A composite material, its preparation and use

Abstract

The application discloses a composite material and a preparation method and application thereof. The composite material is a wax nanoparticle coated with silicon dioxide. The application further provides toner comprising an additive, wherein the additive comprises the composite material. The toner provided by the application has a simple preparation process and is easy to realize industrial production. When the composite material is used as an internal additive, the problem of stickiness of physical color toner can be solved, and the gloss and storage stability of printed matter can be improved. When the composite material is used as an external additive, medium and large particle silicon can be replaced, the charge capacity and page yield can be improved while the toner durability is ensured, and thus the production cost is reduced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of laser printer toner, and relates to a composite material, a preparation method thereof and a use of the composite material as an additive in toner. BACKGROUND

[0002] The physical method toner is a dry toner obtained by melting and mixing a binding resin, a colorant and other internal additives, cooling and pressing into a sheet material, then crushing, grading and finally mixing external additives at high speed. Compared with the chemical method toner, the physical method toner has the advantages of mature production process, stable production batch, no waste liquid and waste residue, low access threshold, good environmental and cost advantages and good popularity. With the popularity of color laser printers, the market urgently needs a physical method color toner with printing quality close to or exceeding that of the chemical method toner, but with lower cost and safer production. However, the performance of the physical method color toner in gloss, durability and toner consumption is still greatly different from that of the chemical method toner, which has become one of the bottlenecks restricting the development of the physical method color toner. At present, the main means for improving gloss is the optimization and modification of toner binding resins. However, due to the high melting point and low flowability of the styrene-acrylic resin, the gloss of the toner is poor, so there are few reports on improving the gloss of the toner based on the styrene-acrylic resin. The research mainly focuses on the cross-linking modification based on polyester resin, such as the granted patent CN108351609B and the published patent CN107250919A. However, compared with the styrene-acrylic resin, the polyester resin also has many shortcomings, such as poor environmental adaptability, insufficient durability, easy sticking to the blade, high viscoelasticity leading to low crushing efficiency and the like.

[0003] From the perspective of the physical method color toner itself, especially various additives in the toner, the following problems exist:

[0004] For the internal additives for toner, there is a lack of necessary chemical bonding between the current internal additives, and the particle size of the internal additives is generally in the micron or sub-micron level, so that the dispersion performance of the internal additives in the resin is not ideal. In particular, the incompatibility between the ester wax and the styrene-acrylic resin will lead to poor dispersion performance of the ester wax in the resin. In addition, the dispersed particle size of the ester wax is usually large (micron level), which ultimately leads to low gloss of the toner, which cannot meet the requirements of color laser printing toner on gloss. Furthermore, during long-term or high-temperature storage, the large-size ester wax has greater kinetic energy and interfacial force, so it is more likely to migrate to the surface of the toner, affecting the charging performance of the toner, and easily leading to sticking of the toner to the blade during printing, resulting in longitudinal white line-shaped printing defects.

[0005] For external additives used in toners, in addition to the commonly used small-particle fumed silica (native particle size 7nm~14nm) which provides charging properties and flowability, medium-to-large-particle silica is also needed to meet the requirements of print durability (i.e., retention and uniformity of print surface). However, these medium-to-large-particle silica (native particle size ≥16nm) have a significantly reduced specific surface area, resulting in generally lower charge density. Excessive use will lead to a significant decrease in the charge of the toner and an increase in toner consumption, while insufficient use will result in poor toner durability, especially in the later stages of printing, leading to poor uniformity of print surface, uneven color distribution, and color differences. Furthermore, the cost of these medium-to-large-particle silica is generally high, further increasing the manufacturing cost of physical color toners. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a composite material that, when used as an additive in toner, can significantly improve the gloss and storage stability of toner and solve the problem of sticking to the blade; it can also increase the charge of toner, reduce toner consumption, improve toner retention, and reduce manufacturing costs.

[0007] Specifically, the present invention provides the following technical solution:

[0008] A composite material comprising silicon dioxide-coated wax nanoparticles.

[0009] According to an embodiment of the present invention, in the silicon dioxide-coated wax nanoparticles, the silicon dioxide and the wax nanoparticles are connected by chemical bonds, which is referred to as the first composite material; or, there are no chemical bonds between the silicon dioxide and the wax nanoparticles, which is referred to as the second composite material.

[0010] According to an embodiment of the present invention, the silica has a coating rate of 80% to 200% on the wax nanoparticles.

[0011] According to an embodiment of the present invention, the mass ratio of the wax nanoparticles to silica is 100:(10-300). Specifically, in the first composite material, the mass ratio of the wax nanoparticles to silica is 100:(10-40), or for example, 100:(20-40); in the second composite material, the mass ratio of the wax nanoparticles to silica is 100:(50-300), or for example, 100:(50-150), or for example, 100:(50-100).

[0012] According to an embodiment of the present invention, in the second composite material, the silicon dioxide is fumed silicon dioxide.

[0013] According to an embodiment of the present invention, the wax in the wax nanoparticles is selected from waxes with a melting range of 50°C to 95°C.

[0014] According to the embodiment of the present application, the wax in the wax nanoparticle is selected from at least one of the following waxes, or a wax modified by copolymerization and / or modification of at least one of the following waxes: paraffin wax, refined wax, low-density polyolefin wax, rice bran wax, sasol wax, Fischer-Tropsch wax, and at least one of ester wax.

[0015] According to the embodiment of the present application, the average particle size of the wax nanoparticle is 50-250 nm.

[0016] The present application also provides an application of the composite material as described above, which is used as an additive in toner.

[0017] According to the embodiment of the present application, the toner is color toner, in particular, physical color toner or chemical color toner.

[0018] According to the embodiment of the present application, the first composite material is used as an internal additive in the toner, and the second composite material is used as an external additive in the toner.

[0019] The present application also provides a toner, which comprises an additive, and the additive comprises the composite material as described above.

[0020] According to the embodiment of the present application, the toner is color toner; in particular, the toner is physical color toner or chemical color toner.

[0021] According to the embodiment of the present application, the toner comprises an internal additive and an external additive; the internal additive comprises the first composite material as described above; and the external additive comprises the second composite material as described above.

[0022] According to the embodiment of the present application, in the toner, the mass ratio of the first composite material to the second composite material is 100:(5-20).

[0023] The present application also provides a preparation method of the toner as described above, which is a dry physical method, and the toner is obtained by mixing the composite material with other components, and then through melt mixing, extrusion, tabletting, crushing, classification, and mixing of external additives.

[0024] According to the embodiment of the present application, the preparation method specifically comprises the following steps:

[0025] a) pre-mixing: pre-mixing the formula proportion of the binding resin, the first composite material, the pigment, and the charge control agent to obtain a mixture;

[0026] b) melt mixing: melt mixing the mixture obtained in step a), extruding, cooling, tabletting, and coarsely crushing to obtain coarse particles;

[0027] c) continuous crushing and grading: the coarse particles obtained in step b) are subjected to continuous crushing and grading to obtain toner grading products;

[0028] d) mixing external additives: the toner grading products obtained in step c) and the second composite material are subjected to low-speed mixing, and then other external additives are added for high-speed mixing to obtain the toner.

[0029] Compared with the prior art, the present application has the following beneficial effects:

[0030] When the first composite material of the present application is used as an internal additive of physical color toner, the gloss and storage stability of the toner can be significantly improved, and the problem of sticking to the blade can be solved; when the second composite material of the present application is used as an external additive of physical color toner, the charge amount of the toner can be further improved, the powder consumption can be reduced, and the toner retention can be improved by replacing large particle silicon, thereby reducing the manufacturing cost.

[0031] The preparation method of the composite material of the present application is simple, the conditions are controllable, the production equipment is mature, and the present application is suitable for industrial production and has good versatility. DETAILED DESCRIPTION

[0032] [Composite material]

[0033] A composite material is a silica-coated wax nanoparticle.

[0034] According to an embodiment of the present application, in the silica-coated wax nanoparticle, the silica and the wax nanoparticle are connected through a chemical bond, which is referred to as a first composite material; or, there is no chemical bond between the silica and the wax nanoparticle, which is referred to as a second composite material.

[0035] According to an embodiment of the present application, in the first composite material, the silica is coated on the surface of the wax nanoparticle through in-situ chemical reaction.

[0036] According to an embodiment of the present application, in the second composite material, the silica is coated on the surface of the wax nanoparticle through physical blending.

[0037] According to an embodiment of the present application, the coating rate of the silica on the wax nanoparticle is 80% to 200%, preferably 100% to 150%.

[0038] According to an embodiment of the present application, the mass ratio of the wax nanoparticles and the silica is 100:(10-300). Specifically, in the first composite material, the mass ratio of the wax nanoparticles and the silica is 100:(10-40), and for example, 100:(20-40); in the second composite material, the mass ratio of the wax nanoparticles and the silica is 100:(50-300), and for example, 100:(50-150), and for example, 100:(50-100).

[0039] According to an embodiment of the present application, the wax in the wax nanoparticles is selected from a wax with a melting range of 50-95℃.

[0040] According to an embodiment of the present application, the wax in the wax nanoparticles is selected from at least one of the following, or a wax modified by copolymerization and / or modification of at least one of the following: paraffin wax, refined wax, low-density polyolefin wax, rice bran wax, sasol wax, Fischer-Tropsch wax, ester wax.

[0041] Preferably, the ester wax is selected from synthetic ester wax and / or natural ester wax. For example, the synthetic ester wax includes at least one of mono-ester wax (e.g. Nippon Oils & Fats WE-2, WE-3), polyol ester wax (e.g. Nippon Oils & Fats WE-5, WE-15), etc.

[0042] According to an embodiment of the present application, the average particle size of the wax nanoparticles is 50-250nm, for example, 50nm, 100nm, 150nm, 200nm, 250nm.

[0043] According to an embodiment of the present application, the wax nanoparticles are prepared by a water-in-wax phase inversion process.

[0044] Specifically, the water-in-wax phase inversion process comprises: after the wax is heated and melted, an emulsifier is added for mixing, ultrapure water is added for emulsification and dispersion, to obtain a wax dispersion liquid; the wax dispersion liquid is centrifuged to obtain the wax nanoparticles.

[0045] According to an embodiment of the present application, in the first composite material, the silica can be obtained by the following method:

[0046] The silica is obtained by an interfacial hydrolysis and polycondensation process in the presence of a dispersion stabilizer and an initiator.

[0047] According to an embodiment of the present application, the silicon source is selected from tetraethoxysilane (TEOS), sodium silicate, silicon tetrachloride, silicon tetrafluoride.

[0048] According to an embodiment of the present application, the dispersion stabilizer is polyethyleneimine (PEI).

[0049] According to an embodiment of the present application, the initiator is selected from the group consisting of γ-aminopropyltriethoxysilane (APTES), bis-[(triethoxysilyl)-propyl] disulfide (TESPD).

[0050] According to an embodiment of the present application, in the second composite material, the silica can be obtained by the following method:

[0051] The fumed silica is surface-modified by at least one of the following treating agents: polydimethylsiloxane (PDMS), dimethyldichlorosilane (DDS), and hexamethyldisilazane (HMDS).

[0052] According to an embodiment of the present application, the fumed silica is hydrophobic silica. Preferably, the fumed silica is surface-modified by at least one of the following treating agents: polydimethylsiloxane (PDMS), dimethyldichlorosilane (DDS), and hexamethyldisilazane (HMDS).

[0053] According to an embodiment of the present application, the fumed silica has an average particle size of 7 nm to 14 nm, for example, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm. Exemplarily, the PDMS-treated silica is at least one of the following: Degussa RY300, R202, RY200L, Cabot TG-7180. Exemplarily, the DDS-treated silica is at least one of the following: Degussa R972, Desano REOLOSIL DM-10, etc. Exemplarily, the HMDS-treated silica is at least one of the following: Degussa R812S, RX300, R8200, Cabot TG-811F, Wacker H2000T, H3004, H20TM, H30TM, Desano HM-30ST, ZD-30ST, etc.

[0054] [First composite material]

[0055] As mentioned above, the present application discloses a first composite material, which can be used as an internal additive of toner.

[0056] According to an embodiment of the present application, in the first composite material, the silica is coated on the surface of the wax nanoparticle preferably by in-situ chemical reaction (hydrolytic polycondensation), and the silica and the wax nanoparticle are connected by chemical bond.

[0057] According to the embodiment of the present application, after mixing the wax nanoparticles and the silicon source, the silicon source is subjected to in-situ chemical reaction in the presence of the dispersion stabilizer and the initiator to coat the surface of the wax nanoparticles with the silica to obtain the silica-coated wax nanoparticles, i.e. the first composite material.

[0058] According to the embodiment of the present application, the mass ratio of the wax nanoparticles to the silicon source is 100:(10-40), specifically 100:(20-40), for example 100:10, 100:20, 100:25, 100:30, 100:35 or 100:40.

[0059] According to the embodiment of the present application, the coating rate of the silica on the wax nanoparticles is 80%-200%, preferably 100%-150%, for example 100%, 110%, 120%, 130%, 140%, 150%.

[0060] [Preparation method of the first composite material]

[0061] The present application also provides a preparation method of the above-mentioned first composite material, which comprises the following steps:

[0062] A1) preparing wax nanoparticles by using water-in-oil phase inversion process;

[0063] A2) adding the wax nanoparticles obtained in step A1) into a premixed solution, then adding a silicon source and mixing uniformly, and then emulsifying to obtain a wax-silicon mixed emulsion;

[0064] A3) taking the wax-silicon mixed emulsion in step A2) and continuously adding an initiator to obtain the first composite material.

[0065] According to the embodiment of the present application, in step A1), the water-in-oil phase inversion process specifically comprises: heating and melting the wax, then adding an emulsifier and mixing, adding ultrapure water and emulsifying and dispersing to obtain a wax dispersion; and centrifuging the wax dispersion to obtain the wax nanoparticles.

[0066] According to the embodiment of the present application, the mass ratio of the emulsifier to the wax is 1:(5-9), for example 1:5, 1:6, 1:7, 1:8 or 1:9.

[0067] According to the embodiment of the present application, the mixing is carried out under stirring, for example under low-speed stirring. Preferably, the low-speed stirring refers to a stirring rate of 1-20 r / s, for example 20 r / s.

[0068] According to the embodiment of the present application, when the ultrapure water is added, the ultrapure water is first heated to a temperature above the melting point of the wax.

[0069] According to an embodiment of the present application, the mass ratio of the added ultrapure water to the wax is (1-10): 1, for example, 4-6: 1.

[0070] According to an embodiment of the present application, the ultrapure water is added in multiple times, and the mass ratio of the ultrapure water to the wax in each time is (0.9-1.2): 1, for example, 1: 1.

[0071] According to an embodiment of the present application, the emulsification and dispersion conditions include high-speed stirring for 35-55 min. Preferably, the high-speed stirring refers to stirring at a rate of 20-100 r / s, for example, 50 r / s.

[0072] According to an embodiment of the present application, the emulsifier is selected from surfactants with a hydrophilic-lipophilic balance (HLB) of 10-19.

[0073] According to an embodiment of the present application, the surfactant is selected from at least one or two or more of polyoxyethylene sorbitan monooleate (such as emulsifier T-81), polyoxyethylene sorbitan trioleate (such as emulsifier T-85), polyoxyethylene oleyl ether (such as emulsifier OE-10, OE-20), polyoxyethylene monolaurate (such as S-307), polyoxyethylene sorbitan monopalmitate (such as emulsifier T-40), polyoxyethylene monostearate (such as Atlas G-2159).

[0074] According to an embodiment of the present application, the centrifugal separation conditions include a rotation speed of 100-200 r / s, for example, 150 r / s. Further, the centrifugal separation time is 1-60 min, for example, 30 min.

[0075] Preferably, after the centrifugal separation, cleaning and / or drying are further included. In the present application, the cleaning and / or drying can be performed by methods known in the art. Illustratively, the cleaning refers to washing with ultrapure water. Illustratively, the drying is selected from vacuum drying, for example, vacuum drying at 50°C for 12 h.

[0076] According to an embodiment of the present application, in A1), the average particle size of the wax nanoparticles is 50-250 nm.

[0077] According to an embodiment of the present application, in A2), the premixed solution includes cetyltrimethylammonium bromide (CTAB), a dispersion stabilizer, and a solvent, and the mass ratio is (10-14):(5-15):1900.

[0078] Preferably, the solvent is selected from at least one of the following: ultrapure water, ethanol, propanol, isopropanol, acetonitrile. Preferably, the solvent comprises ultrapure water and an organic solvent, and the mass ratio of the two is 1500:(100-500). Illustratively, the solvent comprises ultrapure water and ethanol, and the mass ratio is 1500:(100-500), for example 1500:400.

[0079] Preferably, the dispersion stabilizer is selected from a high-molecular cationic surfactant. Preferably, the high-molecular cationic surfactant is polyethyleneimine. Further, the polyethyleneimine is an aqueous solution of polyethyleneimine, and the solid content is 1wt%-50wt%, for example 50wt%.

[0080] Preferably, the molecular weight (M.W.) of the polyethyleneimine is 600-10000.

[0081] In the present application, the high-molecular cationic surfactant can be well wrapped in the wax nanoparticles, which is conducive to reducing the generation rate of silicon dioxide on the surface of ester wax, thereby producing a more compact silicon dioxide layer, which is conducive to improving the coating effect of silicon dioxide on ester wax and improving the stability of the core-shell structure.

[0082] According to an embodiment of the present application, in A2), the emulsification can be performed by a method known in the art, for example under high-speed stirring. Preferably, the high-speed stirring refers to a rotation speed of 100-300r / s, for example 300r / s.

[0083] According to an embodiment of the present application, in A3), the reaction is performed under stirring, for example under low-speed stirring.

[0084] According to an embodiment of the present application, in A3), the reaction conditions include: the reaction temperature is above 50℃, for example 58℃; and the reaction time is 2-4h.

[0085] According to an embodiment of the present application, the mass ratio of the silicon source and the initiator is (20-40):(30-60).

[0086] According to an embodiment of the present application, in A3), after the reaction is completed, centrifugal separation and / or drying can also be performed, and the centrifugal separation and drying have the meanings as described above.

[0087] [Second composite material]

[0088] As described above, the present application discloses a second composite material, which can be used as an external additive of toner.

[0089] According to an embodiment of the present application, the silica is coated on the surface of the wax nanoparticle by physical blending, and there is no chemical bond between the silica and the wax nanoparticle.

[0090] According to an embodiment of the present application, the silica is preferably fumed silica.

[0091] Specifically, the silica is surface-modified by fumed silica through at least one of the following treating agents: polydimethylsiloxane (PDMS), dimethyldichlorosilane (DDS), and hexamethyldisilazane (HMDS).

[0092] According to an embodiment of the present application, the mass ratio of the wax nanoparticle and silica is 100:(50-300), for example, 100:50, 100:80, 100:100, 100:150, 100:200, 100:250, 100:300.

[0093] According to an embodiment of the present application, the coating rate of the silica on the wax nanoparticle is 80%-200%, preferably 100%-150%.

[0094] [Preparation method of the second composite material]

[0095] The present application also provides a preparation method of the above-mentioned second composite material, which comprises:

[0096] B1) preparing a wax nanoparticle by using a water-in-wax phase inversion process;

[0097] B2) sequentially adding the wax nanoparticle prepared in step B1) and silica in a high-speed blender, and physically blending, so that the silica is coated on the surface of the wax nanoparticle to obtain a second composite material.

[0098] According to an embodiment of the present application, in B1), the water-in-wax phase inversion process and the wax nanoparticle have the meanings as described above.

[0099] According to an embodiment of the present application, in B2), the mass ratio of the wax nanoparticle and silica is 100:(50-300).

[0100] According to an embodiment of the present application, the silica is surface-modified by fumed silica through at least one of the following treating agents: polydimethylsiloxane (PDMS), dimethyldichlorosilane (DDS), and hexamethyldisilazane (HMDS). The fumed silica has the meanings as described above.

[0101] According to the embodiment of the present application, in B2), the physical blending specifically comprises: low-speed stirring for 10-200s, followed by high-speed stirring for 200-500s, and standing.

[0102] According to the embodiment of the present application, the low-speed stirring and high-speed stirring have the meanings as described above.

[0103] According to the embodiment of the present application, in B2), the physical blending can be repeated for 1-5 times, for example, 3 times.

[0104] [Application]

[0105] The present application also provides an application of the composite material as described above, which is used as an additive in toner.

[0106] According to the embodiment of the present application, the toner is color toner, specifically, physical color toner or chemical color toner.

[0107] According to the embodiment of the present application, the first composite material is used as an internal additive in the toner, and the second composite material is used as an external additive in the toner.

[0108] According to the embodiment of the present application, the physical color toner comprises an internal additive and an external additive; the internal additive comprises the first composite material; and the external additive comprises the second composite material.

[0109] According to the embodiment of the present application, in the physical color toner, the content of the first composite material is 1%-15% by mass percentage; and / or, the content of the second composite material is 0.5%-4% by mass percentage.

[0110] According to the embodiment of the present application, the chemical color toner comprises an external additive, and the external additive comprises the second composite material.

[0111] According to the embodiment of the present application, in the chemical color toner, the content of the second composite material is 0.5%-4% by mass percentage.

[0112] [toner]

[0113] The present application also provides a toner, which comprises an additive, and the additive comprises the composite material as described above.

[0114] According to the embodiment of the present application, the toner is color toner; specifically, the toner is physical color toner, or is chemical color toner.

[0115] According to an embodiment of the present application, the toner includes an internal additive and an external additive; the internal additive includes the first composite material described above; and the external additive includes the second composite material described above.

[0116] According to an embodiment of the present application, in the toner, the mass ratio of the first composite material to the second composite material is 100:(5-20).

[0117] According to an embodiment of the present application, the toner is prepared by a dry physical method.

[0118] According to an embodiment of the present application, the toner includes the composite material, a binding resin, a pigment, and optionally a charge control agent and / or other additives.

[0119] According to an embodiment of the present application, in the toner, the mass percentage of the first composite material is 1-15%, for example, 1%, 5%, 10%, or 15%.

[0120] According to an embodiment of the present application, in the toner, the mass percentage of the second composite material is 0.5-4%, for example, 0.5%, 1%, 2%, 3%, or 4%.

[0121] According to an embodiment of the present application, the binding resin is selected from at least one of a styrene-acrylic resin, a polyester resin, and a styrene-acrylic-polyester copolymer resin.

[0122] According to an embodiment of the present application, in the toner, the mass percentage of the binding resin is 66-94%, for example, 66%, 70%, 75%, 80%, 85%, 90%, or 94%.

[0123] According to an embodiment of the present application, the pigment is selected from pigments known in the art, and the color of the pigment is, for example, at least one of yellow, magenta, cyan, black, and gold red.

[0124] According to embodiments of the present application, the pigments can be selected from organic pigments and / or inorganic pigments known in the art. Exemplarily, yellow pigments include, but are not limited to, C.I. Pigment Yellow 74, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 155, Pigment Yellow 162, Pigment Yellow 180, Pigment Yellow 185. Exemplarily, magenta pigments include, but are not limited to, C.I. Pigment Red 31, Pigment Red 122, Pigment Red 150, Pigment Red 184, Pigment Red 185, Pigment Red 238, Pigment Red 259, etc. Exemplarily, cyan pigments include, but are not limited to, C.I. Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4. Exemplarily, black pigments mainly include carbon black and iron oxide mixture. Exemplarily, golden red pigments include, but are not limited to, C.I. Pigment Red 53:1, Pigment Red 57:1, Pigment Red 48:2.

[0125] According to embodiments of the present application, the mass percentage content of the pigments in the toner is 3% to 9%, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%.

[0126] According to embodiments of the present application, the charge control agent (CCA) is a white powdery salicylic acid metal complex, for example, at least one selected from zinc salicylate, chromium salicylate, zirconium salicylate and calcium salicylate.

[0127] According to embodiments of the present application, the mass percentage content of the charge control agent in the toner is 0.5% to 3%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%.

[0128] According to embodiments of the present application, the other additives are selected from fumed silica and / or metal stearate.

[0129] According to embodiments of the present application, the fumed silica is preferably treated with PDMS and / or HMDS.

[0130] According to embodiments of the present application, the primary particle size of the fumed silica ranges from 7 nm to 16 nm, for example, 7 nm, 10 nm, 11 nm, 12 nm, 12 nm, 14 nm, 15 nm, 16 nm.

[0131] According to embodiments of the present application, the mass percentage content of the fumed silica in the toner is 0.95% to 2.5%, for example, 1%, 1.5%, 2%, 2.5%.

[0132] According to embodiments of the present application, the metal stearate is at least one selected from calcium stearate, magnesium stearate, zinc stearate and barium stearate.

[0133] According to the embodiment of the present application, the mass percentage of the stearic acid metal salt in the toner is 0.05% to 0.5%.

[0134] [Method for preparing toner]

[0135] The present application also provides a method for preparing the toner as described above, which is a dry physical method, and the toner is obtained by mixing the composite material with other components (such as a binding resin, a charge control agent, a pigment, and other additives), and then by melt kneading, extrusion sheeting, crushing and grading, and mixing external additives.

[0136] According to the embodiment of the present application, the method for preparing the toner specifically comprises the following steps:

[0137] a) Pre-mixing: the binding resin, the first composite material, the pigment, and the charge control agent in the prescribed proportions are pre-mixed to obtain a mixture;

[0138] b) Melt kneading: the mixture obtained in step a) is melt kneaded, extruded, cooled, sheeted, and coarsely crushed to obtain coarse particles;

[0139] c) Continuous crushing and grading: the coarse particles obtained in step b) are continuously crushed and graded to obtain toner grading products;

[0140] d) Mixing external additives: the toner grading products obtained in step c) and the second composite material are first mixed at low speed, and then other external additives are added and mixed at high speed to obtain the toner.

[0141] According to the embodiment of the present application, in step a), the pre-mixing conditions include first low-speed stirring and then high-speed stirring. The pre-mixing of the present application is carried out in devices known in the art, such as in a high-speed mixer. Further, the time for low-speed stirring is 1 to 10 minutes, for example, 5 minutes. Further, the time for high-speed stirring is 1 to 60 minutes, for example, 30 minutes.

[0142] According to the embodiment of the present application, in step b), the kneading temperature is 70°C to 120°C, for example, 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C.

[0143] According to the embodiment of the present application, in step c), the average particle size of the coarse particles is 0.1 to 5 mm, for example, 1.5 mm.

[0144] According to the embodiment of the present application, in step c), the continuous crushing includes air flow crushing and / or fine crushing. In the present application, the air flow crushing, fine crushing, and grading can be selected using methods known in the art, which are not specifically limited in the present application.

[0145] According to the embodiment of the present application, in step c), the toner fraction has at least one of the following properties: volume D50 is 7 μm to 10 μm, for example 7 μm, 8 μm, 9 μm, 10 μm; particle D97 is 2.5 μm to 3.5 μm, for example 2.5 μm, 3 μm, 3.5 μm.

[0146] According to the embodiment of the present application, in step d), the mixing specifically comprises: first mixing the toner fraction and the second composite material, stirring at low speed, standing, then adding other external additives such as fumed silica, metal stearate, etc., and stirring at high speed. Preferably, the low speed stirring and high speed stirring have the meanings as described above. Further, the time of the low speed stirring and high speed stirring in step d) is not specifically limited in the present application, for example 5 min, 8 min.

[0147] According to the embodiment of the present application, the preparation method further comprises the following steps:

[0148] e) post-treatment: the toner can be further sieved and / or packaged.

[0149] The technical solutions of the present application will be further described in detail below in combination with specific examples. It should be understood that the following examples are only illustratively described and explained the present application, and should not be interpreted as limiting the scope of protection of the present application. Any technology realized based on the above description of the present application is covered within the scope of the present application intended to be protected.

[0150] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0151] Example 1

[0152] The present example provides a composite material which can be used as an internal additive for physical color toner, which is prepared according to the following preparation process:

[0153] a) 100 g of ester wax WE-3 is heated to 85°C to melt, then 20 g of mixed emulsifier (mass ratio of T-81 and T-85 is 1:1) is added at a stirring speed of 6 r / s, mixed for 15 min, then 5 times of ultra-pure water at a temperature of 85°C is added at a high speed stirring speed of 30 r / s, each time the amount is equal to the wax, the emulsification and dispersion time is 45 min, to obtain a wax dispersion liquid;

[0154] b) the above wax dispersion liquid is centrifuged at a high speed of 150 r / s for 30 min to obtain a white precipitate, which is washed with ultra-pure water for 4 times, then vacuum dried at 50°C for 12 h to obtain ester wax nanoparticles with an average particle size of 57 nm;

[0155] c) Take 100 g of wax nanoparticles, add a premixed solution containing 10 g of cetyltrimethylammonium bromide (CTAB), 1500 g of ultrapure water, 400 g of ethanol and 15 g of PEI, and then mix 20 g of tetraethoxysilane (TEOS) uniformly, emulsify at a high speed of 300 r / s for 15 min to obtain a wax-silicon mixed emulsion;

[0156] d) Take the wax-silicon mixed emulsion in the above step into a reactor, mechanically stir at 5 r / s, heat to 58°C, and continuously add 30 g of APTES, react for 2 h;

[0157] e) After the reaction is completed, centrifuge and dry according to the step b) to obtain a composite material, marked as CD-A1.

[0158] Comparative Example 1

[0159] Except that the dispersion stabilizer polyethyleneimine (PEI) is removed, the remaining formulation and process parameters are the same as Example 1, and the obtained composite material is marked as C-CD-A1.

[0160] Example 2

[0161] This example provides a composite material for internal additives of physical color toner, which is prepared according to the following preparation process:

[0162] a) After 100 g of ester wax WE-15 is heated to 90°C and melted, 17 g of emulsifier OE-20 is added at a stirring speed of 8 r / s, mixed for 15 min, and then 5 times of ultrapure water at a temperature of 90°C is added at a high stirring speed of 35 r / s, each time with an amount equal to the wax, and the emulsification and dispersion time is 40 min, to obtain a wax dispersion liquid;

[0163] b) The wax dispersion liquid is centrifuged at a high speed of 150 r / s for 30 min to obtain a white precipitate, which is washed with ultrapure water for 4 times, and then vacuum dried at 50°C for 12 h to obtain ester wax nanoparticles with an average particle size of 117 nm;

[0164] c) Take 100 g of ester wax nanoparticles, add a premixed solution containing 12 g of CTAB, 1500 g of ultrapure water, 400 g of ethanol and 11 g of PEI, and then mix 30 g of TEOS uniformly, emulsify at a high speed of 300 r / s for 15 min to obtain a wax-silicon mixed emulsion;

[0165] d) Take the wax-silicon mixed emulsion in the above step into a reactor, mechanically stir at 5 r / s, heat to 58°C, and continuously add 45 g of APTES, react for 3 h;

[0166] e) After the reaction is completed, centrifugation, drying are performed according to the step b) to obtain a composite material, which is marked as CD-A2.

[0167] Example 3

[0168] The present example provides a composite material for internal additives of physical color toner, which is prepared according to the following preparation process:

[0169] a) 100 g of ester wax PETS-4 is heated to 75°C to melt, then 14 g of emulsifier S-307 is added at a stirring speed of 5 r / s, mixed for 15 min, and then 4 times of ultra-pure water at 75°C is added at a high stirring speed of 20 r / s, each time with an amount equal to the wax, and the emulsification and dispersion time is 55 min, to obtain a wax dispersion liquid;

[0170] b) The wax dispersion liquid is centrifuged at a high speed of 150 r / s for 30 min to obtain a white precipitate, which is washed with ultra-pure water for 4 times, and then vacuum dried at 50°C for 12 h to obtain ester wax nanoparticles with an average particle size of 212 nm;

[0171] c) 100 g of ester wax nanoparticles is taken, added into a premixed mixed solution containing 13 g of CTAB, 1500 g of ultra-pure water, 400 g of ethanol and 8 g of PEI, and then mixed uniformly with 35 g of TEOS to obtain a wax-silicon mixed emulsion after emulsification at a high speed of 300 r / s for 15 min;

[0172] d) The wax-silicon mixed emulsion in the above step is taken into a reactor, mechanically stirred at 5 r / s, heated to 58°C, and continuously added with 53 g of APTES for 3.5 h;

[0173] e) After the reaction is completed, centrifugation, drying are performed according to the step b) to obtain a composite material, which is marked as CD-A2.

[0174] Example 4

[0175] The present example provides a composite material for internal additives of physical color toner, which is prepared according to the following preparation process:

[0176] a) 100 g of ester wax T-1 is heated to 95°C to melt, then 12 g of emulsifier Atlas G-2159 is added at a stirring speed of 4 r / s, mixed for 15 min, and then 6 times of ultra-pure water at 95°C is added at a high stirring speed of 40 r / s, each time with an amount equal to the wax, and the emulsification and dispersion time is 35 min, to obtain a wax dispersion liquid;

[0177] b) The wax dispersion solution was centrifuged at 150 r / s for 30 min, and the white precipitate was washed with ultrapure water for 4 times, and then dried at 50 °C for 12 h to obtain the ester wax nanoparticles with an average particle size of 86 nm;

[0178] c) 100 g of the ester wax nanoparticles were added into the premixed solution containing 14 g of CTAB, 1500 g of ultrapure water, 400 g of ethanol and 5 g of PEI, and then mixed uniformly with 40 g of TEOS to obtain a wax-silicon mixed emulsion under emulsification at 300 r / s for 15 min;

[0179] d) The wax-silicon mixed emulsion in the above step was added into a reactor and mechanically stirred at 5 r / s, and then the temperature was increased to 58 °C, and 60 g of APTES was continuously added dropwise, and the reaction was performed for 4 h;

[0180] e) After the reaction was completed, the centrifugation and drying were performed according to the step b) to obtain a composite material, which was marked as CD-A4.

[0181] Comparative Example 2

[0182] Except that the order of adding 100 g of wax and 500 g of water in step a) of Example 4 was interchanged, i.e., the wax was added into the water for dispersion, the remaining process parameters were the same as those in Example 4. The particle size of the obtained composite material was increased to 532 nm, which was marked as C-CD-A4.

[0183] Example 5

[0184] The present example provides a composite material for an external additive of a physical color toner, which is prepared according to the following preparation process:

[0185] The ester wax nanoparticles obtained in step b) of Example 1, 200 g of fumed silica R202 and 50 g of fumed silica H2000T were sequentially added into a high-speed mixer, the rotation speed was adjusted to 20 r / s for 120 s, and then the rotation speed was increased to 60 r / s for 300 s, and then stopped for 60 s, and then the above mixing steps were repeated for 3 times to obtain a composite material, which was marked as CD-B1.

[0186] Example 6

[0187] Except that the ester wax nanoparticles were replaced by the ester wax nanoparticles in step b) of Example 2, and the fumed silica type was replaced by 80 g of H3004, the remaining process steps were the same as those in Example 5 to obtain a composite material, which was marked as CD-B2.

[0188] Example 7

[0189] The process steps are the same as Example 5 except that the ester wax nanoparticles are replaced by the ester wax nanoparticles of Example 3 step b), the fumed silica type is replaced by 50 g RY200L and 10 g HM-30ST, to obtain a composite material, labeled CD-B3.

[0190] Example 8

[0191] The process steps are the same as Example 5 except that the ester wax nanoparticles are replaced by the ester wax nanoparticles of Example 4 step b), the fumed silica type is replaced by 100 g R812S, to obtain a composite material, labeled CD-B4.

[0192] Comparative Example 3

[0193] The process steps are the same as Example 8 except that the stepwise high speed mixing in Example 8 is replaced by one-step high speed mixing, i.e. first mixing at 20 r / s for 360 s, then immediately high speed mixing at 60 r / s for 900 s, to obtain a composite material, labeled C-CD-B2.

[0194] Application Example 1 (yellow toner)

[0195] This example provides a physical method yellow toner containing composite materials CD-A4 and CD-B1, which is prepared according to the following preparation process:

[0196] a) premixing: the formula proportion of styrene-acrylate resin (84%), pigment yellow 180 (3%), composite material CD-A4 (9.5%) and calcium salicylate (1.5%) are sequentially added to a high speed mixer, first low speed stirring for 5 min, then high speed stirring for 15 min, to obtain a mixture;

[0197] b) melt mixing: the above mixture is melt mixed by a continuous twin-screw extruder, the mixing temperature is 120°C, then the extruded material is cooled, tabletted, and coarsely broken into coarse particles of about 1.5 mm;

[0198] c) continuous crushing-classification: the above coarse particles are first coarsely crushed by an air flow crusher, then gradually finely crushed and classified, until toner classification products with a volume D50 = 9.5 μm and a particle D97 = 3.4 μm are obtained;

[0199] d) mixing external additives: first mix the toner classification products obtained in the above step and the composite material CD-B1 (0.5%) at a low speed of 20 r / s for 5 min, then stand for 1 min, then add fumed silica RY300 (0.45%), RX300 (0.5%) and barium stearate (0.5%) and mix at a high speed of 50 r / s for 8 min;

[0200] e) Post-treatment: The mixed toner is sieved and packaged to obtain the yellow toner product.

[0201] Application Comparative Example 1

[0202] This application comparative example provides a yellow toner using C-CD-A1 prepared in Comparative Example 1 as an internal additive and a preparation method, which is prepared according to the following steps:

[0203] Except that C-CD-A1 prepared in Comparative Example 1 is used to replace CD-A4 in an equal amount, the rest of the formulation and process are the same as those in Application Example 1, and a yellow toner is obtained.

[0204] Application Example 2 (Red Toner)

[0205] This example provides a physical method red toner containing composite materials CD-A2 and CD-B2, which is prepared according to the following preparation process:

[0206] a) Premixing: The benzene propyl resin (84%), pigment red 122 (5%), composite material CD-A2 (2%), and zinc salicylate (3%) in the formulation ratio are sequentially added to a high-speed mixer, first stirred at low speed for 5 min, and then stirred at high speed for 15 min to obtain a mixture;

[0207] b) Melt mixing: The above mixture is melt mixed by a continuous double-screw extruder, and the mixing temperature is 100°C. Then, the extruded material is cooled, tabletted, and coarsely broken into coarse particles of about 1.5 mm;

[0208] c) Continuous crushing and grading: The above coarse particles are first coarsely crushed by an air flow crusher, and then gradually finely crushed and graded until a toner grading product with a volume D50 = 8.0 μm and a particle D97 = 3.3 μm is obtained;

[0209] d) Mixing external additives: The toner grading product obtained in the above step and the composite material CD-B2 (4.0%) are first mixed at a low speed of 20 r / s for 5 min, then left to stand for 1 min, and then the fumed silica H20TM (1.8%) and zinc stearate (0.2%) are added and mixed at a high speed of 50 r / s for 8 min;

[0210] e) Post-treatment: The mixed toner is sieved and packaged to obtain the red toner product.

[0211] Application Comparative Example 2

[0212] This application comparative example provides a red toner using C-CD-B2 prepared in Comparative Example 3 as an external additive and a preparation method, which is prepared according to the following steps:

[0213] The rest of the formulation and process and application example 2 are the same except that C-CD-B2 prepared using comparative example 3 is used to replace CD-B2 in equal amount to obtain red toner.

[0214] Application Example 3 (cyan toner)

[0215] This example provides a physical method cyan toner containing composite materials CD-A3 and CD-B3, which is prepared according to the following preparation process:

[0216] a) premixing: the formulation proportion of styrene-acrylic resin (80%), pigment blue 15:4 (7%), composite material CD-A3 (7%) and zirconium salicylate (1%) are sequentially added into a high-speed mixer, first stirring at low speed for 5 min, then stirring at high speed for 15 min to obtain a mixture;

[0217] b) melt mixing: the above mixture is melt mixed by a continuous twin-screw extruder, the mixing temperature is 70°C, then the extruded material is cooled, tabletted, and roughly broken into coarse particles of about 1.5 mm;

[0218] c) continuous crushing and grading: the above coarse particles are first roughly crushed by an air flow crusher, then gradually finely crushed and graded until toner grading products with a volume D50 = 7.5 μm and a particle D97 = 3.0 μm are obtained;

[0219] d) mixing external additives: the toner grading products obtained in the above step and composite material CD-B3 (2.7%) are first mixed at low speed 20 r / s for 5 min, then stand for 1 min, then gas phase silicon dioxide TG-7180 (1.2%), H30TM (1.0%) and calcium stearate (0.1%) are added for high speed 50 r / s mixing for 8 min;

[0220] e) post-treatment: the mixed toner is screened and packaged to obtain cyan toner finished product.

[0221] Application Comparative Example 3

[0222] This application comparative example provides a cyan toner and a preparation method without using the composite material (CD-A3) prepared by the present application as an internal additive, which is prepared according to the following steps:

[0223] The rest of the formulation and process and application example 3 are the same except that ester wax PETS-4 is used to replace CD-A3 in equal amount to obtain cyan toner.

[0224] Application Example 4 (black toner)

[0225] This example provides a physical method black toner containing composite materials CD-A1 and CD-B4, which is prepared according to the following preparation process:

[0226] a) Premixing: the formula proportion of styrene-acrylate resin (72%), carbon black (9%), composite CD-A1 (14%) and chromium salicylate (0.5%) were added into a high-speed mixer in sequence, first stirred at low speed for 5 min, then stirred at high speed for 15 min, to obtain a mixture;

[0227] b) Melt mixing: the above mixture was melt mixed by a continuous twin-screw extruder, the mixing temperature was 90°C, then the extruded material was cooled, tabletted, and roughly broken into coarse particles of about 1.5 mm;

[0228] c) Continuous crushing and grading: the above coarse particles were first roughly crushed by an air flow crusher, then gradually finely crushed and graded, until the toner grading product with a volume D50 = 7.0 μm and a particle D97 = 2.5 μm was obtained;

[0229] d) Mixing external additives: the toner grading product obtained in the above step and the composite CD-B4 (1.9%) were first mixed at low speed of 20 r / s for 5 min, then rested for 1 min, then the fumed silica R812S (2.5%) and magnesium stearate (0.05%) were added and mixed at high speed of 50 r / s for 8 min;

[0230] e) Post-processing: the mixed toner was screened and packaged to obtain the black toner product.

[0231] Application Comparative Example 4

[0232] The application comparative example provides a black toner not using the composite CD-B4 prepared by the application as an external additive and a preparation method, which is prepared according to the following steps:

[0233] Except that the Degussa large particle silicon RY40S (particle size 80 nm) is used to replace CD-B4 in equal amount, the rest of the formula and process are the same as application example 4, to obtain the black toner.

[0234] Application Comparative Example 5

[0235] The application comparative example provides a black toner not using the composite CD-B4 prepared by the application and not using a medium-large particle silicon as an external additive and a preparation method, which is prepared according to the following steps:

[0236] Except that CD-B4 is removed, the amount of styrene-acrylate resin is increased to 73.9%, and the step d) of "mixing at low speed of 20 r / s for 5 min, then resting for 1 min" is omitted, the rest of the formula and process are the same as application example 4, to obtain the black toner.

[0237] Application Comparative Example 6

[0238] The application comparative example provides a black toner obtained from a composite material (i.e. C-CD-A1 in Comparative Example 1) without using PEI as a dispersion stabilizer and a preparation method, which is prepared according to the following steps:

[0239] Except that C-CD-A1 is used to replace CD-A1 in an equal amount, the rest of the formulation and process are the same as those in Application Example 4, and a black toner is obtained.

[0240] Table 1. Evaluation results of toner performance of color physical method toner preparation examples and comparative examples

[0241]

[0242] The printing effects of the yellow, red, cyan and black toners prepared using the composite material of the application and the corresponding comparative examples are evaluated and compared. The test is carried out in accordance with GB / T29300-2012, wherein the glossiness test is measured by using a commercially available conventional glossiness meter, all printing is carried out on the same printer and selenium drum, and the powder loading of all toners is 60 g. The test results are shown in Table 1.

[0243] The comparison of Application Example 1 and Application Comparative Example 1 shows that when the composite material C-CD-A1 prepared by adjusting the process step a) to wax into water is used for yellow toner, the prepared composite additive particle size is too large (532 nm), which makes the dispersion of the composite material in the styrene-acrylic resin poor, resulting in a significant decrease in the glossiness of the printed matter from 10.5 to 2.8, the glossiness is visually lost, and the sticking problem occurs, the page yield also decreases, in addition, the decrease in the blocking temperature makes the storage stability poor, therefore, it cannot meet the printing requirements of high-performance color toner.

[0244] The comparison of Application Example 2 and Application Comparative Example 2 shows that when the composite material C-CD-B2 (Comparative Example 3) obtained by one-step mixing is used to replace CD-B2, the charge amount of the red toner decreases, resulting in a decrease in the page yield and a significant decrease in the uniformity of the manuscript surface, which is due to the fact that the one-step mixing is too strong, and the small particle silicon is easily punched into the wax nano-particles, thereby reducing the charging performance of the composite material C-CD-B2 itself, therefore, it cannot meet the printing requirements of high-performance color toner.

[0245] The comparison of Application Example 3 and Application Comparative Example 3 shows that when only the conventional ester wax PETS-4 is used in the internal additive of the physical method cyan toner, in addition to the significant decrease in the glossiness and the blocking temperature, the serious sticking problem occurs after printing 500 pages under high temperature and high humidity, which is due to the fact that the conventional means cannot achieve the purpose of uniform dispersion of the ester wax in the styrene-acrylic resin, therefore, only by using the scheme of the application example 3, the high-quality cyan toner can be obtained.

[0246] The comparison of application example 4 and application comparative example 4 can find that when the black toner prepared by using the Degussa large particle silicon RY40S (particle size 80 nm) to replace CD-B4 (application example 4) in equal amount, the charging quantity is significantly reduced, the page yield is insufficient, but the preservation is good, which further shows that the commercially available large particle silicon generally has the problem of low charging quantity, although it has the advantage of improving the preservation of toner, but it will make the page yield of toner decrease, and the manufacturing cost of the selenium drum further increases.

[0247] The comparison of application example 4 and application comparative example 5 can find that when the black toner obtained by not using CD-B4 (application example 4) as the external additive, the charging quantity is significantly reduced, the page yield is seriously insufficient, and the uniformity of the manuscript (preservation) is significantly reduced, which shows that the composite material CD-B4 has the dual effect of improving the charging quantity and the preservation of toner, which is a performance index that cannot be met by the commercially available large particle silicon at the same time, and has outstanding advantages and significant progress.

[0248] The comparison of application example 4 and application comparative example 6 can find that when the black toner obtained by using C-CD-A1 (comparative example 1, not using PEI as a dispersing agent) to replace CD-A1, the blocking temperature is all reduced, the storage stability is poor, the gloss is significantly reduced, and the page yield is also reduced. This shows that the dispersing stabilizer PEI plays a key role in the preparation process of the wax nanoparticles, can make the dispersibility of the wax nanoparticles better, and make the coating of the silicon dioxide more dense, thereby improving the dispersibility of the wax in the toner resin, and improving the comprehensive performance of the toner, which cannot be met by other dispersing agents.

[0249] In summary, the preparation method of the composite material for the dry physical method color toner of the embodiment of the application is simple, the raw materials are easy to obtain, when the first composite material prepared is used as an internal additive of toner, the gloss and storage stability (increase the blocking temperature) of the toner can be significantly improved and the occurrence of sticking can be prevented; when the composite material is used as an external additive of toner, the charging quantity and preservation of the toner can be improved at the same time, thereby the page yield is improved and the manufacturing cost is reduced, and the uniformity of the manuscript can also be kept consistent under a higher printing quantity, which is a very key index for color toner, because for color laser printers, CMYK four-color toners are needed to cooperate to present a color pattern, when the uniformity of one color toner decreases in advance, it will inevitably have a fatal impact on the color reproduction of the pattern, so it is required that the four-color toners can keep good uniformity and stable output performance under as high a page number as possible. In addition, since the composite material itself is not limited by the toner preparation process, when used as an external additive, it can be used in physical method color toner and chemical method color toner, and the same effect can be achieved.

[0250] The above has described the exemplary embodiments of the present application. However, the protection scope of the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A toner, characterized by, The toner comprises internal additives and external additives, further comprises a binding resin, a pigment, and optionally a charge control agent and / or other additives; the internal additives comprise a first composite material; the external additives comprise a second composite material; the mass percentage of the first composite material in the toner is 1% to 15%; the mass percentage of the second composite material is 0.5% to 4%; The first composite material refers to silica-coated wax nanoparticles connected by chemical bonds between silica and the wax nanoparticles, the silica is obtained by an interfacial hydrolysis and polycondensation process in the presence of a dispersion stabilizer and an initiator, the silica is coated on the surface of the wax nanoparticles by in-situ chemical reaction, and the coating rate of the silica on the wax nanoparticles is 110% to 200%; The second composite material refers to silica-coated wax nanoparticles without chemical bonds between silica and the wax nanoparticles; The mass ratio of the first composite material to the second composite material is 100:5 to 20; In the first composite material, the mass ratio of the wax nanoparticles to silica is 100:10 to 40; in the second composite material, the mass ratio of the wax nanoparticles to silica is 100:50 to 300; The average particle size of the wax nanoparticles is 50 nm to 250 nm.

2. The toner according to claim 1, characterized by The wax in the wax nanoparticles is selected from waxes with a melting range of 50°C to 95°C.

3. The toner according to claim 2, characterized by The wax in the wax nanoparticles is selected from at least one of the following waxes, or a wax obtained by copolymerization and / or modification of at least one of the following waxes: paraffin wax, refined wax, low-density polyolefin wax, rice bran wax, SASOL wax, Fischer-Tropsch wax, and at least one of ester wax.

4. The toner according to claim 1, characterized by In the second composite material, the silica is fumed silica.

5. The toner according to claim 1, characterized by The toner is a color toner.

6. The method of producing toner according to any one of claims 1 to 5, characterized by, The preparation method is a dry physical method, comprising the following steps: a) Pre-mixing: after pre-mixing the binding resin, the first composite material, the pigment, and the charge control agent in the formula proportion, a mixture is obtained; b) Melt kneading: after melt kneading the mixture obtained in step a), extruding, cooling, tabletting, and coarse crushing to obtain coarse particles; c) Continuous crushing and grading: after continuous crushing and grading the coarse particles obtained in step b), toner grading products are obtained; d) Mixing external additives: after low-speed mixing the toner grading products obtained in step c) and the second composite material, other external additives are added for high-speed mixing to obtain the toner.

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