GB2617469A - Use of quaternary ammonium salt derivative in preparation of red pigment, red pigment, and preparation method - Google Patents

Abstract

In the present application, in order to solve the problems of pigment wettability, poor dispersibility, high viscosity, and poor storage stability, a quaternary ammonium salt derivative is used in the preparation of an azo red pigment for a water-based UV ink; a red pigment and a preparation method therefor are provided, and a water-based UV red ink using the red pigment is further provided. The preparation method for a red pigment comprises a diazotization reaction, the preparation of a coupling liquid, a coupling reaction, post-treatment and other processes; a quaternary ammonium salt derivative is added during the preparation of the coupling solution, and an anionic surfactant and nonionic surfactant compound solution is added during post-treatment, enabling the pigment to have good wettability, high dispersibility, high tinting strength, low viscosity and good storage stability in a water-based UV system.

Description

USE OF QUATERNARY AMMONIUM SALT DERIVATIVE IN PREPARATION OF RED PIGMENT, AND RED PIGMENT AND PREPARATION METHOD THEREOF

CROSS REFERENCE TO RELATED APPLICATION

100011 The present application claims the priority to Chinese Patent Application No. CN202111364893.4, titled "USE OF QUA1ERNARY AMMONIUIVI SALT DERIVATIVE IN PREPARATION OF RED PIGMENT, AND RED PIGMENT AND PREPARATION METHOD THEREOF", filed with China National Intellectual Property Administration (CNIPA) on November 17, 2021, which is incorporated herein by reference in its entirety.

TECHNICAL FIELD

100021 The present disclosure relates to the technical field of pigment production for water-based ultraviolet (UV)-cured inks, in particular to use of a quaternary ammonium salt derivative in preparation of a red pigment, and a red pigment and a preparation method thereof

BACKGROUND

100031 In recent years, there are increasingly stringent requirements on the printing industry for environmental protection, and the requirements for environmental friendliness of the inks have also gradually increased. As a result, the advantages of water-based UV-cured inks have become much more obvious. Therefore, environmental-friendly water-based UV-cured inks are developing rapidly due to their environmental protection performance and application effects. The United States, Japan, South Korea and other countries are also vigorously promoting the use of the environmental-friendly water-based UV-cured inks. Water-based UV-cured pigments may be the best choice for environmental-friendly inks in the future, and have extremely broad development prospects. As one of the important raw materials of printing inks, pigments provide the necessary vivid colors for inks. Moreover, the tinting strength, viscosity, and glossiness of pigments directly affect the quality of water-based UV-cured inks.

100041 In the prior art, the red pigment is mainly prepared from a mixture of 3-amino-4-methoxybenzanilide (10-Base) diazonium salt with N-(4-chloro-2,5-dimethoxypheny1)-3-hydroxy-2-naphthyl carboxami de (AS-LC) and 3-hydroxy-N-(2-methyl-5-dichloropheny1)-2-naphthylcarboxamide (AS-KB). Applying such a red pigment to the water-based UV-cured inks results in poor dispersion, high viscosity, and undesirable storage stability.

[0005] In the prior art, there was a practice of directly adding quaternary ammonium salt derivatives to the ink. However, the quaternary ammonium salt derivatives are physically mixed with the pigment in the ink, which may lead to undesirable phenomena such as crystallization and agglomeration of the ink. Accordingly, it is further necessary to add surfactants, dispersants, and polymer additives to improve the performances of ink when preparing the ink, thereby increasing a production cost of the ink.

SUMMARY

[0006] The present disclosure aims at the deficiencies of the prior art, improves a production process, and protects use of a quaternary ammonium salt derivative in preparation of a red pigment. The present disclosure provides an azo red pigment for a water-based UV-cured ink, a preparation method of the red pigment, and a water-based UV-cured red ink using the red pigment.

[0007] The present disclosure adopts the following technical solutions.

[0008] I. The present disclosure provides use of a quaternary ammonium salt derivative with a chemical abstracts service (CAS) number of 107-64-2 in preparation of an azo red pigment for a water-based UV-cured ink.

[0009] II. The present disclosure provides a preparation method of a red pigment, including the following steps: 100101 Si, diazotization: [0011] dispersing 3-amino-4-methoxybenzanilide (KD-Base) evenly in an aqueous solution, dissolving in an acidic environment, conducting diazotization with excess sodium nitrite, and removing the excess sodium nitrite to obtain a diazotization solution I; [0012] S2, preparation of a coupling solution: [0013] S2.1, dissolving an AS component and a quaternary ammonium salt derivative in an alkaline solution to obtain a coupling component solution 11; and [0014] S2.2, adding the coupling component solution II into an acidic solution to precipitate the AS component and the quaternary ammonium salt derivative, and adjusting a pH value to 3.8 to 6 and a temperature to 20°C to 70°C to obtain a coupling solution III; [0015] S3, coupling [0016] adding the diazotization solution I obtained in step Si to the coupling solution III obtained in step S2.2 to allow coupling to obtain a red color paste; and [0017] S4, post-treatment: [0018] conducting post-treatment on the red color paste to obtain the red pigment; where [0019] in step S2.2, the quaternary ammonium salt derivative has a CAS number of 107-64-2. 100201 Specifically, in step Si, the diazotization includes the following steps: dispersing 3-amino-4-methoxybenzanilide (KD-Base) evenly in an aqueous solution, dissolving in a hydrochloric acid solution, conducting diazotization with an excessive amount of a sodium nitrite solution at -5°C to 0°C, and removing the excess sodium nitrite with sulfamic acid to obtain a diazotization solution I. [0021] Specifically, step S2 includes the following steps: [0022] 52.1, dissolving an AS component and a quaternary ammonium salt derivative in an alkaline solution to obtain a coupling component solution II; and 100231 S2.2, adding the coupling component solution II into an acetic acid aqueous solution to precipitate the AS component and the quaternary ammonium salt derivative, and adjusting a pH value to 3.8 to 6 and a temperature to 20°C to 70°C to obtain a coupling solution III. Preferably, the coupling component solution II is added to the acetic acid aqueous solution at a constant speed for 10 min to 45 min. [0024] In steps S2.1 and S2.2, the AS component may be dissolved in the alkaline solution, and then the quaternary ammonium salt derivative may be dissolved in the alkaline solution. An obtained mixed solution is added to the acetic acid aqueous solution to precipitate the AS component and the quaternary ammonium salt derivative. The quaternary ammonium salt derivative can adjust tinting strength, gloss, wettability, viscosity, and storage stability.

100251 In step S3, the diazotization solution I obtained in step Si is preferably added to the coupling solution III obtained in step S2.2 at a constant speed for 30 min to 150 min. [0026] Specifically, the post-treatment in step S4 includes: conducting resinification on the red color paste by adding rosin, adjusting a crystal shape and a particle size of the red color paste, thereby finally obtaining the red pigment. The rosin is at least one selected from the group consisting of special-grade rosin, disproportionated rosin, maleic rosin, and polymerized rosin.

[0027] Specifically, the AS component is a mixture of 3-hydroxy-N-(4-chloro-2,5-dimethoxypheny1)-2-naphthylcarboxamide (AS-LC) and 3-hydroxy-N-(2-methyl-5-dichloropheny1)-2-naphthylcarboxamide (AS-KB); alternatively, the 30 AS component is one selected from the group consisting of 3-hydroxy-N-phenyl-2-naphthylcarboxamide (AS), 3-hydroxy-N-(2-methoxyphenyI)-2-naphthylcarboxamide (AS-OL), 3-hydroxy-N-(4-methylpheny1)-2-naphthylcarboxamide (AS-RT), 3-hydroxy-N-(2-methylpheny1)-2-naphthylcarboxami de (AS-D), 3-hydroxy-N-(3-nitrophenyI)-2-naphthylcarboxami de (AS-BS), 3-hydroxy-N-(2-methylchloro)-2-naphthylcarboxamide (AS-TR), 3-hydroxy-N-(4-chloropheny1)-2-naphthyl carb oxam i de (AS-E), 3-hydroxy-2-naphthoyl -ortho-ph en eti di de (AS-PH), and 5-(2'-hydroxy-3'-naphthoylamino)-2-benzimidazolone. Different AS components can produce red pigments with different index numbers, such as Pigment Red 184, Pigment Red 146, Pigment Red 269, Pigment Red 31, Pigment Red 32, Pigment Red 147, Pigment Red 176, and Pigment Red 213.

100281 Preferably, the quaternary ammonium salt derivative is added at 5% to 25% of a weight of the AS component.

100291 Preferably, during the post-treatment in step S4 or after the AS component and the quaternary ammonium salt derivative are precipitated in step S2.2, surface modification is conducted by adding a compound solution of an anionic surfactant and a nonionic surfactant.

The surface modification is conducted to improve the transparency, glossiness and other properties of the red pigment in a water-based UV system.

100301 More preferably, the compound solution of the anionic surfactant and the nonionic surfactant is added at 0% to 3% of a weight of the AS component. More preferably, the anionic surfactant and the nonionic surfactant are compounded at a weight ratio of 1:(1-4). Optimally, the anionic surfactant and the nonionic surfactant are compounded at a weight ratio of 1:1. In the present disclosure, the anionic surfactant is at least one selected from the group consisting of a carboxylate, a fatty acid ammonium salt, an alkyl ether carboxylate, a sulfonate, an aryl alkyl sulfonate, a linear alcohol ethoxylate sulfate, and sulfated triglyceride oil; and the nonionic surfactant is at least one selected from the group consisting of dodecylphenol, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether, a fatty alcohol sulfate, an ethylene oxide-propylene oxide copolymer, a long-chain fatty acid ester, propylene glycol, sorbitol, and polyethylene glycol ester. The anionic surfactant is preferably at least one selected from the group consisting of a carboxylate, a fatty acid ammonium salt, an alkyl ether carboxylate, an aryl alkyl sulfonate, and a linear alcohol ethoxylate sulfate; and the nonionic surfactant is preferably at least one selected from the group consisting of dodecylphenol, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, a fatty alcohol sulfate, an ethylene oxide-propylene oxide copolymer, and polyethylene glycol ester.

[0031] III. The present disclosure provides an azo red pigment for a water-based UV-cured ink prepared by the preparation method.

100321 IV The present disclosure provides a water-based UV-cured red ink prepared from the azo red pigment for a water-based UV-cured ink prepared by the preparation method.

[0033] Compared with the prior art, the present application has the following beneficial effects: [0034] (I) The quaternary ammonium salt derivative with a CAS number of 107-64-2 is added in production of the red pigment applied to a water-based UV-cured ink. Since alkyl groups and Chs-disubstituted amino groups are introduced into a molecular structure of the pigment, an application performance of the pigment compound molecule is enhanced. The pigment particles are dispersed in a carrier through an "anchor" effect formed by hydrogen bonds, polar effect, and Van der Waals' force and other affinity effects. Therefore, a dipole moment of the derivative with large polarity is substantially improved compared with that of the existing similar compounds without polar groups, and the surface of each newly-formed pigment particles is covered by the carrier. This prevents re-aggregation of the pigment particles, thereby improving the wettability, dispersibility, and dispersion stability of pigments in the ink. As a result, the use of the quaternary ammonium salt derivative in preparing pigments for the water-based UV-cured inks has more obvious application prospects and better application performances.

[0035] (II) An anionic surfactant is introduced during the pigment reaction. The anionic surfactant can be dissolved in a pigment alkaline solution, slightly improving the wettability of the pigment. If only a nonionic surfactant is introduced, the nonionic surfactant does not dissolve in the pigment alkaline solution. Therefore, the nonionic surfactant has no effect in the synthesis of pigment, but makes the pigment opaque, such that nonionic surfactants are not used in conventional production. In the present disclosure, the anionic surfactant is compounded with the nonionic surfactant in a weight ratio of 1:(1-4). An obtained compound is dissolved in the pigment alkaline solution and has a better pigment wetting effect. Therefore, the surfactants are introduced to treat the surface of pigments and control the arrangement of pigment particles. According to a principle that the smaller the degree of polymerization of the pigment, the greater the water solubility, the size and distribution of pigment particle size, the physical shape of particles, and the surface polarity characteristics all enable the pigments to be dispersed in the water-based UV-cured system with higher tinting strength, lower viscosity, and better storage stability. The anionic surfactant and the nonionic surfactant are at a weight ratio of preferably 1:(1-4) to adjust the glossiness and transparency of the pigment.

[0036] (III) If no quaternary ammonium salt derivative is added during the pigment synthesis, and only 15% to 20% of the anionic surfactant is added, the pigment may be poorly dispersed in the ink. In the present disclosure, the quaternary ammonium salt derivative can not only improve the di spersibility of the pigment in an application medium, but also reduce the viscosity and storage stability of the pigment in the ink. During the preparation of pigments for water-based UV-cured inks, after adding the quaternary ammonium salt derivative, the amount of surfactants, dispersants, and polymer additives is reduced to the greatest extent. The amount of surfactants is reduced from 15% to 20% to 0% to 3% of a weight of the AS component. In this way, under the premise of ensuring a product quality, a production cost of pigments can be reduced to the greatest extent. Moreover, the amount of surfactants, dispersants and polymer additives used in the preparation of inks can be reduced, so as to reduce the production cost of inks.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0037] The following preparation examples and experimental examples can illustrate the present disclosure in more detail, but do not limit the present disclosure in any form.

[0038] Unless otherwise specified, the content of each component used in the following is based on the weight percentage content.

[0039] The following are the raw materials used in each example: [0040] a hydrochloric acid solution: HC1 has a mass percentage content of 30%; 100411 a caustic soda solution: NaOH has a mass percentage content of 20%; 100421 a sodium nitrite solution: NaNO2 has a mass percentage content of 35%; [0043] an acetic acid solution: HAc has a mass percentage content of 80%; [0044] 3-amino-4-methoxybenzanili de (KD-Base) with a mass percentage of 100%; 100451 3-hydroxy-N-(4-chloro-2,5-dimethoxypheny1)-2-naphthylcarboxamide (AS-LC) with a mass percentage of 98%; [0046] 3-hydroxy-N-(2-methy1-5-dichloropheny1)-2-naphthylcarboxamide (AS-KB) with a mass percentage of 98%; 100471 3-hydroxy-N-(2,5-dimethoxypheny1)-2-naphthylcarboxamide (AS-CA) with a mass percentage of 98%; [0048] a quaternary ammonium salt derivative: a FENTACARE 1821 product purchased from Solvay (China), with a stmctural expression formula as: [0049] [0050] sulfamic acid: 98% by mass percentage; [0051] special-grade rosin: 100% by mass percentage; and [0052] polymerized rosin: 100% by mass percentage.

[0053] Example 1

[0054] A quaternary ammonium salt derivative was added at 24% (3 g) of a weight of an AS component, and a surfactant compound solution was added at 0.8% (0.1 g) of a weight of the AS component.

[0055] Si, diazotization: [0056] 110 mL of water was added into a diazotization reaction vessel, and 13.2 g of 3-amino-4-methoxybenzanilide (KD-Base) was added and mixed for 0.5 h while stirring. 19.4 g of a hydrochloric acid solution was added and stirred to dissolve the KD-Base, and cooled to below -5°C with ice. 11.9 g of a sodium nitrite solution was added and stirred for 1 h. The excess sodium nitrite was removed with sulfamic acid until a K1 starch test paper was slightly bluish at an end point, so as to obtain a diazotization solution 1.

[0057] S2, preparation of a coupling solution: [0058] S2.1. 120 mL of water was added into a coupling component dissolution container, 27 g of a sodium hydroxide solution was added, and heated to 85°C. 8.2 g of N-(4-chl oro-2,5-di m eth oxyph eny1)-3 -hy droxy -2-n aphthyl carbox anai de (AS-LC), 4.1 g of 3-hydroxy-N-(2-methyl-5-dichlorophenyI)-2-naphthylcarboxamide (AS-KB), and 3 g of a quaternary ammonium salt derivative were added into the container. A resulting mixture was dissolved by stirring until transparent, cooled to 45°C with ice to obtain a coupling component solution II.

[0059] S2.2. 100 mL of water was added into a coupling container, 10.6 g of acetic acid was added under stirring, and mixed to form an acetic acid aqueous solution. The coupling component solution II was added to the acetic acid aqueous solution within 20 min, and adjusted to pH=6.4 to precipitate the N-(4-chloro-2,5-dimethoxyphenyI)-3 -hydroxy-2-naphthyl carboxami de (AS-LC), the 3-hydroxy-N-(2-methyl-5-dichloropheny1)-2-naphthylcarboxamide (AS-KB), and the quaternary ammonium salt derivative. The coupling component was mixed with the quaternary ammonium salt derivative between particles, and then adjusted to pH=4.6 at 50°C to obtain a coupling solution III [0060] S3, coupling [0061] The diazotization solution I was added to the coupling solution III at 50°C within 60 min to allow coupling to generate a red color paste.

[0062] S4, post-treatment: [0063] The red color paste was stirred for 60 min, adjusted to pH=5.4, and 15 g of a 10% rosin solution was added to conduct resinification on the pigment in the red color paste by stirring for 60 min. 0.1 g of a compound solution of an alkyl ether carboxylate-based surfactant and a fatty alcohol polyoxyethylene ether-based surfactant was added to conduct surface modification on the pigment in the red color paste by stirring for 20 min. An obtained product was heated to 80°C for 120 mm, and then cooled down to below 60°C, filter-pressed, and washed with water. A filter cake was dried to remove moisture to obtain a PR184 pigment for a water-based UV-cured ink.

The alkyl ether carboxylate-based surfactant and the fatty alcohol polyoxyethylene ether-based surfactant were compounded at a ratio of 1:1. A specific compounding process included: 100 mL of water was heated to 50°C, 0.05 g of the alkyl ether carboxylate-based surfactant was added, and stirred until transparent. 0.05 g of the fatty alcohol polyoxyethylene ether-based surfactant was added, and stirred until transparent to obtain the surfactant compound solution.

100641 A preparation method of the rosin solution included: 500 mL of water was heated to 100°C, 75 g of special-grade rosin was added, stirred for 60 mm to make it completely dissolved and transparent, and then cooled down to 50°C to 55°C to obtain the rosin solution.

[0065] The quaternary ammonium salt derivative was FENTACARE 1821 of Solvay (China). 100661 Results: compared with a standard sample, the red pigment of this example had similar hue, 100% tinting strength, similar viscosity, and storage stability.

[0067] Notes: the subsequent examples differ with this example only in some test conditions.

100681 Example 2

[0069] This example differed from Example 1 in that in step S2.1, no quaternary ammonium salt derivative was added.

100701 52.1. 120 mL of water was added into a coupling component dissolution container, 27 g of a sodium hydroxide solution was added, and heated to 85°C. 8.2 g of N-(4-chloro-2,5-dimethoxypheny1)-3-hydroxy-2-naphthylcarboxamide (AS-LC), and 4.1 g of 3-hydroxy-N-(2-methyl-5-dichloropheny1)-2-naphthylcarboxamide (AS-KB) were added into the container. A resulting mixture was dissolved by stirring until transparent, cooled to 45°C with ice to obtain a coupling component solution II. The other steps were the same.

100711 Results: compared with Example 1, the red pigment of this example had a relatively bluish hue, a tinting strength of 90%, and a high viscosity.

[0072] Example 3

[0073] This example differed from Example 1 in that in step S2.1, the quaternary ammonium salt derivative was added at 8.1% (1 g) of a weight of the AS component.

100741 S2.1. 120 mL of water was added into a coupling component dissolution container, 27 g of a sodium hydroxide solution was added, and heated to 85°C. 8.2 g of N-(4-chl oro-2,5-di m eth oxyph eny1)-3 -hydroxy-2-n aphthyl carboxami de (AS-LC), 4.1 g of 3-hydroxy-N-(2-methyl-5-dichloropheny1)-2-naphthylcarboxamide (AS-KB), and 1 g of a quaternary ammonium salt derivative were added into the container. A resulting mixture was dissolved by stirring until transparent, cooled to 45°C with ice to obtain a coupling component solution II. The other steps were the same 100751 Results: compared with Example 1, the red pigment of this example had a slightly bluish hue, a tinting strength of 95%, and a high viscosity.

100761 Example 4

100771 This example differed from Example 1 in that in step S2.1, the quaternary ammonium salt derivative was added at 16.2% (2 g) of a weight of the AS component.

[0078] S2.1. 120 mL of water was added into a coupling component dissolution container, 27 g of a sodium hydroxide solution was added, and heated to 85°C. 8.2 g of N-(4-chloro-2,5-dimethoxypheny1)-3-hydroxy-2-naphthylcarboxamide (AS-LC), 4.1 g of 3-hydroxy-N-(2-methyl-5-dichloropheny1)-2-naphthylcarboxamide (AS-KB), and 2 g of a quaternary ammonium salt derivative were added into the container. A resulting mixture was dissolved by stirring until transparent, cooled to 45°C with ice to obtain a coupling component solution II. The other steps were the same 100791 Results: compared with Example 1, the red pigment of this example had a less bluish hue, a tinting strength of 97%, and a higher viscosity.

[0080] Example 5

[0081] This example differed from Example 1 in that in step S4, no compound solution was added.

[0082] Results: compared with Example 1, the red pigment of this example had Relatively low transparency, a tinting strength of 85%, and a higher viscosity.

[0083] Example 6

[0084] This example differed from Example 1 in that in step S4, only 0.1 g of an anionic surfactant, alkyl ether carboxylate, was added, and no nonionic surfactant, fatty alcohol polyoxyethylene ether, was added.

100851 Results: compared with Example 1, the red pigment of this example had slightly lower transparency, a tinting strength of 90%, and a higher viscosity.

100861 Example 7

[0087] This example differed from Example 1 in that in step S4, only 0.t g of a nonionic surfactant, fatty alcohol polyoxyethylene ether, was added, and no anionic surfactant, alkyl ether carboxylate, was added.

[0088] Results: the fatty alcohol polyoxyethylene ether was insoluble in the aqueous solution; compared with Example 1, the red pigment of this example had a relatively yellowish hue, Relatively low transparency, a tinting strength of 80%, and a relatively high viscosity.

[0089] Example 8

[0090] This example differed from Example 1 in that in step S4, 0.3 g of the compound solution was added.

100911 Results: compared with Example 1, the red pigment of this example had similar transparency, a tinting strength of 100°A, and a less low viscosity. The result of this example was similar to that of Example 1, but there was a high amount of the compound solution added, causing a high product cost.

[0092] Example 9

100931 This example differed from Example 1 in that in step S4, the alkyl ether carboxylate and the fatty alcohol polyoxyethylene ether had a ratio of 1:2 in the compound solution.

[0094] Results: compared with Example 1, the compound solution was opaque in the aqueous solution. Compared with Example 1, the red pigment of this example had a relatively yellowish hue, Relatively low transparency, a lower tinting strength, and a higher viscosity.

[0095] Example 10

[0096] This example differed from Example 1 in that in step S4, the alkyl ether carboxylate-based surfactant and the fatty alcohol polyoxyethylene ether-based surfactant had a ratio of 2:1 in the compound solution.

[0097] Results: compared with Example 1, the red pigment of this example had slightly lower transparency, a tinting strength of 93%, and a higher viscosity.

100981 Example 11

[0099] This example differed from Example 1 in that in step S4, the alkyl ether carboxylate-based surfactant and the fatty alcohol polyoxyethylene ether-based surfactant had a ratio of 1:3 in the compound solution.

[0100] Results: compared with Example 1, the compound solution had flocs in the aqueous solution. Compared with Example 1, the red pigment of this example had a relatively yellowish hue, Relatively low transparency, a tinting strength of 93%, and a higher viscosity.

[0101] Example 12

101021 This example differed from Example 1 in that in step S4, the alkyl ether carboxylate-based surfactant and the fatty alcohol polyoxyethylene ether-based surfactant had a ratio of 1:4 in the compound solution.

[0103] Results: compared with Example 1, the compound solution had obvious insoluble matters in the aqueous solution. Compared with Example 1, the red pigment of this example had a slightly yellowish hue, Relatively low transparency, a tinting strength of 92%, and a higher viscosity.

101041 Example 13

[0105] This example differed from Example 1 in that the AS component had a compounding ratio of 1:1, specifically including 6.15 g of N-(4-chloro-2,5-dimethoxyphenyI)-3-hydroxy-2-naphthylcarboxamide (AS-LC), and 6.15 g of 3-hydroxy-N-(2-methyl-5-dichloropheny1)-2-naphthylcarboxamide (AS-KB).

[0106] Results: compared with Example 1, the red pigment of this example had a relatively bluish hue, and a tinting strength of 87%.

[0107] Example 14

[0108] This example differed from Example 1 in that the AS component had a compounding ratio of 2:3, specifically including 4.92 g of N-(4-chloro-2,5-dimethoxypheny1)-3-hydroxy-2-naphthylcarboxamide (AS-LC), and 7.38 g of 3-hydroxy-N-(2-methyl-5-di chloropheny1)-2-naphthyl carb ox am i de (AS-KB).

[0109] Results: compared with Example 1, the red pigment of this example had a relatively yellowish hue, and a tinting strength of 95%.

[0110] Example 15

[0111] This example differed from Example 1 in that the quaternary ammonium salt derivative was added in step 54, but not in S2.1.

[0112] The method specifically includes the following steps.

[0113] Sl, diazotization: [0114] 110 mL of water was added into a diazotization reaction vessel, and 13.2 g of 3-amino-4-methoxybenzanilide (KD-Base) was added and mixed for 0.5 h while stirring. 19.4 g of a hydrochloric acid solution was added and then stirred to dissolve the KD-Base, and cooled to below -5°C with ice. 11.9 g of a sodium nitrite solution was added and stirred for 1 h. The excess sodium nitrite was removed with sulfamic acid until a 1(1 starch test paper was slightly bluish at an end point, so as to obtain a diazotization solution I. [0115] S2, preparation of a coupling solution: [0116] S2.1. 120 mL of water was added into a coupling component dissolution container, 27 g of a sodium hydroxide solution was added, and heated to 85°C. 8.2 g of N-(4-chloro-2,5-dimethoxypheny1)-3-hydroxy-2-naphthylcarboxamide (AS-LC), and 4.1 g of 3-hydroxy-N-(2-methyl-5-dichloropheny1)-2-naphthylcarboxamide (AS-KB) were added into the container. A resulting mixture was dissolved by stirring until transparent, cooled to 45°C with ice to obtain a coupling component solution II.

[0117] S2.2. 100 mL of water was added into a coupling container, 10.6 g of acetic acid was added under stirring, and mixed to form an acetic acid aqueous solution. The coupling component solution II was added to the acetic acid aqueous solution within 20 mm, and adjusted to pH=6.4, to obtain a precipitate of the N-(4-chloro-2,5-dimethoxyphenyI)-3-hydroxy-2-naphthylcarboxamide (AS-LC) and the 3-hydroxy-N-(2-methyl-5-dichlorophenyI)-2-naphthylcarboxamide (AS-KB). The coupling component was mixed with the quaternary ammonium salt derivative between particles, and then adjusted to pH=4.6 at 50°C to obtain a coupling solution III.

[0118] S3, coupling [0119] The diazotization solution I was added to the coupling solution IR at 50°C within 60 min to allow coupling to generate a red color paste.

[0120] S4, post-treatment: [0121] The red color paste was stirred for 60 min, adjusted to pH=5.4, 3 g of a quaternary ammonium salt derivative solution was added, and 15 g of a 10% rosin solution was added to conduct resinification on the pigment in the red color paste by stirring for 60 min. 0.1 g of a compound surfactant of alkyl ether carboxylate and fatty alcohol polyoxyethylene ether was added. An obtained product was heated to 80°C for 120 min, and then cooled down to below 60°C, filter-pressed, and washed with water. A filter cake was dried to remove moisture to obtain a PRI84 pigment for a water-based UV-cured ink.

[0122] A preparation method of the quaternary ammonium salt derivative solution included: 100 mL of water was added into a beaker, heated to 40°C, and stirred and dissolved until transparent to obtain the quaternary ammonium salt derivative solution.

[0123] A preparation method of the rosin solution included: 500 mL of water was heated to 100°C, 75 g of special-grade rosin was added, stirred for 60 mm to make it completely dissolved and transparent, and then cooled down to 50°C to 55°C to obtain the rosin solution.

[0124] Results: compared with Example 1, the red pigment of this example had a similar hue, and a tinting strength of 92%.

101251 Example 16

[0126] This example differed from Example 1 in that the compound solution of surfactant was added in step S2.1, but not in S4.

101271 S2.1. 120 mL of water was added into a coupling component dissolution container, 27 g of a sodium hydroxide solution was added, and heated to 85°C. 8.2 g of N-(4-chl oro-2,5-di m eth oxyph eny1)-3 -hydroxy-2-n aphthyl carboxami de (AS-LC), 4.1 g of 3-hydroxy-N-(2-methyl-5-dichlorophenyI)-2-naphthylcarboxamide (AS-KB), and 3 g of a quaternary ammonium salt derivative were added into the container. 0.1 g of a compound surfactant of alkyl ether carboxylate and fatty alcohol polyoxyethylene ether was added. A resulting mixture was dissolved by stirring until transparent, cooled to 45°C with ice to obtain a coupling component solution II. The other steps were the same.

101281 Results: compared with Example 1, the red pigment of this example had a similar hue, and a tinting strength of 100%, and a lower viscosity.

[0129] Example 17

[0130] In this example, the type of the compound solution in step S4 of Example I was replaced, that is, the anionic surfactant and the nonionic surfactant were fatty acid ammonium salt and dodecylphenol, respectively, with a ratio of 1:1.

101311 Results: compared with Example 1, the red pigment of this example had a less yellowish hue, a tinting strength of 100%, and similar viscosity and transparency.

[0132] The red pigments obtained in Examples Ito 17 each were PR184, where Example 1 was the optimal example. The PR184 pigment had a chemical structural formula as follows: 0 H3 HO\ /

CONH

[0133] [0134] (1) OCH1 HO N-N OCH3 C NHCi HCO [01351 [0136] (2) [0137] The PR184 pigment had a chemical structural formula of a mixture of formula (1) and formula (2).

[0138] Comparative analysis of Examples 1/5/6/7/9/10/11/12/16: since the anionic surfactant was soluble in water and could react in the red pigment, the application of the anionic surfactant alone might make the pigment slightly lower transparent and less tinting. The nonionic surfactant was insoluble or slightly soluble in water, and there were opaque matters or flocs in the solution, such that the red pigment had lower tinting strength, Relatively low transparency, and high viscosity. Therefore, dissolving with the 1:1 compound solution could make the pigment transparent, with high tinting strength, desirable transparency, and a viscosity close to the standard. When the compound solution was added in different positions, each red pigment in other examples and that in Example 1 have similar results.

101391 Comparative analysis of Examples 1/2/3/4: with the reduction of the quaternary ammonium salt derivative added, the red pigment had increased viscosity and reduced tinting strength.

[0140] Comparative analysis of Examples 1/13/14: in these examples, the N-(4-chloro-2,5-dimethoxypheny1)-3-hydroxy-2-naphthylcarboxamide (AS-LC) and the 3-hydroxy-N-(2-methyl-5-dichloropheny1)-2-naphthylcarboxamide (AS-KB) were added in different ratios, resulting in a relatively bluish or relatively yellowish hue and a lower tinting strength. Therefore, Example 1 had the best ratio.

101411 Comparative analysis of Examples 1/15: the color paste with the red pigment added by the quaternary ammonium salt derivative had a lower tinting strength. The color paste was added in the coupling solution with low viscosity.

101421 Comparative analysis of Examples 1/17: the compound solution of fatty acid ammonium salt and dodecylphenol at a ratio of 1:1 was added to the red pigment, and the test results were similar to those of Example 1. Therefore, preferably the anionic surfactant and the nonionic surfactant could be used interchangeably.

[0143] Example 18

[0144] This example differed from Example 1 in that the AS component was N-(4-chloro-2,5-dimethoxypheny1)-3-hydroxy-2-naphthylcarboxamide (AS-LC). Steps S2 and 53 specifically included: [0145] S2, preparation of a coupling solution: [0146] S2.1. 150 mL of water was added into a coupling component dissolution container, 14.1 g of a sodium hydroxide solution was added, and heated to 85°C. 12.3 g of N-(4-chloro-2,5-dimethoxypheny1)-3-hydroxy-2-naphthylcarboxamide (AS-LC), and 3 g of the quaternary ammonium salt derivative in Example 1 were added into the container under stirring.

A resulting mixture was dissolved by stirring until transparent, to obtain a coupling component solution II.

[0147] S2.2. 120 mL of water was added into a coupling container, 12 g of acetic acid was added under stirring, and mixed to form an acetic acid aqueous solution. The coupling component solution II was added to the acetic acid aqueous solution within 30 min, and adjusted to pH=5.2, to obtain a while precipitate of the N-(4-chloro-2,5-dimethoxypheny1)-3-hydroxy-2-naphthylcarboxamide (AS-LC) and the quaternary ammonium salt derivative. The pH value was adjusted to 5.8, and the temperature was adjusted to 60°C to obtain a coupling solution 101481 S3, coupling [0149] The diazotization solution I was added to the coupling solution In at 60°C within 90 min to generate a red color paste 101501 S4, post-treatment: [0151] The red color paste was stirred for 60 min, adjusted to pH=6. 0.1 g of a compound solution of alkyl ether carboxylate and fatty alcohol polyoxyethylene ether was added to conduct surface modification on the pigment by stirring for 20 min. An obtained product was heated to 80°C for 90 min, and then cooled down to below 60°C, filter-pressed, and washed with water. A filter cake was dried to remove moisture to obtain a PR146 pigment for a water-based ink.

[0152] The PR146 pigment had a chemical structural formula as follows: [0153]

[0154] Example 19

101551 This example differed from Example 1 in that the AS component was 3-hydroxy-N-(2,5-dimethoxypheny1)-2-naphthvIcarboxamide (AS-CA). Steps S2 and S3 specifically included: [0156] S2, preparation of a coupling solution: [0157] S2. I. 150 mL of water was added into a coupling component dissolution container, 28.6 g of a sodium hydroxide solution was added, and heated to 90°C. 12.3 g of 3-hydroxy-N-(2,5-dimethoxyphenyI)-2-naphthylcarboxamide (AS-CA), and 3 g of the quaternary ammonium salt derivative in added Example 1 we re added into the container under stirring. A resulting mixture was dissolved by stirring un til transparent, the pigment was subjected to resinification with 20 g of a rosin solution with a content of 10%, stirred for 30 min, and cooled down to 30°C with ice to obtain a coupling component solution II.

101581 53, coupling [0159] The diazotization solution I was added to the coupling component solution II within 60 min to generate a red color paste.

101601 S4, post-treatment: [0161] The red color paste was stirred for 60 min, adjusted to pH= 5.7. 0.1 g of a compound solution of alkyl ether carboxylate and fatty alcohol polyoxyethylene ether was added to conduct surface modification on the pigment by stirring for 20 min. An obtained product was heated to 85°C for 60 mm, added with 30 g of sodium hydroxide to pH=10, stirred for 20 min, cooled down to below 60°C, filter-pressed, and washed with water. A filter cake was dried to remove moisture to obtain a PR269 pigment for a water-based ink.

101621 A preparation method of the rosin solution included: 500 mL of water was heated to 100°C, 50 g of special-grade rosin was added, stirred for 30 mm to make it completely dissolved and transparent, and then cooled down to 50°C to 55°C to obtain the rosin solution. The rest were the same as those in Example 1.

101631 The PR269 pigment had a chemical structural formula as follows: [01641 101651 Comparative analysis of Examples 1/18/19: the products obtained by different AS components were different, namely: [0166] The Pigment Red 146 was prepared from 3-amino-4-methoxybenzanilide (KD-Base) + N-(4-chloro-2,5-dimethoxypheny1)-3-hydroxy-2-naphthyl carboxami de (AS-LC), and 3-hydroxy-N-(2-methyl-5-di chloropheny1)-2-naphthyl carboxami de (AS-KB).

101671 The Pigment Red 184 was prepared from 3-amino-4-methoxybenzanilide (KD-Base) + N-(4-chloro-2,5-dimethoxypheny1)-3-hydroxy-2-naphthyl carboxanai de (AS-LC).

101681 The Pigment Red 269 was prepared from 3-amino-4-methoxybenzanilide KD-Base) + 3-hydroxy-N-(2,5-dimethoxypheny1)-2-naphthylcarboxamide (AS-CA). The Pigment Red 31, Pigment Red 32, Pigment Red 147, Pigment Red 176, and Pigment Red 213 could also be synthesized with this method by replacing the types of AS components. Adding an appropriate amount of the quaternary ammonium salt derivative and the compound surfactant solution during the synthesis could improve the wettability, transparency, viscosity, tinting strength, gloss, storage stability and other properties of the pigment. The specific amount could be slightly adjusted according to the examples provided in the present disclosure, which were not listed here.

[0169] Table 1: Various example conditions 0170 Examples Condition Compound solution Remarks Amount of quaternary ammonium AS Added position of quaternary ammonium salt derivative Added Added Ratio salt ratio amount position derivative (%) (g) Example 3 2:1 Coupling 0.8 Color 1:1 Pigment 1 solution paste Red 146 Example 0 2:1 Coupling 0.8 Color 1:1 Pigment 2 solution paste Red 146 Example 1 2:1 Coupling 0.8 Color 1-1 Pigment 3 solution paste Red 146 Example 2 2:1 Coupling 0.8 Color 1:1 Pigment 4 solution paste Red 146 Example 3 2:1 Coupling 0 0 Pigment solution Red 146 Example 3 2:1 Coupling 0.8 Color Anionic Pigment 6 solution paste Red 146 Example 3 2:1 Coupling 0.8 Color Nonionic Pigment 7 solution paste Red 146 Example 3 2:1 Coupling 2.4 Color 1:1 Pigment 8 solution paste Red 146 Example 3 2:1 Coupling 0.8 Color 2:1 Pigment 9 solution paste Red 146 Example 3 2:1 Coupling 0.8 Color 1:2 Pigment solution paste Red 146 Example 3 2:1 Coupling 0.8 Color 1:3 Pigment 11 solution paste Red 146 Example 3 2:1 Coupling 0.8 Color 1:4 Pigment 12 solution paste Red 146 Example 3 1.1 Coupling 0.8 Color 1.1 Pigment 13 solution paste Red 146 Example 3 2:3 Coupling 0.8 Color 1:1 Pigment 14 solution paste Red 146 Example 3 2:1 Color 0.8 Color 1-1 Pigment paste paste Red 146 Example 3 2:1 Coupling 0.8 Coupling 1-1 Pigment 16 solution solution Red 146 Example 3 2:1 Coupling 0.8 Color Type Pigment 17 solution paste changed Red 146 Example 3 1 Coupling 0.8 Color 1:1 Pigment 18 solution paste Red 184 Example 3 1 Coupling 0.8 Color 1.1 Pigment 19 solution paste Red 269

[0171] Use Example

101721 In parts by weight, 10 parts of the pigments prepared in Examples 1 to 19 were separately mixed with 90 parts of a binder mixture and 100 parts of 2 mm to 3 mm glass beads according to the proportions below. Each resulting mixture was dispersed with a shaker for 60 min to obtain a water-based UV-cured ink. The viscosity of the water-based UV-cured ink was measured with a 4# Zahn cup. To evaluate the water-based UV-cured ink, the water-based UV-cured ink was used to test other performance indicators of the pigment. Results were shown in Tables 3 to 6.

101731 Proportion of the binder mixture included: 101741 Water-based UV-cured resin 50 parts by weight [0175] Aqueous solvent 350 parts by weight [0176] Ethanol 25 parts by weight [0177] Defoamer [0178] Table 2: Technical indexes of offset printing ink product obtained by pigment prepared in the present disclosure [0179] Name Index of standard Hue Approximate to standard Tinting strength 100+10% of standard Viscosity Standard substance +200 Transparency Compared with standard substance: slightly, relatively, greatly Glossiness Approximate to standard Moisture content <3% DE <2 parts by weight [0180] Table 3 Comparison of Standard Carmine FBB02 with Example 1 0181 Item Inspection result Remarks Hue Tinting Glossiness Transparency Viseosity(Pa.$) Moisture DE strength.% content/9/i, Carmine fliTiO2 Normal 100 81 Normal 450 Example 1 Approximate 99 81174 Approximate 450/452 1.6 0.03 [0182] Through the above comparison, it was clearly seen that all the indicators of the pigment after test were approximate to those of Carmine FBB02, meeting the standard requirements of the Carmine FBB02.

[0183] Table 4: Results of examples [0184] Example Inspection result Remarks s Hue Tinti Glossi ness Transpare Viscosity Moisture DE ng stren gth/ ncy (Pas) content/ % % Example Normal 100 81 Normal 450 1.6 Example Normal 90 81/74 Greatly 450/580 2.2 0.94 -2 low Example Relatively 95 81/79 Relatively 450/558 2.1 1.57 - 3 bluish low Example Slightly 97 81/80 Approxim 450/529 1.8 1.32 4 bluish ate Example Greatly 85 81/67 Greatly 450/610 1.3 2.29 -bluish low Example Slightly 90 81/76 Relatively 450/595 1.1 1.21 6 bluish low Example Greatly 80 81/42 Greatly 450/890 0.9 3.21 Compound solution 7 yellowish low not dissolved Example Approximate 100 81/82 Approxim 450/455 0.7 0.94 High cost due to 8 ate high amount of compound solution Example Greatly 90 81/59 Greatly 450/780 1.3 3.0 Compound solution 9 yellowish low opaque Example Greatly 93 81/68 Relatively 450/578 1.8 1.1 bluish low Example Greatly 93 81/73 Relatively 450/537 1.1 2.0 Compound solution 11 yellowish low with flocs Example Relatively 92 81/67 Relatively 450/582 1.5 1.9 Compound solution 12 yellowish low with obvious insoluble matters Example Greatly 87 81/75 Relatively 450/453 1.8 1.12 13 bluish low Example Greatly 95 81/78 Relative 450/462 1.3 0.91 - 14 yellowish higher Example Approximate 93 81/79 Slightly 450/439 1.1 1.36 -high Example Approximate 100 81/80 Approxim 450/451 2.8 1.19 -16 ate Example Slightly 100 81/81 Approxim 450/448 0.7 0.56 - 17 yellowish ate [0185] Through the test summary of Table 4, it was seen that the auxiliary compound solutions of Example 7, Example 8, Example 9, Example 11, and Example 12 were not available, and the experimental conditions of Example 16 and Example 17 were closer to those of Example 1. [0186] Table 5: Comparison of standard BASF 4610 with Example 18 101871 Item Inspection result Hue Tinting Glossiness Transparency Viscosity(Pa.$) Moisture DE strength/% content/% BASF Normal 100 79 Normal 460 0.8 Example Approximate 100 80 Slightly high 459 0.9 0.03 101881 It was seen from the test summary in Table 5 that the experimental conditions of Example 18 were closer to those of BASF 4610.

[0189] Table 6: Comparison of standard Carmine 3801 with Example 19 Item Inspection result Hue Tinting Glossiness Transparency Viscosity (Pa. s) Moisture DE strength/% content/% Carmine Normal 100 82 Normal 420 0.5 Example 19 Approximate 100 85 Approximate 455 1.6 0.2 [0191] It was seen from the test results in Table 6 that Example 19 had similar hue, tinting strength, and transparency, as well as high glossiness and viscosity. These results were closer to those of BASF 4610.

[0192] The above are merely preferred implementations of the present application. It should be noted that a person of ordinary skill in the art may further make several improvements and modifications without departing from the principle of the present application, but such improvements and modifications should be deemed as falling within the protection scope of the present application.

Claims (15)

1. CLAIMSI. Use of a quaternary ammonium salt derivative with a chemical abstracts service (CAS) number of 107-64-2 in preparation of an azo red pigment for a water-based ultraviolet (UV)-cured ink.
2. 2. A preparation method of a red pigment, comprising the following steps: Sl, diazotization: dispersing 3-amino-4-methoxybenzanilide evenly in water, dissolving in an acidic environment, conducting diazotization with excess sodium nitrite, and removing the excess sodium nitrite to obtain a diazotization solution I; S2, preparation of a coupling solution: S2.1, dissolving an AS component and a quaternary ammonium salt derivative with a CAS number of 107-64-2 in an alkaline solution to obtain a coupling component solution II; and S2.2, adding the coupling component solution II into an acidic solution to precipitate the AS component and the quaternary ammonium salt derivative, and then adjusting a pH value to 3.8 to 6 and a temperature to 20°C to 70°C to obtain a coupling solution III; S3, coupling adding the diazotization solution I obtained in step S1 to the coupling solution Ill obtained in step 52.2 to allow coupling to obtain a red color paste; and S4, post-treatment: conducting post-treatment on the red color paste to obtain the red pigment.
3. 3 The preparation method of a red pigment according to claim 2, wherein in step S2.1 the AS component is a mixture of 3-hydroxy -N-(4-chloro-2,5-dimethoxypheny1)-2-naphthyl carboxami de and 3-hydroxy-N-(2-methyl-5-di chl oropheny1)-2-naphthyl carboxami de; alternatively, the AS component is one selected from the group consisting of 3-hydroxy-N-phenyl-2-naphthylcarboxamide, 3-hydroxy-N-(2-methoxypheny1)-2-naphthyl carboxami de, 3-hydroxy-N-(4-methylpheny1)-2-naphthylcarboxami de, 3-hydroxy-N-(2-methylpheny1)-2-naphthylcarboxami de, 3-hydroxy -N-(3-nitropheny1)-2-naphthylcarboxami de, 3-hydroxy-N-(2-methylchloro)-2-naphthylcarboxamide, 3-hydroxy-N-(4-chlorophenyI)-2-naphthylcarboxamide, 3-hydroxy-2-naphthoyl-ortho-pheneti di de, and 5-(2'-hydroxy-3'-naphthoylamino)-2-benzimidazolone.
4. 4. The preparation method of a red pigment according to claim 2 or 3, wherein the quaternary ammonium salt derivative is added at 5% to 25% of a weight of the AS component.
5. 5. The preparation method of a red pigment according to claim 2 or 3, wherein during the 10 post-treatment in step S4 or after the AS component and the quaternary ammonium salt derivative are precipitated in step S2.2, surface modification is conducted by adding a compound solution of an anionic surfactant and a nonionic surfactant.
6. 6. The preparation method of a red pigment according to claim 5, wherein the anionic surfactant and the nonionic surfactant are compounded at a weight ratio of 1:(1-4).
7. 7 The preparation method of a red pigment according to claim 6, wherein the compound solution of the anionic surfactant and the nonionic surfactant is added at 0% to 3% of a weight of the AS component.
8. 8 The preparation method of a red pigment according to claim 5, 6, or 7, wherein the anionic surfactant is at least one selected from the group consisting of a carboxylate, a fatty acid ammonium salt, an alkyl ether carboxylate, a sulfonate, an aryl alkyl sulfonate, a linear alcohol ethoxylate sulfate, and sulfated triglyceride oil; and the nonionic surfactant is at least one selected from the group consisting of dodecylphenol, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether, a fatty alcohol sulfate, an ethylene oxide-propylene oxide copolymer, a long-chain fatty acid ester, propylene glycol, sorbitol, and polyethylene glycol ester.
9. 9. The preparation method of a red pigment according to claim 2, wherein in step S 1, the acidic environment is made available by a hydrochloric acid solution.
10. 10. The preparation method of a red pigment according to claim 2, wherein in step S2.2, the acidic solution is an acetic acid solution
11. 11. The preparation method of a red pigment according to claim 2, wherein in step S3, the diazotization solution I obtained in step S1 is added into the coupling solution III obtained in step S2.2 at a constant speed for 30 min to 150 min.
12. 12. The preparation method of a red pigment according to claim 2, wherein in step S4, the post-treatment comprises conducting resinification on the red color paste by adding rosin.
13. 13. The preparation method of a red pigment according to claim 12, wherein the rosin is at least one selected from the group consisting of special-grade rosin, disproportionated rosin, maleic rosin, and polymerized rosin.
14. 14. A red pigment prepared by the preparation method according to any one of claims 2 to 13.
15. 15. A water-based UV-cured red ink, comprising the red pigment according to claim 14.