CN106033175B - Color carbon powder and preparation method thereof - Google Patents
Color carbon powder and preparation method thereof Download PDFInfo
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- CN106033175B CN106033175B CN201510117133.1A CN201510117133A CN106033175B CN 106033175 B CN106033175 B CN 106033175B CN 201510117133 A CN201510117133 A CN 201510117133A CN 106033175 B CN106033175 B CN 106033175B
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Abstract
The invention provides color carbon powder and a preparation method thereof. The preparation method of the color carbon powder comprises the following steps: respectively preparing reaction components of high-molecular emulsion, wax dispersion liquid and coloring agent dispersion liquid; adding the three reaction components into deionized water, dispersing, adjusting the pH value of the mixture to be below 4, raising the temperature of the system, and adjusting the pH value to be neutral when the particle size of particles in the mixture reaches 7-9 mu m to obtain carbon powder primary particles; raising the temperature of the system, adding a polymerization reaction monomer and an initiator for polymerization reaction, keeping the temperature of the reaction system at 90-110 ℃ when the particle size of particles in the reaction system reaches 9-11 mu m, stopping keeping the temperature when the circularity of the particles in the reaction system is 0.90-0.98, and cooling, separating and drying the reaction system to obtain carbon powder particles; adding external additive into the carbon powder particles, stirring and mixing to prepare the color carbon powder. The color carbon powder prepared by the preparation method has good photographic fixing property and durability during printing and copying.
Description
Technical Field
The invention relates to the technical field of electrostatic imaging, in particular to color carbon powder and a preparation method thereof.
Background
The electrophotographic process is to form an electrostatic latent image on a photoreceptor or an electrostatic recording medium, then to adhere the electrostatic latent image with color toner to develop it, and then to transfer the toner image onto a paper sheet by heat and pressure using a heat and pressure roller to form a fixed image. The performance and quality of the color toner will directly affect the imaging quality.
The color toner is generally composed of a polymer resin, a colorant (pigment or dye), a wax, an external additive (charge control agent, etc.), and the like. The color carbon powder for electrostatic development is prepared through smelting and crushing process including the steps of smelting, mixing, extruding, cooling, crushing, superfine crushing, grading, adding additive, etc. to prepare color carbon powder. However, the preparation method has the defects that the coloring agent cannot be uniformly dispersed in the resin, the prepared color carbon powder has irregular shape, large particle size and wide distribution, and the like, so that the defects of poor fixability (easy roller sticking), low resolution, poor color, high waste powder rate and the like exist during printing and copying, and the method is relatively complex in process and high in cost.
Since the color carbon powder prepared by physical methods such as melting and crushing has many defects, technologies for preparing the color carbon powder by chemical methods, including suspension polymerization and emulsion polymerization, are gradually developed in the follow-up process.
the suspension polymerization method is that the monomer is suspended in a medium in a small drop form for free radical polymerization, and the method can effectively control the size of the color carbon powder particles, so that the flow property and the charge property of the carbon powder are obviously improved. However, the toner prepared by this method has a wide particle size distribution, so that the transfer efficiency of the toner is reduced and the resolution is not good enough, and the obtained toner particles are too round, so that the recovery and cleaning of the toner are relatively difficult.
Compared with the suspension polymerization method, the emulsion polymerization method can more easily obtain the color carbon powder with smaller particle size distribution. In order to improve the offset resistance of the color carbon powder when the color carbon powder is prepared by the existing emulsion polymerization method, the dosage of wax is generally required to be increased, and at the moment, the wax is easy to migrate to the surface of the carbon powder particles, so that a carrier and a developing sleeve are polluted, and the fixation of the color carbon powder during printing is poor; further, the wax may form a wax film on the photoreceptor, which may result in a decrease in durability.
disclosure of Invention
The invention provides a color carbon powder and a preparation method thereof for solving the technical problems, and the color carbon powder prepared by the preparation method has good photographic fixing property and durability when being printed and copied.
In a first aspect of the present invention, a method for preparing color toner is provided, which comprises the following steps:
1) Respectively preparing reaction components:
Preparing a high-molecular emulsion, wherein the high-molecular emulsion is styrene-acrylic polymer emulsion or polyester resin emulsion;
Adding wax and surfactant into deionized water to prepare wax dispersion liquid;
Adding a colorant and a surfactant into deionized water to prepare a colorant dispersion liquid;
2) Adding the prepared polymer emulsion, wax dispersion liquid and colorant dispersion liquid into deionized water at room temperature, dispersing, adjusting the pH value of the mixture to be below 4, raising the temperature of the system, and adjusting the pH value of the mixture to be neutral when the particle size of particles in the mixture reaches 7-9 μm to obtain carbon powder primary particles;
3) Raising the temperature of a system where the carbon powder primary particles are located, adding a polymerization reaction monomer and an initiator to carry out polymerization reaction, keeping the temperature of the reaction system at 90-110 ℃ when the particle size of the particles in the reaction system reaches 9-11 mu m, stopping keeping the temperature when the circularity of the particles in the reaction system is 0.90-0.98, and then cooling, separating and drying the reaction system to obtain carbon powder particles;
4) Adding external additive into the prepared carbon powder particles, and mixing to prepare the color carbon powder.
In the present invention, the quality parameters of the polymer emulsion, such as glass transition temperature (Tg), molecular weight range, molecular weight distribution, etc., can be controlled in consideration of the printing performance such as durability, fixing ability, etc., of the color toner. The research shows that: if the Tg of the polymer emulsion is lower than 40 ℃, the durability of the carbon powder is poor, and if the Tg of the polymer emulsion is higher than 75 ℃, the fixing temperature of the carbon powder is promoted to be increased, so that the fixing capability is low and the like are caused; therefore, the glass transition temperature of the polymer emulsion can be controlled to be 40-75 ℃ under the comprehensive consideration, and the glass transition temperature can be measured by a Differential Scanning Calorimeter (DSC).
in addition, the weight average molecular weight of the polymer emulsion can be controlled to be 4000-1000000, and the molecular weight distribution is controlled to be 2-30, so that the prepared color carbon powder has more excellent printing performance, and the weight average molecular weight and the molecular weight distribution of the polymer emulsion are measured by Gel Permeation Chromatography (GPC). Also, the present invention does not strictly limit the solid content of the polymer emulsion prepared, and in an embodiment of the present invention, the solid content of the polymer emulsion is preferably less than 50%.
In one embodiment of the present invention, the styrene-acrylic polymer emulsion may be prepared by adding an initiator, a surfactant, a styrene monomer, an acrylate monomer, and a chain transfer agent to deionized water for polymerization.
Further, when preparing the styrene-acrylic polymer emulsion, under an oxygen-free environment, the initiator, the surfactant, the styrene monomer, the acrylate monomer and the chain transfer agent are mixed according to the mass ratio of (0.1-3): (0.2-5): (40-60): (10-30): (0.05-5), adding the mixture into deionized water at the temperature of 70-90 ℃ for polymerization reaction to prepare the styrene-acrylic polymer emulsion; in particular, the polymerization product is cooled and filtered. Wherein, an oxygen-free environment can be realized by introducing inert gas (such as nitrogen) into the reaction system, and the polymerization reaction can be carried out under stirring, and the stirring speed can be controlled at 150-; in addition, the surfactant may be added to the deionized water first, and then the initiator may be added while the styrene monomer, the acrylate monomer and the chain transfer agent are added to perform the polymerization reaction, and the polymerization reaction product may be filtered by a 100 mesh screen.
preferably, the glass transition temperature of the styrene-acrylic polymer emulsion is controlled to be 50-65 ℃, the weight-average molecular weight is 10000-600000, and the molecular weight distribution is 4-15.
in another embodiment of the present invention, the polyester resin emulsion may be prepared by adding the polyester resin to an organic solvent, stirring until completely dissolved, adding deionized water and an alkali for dispersion, and then removing the organic solvent. Wherein the mass ratio of the polyester resin to the organic solvent to the deionized water is controlled to be (1-5): (5-20): (6-30), and controlling the particle size of the polyester resin emulsion to be 50-500nm and the pH to be 6-8; the organic solvent can be alcohols, ketones (methyl ethyl ketone), amides (N, N-dimethylformamide), sulfones (dimethyl sulfoxide), cyclic ethers (tetrahydrofuran), ethyl acetate, or mixture thereof.
Preferably, the glass transition temperature of the polyester resin emulsion is controlled to be 50-70 ℃, and further to be 55-65 ℃; molecular weight is 5000-; the molecular weight distribution is 3-30, further 4-15.
In one embodiment, the adding the wax and the surfactant to the deionized water to form the wax dispersion may include: mixing wax and a surfactant according to a mass ratio of 1: (0.02-0.3) adding into deionized water, heating to make the temperature of the system higher than the melting point of wax, and dispersing to obtain wax dispersion liquid with particle size of 80-500 nm; wherein the melting point of the wax is 50-130 ℃; in particular, waxes having a melting point of 50 to 110 ℃ may be selected; if the melting point of the wax is higher than 130 ℃, the carbon powder is not easy to melt into paper fibers during printing, and the low-temperature fixing performance is affected, and if the melting point of the wax is lower than 50 ℃, the carbon powder can be more easily adhered to the light guide element or the metering scraper. The particle size of the wax dispersion was measured using a malvern laser particle size meter MS 2000.
In embodiments of the invention, the wax used may be a combination of one or more of the following: petroleum waxes and derivatives such as paraffin wax, microcrystalline wax and vaseline; polyolefin waxes such as polyethylene wax and polypropylene wax, and derivatives thereof; synthetic waxes such as Fischer-Tropsch wax; natural waxes such as rice wax and carnauba wax; ester wax, vegetable wax, animal wax, solid silicone wax, montan wax, and the like can also be used.
In addition, the dispersing method is not limited strictly, and for example, stirring dispersion and/or homogeneous dispersion may be performed, wherein the stirring dispersion may be performed by using conventional equipment such as a high-speed shearing machine, and the homogeneous dispersion may be performed by using conventional equipment such as a high-pressure homogenizer. Specifically, when preparing the wax dispersion, the wax dispersion can be stirred and dispersed for 0.5 to 2 hours, and then the wax dispersion is homogenized and dispersed, so that uniform dispersion is realized; also, the present invention is not strictly limited to the solid content of the wax dispersion, and in an embodiment of the present invention, the solid content of the wax dispersion is preferably less than 40%.
In one embodiment, the adding the colorant and the surfactant to deionized water to form the colorant dispersion may include: mixing a colorant and a surfactant according to a mass ratio of 1: (0.02-0.4) adding deionized water, dispersing and grinding to obtain the colorant dispersion liquid with the particle size of 80-800 nm. The particle size of the colorant dispersion was measured by a malvern laser particle size meter MS 2000.
In addition, when the colorant dispersion liquid is prepared, stirring dispersion can be adopted, the rotating speed of the stirring dispersion can be controlled to be 2500-3500rpm, and the dispersion time is 0.5-8 h; also, the present invention is not strictly limited to the solid content of the colorant dispersion liquid, and in an embodiment of the present invention, the solid content of the colorant dispersion liquid is preferably less than 50%.
Further, the mass ratio among the polymer emulsion, the wax dispersion liquid and the colorant dispersion liquid in step 2) may be controlled to (30 to 50): (5-15): (6-20), and raising the temperature of the system to 35-50 ℃ after stirring and dispersing.
The present invention is not particularly limited with respect to the acid and base used for adjusting the pH of the mixture in step 2). The acid can be one or more of sulfuric acid, nitric acid and hydrochloric acid; the alkali can be one or more of sodium hydroxide, potassium hydroxide and ammonia water.
Further, in the step 3), the temperature of a system where the carbon powder primary particles are located is increased to 70-90 ℃, and the mass ratio of the polymerization reaction monomer to the initiator is controlled to be 100: (0.3-0.6) and the mass ratio of the solid in the polymer emulsion to the polymerization reaction monomer is (1-10): 1.
The inventor finds that in the process of carrying out polymerization reaction on carbon powder primary particles, a polymerization reaction monomer and an initiator, when the particle size of the particles in a reaction system reaches 9-11 mu m, the reaction system is kept at 90-110 ℃, meanwhile, the circularity of the particles is detected and controlled to be 0.90-0.98, and the circularity range is beneficial to recovery and cleaning of the carbon powder. In embodiments of the invention, circularity of the particles may be determined based on basic common knowledge and skills possessed by those skilled in the art, for example, circularity may be detected using Sysmex FIPA 3000.
The surfactant used in the present invention is an anionic surfactant and/or a nonionic surfactant. Wherein, the anionic surfactant can be at least one selected from alkyl aryl sulfonate, alkyl sulfate, alkyl ether sulfate, alkyl carboxylate, alkyl alkoxylated carboxylate and the like, and specifically can be sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium methyl stearate polyoxyethylene ether sulfonate, sodium alpha alkenyl sulfonate, sodium secondary alkyl sulfonate, isooctyl alcohol phosphate, lauryl alcohol ether phosphate and the like, and alkyl sulfate is preferred, and sodium dodecyl sulfate is more preferred; the nonionic surfactant may be at least one selected from polyoxyethylene cetyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, nonylphenol polyoxyethylene ether, dialkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, alkanolamide, polyoxyethylene alkanolamide alkyl ethoxylate, alkyl propoxylate, alkyl aryl ethoxylate, alkyl aryl propoxylate, ethylene oxide/propylene oxide copolymer, and the like, preferably alkylphenol polyoxyethylene ether, more preferably alkylphenol polyoxyethylene ether having 8 to 10 carbon atoms.
the colorant used in the present invention is a dye and/or a pigment, and is preferably a pigment from the viewpoint of water resistance, light resistance and gas resistance. The present invention is not limited to a particular choice of pigments, which may include, but is not limited to, cyan pigments, such as c.i. pigment blue 2, pigment blue 3, pigment blue 15: 1. pigment blue 15: 2. pigment blue 15: 3. pigment blue 15: 4, etc.; magenta pigment such as c.i. pigment red 30, pigment red 31, pigment red 32, pigment red 37, pigment red 38, pigment red 48: 1. pigment Red 53: 1. pigment red 57: 1. pigment red 112, pigment red 114, pigment red 122, pigment red 184, and the like; yellow pigments such as c.i. pigment yellow 74, pigment yellow 81, pigment yellow 83, pigment yellow 97, pigment yellow 110, pigment yellow 138, and the like; black pigments such as aniline black, carbon black, nonmagnetic ferrites, copper oxide, activated carbon, and the like.
The polymerization monomers used in the present invention may be a combination of one or more of the following: styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methoxystyrene, p-ethylstyrene, etc.; vinyl ester monomers, for example: vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, and the like; acrylate monomers, for example: methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, etc.; methacrylate monomers, for example: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc.; unsaturated carboxylic acid monomers such as acrylic acid or methacrylic acid; halogen-containing vinyl monomers such as vinyl chloride; copolymers of nitro-type monomers such as nitrostyrene and the like; also employable are acidic polar group-containing polymer monomers such as acrylonitrile, maleic anhydride, vinyl ether, methacrylonitrile, acrylamide, methacrylic acid and maleic acid. The preferable polymerization reaction monomer comprises a styrene monomer and a (methyl) acrylate monomer, wherein the mass ratio of the styrene monomer to the (methyl) acrylate monomer is (40-60): (10-30).
the initiator used in the invention is ammonium persulfate, potassium persulfate, sodium persulfate or hydrogen peroxide and the like.
The molecular weight of the polymer emulsion is adjusted by using a chain transfer agent, and the chain transfer agent can be n-dodecyl mercaptan, tert-dodecyl mercaptan, carbon tetrachloride and the like.
further, in the step 4), the mass ratio of the carbon powder particles to the external additive is 100: (0.1-8), namely: relative to 100 parts by weight of carbon powder particles, the content of the external additive is 0.1-8 parts by weight, preferably 100: (0.2-5). If the content of the external additive is less than 0.1 part by weight, the electrification speed in the carbon powder printing process is low, the fluidity is poor, and the electrification stability at high temperature is poor; if the content of the external additive is more than 8 parts by weight, part of the external additive is easily separated from the surface of the toner, may adhere to the surface of the photoreceptor during printing, easily forms a film, or accumulates inside the developing tank to cause deterioration of the charging function of the developer, etc.
In addition, the external additive may be an inorganic external additive and/or an organic external additive; wherein the inorganic external additive is selected from one or more of silicon dioxide, titanium dioxide, aluminum oxide, zinc oxide and magnesium oxide, and the organic external additive is selected from one or more of polymer beads and metal stearate. The external additive is preferably an inorganic additive, more preferably silica, titania and alumina, in order to improve the fluidity of the carbon powder particles, suppress the adhesion and aggregation between the carbon powder particles, and make it stable for long-term storage and maintain the stability for a long time even in a high-temperature and high-humidity environment.
The second aspect of the invention provides a colored carbon powder prepared by any one of the above preparation methods.
According to the preparation method of the colored carbon powder, the polymerization process implemented step by step is utilized, the carbon powder primary particles containing wax and the colorant are firstly prepared, and further, the surface of the carbon powder primary particles forms a resin coating layer through polymerization reaction, so that the finally obtained colored carbon powder avoids the wax and the colorant particles from being exposed on the surface of the carbon powder particles, and the defects of easy roller sticking, low printing resolution, more waste powder and the like during printing and copying are overcome; moreover, the color carbon powder prepared by the method of the invention can regulate and control the particle size distribution of the carbon powder, and simultaneously, the circularity of the color carbon powder is in a proper range (generally 0.90-0.98), thereby overcoming the problems that the particle size distribution of the carbon powder is difficult to regulate and control and the obtained particles are too round by the polymerization method in the prior art, and leading the carbon powder to be easy to recycle and clean after printing and copying.
The color carbon powder prepared by the preparation method has good photographic fixing property and durability when being printed and copied.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1-1 preparation of styrene-acrylic Polymer emulsion (a-1)
Adding 208g of deionized water and 2.2g of sodium dodecyl sulfate into a reactor with a stirring device, introducing nitrogen into the reactor to exhaust air in the reactor, heating to keep the temperature of a reaction system in the reactor at about 70 ℃, adjusting the stirring speed of the stirring device to about 180rpm, slowly adding a mixture obtained by mixing 80g of styrene monomer, 30g of n-butyl acrylate monomer, 2g of 2-hydroxyethyl methacrylate and 0.11g of n-dodecyl mercaptan into the reactor, simultaneously dropwise adding 30ml of deionized water dissolved with 3.6g of ammonium persulfate to carry out polymerization reaction, and controlling the dropwise adding time within 6 h.
The molecular weight and molecular weight distribution of the polymer in the polymerization reaction system were measured by gel permeation chromatography GPC, and the glass transition temperature Tg of the polymer was measured by differential scanning calorimeter DSC, and when it was measured that the weight average molecular weight of the polymer was 360000, the number average molecular weight was 27000, the molecular weight distribution was 13.3, and the glass transition temperature Tg was 65 ℃, the reaction system was cooled to room temperature and filtered by using a 100 mesh filter, to obtain a styrene-acrylic polymer emulsion (a-1).
Examples 1-2 preparation of styrene-acrylic Polymer emulsion (a-2)
185g of deionized water and 5g of nonylphenol polyoxyethylene ether are added into a reactor with a stirring device, nitrogen is introduced into the reactor to exhaust air in the reactor, the temperature of a reaction system in the reactor is kept at about 80 ℃ by heating, the stirring speed of the stirring device is adjusted to about 200rpm, a mixture obtained by mixing 40g of styrene monomer, 20g of p-methylstyrene monomer, 25g of isobutyl methacrylate, 1g of 2-hydroxypropyl methacrylate and 5g of tert-dodecyl mercaptan is slowly added into the reactor, 30ml of deionized water dissolved with 0.1g of potassium persulfate is added dropwise for polymerization, and the adding time is controlled within 3 h. The weight average molecular weight of the polymer was 145000, the number average molecular weight was 16800, and the molecular weight distribution was 8.6 as measured by gel permeation chromatography GPC; and when the glass transition temperature Tg measured by a differential scanning calorimeter DSC is 61 ℃, cooling the reaction system to room temperature, and filtering by adopting a 100-mesh filter screen to obtain the styrene-acrylic polymer emulsion (a-2).
Examples 1-3 preparation of styrene-acrylic Polymer emulsions (a-3)
Adding 180g of deionized water and 3g of polyoxyethylene cetyl ether into a reactor with a stirring device, introducing nitrogen into the reactor to exhaust air in the reactor, heating to keep the temperature of a reaction system in the reactor at about 90 ℃, adjusting the stirring speed of the stirring device to about 200rpm, slowly adding a mixture obtained by mixing 60g of styrene monomer, 28g of n-butyl methacrylate monomer, 2g of 2-hydroxyethyl methacrylate and 2g of n-dodecyl mercaptan into the reactor, simultaneously dropwise adding 30ml of deionized water dissolved with 3g of sodium persulfate for polymerization, and controlling the dropwise adding time within 3 h. The weight-average molecular weight of the polymer was 33200, the number-average molecular weight was 16000, and the molecular weight distribution was 2.2 as determined by gel permeation chromatography GPC; and when the glass transition temperature Tg measured by a differential scanning calorimeter DSC is 55 ℃, cooling the reaction system to room temperature, and filtering by adopting a 100-mesh filter screen to obtain the styrene-acrylic polymer emulsion (a-3).
Examples 1-4 preparation of polyester resin emulsion (a-4)
80g of a polyester resin NE701 (from Japan Kao corporation) was added to 200g of methyl ethyl ketone at room temperature, and after completely dissolving it by stirring, 200g of deionized water and 15g of a 3% sodium hydroxide solution were added, and dispersed at high speed for 10 minutes, followed by removing the methyl ethyl ketone by reduced pressure distillation using a rotary evaporator, and after cooling to room temperature, a polyester resin emulsion (a-4) was obtained, the pH of which was measured to be 7.8.
The particle size of the polyester resin emulsion was 280nm as measured by a malvern laser particle sizer MS2000, the molecular weight of the polyester resin emulsion was 13000 and the molecular weight distribution was 20 as measured by a gel permeation chromatograph GPC, and the glass transition temperature Tg of the polyester resin emulsion was 56 as measured by a differential scanning calorimeter DSC.
EXAMPLE 2-1 preparation of wax Dispersion (b-1)
Stirring 50g of paraffin with the melting point of about 60 ℃, 1g of anionic surfactant sodium dodecyl sulfate and 149g of deionized water at 85 ℃ for pre-dispersion for 1h, then adding the pre-dispersion into a high-pressure homogenizer for homogeneous dispersion, measuring the particle size range of the dispersion by a Malvern laser particle size analyzer MS2000 to be 80-300nm, and stopping dispersion to obtain the wax dispersion liquid (b-1).
Example 2-2 preparation of wax Dispersion (b-2)
50g of polyethylene wax with the melting point of about 78 ℃, 15g of polyoxyethylene cetyl ether and 140g of deionized water are stirred and pre-dispersed for 0.5h at the temperature of 95 ℃, then the pre-dispersion liquid is added into a high-pressure homogenizer for homogeneous dispersion, the particle size range of the dispersion liquid is measured by a Malvern laser particle size analyzer MS2000 to be 100-350nm, and the dispersion is stopped, thus obtaining the wax dispersion liquid (b-2).
Examples 2 to 3 preparation of wax Dispersion (b-3)
30g of carnauba wax with the melting point of about 84 ℃, 20g of polyethylene wax with the melting point of about 72 ℃, 10g of polyoxyethylene cetyl ether and 140g of deionized water are stirred at the temperature of 90 ℃ for pre-dispersion for 2 hours, then the pre-dispersion liquid is added into a high-pressure homogenizer for homogeneous dispersion, the particle size range of the dispersion liquid is measured by a Malvern laser particle size analyzer MS2000 to be 120-500nm, and the dispersion is stopped, thus obtaining the wax dispersion liquid (b-3).
Example 3-1 preparation of Red colorant Dispersion (c-1)
15g of nonylphenol polyoxyethylene ether is dissolved in 300g of deionized water, 95g of pigment red 122 and 20g of negative charge control agent N-4P (Claien chemical Co., Ltd.) are added, a high-speed shearing dispersion machine is adopted to stir and disperse for 8 hours at the speed of 3000rpm, then a Miller (PUHLER) grinding machine is used for grinding and dispersing the dispersion liquid, and the grinding is stopped when the particle size distribution range of the colorant dispersion liquid is measured by a Malvern laser particle size analyzer MS2000 to be 120-600nm, so that the red colorant dispersion liquid (c-1) is obtained.
Example 3-2 preparation of yellow colorant Dispersion (c-2)
Dissolving 35g of sodium dodecyl sulfate in 300g of deionized water, adding 95g of pigment yellow 74 and 25g of negative charge control agent N-23 (Claien chemical Co., Ltd.) into the deionized water, stirring and dispersing the mixture for 2 hours at the speed of 3000rpm by using a high-speed shear dispersing machine, then grinding and dispersing the dispersion by using a Miller (PUHLER) grinder, and stopping grinding when the particle size distribution range of the colorant dispersion is measured to be 100-360nm by using a Malvern laser particle sizer MS2000, thus obtaining the yellow colorant dispersion (c-2).
Examples 3-3 preparation of blue colorant Dispersion (c-3)
Dissolving 2g of sodium dodecyl sulfate and 2g of polyoxyethylene cetyl ether in 300g of deionized water, adding 95g of pigment blue 15:3 and 25g of negative charge control agent N-24 (Claien chemical Co., Ltd.), stirring and dispersing for 0.5h at 3000rpm by using a high-speed shearing dispersion machine, then grinding and dispersing the dispersion liquid for 1h by using a Miller (PUHLER) grinder, and stopping grinding when the particle size distribution range of the colorant dispersion liquid is measured by a Malvern laser particle sizer MS2000 to be 60-300nm to obtain the blue colorant dispersion liquid (c-3).
Examples 3 to 4 preparation of Black colorant Dispersion (c-4)
20g of sodium dodecyl sulfate and 13g of polyoxyethylene cetyl ether are dissolved in 300g of deionized water, 95g of carbon black and 25g of negative charge control agent N-24 (Claien chemical Co., Ltd.) are added, the mixture is stirred and dispersed for 0.5h at the speed of 3000rpm of a high-speed shearing dispersion machine, then the dispersion liquid is ground and dispersed by a Miller (PUHLER) grinding machine, and the grinding is stopped when the particle size distribution range of the colorant dispersion liquid is measured to be 60-250nm by a Malvern laser particle sizer MS2000, so that the black colorant dispersion liquid (c-4) is obtained.
example 4-1 preparation of Red toner (d-1)
Adding 120g of the prepared wax dispersion liquid (b-1), 120g of the prepared red colorant dispersion liquid (c-1) and 200g of deionized water into a reaction kettle with a stirring device at room temperature, adjusting the stirring speed of the stirring device to about 400rpm, adding 256g of the prepared styrene-acrylic polymer emulsion (a-1) into the reaction kettle, uniformly stirring, detecting the pH value of the mixture by using a pH meter, dropwise adding 300g of a dilute sulfuric acid solution with the mass content of 2% into the reaction kettle at the speed of 15ml/min to ensure that the pH value of the mixture in the reaction kettle is 2.0, then increasing the temperature of the reaction system to 45 ℃, detecting the particle size of the mixture by using a Malvern laser particle sizer MS2000, adding 50g of a sodium hydroxide solution with the mass content of 15% into the reaction system when the particle size reaches about 8.0 mu m, wherein the pH value of the mixture is 7.5, carbon powder primary particles were obtained.
And continuously raising the temperature of a system in which the carbon powder primary particles are positioned to about 85 ℃, and simultaneously dropwise adding a mixture formed by mixing 50g of ammonium persulfate solution with the mass content of 0.4%, 24g of styrene, 11g of butyl acrylate and 1g of methacrylic acid-2-hydroxyethyl into the reaction kettle for polymerization reaction. And when the particle size of the particles in the reaction system is 9.1 mu m, raising the temperature of the system to 105 ℃, preserving the heat, detecting the circularity of the particles in the reaction system by adopting Sysmex FIPA3000, stopping preserving the heat when the circularity of the particles in the reaction system is about 0.952, and cooling, filtering, washing and drying the reaction system to obtain the red solid particles.
to the red solid particulates were added 1% hydrophobic silica R812 (from Evnoic Degussa (SEA) pte., Ltd) and 0.3% silica RX50 (from Evnoic Degussa (SEA) pte., Ltd) in mass percent, and mixed using a henschel mixer to give red carbon powder (d-1); the volume average particle size was measured to be 6.8 μm using a Multisizer 3 Coulter particle size analyzer counter.
Example 4-2 preparation of yellow toner (d-2)
114g of the above-prepared wax dispersion (b-2), 115g of the above-prepared yellow coloring agent dispersion (c-2) and 200g of deionized water were charged at room temperature into a reaction vessel equipped with a stirring device, after the stirring speed of the stirring apparatus was adjusted to about 400rpm, 256g of the polymer emulsion (a-2) prepared above was continuously added to the reactor, and after stirring uniformly, the pH value of the mixture was measured with a pH meter, 300g of dilute sulfuric acid solution with the mass content of 2 percent is dripped into the kettle at the speed of 15ml/min to ensure that the pH value of the mixture is 2.7, then raising the temperature of the reaction system to 43.6 ℃, detecting the particle size of the mixture by adopting a Malvern laser particle sizer MS2000, when the particle diameter reached about 8.7 μm, 45g of a sodium hydroxide solution having a mass content of 15% was added to the reaction system, and the pH of the mixture at this time was 7.0, to obtain carbon powder primary particles.
And continuously raising the temperature of a system in which the carbon powder primary particles are positioned to about 85 ℃, and simultaneously dropwise adding a mixture formed by mixing 30g of ammonium persulfate solution with the mass content of 0.5%, 22g of styrene, 10g of butyl acrylate and 0.5g of methacrylic acid-2-hydroxyethyl into the kettle for polymerization reaction. And when the particle size of the particles in the reaction system is 10.5 microns, raising the temperature of the system to 102 ℃, preserving the heat, detecting the circularity of the particles in the reaction system by adopting Sysmex FIPA3000, stopping preserving the heat when the circularity of the particles in the reaction system is about 0.965, and cooling, filtering, washing and drying the reaction system to obtain yellow solid particles.
To the yellow solid particulates were added, by mass percent, 0.8% hydrophobic silica R202 (from Evnoic Degussa (SEA) pte., Ltd) and 0.5% silica RX50 (from Evnoic Degussa (SEA) pte., Ltd) and mixed using a henschel mixer to give yellow carbon powder (d-2); the volume average particle size was 7.1 μm as determined by Multisizer 3 Coulter particle size analyzer.
Examples 4-3 preparation of blue toner (d-3)
118g of the above-prepared wax dispersion liquid (b-3), 122g of the above-prepared blue colorant dispersion liquid (c-3) and 200g of deionized water were charged at room temperature into a reaction vessel equipped with a stirring device, after the stirring speed of the stirring apparatus was adjusted to about 400rpm, 256g of the polymer emulsion (a-3) prepared above was continuously added to the reactor, and after stirring uniformly, the pH value of the mixture was measured with a pH meter, 300g of dilute sulfuric acid solution with the mass content of 2 percent is dripped into the kettle at the speed of 15ml/min to ensure that the pH value of the mixture is 3.4, then the temperature of the reaction system is raised to 42 ℃, a Malvern laser particle sizer MS2000 is adopted to test the particle size of the mixture, when the particle diameter reached about 8.0. mu.m, 50g of a sodium hydroxide solution was added thereto in an amount of 15% by mass at a pH of the mixture of 7.5 to obtain carbon powder primary particles.
and continuously raising the temperature of a system in which the carbon powder primary particles are positioned to about 85 ℃, and simultaneously dropwise adding a mixture formed by mixing 30g of ammonium persulfate solution with the mass content of 0.5%, 28g of styrene, 7g of n-butyl methacrylate and 1g of methacrylic acid-2-hydroxyethyl into the kettle for polymerization reaction. And when the particle size of the particles in the reaction system is 9.6 microns, raising the temperature of the system to 98 ℃, preserving the heat, detecting the circularity of the particles in the reaction system by adopting Sysmex FIPA3000, stopping preserving the heat when the circularity of the particles in the reaction system is about 0.964, and cooling, filtering, washing and drying the reaction system to obtain the blue solid particles.
1.1% hydrophobic silica R812 (from Evnoic Degussa (SEA) pte, Ltd) and 0.4% silica RY50 (from Evnoic Degussa (SEA) pte, Ltd) were added to the blue solid particulates in mass percent and mixed using a henschel mixer to give blue carbon powder (d-3); the volume average particle size was 6.5 μm as determined by Multisizer 3 Coulter particle size analyzer.
Examples 4-4 preparation of Black carbon powder (d-4)
The polymer emulsion (a-1) in example 1 was replaced with the polymer emulsion (a-3) prepared above, the wax dispersion (b-1) was replaced with the wax dispersion (b-2) prepared above, the red colorant dispersion (c-1) was replaced with the black colorant dispersion (c-4) prepared above, and the other conditions were not changed to obtain black toner (d-4); the volume average particle size was 7.0 μm as determined by Multisizer 3 Coulter particle size analyzer.
Examples 4-5 preparation of Red carbon powder (d-5)
Adding 120g of the prepared wax dispersion liquid (b-1), 120g of the prepared red colorant dispersion liquid (c-1) and 200g of deionized water into a reaction kettle with a stirring device at room temperature, adjusting the stirring speed of the stirring device to about 400rpm, adding 335g of the prepared polyester resin emulsion (a-4) into the reaction kettle, uniformly stirring, detecting the pH value of the mixture by using a pH meter, dropwise adding 300g of a dilute sulfuric acid solution with the mass content of 2% into the reaction kettle at the speed of 15ml/min to ensure that the pH value of the mixture in the reaction kettle is 2.0, then increasing the temperature of the reaction system to 40 ℃, detecting the particle size of the mixture by using a Malvern laser particle sizer MS2000, adding 50g of a sodium hydroxide solution with the mass content of 15% into the reaction system when the particle size reaches about 8.0 mu m, wherein the pH value of the mixture is 7.5, carbon powder primary particles were obtained.
And continuously raising the temperature of a system in which the carbon powder primary particles are positioned to about 85 ℃, and simultaneously dropwise adding a mixture formed by mixing 50g of ammonium persulfate solution with the mass content of 0.4%, 22g of styrene, 12g of butyl acrylate and 3g of methacrylic acid-2-hydroxyethyl into the reaction kettle for polymerization reaction. And when the particle size of the particles in the reaction system is 9.9 microns, raising the temperature of the system to 105 ℃, preserving the heat, detecting the circularity of the particles in the reaction system by adopting Sysmex FIPA3000, stopping preserving the heat when the circularity of the particles in the reaction system is about 0.965, and cooling, filtering, washing and drying the reaction system to obtain the red solid particles.
To the red solid particulates were added 1% hydrophobic silica R812 (from Evnoic Degussa (SEA) pte., Ltd) and 0.3% silica RX50 (from Evnoic Degussa (SEA) pte., Ltd) in mass percent, and mixed using a henschel mixer to give red carbon powder; the volume average particle size was measured to be 6.8 μm using a Multisizer 3 Coulter particle size analyzer counter.
Comparative example 1 preparation of comparative example Red toner (e-1)
120g of the above-prepared wax dispersion (b-1), 120g of the above-prepared red colorant dispersion (c-1) and 200g of deionized water were put into a reaction vessel equipped with a stirring device, adjusting the stirring speed of the stirring device to about 400rpm, continuously adding 326g of the prepared styrene-acrylic polymer emulsion (a-1) into the kettle, uniformly stirring, detecting the pH value of the mixture by using a pH meter, 300g of dilute sulfuric acid solution with the mass content of 2 percent is dripped into the kettle at the speed of 15ml/min to ensure that the pH value of the mixture is 2.6, then the system is heated to 42 ℃, and the particle size of the mixture is tested by a Malvern laser particle sizer MS2000, when the particle size reaches about 10 μm, 50g of sodium hydroxide solution with the mass content of 15% is added into the reaction system, and the pH of the mixture is adjusted to 7.5 to obtain carbon powder primary particles.
And continuously raising the temperature of the system where the carbon powder primary particles are located to about 95 ℃, preserving the heat, detecting the circularity of the particles in the reaction system by adopting Sysmex FIPA3000, stopping preserving the heat when the circularity of the particles in the reaction system is about 0.951, and cooling, filtering, washing and drying the reaction system to obtain red solid particles.
To the red solid particulates were added 1% hydrophobic silica R812 (from Evnoic Degussa (SEA) pte., Ltd) and 0.3% silica RX50 (from Evnoic Degussa (SEA) pte., Ltd) in mass percent, and mixed using a henschel mixer to give comparative example red carbon powder (e-1); the volume average particle size was 7.0 μm as determined by Multisizer 3 Coulter particle size analyzer.
comparative example 2 preparation of comparative example yellow toner (e-2)
The styrene-acrylic polymer emulsion (a-1) in comparative example 1 was replaced with the styrene-acrylic polymer emulsion (a-2) prepared above, the wax dispersion (b-1) was replaced with the wax dispersion (b-2) prepared above, and the red colorant dispersion (c-1) was replaced with the yellow colorant dispersion (c-2) prepared above, and the other conditions were not changed, to obtain comparative example yellow toner (e-2).
Comparative example 3 preparation of comparative example blue toner (e-3)
The styrene-acrylic polymer emulsion (a-1) in comparative example 1 was replaced with the styrene-acrylic polymer emulsion (a-3) prepared above, the wax dispersion (b-1) was replaced with the wax dispersion (b-3) prepared above, and the red colorant dispersion (c-1) was replaced with the blue colorant dispersion (c-3) prepared above, and the other conditions were not changed, to obtain comparative example blue toner (e-3).
Comparative example 4 preparation of comparative example Black carbon powder (e-4)
The styrene-acrylic polymer emulsion (a-1) in comparative example 1 was replaced with the styrene-acrylic polymer emulsion (a-3) prepared above, the wax dispersion (b-1) was replaced with the wax dispersion (b-2) prepared above, the red colorant dispersion (c-1) was replaced with the black colorant dispersion (c-4) prepared above, and the other conditions were not changed to obtain comparative example black toner (e-4).
Comparative example 5 preparation of comparative example Red toner (e-5)
120g of the above-prepared wax dispersion (b-1), 120g of the above-prepared red colorant dispersion (c-1) and 130g of deionized water were put into a reaction vessel equipped with a stirring device, adjusting the stirring speed of the stirring device to about 400rpm, continuously adding 425g of the prepared polyester resin emulsion (a-4) into the kettle, uniformly stirring, detecting the pH value of the mixture by using a pH meter, 300g of dilute sulfuric acid solution with the mass content of 2 percent is dripped into the kettle at the speed of 15ml/min to ensure that the pH value of the mixture is 2.2, then the system is heated to 40 ℃, and the particle size of the mixture is tested by a Malvern laser particle sizer MS2000, when the particle size reaches about 10 μm, 50g of sodium hydroxide solution with the mass content of 15% is added into the reaction system, and the pH of the mixture is adjusted to 7.5 to obtain carbon powder primary particles.
And continuously raising the temperature of the system where the carbon powder primary particles are located to about 92 ℃, preserving the heat, detecting the circularity of the particles in the reaction system by adopting Sysmex FIPA3000, stopping preserving the heat when the circularity of the particles in the reaction system is about 0.962, and cooling, filtering, washing and drying the reaction system to obtain red solid particles.
To the red solid particulates were added 1% hydrophobic silica R812 (from Evnoic Degussa (SEA) pte., Ltd) and 0.3% silica RX50 (from Evnoic Degussa (SEA) pte., Ltd) in mass percent, and mixed using a henschel mixer to give comparative example red carbon powder (e-5); the volume average particle size was 7.0 μm as determined by Multisizer 3 Coulter particle size analyzer.
Application example 1
The Color toners prepared in the above examples and comparative examples were subjected to fixing property (roll sticking property) evaluation and durability evaluation as represented by a Color laser jet 2600 printer of hewlett packard co.
1. Evaluation of fixability:
The printer with the color toner was placed in a low temperature and humidity (10 ℃/RH 10%) environment for 12 hours, then printing E-type plate with 5% coverage for each color, continuously printing 2500 sheets, visually observing whether the toner adhered to the roller at the fixing part, and sampling to test the bottom ash, the results are shown in Table 1.
TABLE 1 results of evaluation of fixability of respective color toners
2. Evaluation of durability:
the printer with the color toner was placed in a high temperature and humidity (35 ℃/RH 80%) environment for 12 hours, then printing was performed on the E-plate with 5% coverage for each color, 2500 sheets were continuously printed, whether the toner was stuck to the roller at the fixing portion was visually observed, and sampling was performed to test the bottom ash, the results are shown in table 2.
TABLE 2 durability evaluation results of the respective color toners
The results in tables 1 and 2 show that:
Compared with the traditional emulsion polymerization method (namely comparative examples 1-4), the invention further forms a resin coating layer on the surface of the prepared carbon powder primary particle containing the wax and the colorant by carrying out polymerization reaction step by step, and finally obtains the color carbon powder, thereby avoiding the wax and the colorant particle from being exposed on the surface of the carbon powder particle, and further solving the defects of easy roller sticking, poor durability and the like of the carbon powder during printing and copying.
In addition, the color carbon powder prepared by the preparation method has proper circularity, less waste powder is generated during printing and copying, and the carbon powder is easy to recover and clean after printing and copying.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of color carbon powder is characterized by comprising the following steps:
1) Respectively preparing reaction components:
Preparing a high-molecular emulsion, wherein the high-molecular emulsion is styrene-acrylic polymer emulsion or polyester resin emulsion;
Adding wax and surfactant into deionized water to prepare wax dispersion liquid;
Adding a colorant and a surfactant into deionized water to prepare a colorant dispersion liquid;
2) Adding the prepared polymer emulsion, wax dispersion liquid and colorant dispersion liquid into deionized water at room temperature, dispersing, adjusting the pH value of the mixture to be below 4, raising the temperature of the system, and adjusting the pH value of the mixture to be neutral when the particle size of particles in the mixture reaches 7-9 μm to obtain carbon powder primary particles;
3) Raising the temperature of a system where the carbon powder primary particles are located to 70-90 ℃, adding a polymerization reaction monomer and an initiator to carry out polymerization reaction, keeping the temperature of the reaction system at 90-110 ℃ when the particle size of the particles in the reaction system reaches 9-11 mu m, stopping keeping the temperature when the circularity of the particles in the reaction system is 0.90-0.98, and then cooling, separating and drying the reaction system to obtain carbon powder particles;
Wherein the mass ratio of the polymerization reaction monomer to the initiator is 100: (0.3-0.6), the mass ratio of the solid in the polymer emulsion to the polymerization reaction monomer is (1-10): 1, the polymerization reaction monomer comprises a styrene monomer and a (methyl) acrylate monomer, and the mass ratio of the styrene monomer to the (methyl) acrylate monomer is (40-60): (10-30);
4) Adding external additive into the prepared carbon powder particles, and mixing to prepare the color carbon powder.
2. The method as claimed in claim 1, wherein the weight average molecular weight of the polymer emulsion is 4000-1000000, the molecular weight distribution is 2-30, and the glass transition temperature is 40-75 ℃.
3. The preparation method according to claim 1 or 2, characterized in that the initiator, the surfactant, the styrene monomer, the acrylate monomer and the chain transfer agent are mixed in a mass ratio of (0.1-3): (0.2-5): (40-60): (10-30): (0.05-5), adding deionized water with the temperature of 70-90 ℃ for polymerization reaction to prepare the styrene-acrylic polymer emulsion.
4. the preparation method according to claim 1 or 2, wherein the polyester resin emulsion is prepared by adding the polyester resin into an organic solvent, stirring until the polyester resin is completely dissolved, adding deionized water and alkali for dispersion, and then removing the organic solvent; wherein the mass ratio of the polyester resin to the organic solvent to the deionized water is controlled to be (1-5): (5-20): (6-30), and controlling the particle size of the polyester resin emulsion to be 50-500nm and the pH to be 6-8.
5. The method of claim 1, wherein the adding the wax and the surfactant to deionized water to form a wax dispersion comprises:
Mixing wax and a surfactant according to a mass ratio of 1: (0.02-0.3) adding into deionized water, heating to make the temperature of the system higher than the melting point of wax, and dispersing to obtain wax dispersion liquid with particle size of 80-500 nm; wherein the melting point of the wax is 50-130 ℃.
6. The method of claim 1, wherein the step of adding the colorant and the surfactant to deionized water to form the colorant dispersion comprises:
Mixing a colorant and a surfactant according to a mass ratio of 1: (0.02-0.4) adding deionized water, dispersing and grinding to obtain the colorant dispersion liquid with the particle size of 80-800 nm.
7. The production method according to claim 1, wherein the mass ratio among the polymer emulsion, the wax dispersion liquid and the colorant dispersion liquid in step 2) is controlled to (30 to 50): (5-15): (6-20), and raising the temperature of the system to 35-50 ℃ after stirring and dispersing.
8. The method according to claim 1, wherein the surfactant is an anionic surfactant and/or a nonionic surfactant, the colorant is a dye and/or a pigment, and the polymerization monomer is one or more selected from the group consisting of a styrene monomer, a vinyl ester monomer, a (meth) acrylic ester monomer, an unsaturated carboxylic acid monomer, a halogen-containing vinyl monomer, and a nitro monomer.
9. The preparation method according to claim 1, wherein in step 4), the mass ratio of the carbon powder particles to the external additive is 100: (0.1-8), wherein the external additive is an inorganic external additive and/or an organic external additive; wherein the inorganic external additive is selected from one or more of silicon dioxide, titanium dioxide, aluminum oxide, zinc oxide and magnesium oxide, and the organic external additive is selected from one or more of polymer beads and metal stearate.
10. A colored carbon powder characterized by being produced by the production method according to any one of claims 1 to 9.
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