KR102183892B1 - Electrostatic charge image developing toner having excellent positively charging properties and method of preparing the same - Google Patents

Abstract

Disclosed are a toner and a method of manufacturing the same. The disclosed toner includes a toner base particle comprising an anionic charge control agent, a cationic polymer layer at least partially attached to the toner base particle to surround the toner base particle, and the cationic polymer layer is a cation chemically bonded to each other. At least one bonding layer including a sexual polymer moiety and a glutaraldehyde (GA) moiety, and an amine group-containing cationic polymer adsorbed on the bonding layer to surround the bonding layer.

Description

Electrostatic charge image developing toner having excellent positively charging properties and method of preparing the same}

Disclosed are a toner for developing an electrostatic charge image having excellent static charge characteristics and a method of manufacturing the same. In more detail, a toner including a cationic polymer layer and a method of manufacturing the same are disclosed.

In general, a positively charged toner is prepared by adding a colorant, a wax, and a small amount of a positively charged charge control agent to a thermoplastic resin serving as a binder resin. Although the toner prepared by adding the positive charge control agent as described above has excellent triboelectric properties, various problems may occur depending on the chemical structure, crystal structure, size, dispersibility, and amount of the positive charge control agent.

In general, since the positive charge control agent added to the toner base particles is not evenly distributed on the toner surface, there is a problem in that the charge distribution of the toner base particles is not uniform. In addition, since the positive charge control agent is not tightly bonded to the surface of the toner base particle, a phenomenon in which the positive chargeability of the toner is lowered frequently occurs due to separation from the toner surface during frictional charging. In particular, when the toner is used for a long time, there is a problem in that the positive charge control agent easily detaches or moves from the toner surface due to stress due to contact with the carrier or agitation in the developing device, thereby deteriorating the positive chargeability of the toner. Accordingly, various image defects such as a decrease in image density and a decrease in print life occur in series.

One embodiment of the present invention provides a toner including a cationic polymer layer.

Another embodiment of the present invention provides a method of manufacturing the toner.

One aspect of the present invention,

Toner base particles containing an anionic charge control agent;

And a cationic polymer layer at least partially attached to the toner base particles and surrounding the toner base particles,

The cationic polymer layer is at least one bonding layer comprising a cationic polymer moiety and a glutaraldehyde (GA) moiety chemically bonded to each other, and an amine group-containing cation adsorbed on the bonding layer to surround the bonding layer It provides a toner containing a polymer.

The anionic charge control agent is 2-carboxyethyl-2-propenoate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, N,N- At least one compound selected from the group consisting of dimethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and dimethylaminoethyl methacrylate It may include.

The cationic polymer moiety may be derived from an amine group-containing cationic polymer having a weight average molecular weight of 500 to 100,000.

The amine group-containing cationic polymer is polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polyacrylamide (PAA), poly lysine (Poly (L-lysine)), and polyvinylimidazole. And at least one compound selected from the group consisting of polyamidoamine (PAMAM).

The content of the cationic polymer layer may be 0.01 to 10 parts by weight based on 100 parts by weight of the toner base particle.

The toner may further include an external additive attached to the cationic polymer layer.

Another aspect of the invention,

Preparing toner base particles containing an anionic charge control agent (S0);

Obtaining a surface-modified toner base particle by adsorbing an amine group-containing cationic polymer on the surface of the toner base particle (S10);

Contacting the surface-modified toner base particles with glutaraldehyde (GA) to react the amine group-containing cationic polymer with glutaraldehyde (GA) to obtain a bonding layer (S20); And

It provides a method for producing a toner comprising the step (S30) of forming a cationic polymer layer by adsorbing an amine group-containing cationic polymer to the bonding layer.

The anionic charge control agent may include a carboxyl group exposed on the surface of the toner base particle, and the amine group may include at least one of a primary amine group and a secondary amine group.

The steps S10, S20, and S30 may be performed in an aqueous medium.

In the method of manufacturing the toner, after the step S40, the steps 10 and 20 may be repeated one or more times for the toner base particles including the cationic polymer layer. .

The method of manufacturing the toner may further include preparing an external toner by attaching an external additive to the cationic polymer layer.

The toner according to an exemplary embodiment of the present invention may have a narrow charge distribution, a uniform positive charge characteristic, and a controlled positive charge characteristic, and has the advantage of a small change in the amount of frictional charge according to a change in ambient humidity.

1 is a schematic diagram of a toner according to an embodiment of the present invention.
2 is a diagram illustrating a method of manufacturing a toner according to an embodiment of the present invention.

Hereinafter, a toner according to an embodiment of the present invention will be described in detail with reference to the drawings.

1 is a schematic diagram of a toner 10 according to an embodiment of the present invention.

Referring to FIG. 1, the toner 10 according to an embodiment of the present invention is at least partially attached to the toner base particle 11 and the toner base particle 11 to surround the toner base particle 11. Layer 12.

The toner base particles 11 contain an anionic charge control agent, although not shown in FIG. 1.

The anionic charge control agent is 2-carboxyethyl-2-propenoate, acrylic acid, methacrylic acid; Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, N,N-dimethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl meth It may contain at least one compound selected from the group consisting of acrylate, 2-ethylhexyl methacrylate, and dimethylaminoethyl methacrylate.

The toner base particles 11 may include at least a binder resin, a colorant, and a wax, although not shown in FIG. 1. The toner base particles 11 may be prepared by any one of methods known in the art, such as pulverization, suspension polymerization, emulsion agglomeration, chemical milling, or dispersion polymerization. For example, the toner base particle 11 may be manufactured by the method disclosed in Korean Patent Laid-Open Patent No. 2010-0048071 or 2010-0115148. However, in the manufacture of the toner base particle 11, the anionic charge control agent is used. Specifically, the anionic charging agent may be used together with a monomer in the process of manufacturing the binder resin, and together with the binder resin, the colorant, and the wax in the process of manufacturing the toner base particles 11 after manufacturing the binder resin. It can also be used. The disclosures of Korean Patent Publication Nos. 2010-0048071 and 2010-0115148 are incorporated herein by reference in their entirety.

The cationic polymer layer 12 allows the toner 10 to exhibit positive charging characteristics when the toner 10 is triboelectrically charged, and evenly covers the entire surface of the toner base particles 11 to ensure uniformity of charging of the toner 10 And the frictional charge amount of the final toner is hardly changed according to the ambient humidity change.

Cationic polymer layer 12, although not specifically shown in FIG. 1, at least one bonding layer comprising a cationic polymer moiety and a glutaraldehyde (GA) moiety chemically bonded to each other, and the bonding It includes an amine group-containing cationic polymer adsorbed to the layer and surrounding the bonding layer.

For example, when the cationic polymer layer 12 includes two bonding layers, the cationic polymer moiety of the first bonding layer close to the toner base particle adheres to the surface of the toner base particle 11 (for example, For example, adsorption), and the cationic polymer moiety of the second bonding layer distant from the toner base particle 11 is adsorbed to the glutaraldehyde (GA) moiety of the first bonding layer. In addition, the cationic polymer is adsorbed to the glutaraldehyde (GA) moiety of the second bonding layer. In this way, the cationic polymer layer 12 may include three or more bonding layers.

The cationic polymer moiety may be derived from the same compound as the amine group-containing cationic polymer.

The cationic polymer moiety may be derived from an amine group-containing cationic polymer having a weight average molecular weight of 500 to 100,000. If the weight average molecular weight of the amine group-containing cationic polymer is within the above range, the amine group-containing cationic polymer does not easily adsorb to the toner base particles during the production of the toner and does not fall off, and the aggregation between the toner base particles is suppressed. Thus, the generation amount of large aggregates can be reduced.

The amine group-containing cationic polymer is polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polyacrylamide (PAA), poly lysine (Poly (L-lysine)), and polyvinylimidazole. And at least one compound selected from the group consisting of polyamidoamine (PAMAM).

The content of the cationic polymer layer 12 may be 0.01 to 10 parts by weight based on 100 parts by weight of the toner base particle 11. If the content of the cationic polymer layer 12 is within the above range, the cationic polymer layer 12 may cover the entire surface of the toner base particles 11, and unreacted functional groups remaining in the cationic polymer layer 12 Since the content of is small, it is possible to reduce the change in the frictional charge amount of the toner due to the change in ambient humidity.

The toner 10 may further include an external additive 13 attached to the cationic polymer layer 12.

The external additive 13 may be attached to the surface of the cationic polymer layer 12, as shown in FIG. 1.

The external additive 13 may contain inorganic particles. The inorganic particles may contain, for example, inorganic fine particles having a particle diameter of 0.15 μm or less. Specifically, the external additive 13 may include at least one compound selected from the group consisting of large particle diameter silica (particle diameter ≥ 40 nm), small particle diameter silica (7 nm ≤ particle diameter ≤ 30 nm), titanium oxide and aluminum oxide. .

The content of the external additive 13 may be 2 to 7 parts by weight based on 100 parts by weight of the toner base particle 11. When the content of the external additive 13 is within the above range, the adhesion strength of the external additive 13 to the toner base particle 11 is high, and the charge amount and fluidity of the toner 10 may increase.

In the toner 10 having the above configuration, the cationic polymer layer 12 is evenly distributed over the entire surface of the toner base particle 11 to have uniform positive charge characteristics, and the cationic polymer layer 12 The positive charge characteristics may be adjusted according to the content, and may have an appropriate level of positive charge characteristics (ie, triboelectric charge) regardless of changes in the surrounding environment (ie, changes in humidity).

Hereinafter, a method of manufacturing a toner according to an embodiment of the present invention will be described in detail with reference to FIG. 2.

A method of manufacturing a toner according to an embodiment of the present invention includes the step of preparing a toner base particle 11 containing an anionic charge control agent (S0) (not shown), containing an amine group on the surface of the toner base particle 11 Adsorbing the cationic polymer 20 to obtain the surface-modified toner base particles 11 (S10), contacting the surface-modified toner base particles with glutaraldehyde (GA) to form an amine group-containing cationic polymer 20 ) Reacting with glutaraldehyde (GA) to obtain a bonding layer (S20), and adsorbing an amine group-containing cationic polymer to the bonding layer to form a cationic polymer layer (S30) (not shown) Includes.

The toner base particles 11, the anionic charge control agent, the amine group-containing cationic polymer 20, the binding layer and the cationic polymer layer are the same as those described in the toner 10 of FIG. Can be

The anionic charge control agent contains a functional group (not shown) exposed on the surface of the toner base particle 11.

The functional group is not limited thereto, but may include a carboxyl group.

The step S0 may be performed by the methods described in the toner 10 of FIG. 1.

The step (S10) may be performed in an aqueous medium. For example, the step (S10) may be performed by dispersing the toner base particles 11 in the aqueous medium to obtain a toner slurry, and then adding the amine group-containing cationic polymer 20 to the toner slurry. The aqueous medium may be water.

The content of the amine group-containing cationic polymer 20 added to the step (S10) may be 0.1 to 10 parts by weight based on 100 parts by weight of the toner base particle 11. If the content of the amine group-containing cationic polymer 20 added in the step (S10) is within the above range, the effect of adding the amine group-containing cationic polymer 20 even with a small amount of the amine group-containing cationic polymer 20 You can get enough.

The toner base particles 11 surface-modified in step S10 are shown in the middle of FIG. 2. The amine group-containing cationic polymer 20 is adsorbed on the surface of the toner base particle 11. In the present specification, the "surface-modified toner base particles 11" collectively refer to the toner base particles 11 and the amine group-containing cationic polymer 20 that are not surface-modified.

The step (S20) may be performed in an aqueous medium similar to the step (S10).

The content of glutaraldehyde (GA) added in the step (S20) may be 0.1 to 10 parts by weight based on 100 parts by weight of the toner base particles 11 without surface modification. If the content of glutaraldehyde (GA) added in the step (S20) is within the above range, the effect of adding glutaraldehyde (GA) can be sufficiently obtained even with a small amount of glutaraldehyde (GA).

The step (S20) may be performed for 0.5 to 6 hours at a temperature of 30 to 60 ℃. When the temperature and the time are within the above ranges, reaction (eg, dehydration condensation reaction) between the amine group-containing cationic polymer and the glutaraldehyde (GA) sufficiently occurs, and toner components such as wax Can be prevented from moving to the surface.

The bonding layer formed in step S20 is shown in the right part of FIG. 2. 2, the bonding layer is a cationic polymer moiety (20') attached to the toner base particle (11), and glutaraldehyde (GA) chemically bonded to the cationic polymer moiety (20'). It includes a moiety 30'.

The amine group may include at least one of a primary amine group and a secondary amine group. For example, the amine group may include a primary amine group.

The step (S30) may be performed in an aqueous medium similar to the step (S10). For example, the step (S30) may be performed by further adding an amine group-containing cationic polymer 20 to the toner slurry obtained in the step (S20).

The content of the amine group-containing cationic polymer 20 added to the step (S30) may be 0.1 to 10 parts by weight based on 100 parts by weight of the toner base particles 11 without surface modification. If the content of the amine group-containing cationic polymer 20 added in the step (S30) is within the above range, the addition of the amine group-containing cationic polymer 20 even with a small amount of the amine group-containing cationic polymer 20 You can get enough effect.

The method of manufacturing the toner may further include a step (S40) of drying and grinding the resultant product obtained in the step (S30). The drying process may be performed at a temperature of 30 to 60°C. The pulverization process may be performed by stirring the dried product in a mixer (eg, Henschel mixer) when an aggregate is formed in the drying process.

The method of manufacturing the toner may further include a step (S50) of preparing an external toner by attaching an external additive to the cationic polymer layer. In the present specification, "external toner" refers to a toner including a toner base particle and an external additive attached thereto.

The external additive may be the same as described in the toner 10 of FIG. 1.

The step (S50) may be performed by mixing and stirring the resultant obtained in the step (S30) or the step (S40) with the external additive. The stirring may be performed at a mixture temperature of 20 to 55° C. at a stirring speed of 8,000 to 12,000 rpm.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example

Manufacturing example 1: Latex dispersion for core and For shell Preparation of latex dispersion

The core latex dispersion and the shell latex dispersion were prepared in the same manner by the following method. Specifically, a reactor having a volume of 30 liters in which a stirrer, thermometer and condenser were installed was installed in an oil tank. Distilled water and a surfactant (Dowfax 2A1) were added to each of 6,600 g and 32 g, respectively, in the reactor thus installed, and the temperature of the reactor was increased to 70° C. and stirred at a stirring speed of 100 rpm. Thereafter, monomers, i.e. 8,380 g of styrene, 3,220 g of butyl acrylate, 150 g of 2-carboxyethyl acrylate and 226 g of 1,10-decanediol diacrylate, 5,075 g of distilled water, 226 g of surfactant (Dowfax 2A1), as a macromonomer Emulsion mixture of polyethylene glycol ethyl ether methacrylate 530 g, 1-dodecanethiol 188 g as a chain transfer agent, and 2-carboxyethyl-2-propenoate 200 g as anionic charge control agent at 400-500 rpm for 30 minutes with a disk type impeller After stirring for 1 hour, it was slowly added to the reactor. Subsequently, after 10 minutes elapsed, a solution of 3,277 g of distilled water and 175 g of ammonium persulfate was further added to the reactor, and the reaction was allowed to proceed for about 8 hours and then slowly cooled to room temperature to complete the reaction. As a result, a latex dispersion (that is, a latex dispersion for a core and a latex dispersion for a shell) was obtained.

After completion of the reaction, the glass transition temperature (Tg) of the binder resin in the latex dispersion was measured using a differential scanning calorimeter (DSC), and the temperature was 62°C. In addition, the number average molecular weight of the binder resin was measured by gel permeation chromatography (GPC) using a polystyrene reference sample, and as a result, the number average molecular weight was 50,000.

Manufacturing example 2: Preparation of colorant dispersion

540 g of cyan pigment (ECB303, manufactured by Daeil Jeonghwa Co., Ltd.), 27 g of surfactant (Dowfax 2A1), and 2,450 g of distilled water were added to a 5 liter reactor equipped with a stirrer, thermometer, and condenser, and then pre-dispersion was performed while slowly stirring for 10 hours. I did. After performing the pre-dispersion for 10 hours, it was dispersed for 4 hours using a beads mill (Germany Netzsch, Zeta RS). As a result, a colorant dispersion was obtained.

After completion of the dispersion, the particle size of the cyan pigment particles was measured using a Multisizer 2000 (manufactured by Malvern), and the D50(v) was 170 nm. Here, D50(v) means a particle diameter corresponding to 50% of the volume average particle diameter, that is, a particle diameter corresponding to 50% of the total volume when the volume is accumulated from small particles by measuring the particle diameter.

Manufacturing example 3: Preparation of wax dispersion

After adding 65 g of surfactant (Dowfax 2A1) and 1,935 g of distilled water to a 5-liter reactor equipped with a stirrer, thermometer, and condenser, the mixture was slowly stirred at 95° C. for about 2 hours while waxing (Nippon 　 Seiro, paraffin wax, 1,000 g of HNP9) was added to the reactor. The mixture was dispersed for 30 minutes using a pressure discharge type homogenizer (Homogenizer, Japan Precision Machinery). As a result, a wax dispersion was obtained.

After completion of the dispersion, the particle size of the dispersed wax particles was measured using a Multisizer 2000 (manufactured by Malvern), and the D50(v) was 200 nm.

Manufacturing example 4: toner Parent particle Produce

In a 70-liter reactor, 13,881 g of the latex dispersion for the core prepared above, 2,238 g of the colorant dispersion, and 2,873 g of the wax dispersion were added, and then stirred at 25° C. for about 15 minutes at a stirring linear speed of 1.21 m/sec and mixed. Here, 4,500 g of a mixed solution of PAC (polyaluminium chloride) and nitric acid aqueous solution (concentration = 1.88% by weight) as a coagulant was added (PAC/nitric acid aqueous solution = 1/2 (weight ratio)), and a homogenizer (IKA, T -50) was used to stir the contents of the reactor for 30 minutes at 25° C. at a stirring speed of 50 rpm (stirring linear speed: 1.79 m/sec) to proceed with a homogenization process. At this time, the pH of the reactor contents was 1.8. Thereafter, the temperature of the reactor was raised to 51 °C, and then agitated at 2.42 m/sec to continue aggregation until the D50 (v) of the toner base particles becomes 5.4 to 5.6 μm, and then 5,398 g of the latex dispersion for shell was added. It was added over 20 minutes. Thereafter, stirring was continued until the average particle diameter of the toner base particles became 6.0 to 6.2 μm, and then a 4% by weight aqueous sodium hydroxide solution was added to the reactor and stirred at 1.90 m/sec until the pH reached 4, and the pH It was stirred at 1.55 m/sec until it became 7. Thereafter, while maintaining the stirring speed, the temperature of the reactor was raised to 96° C. so that the toner base particles were united. Thereafter, when the circularity was measured using FPIA-3000 (manufactured by sysmex, made in Japan), when the measured circularity was 0.985 to 0.990, the temperature of the reactor was cooled to 40°C, and the pH of the reactor contents was changed to 9.0. Adjusted to separate the toner base particles using nylon mesh (pore size: 16㎛), and after washing the separated toner base particles 4 times with distilled water, prepared by mixing 1.88% by weight of nitric acid aqueous solution with distilled water. Re-washed with a mixed solution having a pH of 1.5, and then re-washed with distilled water four times to remove all surfactants. As a result, dried toner base particles were obtained.

Example 1-6: Preparation of toner

In the same embodiment, in all steps of using an amine group-containing cationic polymer or glutaraldehyde (GA), the same type and content of an amine group-containing cationic polymer, and/or the same content of glutaraldehyde (GA) are used. I did.

(Step 1: Surface modification process of toner base particles)

A first toner slurry was obtained by dispersing 7 kg (moisture content: 30 wt%) of the toner base particles containing moisture prepared in Preparation Example 4 in 20,000 g of distilled water at 30°C. Thereafter, an amine group-containing cationic polymer was added to the first toner slurry. As a result, a second toner slurry containing surface-modified toner base particles was obtained. The types and contents of the amine group-containing cationic polymer used in each example are shown in Table 1 below.

(Step 2: forming a bonding layer by dehydration condensation reaction)

Glutaraldehyde (GA) was added to the second toner slurry. As a result, a third toner slurry was obtained. Thereafter, the third toner slurry was heat-treated at 45° C. for 2 hours under stirring. As a result, a fourth toner slurry was obtained. The content of glutaraldehyde (GA) used in each example is shown in Table 1 below.

(Step 3: Cationic polymer layer formation process)

Thereafter, an amine group-containing cationic polymer was further added to the fourth toner slurry. As a result, a fifth toner slurry was obtained. The type and content of the amine group-containing cationic polymer used in step 3 of each example were the same as the type and content of the amine group-containing cationic polymer used in step 1 of each example.

(Step 4: iterative process)

Steps 2 and 3 were repeated. As a result, a sixth toner slurry was obtained.

(Step 5: drying and grinding process)

The fifth toner slurry or the sixth toner slurry was dried at 60° C. for 2 hours, and then put into a 75-liter Henschel mixer and stirred at a speed of 35 m/s to pulverize the aggregate.

Comparative example 1: Preparation of toner

7 kg of toner base particles containing moisture prepared in Preparation Example 4 (moisture content: 30 wt%) were dispersed in 20,000 g of distilled water at 30° C. to obtain a toner slurry. Thereafter, glutaraldehyde (GA) was added to the toner slurry. The content of glutaraldehyde (GA) used in Comparative Example 1 is shown in Table 1 below. Subsequently, the toner slurry was dried at 60° C. for 2 hours, and then put into a 75 liter Henschel mixer and stirred at a speed of 35 m/s to pulverize the aggregate.

Comparative example 2: Preparation of toner

Except for omitting steps 3 and 4, toners were prepared in the same manner as in Examples 1 to 6.

Comparative example Example One 2 One 2 3 4 5 6 Step 1 Amine group-containing cationic polymer - PAH PAH PAH PAH PAH PEI PEI content
(Part by weight ^*1 ) - One 0.5 One 2 One 0.5 One Step 2 GA content (parts by weight ^*1 ) One One One One One One One One Step 3 Amine group-containing cationic polymer - - PAH PAH PAH PAH PEI PEI content
(Part by weight ^*1 ) - 0 0.5 One 2 One 0.5 One Number of 4 steps (repeated process) 0 0 0 0 0 One 0 0

*1: Value calculated based on 100 parts by weight of dried toner base particles before surface modification.

*2: PAH (weight average molecular weight: 17000)

*3: PEI (weight average molecular weight: 2000)

Evaluation example

For each of the toners prepared in Examples 1 to 6 and Comparative Examples 1 to 2, the ratio of the reverse charge toner and the frictional charge amount were evaluated as follows, and the results are shown in Table 2 below.

Rate evaluation of previous toners

A q/d meter (Epping, Germany) was used to measure the frictional charge amount distribution of the toner. 0.7 g of the toner prepared in each of the Examples and Comparative Examples, and 9.3 g of the carrier (100 μm, Japanese Burn Society) were added to a 100 mL photosphere bottle, and then under N/N conditions (25° C., RH 50%) for 15 hours. Left unattended. Then, it was mixed for 5 minutes at 96 rpm using a Turbula mixer (WAB, Switzerland).

After mixing, 0.1 g of a sample was put into a measuring cell of a q/d meter and scanned under conditions of 160 ml/min and 1,000 voltage to measure the ratio of the reverse charge toner.

Evaluation of triboelectric charge

The frictional charge amount of the toner was measured using a q/m meter (Epping, Germany). 0.7 g of the toner prepared in each of the Examples and Comparative Examples, and 9.3 g of the carrier (100 μm, Japanese Burn Society) were added to a 100 mL photosphere bottle, and then under N/N conditions (25° C., RH 50%) for 15 hours. Left unattended. Then, it was mixed for 5 minutes at 96 rpm using a Turbula mixer (WAB, Switzerland). After mixing, 0.1 g of a sample was put into a measuring cell of a q/m meter and scanned under conditions of 80 ml/min and 1,000 voltage to measure the amount of charge.

Comparative example Example One 2 One 2 3 4 5 6 Ratio of reverse charge toner (%) 5.7 6.2 4.7 4.2 4.5 4.1 4.4 4.3 Frictional charge
(μC/g) -45 34 42 46 47 49 40 43

Referring to Table 2, the toners prepared in Examples 1 to 6 showed a positively charged frictional charge amount, unlike the toner prepared in Comparative Example 1, and the ratio of the reversely charged toner compared to the toner prepared in Comparative Example 2. It was found that this was low and the amount of triboelectric charge was large.

The present invention has been described with reference to the drawings and embodiments, but these are merely exemplary, and those of ordinary skill in the art will appreciate that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical scope of the present invention should be determined by the technical spirit of the appended claims.

10: toner 11: toner base particles
12: cationic polymer layer 20: amine group-containing cationic polymer
20': cationic polymer moiety 30': GA moiety

Claims (11)

Toner base particles containing an anionic charge control agent;
And a cationic polymer layer at least partially attached to the toner base particles and surrounding the toner base particles,
The cationic polymer layer is at least one bonding layer comprising a cationic polymer moiety and a glutaraldehyde (GA) moiety chemically bonded to each other, and an amine group-containing cation adsorbed on the bonding layer to surround the bonding layer Toner containing a polymer. The method of claim 1,
The anionic charge control agent is 2-carboxyethyl-2-propenoate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, N,N- At least one compound selected from the group consisting of dimethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and dimethylaminoethyl methacrylate Toner comprising a. The method of claim 1,
The cationic polymer moiety is a toner derived from an amine group-containing cationic polymer having a weight average molecular weight of 500 to 100,000. The method of claim 3,
The amine group-containing cationic polymer is polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polyacrylamide (PAA), poly lysine (Poly (L-lysine)), and polyvinylimidazole. And at least one compound selected from the group consisting of polyamidoamine (PAMAM). The method of claim 1,
The content of the cationic polymer layer is 0.01 to 10 parts by weight based on 100 parts by weight of the toner base particles. The method of claim 1,
Toner further comprising an external additive attached to the cationic polymer layer. Preparing toner base particles containing an anionic charge control agent (S0);
Obtaining a surface-modified toner base particle by adsorbing an amine group-containing cationic polymer on the surface of the toner base particle (S10);
Contacting the surface-modified toner base particles with glutaraldehyde (GA) to react the amine group-containing cationic polymer with glutaraldehyde (GA) to obtain a bonding layer (S20); And
A method for producing a toner comprising the step (S30) of forming a cationic polymer layer by adsorbing an amine group-containing cationic polymer to the bonding layer. The method of claim 7,
The anionic charge control agent includes a carboxyl group exposed on the surface of the toner base particle, and the amine group includes at least one of a primary amine group and a secondary amine group. The method of claim 7,
The steps (S10, S20, and S30) are performed in an aqueous medium. The method of claim 7,
After the step (S30), the step (20) and the step (30) are repeated one or more times for the toner base particles including the cationic polymer layer. The method of claim 7,
A method for producing a toner further comprising the step of preparing an external toner by attaching an external additive to the cationic polymer layer.

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