CN-119684816-B - Fine surface treatment method of zinc halide phthalocyanine

Abstract

The present invention relates to a surface treatment method of pigment, in particular to a fine surface treatment method of green zinc halide phthalocyanine (pigment). Adding the zinc phthalocyanine halide into NaCl-AlCl 3 molten salt system, then adding esters, reacting, and separating out zinc phthalocyanine halide from the reactant by water to obtain the finished pigment zinc phthalocyanine halide with excellent performance. The method of the invention prepares the green zinc phthalocyanine pigment with small particle size, concentrated distribution and excellent performance by controlling the parameter conditions of the reaction and using a brand new method, and simultaneously provides a new process route for carrying out surface fine treatment on the zinc halide phthalocyanine to reduce the secondary agglomeration of the zinc halide phthalocyanine.

Inventors

• SUN SHANGQI
• XIU DI
• WANG PENG
• ZHAO RONGHUI
• XU YIWEI
• SUN XUCHEN
• XING YING
• TANG LIQIANG

Assignees

• 沈阳化工研究院有限公司

Dates

Publication Date

20260512

Application Date

20241219

Claims (3)

1. 1. A fine surface treatment method of zinc halide phthalocyanine is characterized in that zinc halide phthalocyanine is adopted as a raw material, the zinc halide phthalocyanine is gradually added into a NaCl-AlCl 3 mixture system under the protection of nitrogen and the temperature T1, the mixture is heated to T2, ester substances are added into the system when the system is completely free of solid particles, the reaction is kept at 2-4 h, the temperature is reduced to T3, the reaction solution is slowly added into water, the temperature is kept at 15-25 ℃, the temperature is kept at 30-50 min after the reaction solution is kept at the temperature, the mixture is filtered and washed until the electric conductivity of filtrate is less than 20 mu s/cm, a zinc halide phthalocyanine filter cake is obtained, and a pigment finished product is obtained after drying; the T1 is selected from 0 ℃ to 50 ℃; the T2 is selected from 110-150 ℃; the T3 is selected from 30-50 ℃; the zinc halide phthalocyanine accounts for 0.1 to 0.8 times of the mass ratio of the NaCl-AlCl 3 molten salt system; The molar ratio of the ester substance to the zinc halide phthalocyanine is 0.01-0.2 times; The ester substance is one or more of beta-propiolactone, gamma-butyrolactone, delta-valerolactone, 6-caprolactone, delta-octanol lactone and delta-undecalactone.
2. 2. A process for the fine surface treatment of zinc phthalocyanine halides according to claim 1, characterized in that the molten salt system NaCl-AlCl 3 , in which the mass ratio of NaCl to AlCl 3 is from 1:10 to 10:1.
3. 3. A process for the fine surface treatment of zinc phthalocyanine halides according to claim 1, wherein said drying is carried out at 105 ℃ until the pigment solids moisture content is less than 0.5%.

Description

Fine surface treatment method of zinc halide phthalocyanine Technical Field The present invention relates to a surface treatment method of pigment, in particular to a fine surface treatment method of green zinc halide phthalocyanine (pigment). Background Zinc halide phthalocyanine is an important organic pigment, and according to JP19970285066, it is known that zinc halide phthalocyanine is widely used in the fields of textile, printing, ink, paint and the like. However, the zinc halide phthalocyanine pigment has some problems in practical application, such as agglomeration easily occurs in a humid environment, which affects the dispersibility and coloring effect of the colorant, and in addition, the crystal structure and surface morphology of the zinc halide phthalocyanine pigment affect the transparency, color vividness and light resistance. To solve these problems, zinc phthalocyanine pigments have been improved by surface fine treatment techniques. For the problem of easy agglomeration of the zinc halide phthalocyanine pigment, a surface treatment technology, such as a surfactant or polymer coating method, can be adopted to form a stable surface coating layer, and the mutual adsorption between pigment particles is prevented, so that the moisture resistance is improved, the pigment can be dispersed in a medium more stably, and the good dyeing effect is maintained. Aiming at the problems of the crystal structure and the surface morphology of the zinc halide phthalocyanine pigment, the chemical synthesis method can be utilized to enable the zinc halide phthalocyanine to be recrystallized, and the morphology and the size of the pigment crystal are regulated and controlled by controlling the conditions in the crystal nucleation and growth process, so that the transparency and the color vividness of the pigment crystal are further influenced. Meanwhile, the surface modification technology, such as means of surface modification, nanostructure design and the like, can be utilized to regulate the morphology and structure of the pigment surface so as to improve the uniform deposition and color stability of the pigment on the material surface, thereby improving the application effect of the pigment on materials such as textiles, plastic products and the like. For example, JP20210514647 discloses that the inventors use a method of recrystallizing a zinc halide phthalocyanine to change the crystal form so that the zinc halide phthalocyanine can meet the production requirements. For the problem of light resistance of the zinc halide phthalocyanine pigment, a surface protection layer with ultraviolet light and visible light resistance can be formed by a surface fine treatment technology, such as the introduction of a surface light stabilizer, so that the irradiation and oxidative damage of light to the pigment are effectively prevented, the light attenuation resistance of the pigment is improved, and the durability of the pigment in actual use is prolonged. In recent years, studies in the fields of molten salt physics and electrochemistry have been active. For example, as described in KR20130011317A, the molten salt electrolyte has the advantages of high conductivity, high electrode reaction speed, high decomposition potential of the molten salt electrolyte itself and the like compared with the aqueous solution and the organic electrolyte. From a chemical point of view, the characteristics of haloaluminates are their structure and their strongly acidic nature. Although the aluminum bond is predominantly ionic, alCl 3 has a tendency to form stable dimeric molecules, forming non-ionized melts, so the addition of NaCl can combine with AlCl 3 to form a highly ionized liquid mixture while lowering the overall melting point of the system. Aiming at the problems of the zinc halide phthalocyanine and in order to better meet the requirements of different fields on pigment quality, the wide application of the zinc halide phthalocyanine pigment in the fields of textile, printing ink, coating and the like is promoted, and a fine surface treatment method of the zinc halide phthalocyanine is further provided. Disclosure of Invention The invention aims to provide a fine surface treatment method of zinc halide phthalocyanine. In order to achieve the above purpose, the invention adopts the technical scheme that: A process for fine surface treatment of zinc phthalocyanine halide includes such steps as adding NaCl-AlCl 3 to form molten salt system, adding esters, reacting, and water separation of zinc phthalocyanine halide from reactant. The zinc halide phthalocyanine is shown in a general formula I, Wherein X1-X16 may be the same or different and are selected from H, cl, br, and X1-X16 cannot be H at the same time. Preferably, X1-X16 contains at least 10 halogens. More preferably, the zinc halide phthalocyanine is a mixture having a degree of halogenation such that the average total number of chlorine and bromine is 15 or more, wherein