Method for increasing the solubility and dissolution rate of dyes in supercritical carbon dioxide medium

Abstract

The objective of the present invention is to provide a method for increasing the solubility and dissolution rate of a dye in a supercritical carbon dioxide medium. [Solution] The method of the present invention for increasing the solubility and dissolution rate of a dye agent in a supercritical carbon dioxide medium comprises heating and melting the dye agent to a target temperature above the melting point of the dye agent, mixing supercritical carbon dioxide having an initial temperature with the molten dye agent in a certain weight ratio, and then cooling the supercritical carbon dioxide dissolving the dye agent to the initial temperature, and repeating the cycle between the mixing process and the cooling process for a certain period of time without changing any temperature control, wherein the dye agent is a dye and / or an auxiliary, the initial temperature is lower than the target temperature, and the pressure of the supercritical carbon dioxide is consistent, i.e., the three pressures of the supercritical carbon dioxide having the initial temperature, the pressure of the supercritical carbon dioxide medium after mixing, and the pressure of the supercritical carbon dioxide dissolving the dye agent after cooling to the initial temperature are the same.

Description

[Technical field]

[0001] The present invention relates generally to dyeing technology, and more particularly to a method for increasing the solubility and dissolution rate of dyes in a type of supercritical carbon dioxide medium. [Background technology]

[0002] The solubility of weakly polar dyes in supercritical carbon dioxide medium is low and the dissolution rate is slow, so supercritical carbon dioxide must be transported to the dyeing system by a circulation pump to dissolve dyes that meet the coloring or finishing effect. On the other hand, the solubility of some high melting dyes in supercritical carbon dioxide medium is also very low, which reduces their utilization rate. Therefore, the development of dyeing and finishing technology in supercritical carbon dioxide medium is severely restricted.

[0003] At present, the main method for increasing the solubility and dissolution rate of dyes in supercritical carbon dioxide medium is to add co-solvents. However, these co-solvents are low-boiling organic polar compounds that become toxic vapors at the operating temperature of supercritical carbon dioxide. If they leak, they will cause serious harm to the human body. Furthermore, after the dyeing and finishing process is completed, the co-solvents are difficult to separate and remove.

[0004] In other words, it is a significant challenge to develop a simple method for improving the solubility and dissolution rate of dyes in supercritical carbon dioxide medium without using cosolvents. Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a method for increasing the solubility and dissolution rate of dyes in a supercritical carbon dioxide medium, and overcomes the difficulties in the prior art. [Means for solving the problem]

[0006] In response to the above problems, the present invention selects the following means for solving the problems.

[0007] A method for increasing the solubility and dissolution rate of a dye in a supercritical carbon dioxide medium is to heat the dye to a target temperature above its melting point until it melts, mix supercritical carbon dioxide having an initial temperature with the melted dye at a certain weight ratio, and then cool the supercritical carbon dioxide in which the dye is dissolved to the initial temperature. Without changing all the temperature controls, repeat the circulation between the mixing step and the cooling step for a certain period of time. Moreover, the dye is a dye and / or an auxiliary agent, the initial temperature is lower than the target temperature, and the pressure of the supercritical carbon dioxide is consistent, that is, the pressures of the supercritical carbon dioxide having the initial temperature, the supercritical carbon dioxide medium after mixing, and the supercritical carbon dioxide in which the dye is dissolved after cooling to the initial temperature are the same.

[0008] Preferably, in the method for increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium, the melting point of the described dye is A (60 - 230) °C, the described target temperature is A to (A + 20) °C, the initial temperature of the described supercritical carbon dioxide is B °C (31.2 < B < A - 20, 31.2 °C is the critical temperature of supercritical carbon dioxide), the weight ratio of the described dye to supercritical carbon dioxide is 5×10 -5 ~5×10 -3 g·g -1 and, the described heating rate is 1 - 2 °C / min, the flow rate of the described supercritical carbon dioxide is 1 - 120 tons / hr, the pressure of the described supercritical carbon dioxide exceeds 10 MPa (although the critical pressure of supercritical carbon dioxide is 7.38 MPa, when the temperature is too high, a certain pressure is required to ensure the supercritical state and make the density of supercritical carbon dioxide higher. The present invention meets the pressure conditions with a booster pump.), the described repeated time is 5 minutes to 2 hours, the described cooling rate is 1 - 20 °C / min (if the cooling rate is too slow, it takes a long time and the dissolution efficiency of the dye becomes low; if it is too fast, the dye dissolved at a high temperature becomes unstable and precipitates), The mentioned auxiliary is an antioxidant or a flame retardant, furthermore, the antioxidant is a polyphenolic compound such as ferulic acid or dopamine, and the flame retardant is Klein 5060 flame retardant or DOPO flame retardant; The dyes mentioned may be one or more of non-ionic type dyes such as disperse dyes, disperse reactive dyes, solvent dyes, non-ionic food dyes, organic pigments or natural dyes.

[0009] The principles of the invention are as follows:

[0010] When the supercritical carbon dioxide medium having an initial temperature is mixed with the molten dye, the initial temperature is lower than the target temperature (i.e., the temperature of the dye), so the temperature increases. In addition, under a certain pressure, the density of supercritical carbon dioxide is always affected by the temperature. Therefore, generally speaking, when the supercritical carbon dioxide is heated in the mixing process, its density decreases and its dissolving ability for dyes should also decrease. However, the target temperature in the present invention is set to be equal to or higher than the melting point of the dye, in order to melt the dye and increase the contact area between the dye and supercritical carbon dioxide, thereby increasing the dissolution rate of the dye, while disintegrating the crystal structure of the dye and reducing the intermolecular interaction of the dye, thereby facilitating the dissolution of the dye in supercritical carbon dioxide. Therefore, the solubility of the dye that is difficult to dissolve in carbon dioxide having an initial temperature increases. Furthermore, the temperature of the mixed system in the present invention is cooled to the initial temperature of supercritical carbon dioxide in order to reduce the density of supercritical carbon dioxide and improve its dissolving ability, so that the dye, which should be coagulated and precipitated when the temperature drops below the melting point, remains dissolved in the medium without precipitating. By cycling between mixing and cooling several times, the solubility and dissolution rate of the dye, which has low solubility and slow dissolution rate at the initial temperature, in supercritical carbon dioxide can be improved. Effect of the Invention

[0011] Advantages of the present invention include: (1) In the method of increasing the solubility and dissolution rate of a dye agent in a supercritical carbon dioxide medium proposed in the present invention, the dye agent is first melted to break down its intermolecular interaction and increase the contact area with supercritical carbon dioxide, while utilizing the improvement in the dissolving ability of supercritical carbon dioxide accompanying the decrease in temperature, the solubility and dissolution rate of the dye agent in the supercritical carbon dioxide medium are improved simply by modifying the process conditions, and there is no need to add other co-solvents, no harm to the human body, and no need to consider the separation and removal of co-solvents. (2) The method proposed in the present invention for increasing the solubility and dissolution rate of dyes in supercritical carbon dioxide medium is simple to operate and has a wide range of application.

[0012] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not exceed the gist of the present invention. Even if a person skilled in the art who reads the contents of the present invention is allowed to modify the present invention in various ways, they are also limited within the scope of the claims of the present invention as equivalent forms of the present invention.

[0013] For information on how to measure solubility and dissolution rate, see First, the absorption spectrum of a known amount of dye in supercritical carbon dioxide is measured using in-situ infrared, Raman or UV-visible spectroscopy, and a linear relationship is clarified between the dye concentration (the amount of dissolved dye divided by the amount of supercritical carbon dioxide) and the intensity of the characteristic absorption peak in the spectrum. The time counted from when the dye and supercritical carbon dioxide start to be mixed until the intensity of the characteristic peak of the dye does not change even after 30 minutes is recorded as t1. The method for calculating the solubility is to calculate the concentration of the characteristic peak at time t1, i.e., the solubility of the dye at that temperature and pressure, based on the linear relationship between the concentration and the intensity of the characteristic absorption peak in the spectrum. The method for calculating the dissolution rate is to divide the solubility above by t1.

[0014] The components in Examples 1 to 22 are shown in the table below. [Table 1]

[0015] Example 1 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Disperse Yellow 163) with a melting point of 182°C to the target temperature (i.e., 190°C) at 20°C / min using heat transfer oil, and melt it at a weight ratio of 3×10 -4 g g -1 The supercritical carbon dioxide with an initial temperature of 130°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 130°C) by natural air cooling at a rate of 1°C / min. Without changing any temperature control, the circulation between the mixing process and the cooling process is repeated for 30 minutes, during which the pressure of the supercritical carbon dioxide is kept at 20MPa and the flow rate is kept at 20 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0016] Comparative Example 1 The method of increasing the solubility and dissolution rate of dye in supercritical carbon dioxide medium is almost the same as in Example 1, with the only difference being that the initial temperature of supercritical carbon dioxide is 130°C and the room temperature of Disperse Yellow 163 are mixed. The solubility and dissolution rate of dye in supercritical carbon dioxide under this process condition are measured, and the results are shown in Table 1.

[0017] Comparative Example 2 The method of increasing the solubility and dissolution rate of dye in supercritical carbon dioxide medium is almost the same as that in Example 1, the only difference being that the initial temperature of supercritical carbon dioxide is replaced by 182°C instead of 130°C (i.e., when supercritical carbon dioxide and Disperse Yellow 163 start to mix, their temperatures are the same). The solubility and dissolution rate of dye in supercritical carbon dioxide under the process conditions are measured, and the results are shown in Table 1.

[0018] Comparative Example 3 The method of increasing the solubility and dissolution rate of dye in supercritical carbon dioxide medium is almost the same as that in Example 1, the only difference is that the pressure of supercritical carbon dioxide with initial temperature is 20MPa, the pressure of supercritical carbon dioxide mixed with dye is 15MPa, and the pressure of supercritical carbon dioxide after dissolving dye and cooling to initial temperature is 20MPa.The solubility and dissolution rate of dye in supercritical carbon dioxide under this process condition are measured, and the results are shown in Table 1.

[0019] Comparative Example 4 The method of increasing the solubility and dissolution rate of dye in supercritical carbon dioxide medium is almost the same as that in Example 1, the only difference is that the pressure of supercritical carbon dioxide with initial temperature is 20MPa, the pressure of supercritical carbon dioxide mixed with dye is 20MPa, and the pressure of supercritical carbon dioxide that dissolves dye and cools to initial temperature is 15MPa.The solubility and dissolution rate of dye in supercritical carbon dioxide under this process condition are measured, and the results are shown in Table 1.

[0020] Example 2 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Disperse Blue 60) with a melting point of 191°C to the target temperature (i.e., 205°C) by electrical heating at a rate of 15°C / min, and melt it. -4 g g -1 The supercritical carbon dioxide with an initial temperature of 135°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 135°C) by air cooling at a rate of 3°C / min. Without changing any temperature control, the cycle between the mixing process and the cooling process is repeated for 60 minutes, during which the pressure of the supercritical carbon dioxide is kept at 24MPa and the flow rate is 40 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0021] Example 3 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Disperse Yellow 42) with a melting point of 156°C at 12°C / min by infrared heating to the target temperature (i.e., 170°C) and melt it, and then reduce the weight ratio of the dye to CO2 by 7.5 x 10 -4 g g -1 The supercritical carbon dioxide with an initial temperature of 125°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 125°C) by water cooling at a rate of 5°C / min. Without changing any temperature control, the cycle between the mixing process and the cooling process is repeated for 75 minutes, during which the pressure of the supercritical carbon dioxide is kept at 27MPa and the flow rate is kept at 50 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0022] Example 4 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Disperse Blue 354) with a melting point of 134°C at 16°C / min by infrared heating to the target temperature (i.e., 140°C) and melt it, and then reduce the weight ratio of the dye to CO2 by 1.5 x 10 -3 g g -1 The supercritical carbon dioxide with an initial temperature of 100°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 100°C) by water cooling at a rate of 4°C / min. Without changing any temperature control, the cycle between the mixing process and the cooling process is repeated for 20 minutes, during which the pressure of the supercritical carbon dioxide is kept at 25MPa and the flow rate is kept at 100 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0023] Example 5 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (azo vinyl sulfone reactive disperse orange) with a melting point of 143°C at 15°C / min with nitrogen heating to the target temperature (i.e., 150°C) and melt it, and then reduce the weight ratio of the dye to CO2 by 1 x 10 -3g g -1 The supercritical carbon dioxide with an initial temperature of 110°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 110°C) by liquid nitrogen at a rate of 20°C / min. Without changing any temperature control, the cycle between the mixing process and the cooling process is repeated for 15 minutes, during which the pressure of the supercritical carbon dioxide is kept at 20MPa and the flow rate is kept at 120 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0024] Example 6 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (azo homotriazine reactive disperse grade) with a melting point of 128°C at 12°C / min by infrared heating to the target temperature (i.e., 135°C) and melt it, and then increase the weight ratio of the dye to CO2 by 6 x 10 -4 g g -1 The supercritical carbon dioxide with an initial temperature of 105°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 105°C) by air cooling at a rate of 10°C / min. Without changing any temperature control, the circulation between the mixing process and the cooling process is repeated for 35 minutes, during which the pressure of the supercritical carbon dioxide is kept at 23MPa and the flow rate is kept at 90 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0025] Example 8 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Solventrade 24) with a melting point of 184°C at 20°C / min to the target temperature (i.e., 190°C) by nitrogen heating and melt it, and then reduce the weight ratio of the dye to CO2 by 8 x 10 -4 g g -1The supercritical carbon dioxide with an initial temperature of 135°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 135°C) by natural air cooling at a rate of 2°C / min. Without changing any temperature control, the circulation between the mixing process and the cooling process is repeated for 15 minutes, during which the pressure of the supercritical carbon dioxide is kept at 25MPa and the flow rate is kept at 85 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0026] Example 9 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Solvent Blue 63) with a melting point of 118°C to the target temperature (i.e., 120°C) at 15°C / min using heat transfer oil, and melt it at a weight ratio of 7 x 10 -4 g g -1 The supercritical carbon dioxide with an initial temperature of 85°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 85°C) by liquid nitrogen at a rate of 15°C / min. Without changing any temperature control, the cycle between the mixing process and the cooling process is repeated for 10 minutes, during which the pressure of the supercritical carbon dioxide is kept at 20MPa and the flow rate is kept at 70 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0027] Example 10 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Acid Yellow 10) with a melting point of 104°C to the target temperature (i.e., 115°C) by electrical heating at a rate of 12°C / min, and melt it at a weight ratio of 4 x 10 -4 g g -1The supercritical carbon dioxide with an initial temperature of 70°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 70°C) by water cooling at a rate of 10°C / min. Without changing any temperature control, the cycle between the mixing process and the cooling process is repeated for 15 minutes, during which the pressure of the supercritical carbon dioxide is kept at 16MPa and the flow rate is kept at 35 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0028] Example 11 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Acid Orange 3) with a melting point of 160°C at 14°C / min by infrared heating to the target temperature (i.e., 165°C) and melt it, and then melt it at a weight ratio of 7 x 10 -5 g g -1 The supercritical carbon dioxide with an initial temperature of 125°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 125°C) by air cooling at a rate of 8°C / min. Without changing any temperature control, the circulation between the mixing process and the cooling process is repeated for 100 minutes, during which the pressure of the supercritical carbon dioxide is kept at 19MPa and the flow rate is kept at 75 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0029] Example 12 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Pigment Yellow 5) with a melting point of 206°C to the target temperature (i.e., 210°C) at 20°C / min by nitrogen heating, and melt it at a weight ratio of 6 x 10 -5 g g -1The supercritical carbon dioxide with an initial temperature of 140°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 140°C) by liquid nitrogen at a rate of 18°C / min. Without changing any temperature control, the cycle between the mixing process and the cooling process is repeated for 110 minutes, during which the pressure of the supercritical carbon dioxide is always 25MPa and its flow rate is 100 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0030] Example 13 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Pigment Trade 50) with a melting point of 176°C at 14°C / min to the target temperature (i.e., 185°C) by infrared heating, and melt it at a weight ratio of 8 x 10 -5 g g -1 The supercritical carbon dioxide with an initial temperature of 132°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 132°C) by water cooling at a rate of 5°C / min. Without changing any temperature control, the circulation between the mixing process and the cooling process is repeated for 90 minutes, during which the pressure of the supercritical carbon dioxide is kept at 22MPa and the flow rate is 80 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0031] Example 14 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Pigment Trade 147) with a melting point of 210°C at 10°C / min in a water bath to the target temperature (i.e., 215°C) and melt it, and then melt it at a weight ratio of 6 x 10 -5 g g -1The supercritical carbon dioxide with an initial temperature of 138°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 138°C) by air cooling at a rate of 12°C / min. Without changing any temperature control, the circulation between the mixing process and the cooling process is repeated for 120 minutes, during which the pressure of the supercritical carbon dioxide is kept at 27MPa and the flow rate is kept at 120 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0032] Example 15 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (curcumin) with a melting point of 180°C to the target temperature (i.e., 180°C) at 12°C / min using heat transfer oil, and melt it at a weight ratio of 7.5 x 10 -5 g g -1 The supercritical carbon dioxide with an initial temperature of 135°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 135°C) by water cooling at a rate of 10°C / min. Without changing any temperature control, the cycle between the mixing process and the cooling process is repeated for 90 minutes, during which the pressure of the supercritical carbon dioxide is always 20MPa and its flow rate is 80 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0033] Example 16 The method of increasing the solubility and dissolution rate of dyes in supercritical carbon dioxide medium is to heat the dye (cochineal) with a melting point of 136°C at 14°C / min by infrared heating to the target temperature (i.e., 140°C) and melt it, and then increase the weight ratio of dye to CO2 by 1.5 x 10 -4 g g -1The supercritical carbon dioxide with an initial temperature of 100°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 100°C) at a rate of 5°C / min by natural air cooling. Without changing any temperature control, the cycle between the mixing process and the cooling process is repeated for 30 minutes, during which the pressure of the supercritical carbon dioxide is kept at 15MPa and the flow rate is kept at 40 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0034] Example 17 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (rutin) with a melting point of 195°C to the target temperature (i.e., 200°C) by microwave heating at 16°C / min, and melt it. -5 g g -1 The supercritical carbon dioxide with an initial temperature of 140°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 140°C) by liquid nitrogen at a rate of 16°C / min. Without changing any temperature control, the cycle between the mixing process and the cooling process is repeated for 100 minutes, during which the pressure of the supercritical carbon dioxide is kept at 22MPa and the flow rate is 100 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0035] Example 18 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (ferulic acid) with a melting point of 170°C to the target temperature (i.e., 180°C) by electrical heating at 15°C / min, and melt it. -4 g g -1The supercritical carbon dioxide with an initial temperature of 120°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 120°C) by water cooling at a rate of 15°C / min. Without changing any temperature control, the circulation between the mixing process and the cooling process is repeated for 30 minutes, during which the pressure of the supercritical carbon dioxide is kept at 18MPa and the flow rate is kept at 60 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0036] Example 19 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (dopamine) with a melting point of 218°C to the target temperature (i.e., 220°C) by microwave heating at 10°C / min, and melt it. -5 g g -1 The supercritical carbon dioxide with an initial temperature of 130°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 130°C) by air cooling at a rate of 18°C / min. Without changing any temperature control, the circulation between the mixing process and the cooling process is repeated for 40 minutes, during which the pressure of the supercritical carbon dioxide is kept at 20MPa and the flow rate is kept at 100 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0037] Example 20 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (Klein 5060 flame retardant) with a melting point of 233°C at 18°C / min by nitrogen heating to the target temperature (i.e., 240°C) and melt it, and then melt it at a weight ratio of 5.5 x 10 -5 g g -1The supercritical carbon dioxide with an initial temperature of 135°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 135°C) by liquid nitrogen at a rate of 20°C / min. Without changing any temperature control, the cycle between the mixing process and the cooling process is repeated for 60 minutes, during which the pressure of the supercritical carbon dioxide is kept at 18MPa and the flow rate is kept at 120 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1.

[0038] Example 21 The method of increasing the solubility and dissolution rate of the dye in the supercritical carbon dioxide medium is to heat the dye (DOPO flame retardant) with a melting point of 119°C at 5°C / min to the target temperature (i.e., 120°C) by heating in a water bath, and melt it at a weight ratio of 8.5 x 10 -4 g g -1 The supercritical carbon dioxide with an initial temperature of 100°C is mixed with the molten dye, and the supercritical carbon dioxide with the dye dissolved therein is cooled to the initial temperature (i.e., 100°C) by natural air cooling at a rate of 5°C / min. Without changing any temperature control, the circulation between the mixing process and the cooling process is repeated for 10 minutes, during which the pressure of the supercritical carbon dioxide is kept at 16MPa and the flow rate is kept at 30 tons / hr. The solubility and dissolution rate of the dye in supercritical carbon dioxide under the process conditions were measured, and the results are shown in Table 1. [Table 2] Comparing Comparative Example 1 with Example 1, it can be seen that the solubility and dissolution rate in Example 1 are significantly improved compared to Comparative Example 1. This is because the method in Example 1 destroys the intermolecular interactions inside Disperse Yellow 163, making the dye more easily soluble in the supercritical CO2 medium, improving the solubility, and increasing the contact area of ​​the molten Disperse Yellow 163 with the supercritical CO2 medium, thereby improving the dissolution rate. Comparing Comparative Example 2 with Example 1, it can be seen that the solubility and dissolution rate in Example 1 are significantly improved compared to Comparative Example 2. This is because, compared to the temperature after mixing in Example 1 (between 130°C and 190°C, but clearly lower than 190°C), the supercritical carbon dioxide mixed into the disperse dye at 182°C in Comparative Example 2 has a reduced density and a reduced ability to dissolve Disperse Yellow 163, so that even if the dye melts, its solubility and dissolution rate are still low. Comparing Comparative Example 3 with Example 1, it can be seen that the solubility and dissolution rate in Example 1 are significantly improved compared to Comparative Example 3. This is because the density of supercritical carbon dioxide is reduced due to the pressure reduction during the mixing process, and the dissolving ability for Disperse Yellow 163 is reduced, so that even if the dye melts, its solubility and dissolution rate are still low. Comparing Comparative Example 4 with Example 1, it can be seen that the solubility and dissolution rate in Example 1 are significantly improved compared to Comparative Example 4. This is because the density of supercritical carbon dioxide is reduced due to the pressure reduction during the cooling process, and the dissolving ability for Disperse Yellow 163 is reduced, so that even if the dye melts, its solubility and dissolution rate are still low.

Claims

1. A dye agent, which is a dye, is heated to a target temperature equal to or higher than the melting point of the dye agent to melt it, the molten dye agent is mixed in a certain weight ratio with a supercritical carbon dioxide fluid having an initial temperature lower than the target temperature, the supercritical carbon dioxide fluid in which the dye agent is dissolved is cooled to the initial temperature, and the mixing and cooling steps are repeated within a certain period of time without changing any temperature control, and the pressure of the supercritical carbon dioxide fluid is kept constant throughout. A method for increasing the solubility and dissolution rate of a dye in a supercritical carbon dioxide fluid, comprising:

2. The method for increasing the solubility and dissolution rate of a dye in supercritical carbon dioxide fluid according to claim 1, characterized in that the melting point of the dye is 60 to 230 A°C.

3. The method for increasing the solubility and dissolution rate of a dye in supercritical carbon dioxide fluid according to claim 2, wherein the target temperature is A°C to (A+20)°C.

4. 4. The method for increasing the solubility and dissolution rate of a dye in supercritical carbon dioxide fluid according to claim 3, wherein the initial temperature of the supercritical carbon dioxide is B° C., which satisfies 31.2<B<A-20.

5. The weight ratio of the dye to the supercritical carbon dioxide fluid is 5×10 －５ ~5×10 －３ g.g. －１ The method for increasing the solubility and dissolution rate of a dye in a supercritical carbon dioxide fluid according to claim 4,

6. 2. The method for increasing the solubility and dissolution rate of a dye in supercritical carbon dioxide fluid according to claim 1, wherein the heating rate is 1-2° C. / min.

7. 2. The method for increasing the solubility and dissolution rate of a dye in supercritical carbon dioxide fluid according to claim 1, wherein the flow rate of the supercritical carbon dioxide is 1 to 120 tons / hr.

8. The method for increasing the solubility and dissolution rate of a dye in supercritical carbon dioxide fluid according to claim 1, characterized in that the pressure of the supercritical carbon dioxide is more than 10 MPa.

9. 2. The method for increasing the solubility and dissolution rate of a dye in supercritical carbon dioxide fluid according to claim 1, wherein the certain period of time is 5 minutes to 2 hours.

10. 2. The method for increasing the solubility and dissolution rate of a dye in supercritical carbon dioxide fluid according to claim 1, wherein the cooling rate is 1 to 20° C. / min.

11. 2. The method for increasing the solubility and dissolution rate of a dye in supercritical carbon dioxide fluid according to claim 1, wherein the dye is a non-ionic dye.

12. The method for increasing the solubility and dissolution rate of a dye in a supercritical carbon dioxide fluid according to claim 11, characterized in that the non-ionic dye is one or more of disperse dyes, disperse reactive dyes, oil-soluble dyes, non-ionic food dyes, organic pigments, and natural dyes.

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