阅读说明：本技术 采用悬浮聚合法制备的蓝色陶瓷墨粉及其方法 (Blue ceramic toner prepared by suspension polymerization method and preparation method thereof ) 是由 叶明泉 张羽 韩爱军 陈昕 丁成 杨计玲 张奎 于 2018-07-25 设计创作，主要内容包括：本发明公开了一种采用悬浮聚合法制备的蓝色陶瓷墨粉及其方法,采用苯丙树脂对陶瓷颜料、电荷调节剂和蜡进行包覆,得到包覆完整的微米级复合粒子,再经过外添得到最终的陶瓷墨粉。本发明采用球磨分散技术以及悬浮聚合方法制备陶瓷墨粉,有效的解决了传统熔融粉碎法陶瓷墨粉组分不均匀及容易外漏的问题,制备的蓝色陶瓷墨粉具有各组分分散均匀、形貌规则、表面光滑,粒径可控且粒径分布较窄等优点。(The invention discloses a blue ceramic ink powder prepared by a suspension polymerization method and a preparation method thereof. The invention adopts the ball milling dispersion technology and the suspension polymerization method to prepare the ceramic ink powder, effectively solves the problems of uneven components and easy leakage of the ceramic ink powder prepared by the traditional melting and crushing method, and has the advantages of uniform dispersion of the components, regular appearance, smooth surface, controllable particle size, narrow particle size distribution and the like.)

1. The blue ceramic toner is characterized by comprising the following components in parts by weight:

10-40 parts of blue ceramic pigment

65-80 parts of styrene

10-20 parts of butyl acrylate

1-3 parts of charge regulator

3-6 parts of wax

1.5-3 parts of initiator

10-20 parts of dispersant

1-2 parts of surfactant

3-5 parts of hydrophobic silicon dioxide

750 portions of deionized water and 1000 portions of deionized water.

2. The blue ceramic toner according to claim 1, wherein the blue ceramic pigment is any one of cobalt blue PB-28, chromium cobalt blue PB-36, and vanadium zirconium blue.

3. The blue ceramic toner according to claim 1, wherein the charge control agent is a metal complex produced by Hubeidinglong chemical Co.

4. The blue ceramic toner according to claim 1, wherein the wax is one of a sliced paraffin wax and a polyethylene wax.

5. The blue ceramic toner according to claim 1, wherein the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, and lauroyl peroxide.

6. The blue ceramic toner according to claim 1, wherein the dispersant is one of polyvinyl alcohol 1788, polyvinyl alcohol 1750 ± 50, gelatin, and methyl cellulose.

7. The blue ceramic toner according to claim 1, wherein the surfactant is one of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, tween-60, and tween-80.

8. The method for producing a blue ceramic toner according to any one of claims 1 to 7, characterized by comprising the steps of:

(1) modified blue ceramic pigment: adding blue ceramic pigment into toluene solution for ultrasonic dispersion, adding silane coupling agent into the toluene solution, performing ultrasonic homogenization, heating the mixture to 80 +/-5 ℃, stirring for more than 5 hours, cleaning, drying and grinding for later use;

(2) preparing an oil phase: adding wax into a mixed monomer of styrene and butyl acrylate, heating to dissolve the wax, adding the modified blue ceramic pigment obtained in the step (1), a charge regulator and an initiator into the mixed monomer, performing ultrasonic dispersion uniformly, and performing ball milling for 4-6h to obtain a uniform and stable dispersion liquid;

(3) preparing an aqueous phase: adding a dispersing agent and a surfactant into deionized water, and heating to dissolve the dispersing agent and the surfactant;

(4) preparing a mixed phase: slowly dripping the oil phase in the step (2) into the water phase in the step (3) and carrying out high-speed shearing;

(5) polymerization: heating the mixed phase in the step (4) to 75-85 ℃ under the protection of nitrogen, and stirring for reacting for 6-10 h;

(6) and (3) separation and drying: filtering and washing the polymerization product obtained in the step (5), and then drying the polymerization product in vacuum for 6 to 10 hours at the temperature of between 35 and 50 ℃ to obtain dry and pure quasi-ceramic powdered ink particles;

(7) adding externally: and (4) adding hydrophobic silica, and carrying out modification treatment on the quasi-ceramic toner particles obtained in the step (6) to obtain the blue ceramic toner.

9. The method according to claim 8, wherein in the step (1), the silane coupling agent accounts for 5wt% of the weight of the blue ceramic pigment.

10. The method according to claim 8, wherein in the step (1), the stirring speed is 400-500 r/min.

Technical Field

The invention relates to a blue ceramic toner and a preparation method thereof, in particular to a blue ceramic toner for ceramic laser printing and a preparation method thereof.

Background

The decoration means of the ceramic material mainly comprises three processes of applique, roller printing and ink-jet printing at present, the three decoration processes can basically meet the large-scale decoration requirements of various ceramic products, but the existing decoration means gradually becomes insufficient along with the improvement of the requirements of people on the appearance quality of the ceramic products and the expansion of the personalized market demand. Recently, a ceramic laser printing process has better, finer and more real decoration effect and can design decoration patterns for customers, so that the ceramic laser printing process is more and more popular with enterprises and customers. Therefore, the technology will be the next technical revolution in the field of ceramic decoration.

At present, the preparation method of the ceramic toner is mainly a melting and crushing method. The melt crushing method is still the mainstream technology for industrially preparing the ceramic ink powder at present because of the advantages of mature technology, easy and safe operation, stable production quality, lower production cost and the like. For example, Zhongtianjia electronics Co., Ltd. in Tianjin City (patent CN 20101010413.3), black ceramic pigment, styrene acrylic resin, charge regulator, polypropylene wax and other components are mixed by mixing equipment, and then coarse crushing, micro crushing and grading are carried out to remove large and small particles, and particles with the particle size of 6-10 μm are reserved. Wuxi Jiateng magnetic powder Co., Ltd (patent CN 201110327960.5) pours blue inorganic ceramic pigment, styrene-acrylic resin, polypropylene wax and charge regulator into a mixing roll, mixes them evenly to prepare a mixture, puts into an extruding machine, tabletting at high temperature, cooling and crushing, and grading to obtain particles with average particle size of 6-8 μm. In a similar patent CN201510302129.1, a high-temperature resistant color toner is prepared by a melting and crushing method, and the diameter of the screened toner is 8-20 μm. However, the toner particles prepared by the fusion method have irregular shapes, rough particle appearance, wide particle size distribution and uneven distribution of all components, and the ceramic pigment is easy to fall off, so that high-resolution and high-quality color patterns cannot be printed.

Disclosure of Invention

The invention provides a method for preparing blue ceramic ink powder for ceramic printing by ball milling and suspension polymerization, which has the advantages of uniform distribution of components, regular appearance, controllable particle size, narrow particle size distribution, simple process, energy conservation, environmental protection and low cost, and aims to overcome the technical defects of irregular shape, rough particle appearance, wide particle size distribution, non-uniform distribution of the components, easiness in falling off, incapability of printing high-resolution high-quality color images and high cost of the ink powder prepared by the prior art.

The technical scheme for realizing the purpose of the invention is as follows:

the blue ceramic toner provided by the invention comprises the following components in parts by weight:

10-40 parts of blue ceramic pigment

65-80 parts of styrene

10-20 parts of butyl acrylate

1-3 parts of charge regulator

3-6 parts of wax

1.5-3 parts of initiator

10-20 parts of dispersant

1-2 parts of surfactant

3-5 parts of hydrophobic silicon dioxide

750 portions of deionized water and 1000 portions of deionized water.

Furthermore, the blue ceramic pigment adopts any one of cobalt blue PB-28, chromium cobalt blue PB-36 and vanadium zirconium blue.

Further, the charge regulator is a metal complex produced by Hubeidinglong chemical industry Co.

Further, the wax is one of slice paraffin and polyethylene wax.

Further, the initiator is one of Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, Benzoyl Peroxide (BPO) and lauroyl peroxide.

Further, the dispersing agent is one of polyvinyl alcohol 1788, polyvinyl alcohol 1750 +/-50, gelatin and methyl cellulose.

Further, the surfactant is one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, tween-60 and tween-80.

The preparation method of the blue ceramic toner comprises the following steps:

(1) surface modification of ceramic pigment, namely adding blue ceramic pigment into toluene solution and carrying out ultrasonic treatment for 30 minutes, adding silane coupling agent into the toluene solution and carrying out ultrasonic treatment for 30 minutes, heating the mixture to 80 ℃ and stirring for 5 hours, finally washing with ethanol for several times, drying at 60 ℃ for 12 hours, and grinding for later use;

(2) preparing an oil phase: adding wax into a monomer mixed by styrene and butyl acrylate, heating to dissolve the wax, then adding the modified blue ceramic pigment, the charge regulator and the initiator into the monomer, ultrasonically dispersing for 5min, transferring the mixed solution into a ball milling tank containing zirconium dioxide microspheres, and performing ball milling for 4-6h to obtain uniform and stable dispersion liquid;

(3) preparing an aqueous phase: adding a dispersing agent and a surfactant into deionized water, and heating to dissolve the dispersing agent and the surfactant;

(4) preparing a mixed phase: slowly dropping the oil phase liquid into the water phase and shearing at high speed under the action of a high-shear emulsifying machine;

(5) polymerization: transferring the sheared mixed solution into a container, heating to 75-85 ℃ under the protection of nitrogen, and stirring for reacting for 6-10 h;

(6) and (3) separation and drying: filtering and separating the product obtained in the step (5), washing with deionized water for 1-3 times to remove redundant dispersing agent and surfactant, washing with absolute ethyl alcohol for 1-3 times to remove a small amount of unreacted monomer, transferring the product to a vacuum oven, and drying in vacuum at 35-50 ℃ for 6-10h to obtain dry and pure quasi-ceramic powdered ink particles;

(7) adding externally: and adding hydrophobic silicon dioxide, and carrying out modification treatment on the dried quasi-ceramic toner particles to obtain the ceramic toner for the ceramic laser printer.

Further, in the step (1), the silane coupling agent accounts for 5wt% of the ceramic pigment, and the stirring speed is 400-500 r/min.

Further, in the step (2), zirconium dioxide microspheres with the diameter of 1.2-1.6mm are adopted for ball milling, the mass ratio of the zirconium dioxide microspheres to the ceramic pigment is 50:1-100:1, and the rotating speed of the ball mill is 500-.

Further, in the step (4), the rotation speed of the high shear emulsifying machine is 4000-.

Further, in the step (5), the stirring speed is 300-500 r/min.

Compared with the prior art, the invention has the advantages and beneficial effects that:

(1) the invention is favorable for solving the problem of uniform dispersion of each functional component by a ball milling dispersion technology.

(2) The invention uses the styrene-acrylic resin to coat the pigment, the wax and the charge agent, and can effectively solve the problem of leakage of the pigment and the wax particles.

(3) The invention prepares the composite particles with the particle size of 6-10 microns through suspension polymerization, so that the blue ceramic toner which is spherical in shape, smooth in surface, uniform in particle size and narrow in distribution is finally obtained.

(4) The ceramic ink powder is prepared by suspension polymerization, and the preparation method has the advantages of simple process, energy conservation, environmental protection and low cost.

Drawings

FIG. 1 is a block diagram of the process flow of the present invention.

FIG. 2 is an SEM image of a ceramic toner prepared by suspension polymerization in example 1 of the present invention, in which a: overall view, b: individual ink particle patterns.

FIG. 3 is a graph showing the particle size distribution of the ceramic toner prepared in example 1 of the present invention.

FIG. 4 is a DSC chart of the ceramic toner prepared in example 2 of the present invention.

FIG. 5 is an XRD pattern of the calcined and cobalt blue pigment of the ceramic toner of example 3 of the present invention at 1000 ℃.

Detailed Description