Solid solution pigment based on pigment red 122 and pigment red 177 and preparation method thereof

Abstract

The invention belongs to the field of pigments, and particularly relates to a novel single-phase solid solution formed by pigment red 122 and pigment red 177, namely a solid solution pigment based on the pigment red 122 and the pigment red 177, a preparation method of the solid solution pigment and application of the solid solution pigment to ink-jet ink. The solid solution pigment is a solid solution formed by pigment red 122 and pigment red 177 according to the corresponding ratio of 70-90% (mass): 30-10% (mass), the solid solution pigment is used for coloring ink-jet ink, the pigment obtained by mechanically mixing the pigment according to the corresponding ratio has higher saturation degree, the saturation degree is improved by 1.5 or above, the pigment has a hue which is closer to yellow phase, delta H is larger than or equal to 0.5, and the color of the solid solution pigment is larger than that of the pigment obtained by mechanically mixing the pigment according to the corresponding ratio. The solid solution is suitable for use in inkjet printing inks.

Description

Technical Field

[0001] This invention belongs to the field of pigments, and particularly relates to a new single-phase solid solution formed by Pigment Red 122 and Pigment Red 177, namely, a solid solution pigment based on Pigment Red 122 and Pigment Red 177, a method for preparing the pigment, and its application in inkjet inks. Background Technology

[0002] Inkjet recording is a method of recording text or images by directly ejecting ink droplets from very fine nozzles onto a recording element and allowing them to adhere. This method is widely used due to its many advantages, including easy full-color printing, low cost, ability to use ordinary paper as the recording element, and non-contact printing.

[0003] Recently, inks using organic pigments as colorants have been widely used to impart weather and water resistance to printed materials and for color printing. Pigment Red 146 is an azo-structured organic pigment widely used in inkjet printing, possessing very high saturation and color density; however, its weather resistance is not suitable for outdoor applications. Pigment Red 122, and the solid solution pigment formed by Pigment Red 122 and Pigment Violet 19, while exhibiting good weather resistance, have a bluish tint and significantly lower saturation and color density than Pigment Red 146. Summary of the Invention

[0004] To address the above problems, this invention provides a solid solution pigment based on Pigment Red 122 (2,9-dimethylquinacridone) and Pigment Red 177 (4,4'-diamino-1,1'-dianthraquinone) with good weather resistance and water resistance.

[0005] A solid solution pigment based on Pigment Red 122 and Pigment Red 177 is formed by Pigment Red 122 (Formula 1) and Pigment Red 177 (Formula 2) in a mass ratio of 70-90%:30-10%; preferably, a solid solution is formed in a mass ratio of 80-90%:20-10%. The solid solution is formed by Pigment Red 177 as a guest element within the lattice of the host Pigment Red 122, forming a single-phase solid solution.

[0006] In addition, this application also provides a method for preparing solid solution pigments based on Pigment Red 122 and Pigment Red 177, as well as the products obtained therefrom and their uses.

[0007] The preparation method of solid solution pigments based on Pigment Red 122 and Pigment Red 177 involves mixing primary particle filter cakes of Pigment Red 122 and Pigment Red 177 at a mass ratio of 70-90%:30-10% to obtain a mixture of primary particle filter cakes; the mixture of primary particle filter cakes is then fully contacted in a polar organic solvent to obtain a solid solution.

[0008] Preferably, the primary particle filter cake of Pigment Red 122 is a semi-finished filter cake obtained after the ring-closing reaction is completed; the primary particle filter cake of Pigment Red 177 is a semi-finished filter cake obtained after the desulfurization reaction is completed.

[0009] Another method for preparing solid solution pigments based on Pigment Red 122 and Pigment Red 177 involves mixing Pigment Red 122 and Pigment Red 177 at a mass ratio of 70-90%:30-10%, and obtaining a primary particle filter cake mixture by acid leaching. The primary particle filter cake mixture is then fully contacted in a polar solvent to transform into a single-phase solid solution.

[0010] Preferably, the acid solubility of the mixture of Pigment Red 122 and Pigment Red 177 is obtained by converting 2,5-bis(p-toluidine)-terephthalic acid of formula (3) into formula (1) through a ring-closing reaction in polyphosphoric acid, followed by adding the finished dry powder of formula (2) and then acid solubilizing it in polyphosphoric acid. The structural formula of formula (3) is as follows: .

[0011] Preferably, the contact in the polar solvent is achieved by stirring at or above the reflux temperature; the polar solvent is methanol or ethanol.

[0012] An inkjet pigment dispersion is prepared using solid solution pigments based on Pigment Red 122 and Pigment Red 177.

[0013] An inkjet ink, characterized in that it is prepared using an inkjet pigment dispersion made from solid solution pigments based on Pigment Red 122 and Pigment Red 177.

[0014] Solid solution pigments based on Pigment Red 122 and Pigment Red 177, or inkjet pigment dispersions or inkjet inks prepared therefrom, are intended for use in weather-resistant and water-resistant printing. Preferably, the intended use is for outdoor printing.

[0015] The inventors of this application made a surprising discovery: in the presence of Pigment Red 122 (2,9-dimethylquinacridone), Pigment Red 177 (4,4'-diamino-1,1'-dianthraquinone) acts as a guest and falls within its host crystal lattice, forming a single-phase solid solution. This solid solution exhibits the same crystal structure as Pigment Red 122; in other words, the guest Pigment Red 177 completely loses its crystal structure under these conditions, while the resulting single-phase solid solution has the same crystal form as the host Pigment Red 122.

[0016] This application describes a solid solution formed from Pigment Red 122 and Pigment Red 177 in a ratio of 70-90% (by mass): 30-10% (by mass). The solid solution pigment of this application is used for coloring inkjet inks. The pigment obtained by mechanically mixing the solid solution pigments in the corresponding ratio has higher saturation, with a saturation increase of more than 1.5, a more yellowish hue, and ΔH ≥ 0.5. This solid solution is suitable for inkjet printing inks. Attached Figure Description

[0017] Figure 1 Comparison of X-ray diffraction crystal form analysis of Examples 1-3 and Pigment Red 122 finished dry powder 1221D (blank sample, pure Pigment Red 122, produced by Wenzhou Jinyuan New Material Technology Co., Ltd.).

[0018] Figure 2 X-ray diffraction crystal form analysis of Pigment Red 177 finished dry powder 1772 (pure Pigment Red 177, produced by Wenzhou Jinyuan New Material Technology Co., Ltd.). Detailed Implementation

[0019] The Pigment Red 122 used in this application embodiment is finished with 1221D (produced by Wenzhou Jinyuan New Material Technology Co., Ltd.), and the Pigment Red 177 used is finished with 1772 (produced by Wenzhou Jinyuan New Material Technology Co., Ltd.).

[0020] The preparation of the Pigment Red 122 primary particle filter cake used in the examples was carried out using conventional methods as follows: 210 parts of polyphosphoric acid were added to a four-necked flask, and 60 parts of 2,5-bis(p-toluidine)-terephthalic acid (Formula 3) were added while maintaining the temperature at 100-110℃. The temperature was then raised to 140-145℃ and maintained for 3 hours. The closed-loop material was precipitated into 1200 parts of water at 30-35℃. After precipitation, the mixture was stirred for 3 hours, filtered, and washed to obtain Pigment Red 122 primary particle filter cake. Formula 3 is as follows:

[0021] The preparation of the Pigment Red 177 primary particle filter cake used in the examples was carried out using conventional methods as follows: Sodium 4-bromo-1-aminoanthraquinone-2-sulfonate, purified by Ullmann condensation reaction, yielded 60 parts of filter cake (containing approximately 60% solids) of sodium 4,4'-diamino-1,1'-dianthraquinone-3,3'-disulfonate (formula 4) in a four-necked flask. A suitable amount of water was added, along with 540 parts of 98% industrial concentrated sulfuric acid. The sulfuric acid concentration in the reaction system was approximately 80%. The mixture was stirred for 1 hour, heated to 145-150°C, and maintained at this temperature for 5 hours. The solution was then cooled to 90-100°C and slowly precipitated into 3000 parts of water at 18-20°C. The mixture was stirred for 30 minutes, filtered, and washed to obtain the primary particle filter cake of Pigment Red 177. Formula 4 is as follows:

[0022] The following examples will illustrate the invention in more detail. Unless otherwise specified, all parts refer to parts by weight. Example 1

[0023] Add 43.2 parts of Pigment Red 122 primary particle filter cake (containing approximately 22% solids) to a 2000 mL three-necked flask, add 10.8 parts of Pigment Red 177 primary particle filter cake (containing approximately 18% solids), add 700 parts of methanol, stir for 1 hour, then heat to reflux, reflux for 8 hours, filter to separate the filter cake, wash, dry, and pulverize to obtain the sample of Example 1. Comparative Example 1 43.2 parts of Pigment Red 122 finished dry powder 1221D (produced by Wenzhou Jinyuan New Material Technology Co., Ltd.) and 10.8 parts of Pigment Red 177 finished dry powder 1772 (produced by Wenzhou Jinyuan New Material Technology Co., Ltd.) were mechanically mixed evenly to obtain the dry powder sample of Comparative Example 1.

[0024] Preparation of inkjet pigment dispersions

[0025] 10 grams of the pigment obtained in Example 1 above, 7 grams of styrene-acrylic resin (manufactured by BASF) with an acid value of 170 mg / g (containing 3 grams of resin component), 83 grams of deionized water, and 250 grams of 0.5 mm zirconia beads were placed in a 200 ml polypropylene wide-mouth bottle and dispersed using a paint shaker for 3 hours. The resulting pigment dispersion was then centrifuged at 6000 G for 30 minutes using a high-speed centrifuge, and the supernatant was collected, thus obtaining an aqueous inkjet dispersion with a pigment concentration of 9.5%.

[0026] Preparation of inkjet ink

[0027] 42 g of the above-obtained water-based inkjet dispersion, 1 g of surfactant (Surfynol 465), 15 g of glycerin as a humectant, 10 g of propylene glycol, and 32 g of deionized water were mixed to obtain a water-based inkjet with a pigment concentration of 4%.

[0028] Color evaluation

[0029] The water-based inkjet obtained above was printed on Canon photo paper. The resulting sample was placed at room temperature for 12 hours, and the colors a, b, C, and H were measured using X-rite exact (manufactured by X-rite Corporation) under a D65 light source. This invention compares Example 1 with Comparative Example 1 (with Comparative Example 1 as a reference) and measures the values ​​of Δa, Δb, ΔC, and ΔH, as shown in Table 1 below. Example 2

[0030] 210 parts of polyphosphoric acid were added to a four-necked flask, and 48 parts of 2,5-bis(p-toluidine)-terephthalic acid were added while maintaining the temperature at 100-115℃. The temperature was then raised to 140-145℃ and held for 3 hours. After holding, 10.8 parts of Pigment Red 177 finished dry powder 1772 were added, and the mixture was stirred for 30 minutes. The material was then precipitated into 1200 parts of water at 30-35℃, stirred for 3 hours, filtered, and washed to obtain a closed-loop filter cake. The closed-loop filter cake was added to a 2000 ml three-necked flask, and 700 parts of methanol were added. The mixture was stirred for 1 hour, heated to reflux, and refluxed for 8 hours. The mixture was then filtered, washed, dried, and pulverized to obtain the sample of Example 2. Using the above inkjet evaluation method, with Comparative Example 1 as a reference, the test data are shown in Table 1. Example 3

[0031] Add 37.8 parts of Pigment Red 122 primary particle filter cake (containing approximately 22% solids) to a 2000 mL three-necked flask, add 16.2 g of Pigment Red 177 primary particle filter cake (containing approximately 18% solids), add 700 parts of methanol, stir for 1 hour, heat to reflux, reflux for 8 hours, filter, wash, dry, and pulverize to obtain the sample of Example 3.

[0032] Comparative Example 2

[0033] 37.8 parts of Pigment Red 122 finished dry powder 1221D (produced by Wenzhou Jinyuan New Material Technology Co., Ltd.) and 16.2 parts of Pigment Red 177 finished dry powder 1772 (produced by Wenzhou Jinyuan New Material Technology Co., Ltd.) were mechanically mixed evenly to obtain Comparative Example 2 sample.

[0034] Using the above inkjet evaluation method, with Comparative Example 2 as a reference, the test data of Example 3 compared with Comparative Example 2 are shown in Table 1.

[0035] The inkjet printing steps for the samples of Examples 2-3 and Comparative Examples 1-2 were the same as those for Example 1, and the samples were evaluated under the same conditions.

[0036] Table 1. Inkjet Evaluation Colorimetric Data .

[0037] As shown in Table 1 above, the color saturation and hue of Examples 1-3 are higher than those of mechanically mixed samples with the same ratio, with ΔC≥1.5, a significant yellow tint, and ΔH≥0.5.

[0038] Comparison of X-ray diffraction crystal form analysis of Examples 1-3 and Pigment Red 122 finished dry powder 1221D (blank sample, pure Pigment Red 122, produced by Wenzhou Jinyuan New Material Technology Co., Ltd.) is shown in the figure below. Figure 1 X-ray diffraction crystal form analysis of Pigment Red 177 finished dry powder 1772 (pure Pigment Red 177, produced by Wenzhou Jinyuan New Material Technology Co., Ltd.) is as follows: Figure 2 As can be seen from this, Examples 1-3 formed a solid solution, which is a single-phase solid solution of the crystal structure of Pigment Red 122. In other words, the guest Pigment Red 177 completely lost its crystal structure in this case, and the resulting single-phase solid solution has the same crystal form as the host Pigment Red 122.

Claims

1. A solid solution pigment based on Pigment Red 122 and Pigment Red 177, characterized in that: A solid solution formed by pigment red 122 as shown in Formula 1 and pigment red 177 as shown in Formula 2 in a mass ratio of 70-90%:30-10%. 。 2. The method for preparing the solid solution according to claim 1, characterized in that: A mixture of primary particle filter cakes is obtained by mixing primary particle filter cakes of Pigment Red 122 and Pigment Red 177 at a mass ratio of 70-90%:30-10%; the mixture of primary particle filter cakes is then fully contacted in a polar organic solvent to obtain a solid solution.

3. The preparation method according to claim 2, characterized in that: The primary particle filter cake of Pigment Red 122 is a semi-finished filter cake obtained after the ring-closing reaction is completed; the primary particle filter cake of Pigment Red 177 is a semi-finished filter cake obtained after the desulfonation reaction is completed.

4. The method for preparing the solid solution according to claim 1, characterized in that: Pigment Red 122 and Pigment Red 177 are mixed at a mass ratio of 70-90%:30-10%, and the resulting mixture is precipitated by acid dissolution to obtain a primary particle filter cake mixture. The primary particle filter cake mixture is then fully contacted in a polar solvent to transform into a single-phase solid solution.

5. The preparation method according to claim 4, characterized in that: The acid solubility of the mixture of Pigment Red 122 and Pigment Red 177 is obtained by converting 2,5-bis(p-toluidine)-terephthalic acid of formula (3) into formula (1) through a ring-closing reaction in polyphosphoric acid, followed by adding the finished dry powder of formula (2) and then precipitating it out by acid solubility in polyphosphoric acid. The structural formula of formula (3) is as follows: 。 6. The preparation method according to claim 2 or 4, characterized in that: The contact in the polar solvent is achieved by stirring at or above the reflux temperature; the polar solvent is methanol or ethanol.

7. An inkjet pigment dispersion, characterized in that: It was prepared using the solid solution pigment based on Pigment Red 122 and Pigment Red 177 as described in claim 1.

8. An inkjet ink, characterized in that: It was prepared using the inkjet pigment dispersion of claim 8.

9. The use of the solid solution pigment based on Pigment Red 122 and Pigment Red 177 as claimed in claim 1, or the inkjet pigment dispersion as claimed in claim 7, or the inkjet ink as claimed in claim 8, for weather-resistant and water-resistant printing.

10. The use according to claim 9, characterized in that: For outdoor printing.

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