Modified carbon black for water-based inks, and preparation method and application thereof

Abstract

The application discloses modified carbon black for water-based ink and a preparation method and application thereof, and the preparation method comprises the following steps: mixing carbon black with a hydrogen peroxide solution, and then performing a pre-oxidation reaction to obtain pre-oxidized carbon black; mixing the pre-oxidized carbon black with a potassium permanganate solution dissolved in a strong acid, and then performing an oxidation reaction to obtain oxidized carbon black; soaking the oxidized carbon black in dilute acid, filtering, and then washing with water to obtain the modified carbon black. The carbon black is fully oxidized, the dispersion stability of carbon black particles in water-based ink is improved, when the carbon black is applied to water-based ink, excellent blue phase, blackness and stability can be simultaneously achieved, and the carbon black can be widely applied to the automobile paint, industrial paint and inkjet printing industry.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of ink, and particularly relates to a modified carbon black for water-based ink and a preparation method and application thereof. BACKGROUND

[0002] Carbon black is a nanoscale carbon particle formed by pyrolysis of hydrocarbon substances at high temperature, and has good electrical conductivity, thermal conductivity and adsorption performance. High pigment carbon black is a special carbon black with extremely high blackness, excellent tinting power and good dispersibility, and is widely used in high-grade ink, automotive paint finish, cosmetics and other fields. Water-based system has a very good prospect in safety, convenience of construction and user experience compared with traditional oily system.

[0003] Due to the small particle size, large specific surface area and high surface free energy of pigment carbon black, strong aggregation force is easily formed between carbon black particles, so that the carbon black particles exhibit hydrophobic properties and are difficult to disperse in a water-based system. At present, there are various carbon black oxidation modification processes for improving the dispersion performance of carbon black in a water-based system, such as chemical oxidation modification of carbon black using a nitrogen-containing oxidizing agent. However, such oxidizing agent not only pollutes the environment, but also easily introduces other by-products and impurities, and the process route for modifying carbon black is long and the processing process is complicated. Considering that pigment carbon black particles cannot be fully dispersed in a water-based system, carbon black paste cannot exhibit high blackness and high blue phase, and thus cannot meet the blackness and blue phase requirements of high-end markets. Therefore, it is of great significance to improve the dispersion stability of pigment carbon black in water and enable it to be applied to water-based ink. SUMMARY

[0004] In view of the above technical problems, the present application provides a modified carbon black for water-based ink and a preparation method and application thereof. By fully oxidizing the carbon black, the dispersion stability of the carbon black particles in the water-based ink is improved. When the carbon black is applied to the water-based ink, excellent blue phase, blackness and stability can be simultaneously achieved, and the carbon black can be widely applied to the automotive paint, industrial paint and inkjet printing industry.

[0005] The preparation method of the modified carbon black for water-based ink provided by the present application comprises the following steps:

[0006] S1, mixing carbon black and hydrogen peroxide solution to perform pre-oxidation reaction to obtain pre-oxidized carbon black;

[0007] S2, mixing the pre-oxidized carbon black with potassium permanganate solution dissolved in strong acid to perform oxidation reaction to obtain oxidized carbon black;

[0008] S3, soaking the oxidized carbon black in dilute acid, filtering and washing to obtain the oxidized carbon black, that is, the modified carbon black.

[0009] Compared with the oxidation degree of carbon black obtained by a traditional oxidation method, the oxidation degree is low, and the effect of stable dispersion in water cannot be achieved, in the application, hydrogen peroxide is used for pretreatment of carbon black to activate the carbon black, and then potassium permanganate dissolved in strong acid is used for deep oxidation treatment of the carbon black, so that the structural properties of the surface of the carbon black change, some oxygen-containing groups (-COOH, -OH, etc.) with good hydrophilic properties are introduced, the dispersibility and stability of the carbon black in the aqueous system are obviously improved, the technical problem of low dispersibility and stability of carbon black in the aqueous system in the traditional carbon black modification process is solved, and the modified carbon black exhibits high blackness and high blue phase, so that the product has a more senior feeling and a better visual effect.

[0010] Preferably, in step S1, the carbon black is furnace carbon black.

[0011] The average particle size of the furnace carbon black is 20-25 mu m, and the nitrogen adsorption specific surface area is 200-300 m 2 / g.

[0012] Preferably, in step S1, the concentration of hydrogen peroxide is 20-30 wt%, the pre-oxidation reaction temperature is 10-30 DEG C, and the time is 20-40 min.

[0013] Preferably, in step S2, the strong acid is sulfuric acid, and the concentration is 35-50 wt%;

[0014] The mass ratio of the pre-oxidized carbon black to potassium permanganate is 1:0.1-0.3.

[0015] Preferably, in step S2, the oxidation reaction temperature is 40-80 DEG C, and the time is 4-12 h.

[0016] Preferably, in step S3, the dilute acid is dilute hydrochloric acid, and the concentration is 1-10 wt%;

[0017] The soaking time is 6-8 h.

[0018] Preferably, in step S3, the oxidation carbon black is further modified, and the modification comprises coupling reaction of the oxidation carbon black with a tertiary amine-based silane coupling agent first, and then quaternary ammonium reaction of the oxidation carbon black with (3-bromopropyl) trimethylammonium bromide to obtain;

[0019] Preferably, the tertiary amine-based silane coupling agent is at least one of N, N-diethylaminopropyl trimethoxysilane, (diethylaminomethyl) trimethoxysilane or N-imidazole propyl triethoxysilane;

[0020] Preferably, the mass ratio of the oxidation carbon black, the tertiary amine-based silane coupling agent and (3-bromopropyl) trimethylammonium bromide is 1:0.01-0.05:0.01-0.1.

[0021] In the present application, the surface of the oxidized carbon black is grafted and modified by a tertiary amine group silane coupling agent, the tertiary amine group is introduced on the surface of the oxidized carbon black, which can be subjected to a quaternary ammonium reaction with (3-bromopropyl) trimethylammonium bromide, and finally a double quaternary ammonium salt group is introduced on the surface of the carbon black, which has high polarity and is hydrophilic and easy to disperse, so that the polarity of the carbon black itself can be further changed, and the dispersibility and stability of the carbon black in the aqueous system are further increased, so that the suspension stability of the colorant is ensured, and the carbon black particles are not easy to settle; in addition, the double quaternary ammonium salt group can form electrostatic adsorption with the water-based acrylic resin, thereby increasing the compatibility between the obtained modified carbon black and the water-based acrylic resin, and further improving the adhesion of the ink and the storage stability.

[0022] The present application also provides a modified carbon black for water-based ink, which is prepared by the above preparation method.

[0023] The present application also provides a water-based ink, which comprises the modified carbon black.

[0024] Preferably, the water-based ink further comprises a water-based acrylic resin.

[0025] Preferably, the amount of the water-based acrylic resin is 30-60 wt% of the total amount of the water-based ink, and the amount of the modified carbon black is 1-30% of the total amount of the water-based ink.

[0026] The present application has the following advantages:

[0027] (1) In the present application, by selecting appropriate carbon black, pre-oxidation is performed using hydrogen peroxide, and then under appropriate reaction conditions, the carbon black is subjected to a deep oxidation reaction with potassium permanganate dissolved in strong acid, so that the oxidized carbon black has good hydrophilicity and excellent dispersion stability in the aqueous system.

[0028] (2) In the present application, the oxidized carbon black is also modified by a surface modification method, and the prepared modified carbon black can be more stably dispersed in water and can be more compatible with the water-based acrylic resin. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The infrared spectrum of the modified carbon black described in Example 1 of the present application;

[0030] Figure 2 The structural schematic diagram of the modified carbon black described in Example 4 of the present application;

[0031] Figure 3 The effect diagram of the ink product corresponding to Example 1 of the present application. DETAILED DESCRIPTION

[0032] Hereinafter, the present invention will describe the technical solution in detail through specific embodiments. However, it should be clearly stated that these embodiments are provided for illustration only and are not to be construed as limiting the scope of the present invention.

[0033] Example 1

[0034] This embodiment provides a method for preparing modified carbon black for water-based ink, which is prepared by the following method:

[0035] (1) Furnace carbon black (average particle size 23 μm, nitrogen adsorption specific surface area 260 m 2 / g) was added into a 30wt% hydrogen peroxide solution, stirred for reaction for 30min, and then the water was evaporated to obtain pre-oxidized carbon black;

[0036] (2) Pre-oxidized carbon black was added to a potassium permanganate solution dissolved in sulfuric acid (with a concentration of 45 wt%), wherein the content of potassium permanganate in the solution was 3.6 wt%, and the amount of potassium permanganate used was 20 wt% of the furnace carbon black. The reaction was stirred in a water bath at 60°C for 8 h, and then naturally cooled to room temperature. The mixture was added to dilute hydrochloric acid (with a concentration of 5 wt%) and soaked for 7 h. The mixture was filtered, washed with water, and dried to obtain the modified carbon black.

[0037] The infrared spectrum of the modified carbon black is shown in FIG. Figure 1 As shown, refer to Figure 1 It can be seen that the modified carbon black has a -1 -OH bending vibration absorption peaks at 1750cm -1 -C=O stretching vibration absorption peaks on the left and right, 2300cm -1 The -COOH peaks on the left and right and 3600 cm -1 The -OH stretching vibration absorption peaks on the left and right are significantly enhanced, indicating that the oxygen-containing functional groups of carbon black, especially -OH and -C=O, are significantly increased after oxidation modification.

[0038] Example 2

[0039] This embodiment provides a method for preparing modified carbon black for water-based ink, which is prepared by the following method:

[0040] (1) Furnace carbon black (average particle size 23 μm, nitrogen adsorption specific surface area 260 m 2 / g) was added into a 20wt% hydrogen peroxide solution, stirred for reaction for 20min, and then the water was evaporated to obtain pre-oxidized carbon black;

[0041] (2) The pre-oxidized carbon black is added into a potassium permanganate solution dissolved in sulfuric acid (concentration of 45 wt%), the content of potassium permanganate in the solution is 3.6 wt%, the amount of potassium permanganate is 10 wt% of the furnace carbon black, after stirring for 4 h under the condition of water bath at 80℃, it is naturally cooled to room temperature, then it is soaked in dilute hydrochloric acid (concentration of 5 wt%) for 7 h, and then it is filtered, washed with water and dried, thereby the modified carbon black is obtained.

[0042] Example 3

[0043] The present example provides a preparation method of modified carbon black for water-based ink, which is prepared by the following method:

[0044] (1) The furnace carbon black (average particle size of 23 μm, nitrogen adsorption specific surface area of 260 m 2 / g) is added into a 30 wt% hydrogen peroxide solution, after stirring for 40 min, the water is evaporated, thereby the pre-oxidized carbon black is obtained;

[0045] (2) The pre-oxidized carbon black is added into a potassium permanganate solution dissolved in sulfuric acid (concentration of 45 wt%), the content of potassium permanganate in the solution is 3.6 wt%, the amount of potassium permanganate is 30 wt% of the furnace carbon black, after stirring for 12 h under the condition of water bath at 40℃, it is naturally cooled to room temperature, then it is soaked in dilute hydrochloric acid (concentration of 5 wt%) for 7 h, and then it is filtered, washed with water and dried, thereby the modified carbon black is obtained.

[0046] Example 4

[0047] The present example provides a preparation method of modified carbon black for water-based ink, which is prepared by the following method:

[0048] (1) The furnace carbon black (average particle size of 23 μm, nitrogen adsorption specific surface area of 260 m 2 / g) is added into a 30 wt% hydrogen peroxide solution, after stirring for 30 min, the water is evaporated, thereby the pre-oxidized carbon black is obtained;

[0049] (2) The pre-oxidized carbon black is added into a potassium permanganate solution dissolved in sulfuric acid (concentration of 45 wt%), the content of potassium permanganate in the solution is 3.6 wt%, the amount of potassium permanganate is 20 wt% of the furnace carbon black, after stirring for 8 h under the condition of water bath at 60℃, it is naturally cooled to room temperature, then it is soaked in dilute hydrochloric acid (concentration of 5 wt%) for 7 h, and then it is filtered, washed with water and dried, thereby the modified carbon black is obtained.

[0050] (3) The oxidized carbon black is added into water and stirred to disperse uniformly, and N, N-diethylaminopropyl trimethoxysilane is added, the amount of N, N-diethylaminopropyl trimethoxysilane is 3wt% of the oxidized carbon black, after stirring at 60℃ for 3h, (3-bromopropyl) trimethylammonium bromide is added, the amount of (3-bromopropyl) trimethylammonium bromide is 5wt% of the oxidized carbon black, after stirring at 80℃ for 12h, centrifugation, water washing and drying, the modified carbon black is obtained.

[0051] Comparative Example 1

[0052] The present comparative example proposes a preparation method of a modified carbon black for water-based ink, which is prepared by the following method:

[0053] The furnace carbon black (average particle size of 23μm, nitrogen adsorption specific surface area of 260m 2 / g) is added into 30wt% hydrogen peroxide solution, after stirring for 30min, the water is evaporated, and the modified carbon black is obtained.

[0054] Comparative Example 2

[0055] The present comparative example proposes a preparation method of a modified carbon black for water-based ink, which is prepared by the following method:

[0056] The furnace carbon black (average particle size of 23μm, nitrogen adsorption specific surface area of 260m 2 / g) is added into potassium permanganate solution dissolved in sulfuric acid (concentration of 45wt%), the content of potassium permanganate in the solution is 3.6wt%, the amount of potassium permanganate is 20wt% of the furnace carbon black, after stirring at 60℃ for 8h, it is naturally cooled to room temperature, then it is soaked in dilute hydrochloric acid (concentration of 5wt%) for 7h, after filtration, water washing and drying, the modified carbon black is obtained.

[0057] Comparative Example 3

[0058] The present comparative example proposes a preparation method of a modified carbon black for water-based ink, which is prepared by the following method:

[0059] The furnace carbon black (average particle size of 23μm, nitrogen adsorption specific surface area of 260m 2 / g) is added into potassium permanganate solution dissolved in sulfuric acid (concentration of 45wt%), the content of potassium permanganate in the solution is 3.6wt%, the amount of potassium permanganate is 20wt% of the furnace carbon black, after stirring at 60℃ for 8h, it is naturally cooled to room temperature, then 30wt% hydrogen peroxide solution is added, after stirring for 30min, it is soaked in dilute hydrochloric acid (concentration of 5wt%) for 7h, after filtration, water washing and drying, the modified carbon black is obtained.

[0060] Comparative Example 4

[0061] The present comparative example provides a preparation method of modified carbon black for water-based ink, which is prepared by the following method:

[0062] (1) The furnace carbon black (average particle size of 23 μm, nitrogen adsorption specific surface area of 260 m 2 / g) is added into 30 wt% hydrogen peroxide solution, stirred for 30 min, and then the water is evaporated to obtain pre-oxidized carbon black;

[0063] (2) The pre-oxidized carbon black is added into the potassium permanganate solution dissolved in sulfuric acid (concentration of 45 wt%), the content of potassium permanganate in the solution is 3.6 wt%, and the amount of potassium permanganate is 20 wt% of the furnace carbon black. After stirring at 60°C for 8 h in a water bath, it is naturally cooled to room temperature, then soaked in dilute hydrochloric acid (concentration of 5 wt%) for 7 h, filtered, washed with water, and dried to obtain the oxidized carbon black;

[0064] (3) The oxidized carbon black is added into water and stirred to disperse uniformly, and then the quaternary ammonium silane coupling agent (3-(trimethoxysilylpropyl) dimethyl octadecyl ammonium chloride) is added, and the amount of the quaternary ammonium silane coupling agent is 3 wt% of the oxidized carbon black. After stirring at 60°C for 3 h, centrifugation, washing with water, and drying, the modified carbon black is obtained.

[0065] The modified carbon black obtained in the examples and comparative examples is used in water-based ink, and the water-based ink includes, by mass percentage, 45 wt% water-based acrylic resin, 10 wt% modified carbon black, and the balance of water. An 80 μm wire bar is used to scrape the card on the black and white card paper, and the results of the ink product corresponding to Example 1 are shown in Table 1. Then, the 45° color data (L, a, b) are measured by a hexagonal colorimeter (BYK7030) to calculate the blackness (Mc, My), and the appearance state is observed, such as soft sinking, which indicates poor storage stability. The specific test results are shown in Table 1. Figure 3

[0066]

[0067] From the above table, it can be seen that the modified carbon black provided by each embodiment of the present application has excellent blue phase (the smaller the b value, the larger the dM value, the more excellent the blue phase), blackness (the larger the My value, the higher the blackness), and stability (no soft sinking) when used in water-based ink; compared with the single quaternary ammonium salt group modified carbon black (Comparative Example 4), the blackness and blue phase modification effect of the double quaternary ammonium salt group modified carbon black (Example 4) are obvious.

[0068] ​The above merely describes preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art, according to the technical solution and inventive concept of the present application, makes equivalent replacement or change within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A method for preparing modified carbon black for water-based ink, characterized in that: The steps include: S1, mixing carbon black with a hydrogen peroxide solution and performing a pre-oxidation reaction to obtain pre-oxidized carbon black; S2, mixing the pre-oxidized carbon black with a potassium permanganate solution dissolved in a strong acid and performing an oxidation reaction to obtain oxidized carbon black; S3, soaking the oxidized carbon black in dilute acid, filtering, and washing with water to obtain oxidized carbon black, which is the modified carbon black; Step S3 further includes modifying the oxidized carbon black, wherein the modification includes first subjecting the oxidized carbon black to a coupling reaction with a tertiary amino silane coupling agent, and then subjecting the oxidized carbon black to a quaternization reaction with (3-bromopropyl)trimethylammonium bromide; The tertiary amino silane coupling agent is at least one of N,N-diethylaminopropyltrimethoxysilane, (diethylaminomethyl)trimethoxysilane or N-imidazolepropyltriethoxysilane; The mass ratio of the oxidized carbon black, the tertiary amino silane coupling agent and (3-bromopropyl)trimethylammonium bromide is 1:0.01-0.05:0.01-0.

1.

2. The method for preparing modified carbon black for water-based ink according to claim 1, characterized in that: In step S1, the carbon black is furnace black; The average particle size of the furnace carbon black is 20-25 μm, and the nitrogen adsorption specific surface area is 200-300 m 2 / g.

3. The method for preparing modified carbon black for water-based ink according to claim 1, characterized in that: In step S1, the concentration of the hydrogen peroxide is 20-30 wt %, the pre-oxidation reaction temperature is 10-30° C., and the time is 20-40 min.

4. The method for preparing modified carbon black for water-based ink according to any one of claims 1 to 3, characterized in that: In step S2, the strong acid is sulfuric acid with a concentration of 35-50wt%; The mass ratio of the pre-oxidized carbon black to potassium permanganate is 1:0.1-0.

3.

5. The method for preparing modified carbon black for water-based ink according to any one of claims 1 to 3, characterized in that: In step S2, the oxidation reaction temperature is 40-80° C. and the time is 4-12 hours.

6. The method for preparing modified carbon black for water-based ink according to any one of claims 1 to 3, characterized in that: In step S3, the dilute acid is dilute hydrochloric acid with a concentration of 1-10wt%; The soaking time is 6-8 hours.

7. A modified carbon black for water-based ink, characterized in that: The compound is prepared by the preparation method according to any one of claims 1 to 6.

8. A water-based ink, characterized in that: It comprises the modified carbon black according to claim 7.

9. The water-based ink according to claim 8, characterized in that: It also includes a water-based acrylic resin; the amount of the water-based acrylic resin is 30-60wt% of the total amount of the water-based ink, and the amount of the modified carbon black is 1-30wt% of the total amount of the water-based ink.

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