and anhydrous ethanol, stir and disperse for 2 hours, adjust the pH of the solution to 6-7 to obtain a mixed solution A, continue to add acidified carbon nanotubes at 40°C, and stir at a speed of 450 r / min for 5 hours to obtain modified carbon nanotubes, wherein the solid-liquid ratio of the acidified carbon nanotubes and the mixed solution A is 1 g:20 mL, and the mass ratio of the water-soluble polymerized cyclodextrin, deionized water, methyltriethoxysilane and anhydrous ethanol is 17:90:8:90.

[0050] Preparation of modified zein:

[0051] Zein with a mass ratio of 1:5 was mixed with an ethanol aqueous solution with a mass fraction of 80%, and stirred at a speed of 400 r / min for 1 hour to obtain a mixed solution B. 4% of the mass of the mixed solution B was added to the mixed solution B, and the stirring and mixing were continued for 80 minutes while maintaining the speed to obtain modified zein.

[0052] Preparation of waterproof ink:

[0053] S1. Add surfactant and deionized water into the reaction kettle at room temperature according to weight, stir at 500 r / min for 70 min, then add pigment, and continue stirring for 80 min;

[0054] S2, adding modified carbon nanotubes in sequence while maintaining stirring, stirring again at room temperature for 90 minutes to obtain a mixed slurry, and letting it stand for 2 hours to obtain slurry A;

[0055] S3, mixing the pigment and the modified zein at room temperature, stirring at a speed of 500 r / min for 70 min, to obtain slurry B;

[0056] S4. Keep stirring, mix slurry A and slurry B, add acrylic resin, glycerin, defoaming agent and film-forming agent, and continue stirring at room temperature for 1.5 hours to prepare the waterproof ink.

[0057] Example 3

[0058] The invention comprises the following raw materials in parts by weight: 10 parts of acrylic resin, 3 parts of fatty alcohol polyoxyethylene ether, 20 parts of carbon black, 10 parts of glycerol, 60 parts of deionized water, 2 parts of BYK-410, 3 parts of sorbitan oleate, 8 parts of modified carbon nanotubes and 5 parts of modified zein.

[0059] Preparation of modified carbon nanotubes:

[0060] S1.1, adding carbon nanotubes to a mixed acid solution of sulfuric acid and nitric acid in a volume ratio of 3:1, heating to 80°C and reflux for 6 hours, washing until the solution pH is 6.5-7.5, and drying at 80°C for 12 hours to obtain acidified carbon nanotubes, wherein the amount ratio of the carbon nanotubes to the mixed acid solution is 0.5 mg / mL;

[0061] S1.2. Dissolve water-soluble polymerized cyclodextrin in deionized water, add methyltriethoxysilane and anhydrous ethanol, stir and disperse for 2 hours, adjust the pH of the solution to 6-7 to obtain a mixed solution A, continue to add acidified carbon nanotubes at 40°C, and stir at a speed of 450 r / min for 5 hours to obtain modified carbon nanotubes, wherein the solid-liquid ratio of the acidified carbon nanotubes and the mixed solution A is 1 g:20 mL, and the mass ratio of the water-soluble polymerized cyclodextrin, deionized water, methyltriethoxysilane and anhydrous ethanol is 20:100:10:100.

[0062] Preparation of modified zein:

[0063] Zein with a mass ratio of 1:5 was mixed with an ethanol aqueous solution with a mass fraction of 80%, and stirred at a speed of 400 r / min for 1 hour to obtain a mixed solution B. 5% of the mass of the mixed solution B was added to the mixed solution B, and the stirring and mixing were continued for 90 minutes while maintaining the speed to obtain modified zein.

[0064] Preparation of waterproof ink:

[0065] S1. Add surfactant and deionized water into the reaction kettle at room temperature according to weight, stir at 500r / min for 90min, then add pigment and continue stirring for 90min;

[0066] S2, adding modified carbon nanotubes in sequence while maintaining stirring, stirring again for 120 min at room temperature to obtain a mixed slurry, and letting it stand for 2 h to obtain slurry A;

[0067] S3, mixing the pigment and the modified zein at room temperature, and stirring at a speed of 500 r / min for 90 min to obtain slurry B;

[0068] S4. Keep stirring, mix slurry A and slurry B, add acrylic resin, glycerin, defoaming agent and film-forming agent, and continue stirring at room temperature for 2 hours to prepare the waterproof ink.

[0069] Comparative Example 1

[0070] The difference between Comparative Example 1 and Example 1 is that no methyltriethoxysilane is added during the preparation of the modified carbon nanotubes in Comparative Example 1, and the other operations are the same.

[0071] Comparative Example 2

[0072] The difference between Comparative Example 2 and Example 1 is that step S1.2 is not performed during the preparation of the modified carbon nanotubes in Comparative Example 2, and the remaining operations are the same.

[0073] Comparative Example 3

[0074] The difference between Comparative Example 3 and Example 1 is that no cocamidopropyl betaine is added during the preparation of the modified zein in Comparative Example 3, and the other operations are the same.

[0075] Performance Testing:

[0076] 1. Referring to the method and steps provided in the standard "GB / T 9286-2021 Paint and Varnish Scratch Test", the ink prepared in Examples 1-3 was used to test the adhesion of the handwriting after writing with a marker pen, and the adhesion grade of the handwriting after curing reached 4B.

[0077] 2. Viscosity: refer to GB / T 13217.4-2008;

[0078] Writing performance: refer to QB / T 2777-2006;

[0079] Waterproofness: Refer to QB / T 2777-2006, test the longest time to get clear traces after being immersed in water, the results are as follows:

[0080]

[0081] According to the above data, it can be seen that the ink prepared by the present invention has excellent water resistance.

[0082] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A waterproof ink, characterized in that: The waterproof ink comprises the following raw materials in parts by weight: 5 to 10 parts of acrylic resin, 1 to 3 parts of surfactant, 15 to 20 parts of pigment, 5 to 10 parts of glycerol, 50 to 60 parts of deionized water, 0.5 to 2 parts of defoaming agent, 1 to 3 parts of film-forming agent, 5 to 8 parts of modified carbon nanotubes and 3 to 5 parts of modified zein; The preparation process of modified carbon nanotubes is as follows: S1.1, adding carbon nanotubes to a mixed acid solution of sulfuric acid and nitric acid in a volume ratio of 3:1, heating to 70-80°C and reflux for 5-6 hours, washing until the solution pH is 6.5-7.5, and drying at 80°C for 12 hours to obtain acidified carbon nanotubes; S1.

2. Dissolve water-soluble polymerized cyclodextrin in deionized water, add methyltriethoxysilane and anhydrous ethanol, stir and disperse for 2 hours, adjust the pH of the solution to 6-7 to obtain a mixed solution A, continue to add acidified carbon nanotubes at 40°C, stir at 450 r / min for 5 hours to obtain modified carbon nanotubes, wherein the solid-liquid ratio of the acidified carbon nanotubes and the mixed solution A is 1g:20mL.

2. The waterproof ink according to claim 1, characterized in that: The preparation method of the modified zein is as follows: Zein and ethanol aqueous solution in a mass ratio of 1:5 are mixed, and stirred at a speed of 400 r / min for 1 hour to obtain a mixed solution B. 3-5% of the mass of the mixed solution B is added to the mixed solution B, and the stirring and mixing are continued for 60-90 minutes while maintaining the speed to obtain modified zein.

3. The waterproof ink according to claim 1, characterized in that: The surfactant is one of sodium lauryl sulfate, polyoxyethylene lauryl ether, fatty alcohol polyoxyethylene ether, sodium carboxymethyl cellulose and sodium stearate.

4. The waterproof ink according to claim 1, characterized in that: The defoamer is one of BYK-410, DAPROAP7015 and Sago-1551.

5. The waterproof ink according to claim 1, characterized in that: The film-forming agent is one of sorbitan oleate and glyceryl monostearate.

6. The waterproof ink according to claim 1, characterized in that: The pigment is one of natural red, blue or black plant pigment and carbon black.

7. The waterproof ink according to claim 1, characterized in that: In step S1.1, the usage ratio of the carbon nanotubes to the mixed acid solution is 0.3-0.5 mg / mL.

8. The waterproof ink according to claim 1, characterized in that: In step S1.2, the mass ratio of the water-soluble polymerized cyclodextrin, deionized water, methyltriethoxysilane and anhydrous ethanol is (15-20): (80-100): (5-10): (80-100).

9. The waterproof ink according to claim 2, characterized in that: The mass fraction of ethanol in the ethanol aqueous solution is 80%.

10. A method for preparing the waterproof ink according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1. Add surfactant and deionized water into the reaction kettle at room temperature according to weight, stir at 500r / min for 60-90min, then add pigment, and continue stirring for 60-90min; S2, adding modified carbon nanotubes in sequence while maintaining stirring, stirring again at room temperature for 60 to 120 minutes to obtain a mixed slurry, and letting it stand for 2 hours to obtain slurry A; S3, mixing the pigment and the modified zein at room temperature, stirring at a speed of 500 r / min for 60 to 90 min, to obtain slurry B; S4. Keep stirring, mix slurry A and slurry B, add acrylic resin, glycerin, defoaming agent and film-forming agent, and continue stirring at room temperature for 1 to 2 hours to prepare the waterproof ink.

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