KR102132012B1 - Electrostatic charge image developing toner having excellent positively charging properties and method of preparing the same - Google Patents

Abstract

Disclosed is a toner and a method of manufacturing the same. The disclosed toner includes toner base particles containing an anionic charge control agent moiety, and cationic compound moieties linked by an amide bond with the anionic charge control agent moiety, wherein the amide bond is external to the toner base particle. exist.

Description

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

Disclosed is a toner for developing an electrostatic charge image having excellent static charge characteristics and a method for manufacturing the same. More specifically, a toner comprising a cationic compound chemically bonded to the surface of the toner base particles and a method of manufacturing the same are disclosed.

In general, a positively charged toner is produced 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. The toner produced by adding the antistatic charge control agent as described above may cause various problems depending on the chemical structure, crystal structure, size, dispersibility, and amount of addition of the antistatic charge control agent, despite having excellent triboelectric charge characteristics.

In general, since the static charge control agent added to the toner base particles is not evenly distributed on the toner surface, there is a problem that the charge distribution of the toner base particles is not uniform. In addition, since the positively charged charge control agent is not firmly bonded to the surface of the toner base particles, a phenomenon in which the static charge of the toner deteriorates due to separation from the toner surface during frictional charging frequently occurs. In particular, when the toner is used for a long time, there is a problem in that the static charge of the toner is deteriorated while the static charge control agent is easily displaced or moved from the toner surface due to stress due to contact of the carrier or agitation in the developer. 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 comprising a cationic compound chemically bonded to the surface of the toner base particles.

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

One aspect of the invention,

Toner base particles comprising an anionic charge control agent moiety; And

The anionic charge control agent moiety and a cationic compound moiety linked by an amide bond, wherein the amide bond provides a toner present outside the toner base particles.

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

The cationic compound moiety may be derived from an amine group-containing compound.

The amine group-containing compound is 1,6-diaminohexane, 1,5-diaminopentane, 1,4-diaminopentane, pentane-1,3-diamine, 1,4-diaminobutane, 1,3- It may include at least one compound selected from the group consisting of diaminopropane and 1,2-diaminopropane.

The amine group-containing compound may include a cationic polymer having a weight average molecular weight of 500 to 100,000.

The cationic polymer is polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polyacrylamide (PAA), poly(L-lysine), polyvinylimidazole and polyamido It may include at least one compound selected from the group consisting of amines (PAMAM).

The content of the cationic compound moiety may be 0.01 to 10 parts by weight based on 100 parts by weight of the toner base particles.

The toner may further include an external additive attached to the toner base particles.

Another aspect of the invention,

Adding an anionic charge control agent to prepare surface-exposed functional group-containing toner base particles (S0);

The surface is formed by contacting the toner base particles with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter referred to as EDC) to form an intermediate by reaction of the surface-exposed functional group with the EDC. Obtaining modified toner base particles (S10); And

It provides a method of producing a toner comprising the step (S20) of contacting the surface-modified toner base particles with an amine group-containing compound to advance an amide bond reaction between the intermediate and the amine group-containing compound.

The surface-exposed functional group may include a carboxyl group, and the amine group may include at least one of a primary amine group and a secondary amine group.

In the step (S10), the content of the EDC in contact with the toner base particles may be 1 to 10 parts by weight with respect to 100 parts by weight of the toner base particles.

The steps (S10 and S20) can be carried out in the presence of a catalyst in an aqueous medium.

The catalyst is at least one selected from the group consisting of N-hydroxysuccinimide (NHS), N-hydroxysulfosuccinimide (sulfo-NHS), its derivatives and its sodium salt It may include a compound.

The manufacturing method of the toner may further include a step of preparing an external toner by attaching an external additive to the toner base particles after the step (S20).

The toner according to the embodiment of the present invention may have a narrow charge distribution, uniform constant charge characteristics, and controlled constant charge characteristics, and have a small advantage in that the amount of change in the friction charge amount according to the change in ambient humidity.

1 is a view for explaining a method of manufacturing a toner according to an embodiment of the present invention.

Hereinafter, the toner according to the embodiment of the present invention will be described in detail.

The toner according to an embodiment of the present invention includes toner base particles comprising an anionic charge control agent moiety, and a cationic compound moiety linked by an amide bond with the anionic charge control agent moiety, wherein the amide bond is It exists outside of the toner base particles. In the present specification, the "outside of the toner base particle" means a portion that is not inside the toner base particle, and is spaced apart at a predetermined distance from the surface of the toner base particle or the surface of the toner base particle.

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

The toner base particles may include at least a binder resin, a colorant, and a wax. The toner base particles may be prepared by any one of methods known in the art, such as pulverization, suspension polymerization, emulsion aggregation, chemical milling, or dispersion polymerization. For example, the toner base particles may be manufactured by the method disclosed in Korean Patent Publication No. 2010-0048071 or 2010-0115148. However, when producing the toner base particles, the anionic charge control agent is used. Specifically, the anionic charge agent may be used together with the monomer in the process of manufacturing the binder resin, or may be used together with the binder resin, the colorant and the wax in the process of preparing toner base particles after the binder resin is prepared. . The disclosures of Korean Patent Publication Nos. 2010-0048071 and 2010-0115148 are incorporated herein by reference in their entirety by reference.

The cationic compound moiety, during frictional charging of the toner, causes the toner to exhibit positive charge characteristics, is uniformly disposed on the entire surface of the toner base particles, improves the charging uniformity of the toner, and It plays a role in that the frictional charge amount hardly changes according to the change in the ambient humidity.

A portion of the anionic charge control agent moiety is exposed on the surface of the toner base particle, and a portion of the anionic charge control agent moiety exposed on the surface of the toner base particle is amide-bonded with the cationic compound moiety Are connected by.

The cationic compound moiety may be derived from an amine group-containing compound.

The amine group-containing compound is 1,6-diaminohexane, 1,5-diaminopentane, 1,4-diaminopentane, pentane-1,3-diamine, 1,4-diaminobutane, 1,3- It may include at least one compound selected from the group consisting of diaminopropane and 1,2-diaminopropane.

The amine group-containing compound may include a cationic polymer having a weight average molecular weight of 500 to 100,000. When the weight-average molecular weight of the cationic polymer is within the above range, the cationic polymer is not easily adsorbed to the toner base particles and does not fall off when the toner is prepared, and suppresses agglomeration of the toner base particles, thereby suppressing toner aggregation. ) Can be reduced.

The cationic polymer is polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polyacrylamide (PAA), poly(L-lysine), polyvinylimidazole and polyamido It may include at least one compound selected from the group consisting of amines (PAMAM).

The content of the cationic compound moiety may be 0.01 to 10 parts by weight based on 100 parts by weight of the toner base particles. When the content of the cationic compound moiety is within the above range, the cationic compound moiety may be uniformly disposed on the entire surface of the toner base particles, and the content of unreacted functional groups remaining on the surface of the toner base particles This can be reduced to reduce the change in the frictional charge amount of the toner according to the change in ambient humidity.

The toner may further include an external additive attached to the toner base particles.

The external additive may be attached to the surface of the toner base particles.

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

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

The toner having the above-described configuration has the uniformly charged property as the cationic compound moiety is evenly distributed over the entire surface of the toner base particles, and the charged property has a positive charge property according to the content of the cationic compound moiety. It can be adjusted and can have an appropriate level of static charge property (ie, frictional charge) regardless of changes in the surrounding environment (ie, humidity change).

Hereinafter, a method of manufacturing a toner according to an embodiment of the present invention will be described in detail with reference to FIG. 1.

Referring to FIG. 1, a method of manufacturing a toner according to an embodiment of the present invention comprises the steps of preparing a toner base particle 10 containing a functional group 20 exposed by adding an anionic charge control agent (S0), The surface exposed functional group 20 and the EDC (by contacting the toner base particles 10 with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter referred to as EDC) 30 Step S10 of obtaining the surface-modified toner base particles 10 by forming the intermediate 35 by the reaction of 30), and contacting the surface-modified toner base particles 10 with the amine group-containing compound 40 It comprises the step of proceeding the amide bond between the intermediate (35) and the amine group-containing compound (40) (S20).

1, 1,6-diaminohexane is shown as an example of the amine group-containing compound 40, but the present invention is not limited thereto.

The toner base particles 10, the anionic charge control agent and the amine group-containing compound 40 may be the same as those described in the toner section described above.

The surface-exposed functional group 20 may include, but is not limited to, a carboxyl group.

The step S0 may be performed by the methods described in the toner portion described above.

The step (S10) may be performed in the presence of a catalyst in an aqueous medium. For example, the step S10 may be performed by dispersing the toner base particles 10 in the aqueous medium to obtain a toner slurry, and then adding the EDC 30 and the catalyst to the toner slurry. The aqueous medium can be water. However, the present invention is not limited to this, and the step (S10) may be performed without a catalyst.

The content of the EDC 30 added to the step (S10) may be 0.1 to 10 parts by weight based on 100 parts by weight of the toner base particles (10). If the content of the EDC 30 added to the step (S10) is within the above range, the effect of adding the EDC 30 can be sufficiently obtained even with a small amount of the EDC 30.

The catalyst is at least one selected from the group consisting of N-hydroxysuccinimide (NHS), N-hydroxysulfosuccinimide (sulfo-NHS), its derivatives and its sodium salt It may include a compound.

When the step (S10) proceeds in the presence of a catalyst, the content of the catalyst added to the step (S10) may be 1 to 5 parts by weight based on 100 parts by weight of the toner base particles (10).

The intermediate body 35 formed in the step S10 may be a covalent bond of the surface-exposed functional group 20 and the EDC 30.

The step (S10) may be carried out for 3 to 24 hours at a temperature of 10 to 60 ℃ under stirring. When the temperature and the time are each within the above range, a reaction (ie, covalent bond formation reaction) between the surface-exposed functional group 20 and the EDC 30 occurs sufficiently, and toner components such as wax are transferred to the surface of the toner. It can be prevented from moving.

The step (S20) may be carried out in the presence of a catalyst in an aqueous medium as in the step (S10). For example, the step (S20) may be performed by further adding an amine group-containing compound (40) to the toner slurry obtained in the step (S10). The catalyst used in the step (S20) may be a catalyst added separately to the step (S20), or may be a catalyst already added to the step (S10). However, the present invention is not limited to this, and the step (S20) may be performed without a catalyst.

When the step (S10) proceeds without a catalyst and the step (S20) proceeds in the presence of a catalyst, the catalyst described above is added to the step (S20), and the content of the catalyst added to the step (S20) is The toner base particles 10 may be 1 to 5 parts by weight based on 100 parts by weight.

The step (S20) may be carried out for 3 to 24 hours at a temperature of 10 to 60 ℃ under stirring. When the temperature and the time are each within the above range, an amide bond reaction between the intermediate 35 and the amine group-containing compound 40 proceeds sufficiently, and toner components such as wax are prevented from moving to the surface of the toner. can do.

The content of the amine group-containing compound 40 added to the step (S20) may be 0.01 to 10 parts by weight based on 100 parts by weight of the surface-modified toner base particles (10).

In the step (S20), the amide bond formation reaction between the intermediate 35 and the amine group-containing compound 40 proceeds rapidly, resulting in direct amide between the surface-exposed functional group 20 and the amine group-containing compound 40. The final product 50 in the same form as produced by the binding is obtained.

When the surface-exposed functional group 20 is in direct contact with the amine group-containing compound 40 without forming the intermediate 35, the amide bond formation reaction does not proceed well between them. However, when the surface-exposed functional group 20 reacts with the EDC 30 to form the intermediate 35, the intermediate 35 contacts the amine group-containing compound 40, the intermediate 35 ) And the reaction for forming an amide bond between the amine group-containing compound (40) proceeds rapidly.

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 manufacturing method of the toner may further include a step (S30) of drying and crushing the result obtained in the step (S20). The drying process may be performed at a temperature of 30 ~ 60 ℃. The crushing process may be performed by agitating the dried product in a mixer (for example, a Henschel mixer) when aggregates are formed in the drying process.

The manufacturing method of the toner may further include the step of preparing an externally added toner by attaching an external additive to the toner base particles 10 (S40). In the present specification, the term “external toner” means a toner comprising toner base particles and an external additive attached thereto.

The external additive may be the same as described in the toner section described above.

The step (S40) may be performed by mixing and stirring the resultant obtained in the step (S20) or the step (S30) and the external additive. The stirring may be carried out at a stirring speed of 8,000 ~ 12,000rpm at a mixture temperature of 20 ~ 55 ℃.

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

Preparation Example 1: Preparation of latex dispersion for core and latex dispersion for shell

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

After completion of the reaction, a 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 binding 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.

Preparation Example 2: Preparation of colorant dispersion

After adding 540 g of cyan pigment (ECB303, manufactured by Daeil Junghwa Co., Ltd.), 27 g of surfactant (Dowfax 2A1), and 2,450 g of distilled water to a reactor with a volume of 5 liters equipped with a stirrer, thermometer, and condenser, pre-dispersion is performed while slowly stirring for 10 hours. Did. After 10 hours of pre-dispersion, the beads were dispersed for 4 hours using Biz Mill (Netzsch, Germany, Zeta RS). As a result, a colorant dispersion was obtained.

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

Preparation Example 3: Preparation of wax dispersion

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

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

Production Example 4: Preparation of toner base particles

In the 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, followed by stirring at 25° C. for 15 minutes at 1.21 m/sec. Here, 4,500 g of a mixed solution of PAC (polyaluminium chloride) and an aqueous nitric acid solution (concentration = 1.88 wt%) (PAC/aqueous nitric acid solution = 1/2 (weight ratio)) was added, and a homogenizer (IKA, T -50) was used to agitate the reactor contents for 30 minutes at a stirring speed of 50 rpm at 50°C (stirring speed: 1.79 m/sec) to carry out 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 stirred at 2.42 m/sec to continue agglomeration until D50 (v) of the toner base particles became 5.4 to 5.6 μm, and 5,398 g of latex dispersion for shell was about It was added over 20 minutes. Thereafter, stirring was continued until the average particle diameter of the toner base particles was 6.0 to 6.2 µm, and then 4 wt% sodium hydroxide aqueous solution was added to the reactor to stir at 1.90 m/sec until the pH was 4, and Stir at 1.55m/sec until is 7 Thereafter, the temperature of the reactor was raised to 96° C. while maintaining the stirring speed so that the toner base particles were united. Thereafter, when the circularity was measured using FPIA-3000 (manufactured by sysmex, Japan), when the measured circularity was 0.985 to 0.990, the reactor temperature was cooled to 40°C, and the pH of the reactor contents was 9.0. By adjusting and separating the toner base particles using a nylon mesh (pore size: 16㎛), and then washing the separated toner base particles four times with distilled water, a 1.88% by weight aqueous nitric acid solution was mixed with distilled water. The mixture was washed again with a mixed solution having a pH of 1.5, and then washed four times with distilled water to remove all surfactants.

Examples 1 to 4: Preparation of toner

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

7 kg (moisture content: 30 wt%) of the toner base particles containing moisture prepared in Preparation Example 4 was dispersed in 20,000 g of distilled water at 30° C. to obtain a first toner slurry. Then, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) was added to the first toner slurry, followed by heat treatment at 40° C. for 12 hours with stirring. As a result, a second toner slurry containing surface-modified toner base particles was obtained. The contents of EDC used in each example are shown in Table 1 below.

(Step 2: amide bond formation process)

An amine-containing compound (ACC) and a catalyst (Aldrich, N-hydroxysulfosuccinimide sodium salt) were added to the second toner slurry. As a result, a third toner slurry was obtained. Thereafter, the third toner slurry was heat-treated at 40° C. for 12 hours under stirring. As a result, a fourth toner slurry was obtained. The types and contents of amine-containing compounds (ACC) and catalysts used in each example are shown in Table 1 below.

(Step 3: Drying and grinding process)

The fourth toner slurry was dried at 60° C. for 12 hours, and then put into a 75 liter Henschel mixer to stir the agglomerates by stirring at a rate of 35 m/s.

Comparative Example 1: Preparation of toner

Toner base particles containing water prepared in Preparation Example 4 were dispersed 7kg (moisture content: 30wt%) in 20,000g of distilled water at 30℃ to obtain a toner slurry. Thereafter, the toner slurry was dried at 60° C. for 12 hours, and then charged into a 75 liter Henschel mixer to stir the agglomerates by stirring at a rate of 35 m/s.

Comparative Example 2: Preparation of toner

Toners were prepared in the same manner as in Examples 1 to 4, except that Step 2 was omitted.

Comparative example Example One 2 One 2 3 4 EDC content
(Parts by weight ^*1 ) 0 2 2 2 2 2 Catalyst content
(Parts by weight ^*1 ) 0 0 0.1 0.1 0.1 0.1 ACC Kinds - - DAH ^*2 DAH ^*2 DAB ^*3 PAH ^*4 Content (parts by weight ^*1 ) 0 0 One 3 3 3

*1: Calculated based on 100 parts by weight of the dried toner base particles.

*2: 1,6-diaminohexane

*3: 1,4-diaminobutane

*4: Polyallylamine hydrochloride (weight average molecular weight: 58000)

Evaluation example

For each toner produced in Examples 1 to 4 Pa and Comparative Examples 1 to 2, the ratio of the anti-static toner and the amount of triboelectric charging were evaluated as follows, and the results are shown in Table 2 below.

Former toner Rate evaluation

The frictional charge distribution of the toner was measured using a q/d meter (Epping, Germany). 0.7 g of the toner prepared in each of the above Examples and Comparative Examples, and 9.3 g of a carrier (100 µm, Japanese Society of Burns) were put into a 100 mL photonic bottle, and then under N/N conditions (25° C., RH 50%) for 15 hours. Left unattended. Subsequently, the mixture was mixed at 96 rpm for 5 minutes using a Turbula mixer (WAB, Switzerland).

After mixing, 0.1 g of the sample was placed in a measurement cell of a q/d meter and scanned under conditions of 160 ml/min and 1,000 voltage to measure the proportion of anti-static toner.

Friction charge evaluation

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 above Examples and Comparative Examples, and 9.3 g of a carrier (100 µm, Japanese Society of Burns) were put into a 100 mL photonic bottle, and then under N/N conditions (25° C., RH 50%) for 15 hours. Left unattended. Subsequently, the mixture was mixed at 96 rpm for 5 minutes using a Turbula mixer (WAB, Switzerland). After mixing, 0.1 g of the sample was placed in a measurement cell of a q/m meter, and the charge amount was measured by scanning under conditions of 80 ml/min and 1,000 voltage.

Comparative example Example One 2 One 2 3 4 Percentage of anti-static toner (%) 5.2 7 4.3 3.6 3.5 3.1 Friction charge
(μC/g) -38 +22 +30 +35 +34 +40

Referring to Table 2, unlike the toners prepared in Comparative Examples 1, the toners prepared in Examples 1 to 4 show a positively charged frictional charge amount, and the proportion of anti-toner compared to the toners prepared in Comparative Example 2 It was found that this was low and the frictional charge was large.

Although the present invention has been described with reference to the drawings and examples, it is only exemplary, and those skilled in the art will understand that various modifications and equivalent other implementations are possible therefrom. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.

10: toner base particle 11: toner base particle surface
20: functional group 30: EDC
35: intermediate 40: cationic compound
50: final product

Claims (14)

Toner base particles comprising an anionic charge control agent moiety; And
A toner comprising the anionic charge control agent moiety and a cationic compound moiety linked by an amide bond, wherein the amide bond exists outside the toner base particles. According to claim 1,
The anionic charge control agent moiety is 2-carboxyethyl-2-propenoate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, N, At least one member selected from the group consisting of N-dimethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and dimethylaminoethyl methacrylate Toner derived from anionic charge control agent. According to claim 1,
The toner wherein the cationic compound moiety is derived from an amine group-containing compound. According to claim 3,
The amine group-containing compound is 1,6-diaminohexane, 1,5-diaminopentane, 1,4-diaminopentane, pentane-1,3-diamine, 1,4-diaminobutane, 1,3- A toner comprising at least one compound selected from the group consisting of diaminopropane and 1,2-diaminopropane. According to claim 3,
The amine group-containing compound is a toner containing a cationic polymer having a weight average molecular weight of 500 to 100,000. The method of claim 5,
The cationic polymer is polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polyacrylamide (PAA), poly(L-lysine), polyvinylimidazole and polyamido A toner comprising at least one compound selected from the group consisting of amines (PAMAM). According to claim 1,
The content of the cationic compound moiety is 0.01 to 10 parts by weight based on 100 parts by weight of the toner base particles. According to claim 1,
The toner further includes an external additive attached to the toner base particles. Adding an anionic charge control agent to prepare surface-exposed functional group-containing toner base particles (S0);
The surface is formed by contacting the toner base particles with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter referred to as EDC) to form an intermediate by reaction of the surface-exposed functional group with the EDC. Obtaining modified toner base particles (S10); And
A method of manufacturing a toner, comprising contacting the surface-modified toner base particles with an amine group-containing compound to advance an amide bond reaction between the intermediate and the amine group-containing compound (S20). The method of claim 9,
The surface-exposed functional group includes a carboxyl group, and the amine group includes at least one of a primary amine group and a secondary amine group. The method of claim 9,
In the step (S10), the content of the EDC in contact with the toner base particles is 1 to 10 parts by weight relative to 100 parts by weight of the toner base particles. The method of claim 9,
The step (S10 and S20) is a method of manufacturing a toner that proceeds in the presence of a catalyst in an aqueous medium. The method of claim 12,
The catalyst is at least one selected from the group consisting of N-hydroxysuccinimide (NHS), N-hydroxysulfosuccinimide (sulfo-NHS), its derivatives and its sodium salt Method of manufacturing a toner comprising a compound of the. The method of claim 9,
After the step (S20), a method of manufacturing a toner further comprising the step of preparing an external toner by attaching an external additive to the toner base particles.

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