JP2019184662A - Method of manufacturing toner - Google Patents

Abstract

To provide a method of manufacturing a toner that offers both high electrostatic chargeability and low adhesivity.SOLUTION: A method of manufacturing a toner comprising toner resin having an acid group and toner particles containing a release agent is provided, the method comprising a step of exchanging acid group-derived cations with lithium ions and ammonium ions in an aqueous medium.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a toner for developing an electrostatic image used in electrophotography, electrostatic recording, and the like.

In recent years, with the increase in image quality and resolution in printers and copiers using electrophotography, the physical properties required of toner have become stricter, and in particular, further improvements in developability and transferability have been demanded.
In consideration of these requirements, toner adhesion is an important physical property because it affects processes such as development and transfer. Development and transfer are mainly performed by electrostatic force generated by the voltage applied in the same process, but if the adhesion between the toner and between the toner and the member is high, the movement of the toner is inhibited, which may cause image defects. obtain.

  As a measure for reducing the adhesion of the toner, an external additive such as inorganic fine particles is generally added to the toner (Patent Documents 1 to 3).

JP-A-6-266152 JP 2008-9072 A JP 2009-98700 A

However, only the method using the external additive described above has an effect of reducing adhesion at an early stage of using the developing device. However, when used over a long period of time, an external additive is easily embedded in the toner particles by continuing to add a mechanical share inside the developing device. As a result, the effect of the external additive is weakened, and the effect of reducing adhesion may be reduced.
In order to improve such problems, the present invention focuses on the adhesion of the toner particles themselves.
The adhesion of toner particles is influenced by, for example, the shape and surface components, but in the present invention, a release agent (wax) present in the vicinity of the toner particle surface was examined.
Specifically, when toner particles are produced in an aqueous medium such as an emulsion aggregation method, the amount of metal ions (for example, sodium ions) to be added is reduced when a resin having an acid group is used. I examined that. In this case, the surface analysis revealed that the amount of wax present near the toner particle surface decreased. As a result, toner particles with reduced adhesion could be obtained.
However, as a result of reducing the amount of metal ions, a new problem has occurred that the chargeability of the toner is reduced. Although the reason is not clear, it is considered that the amount of charged sites is reduced as a result of the reduction of the ionic component remaining in the toner particles.
As described above, when toner is produced in an aqueous medium, the chargeability and adhesion of the toner are in a trade-off relationship. In other words, it has been difficult to produce a toner in which two physical properties of the toner, the chargeability and adhesion, are compatible in an aqueous medium.

In the present invention, by adding ammonium ions together with lithium ions as metal ions, both high chargeability and low adhesion are achieved, reaching a physical property region that could not be achieved with conventional metal ions such as sodium ions. It was found that the toner can be manufactured.
Since lithium ions have a small ionic radius, the interaction with a hydrophobic compound such as wax is weakened, and as a result, it is presumed that the wax does not easily migrate to the toner particle surface.
Therefore, unlike conventional metal ions, even if the amount added is increased, the wax is less likely to migrate to the toner particle surface and the adhesion of the toner particles is reduced. Further, since the amount of ions remaining in the toner particles is increased, the chargeability of the toner particles is improved.
Furthermore, it is considered that the addition of ammonium ions prevents the amount of remaining lithium ions from becoming excessive, and suppresses a decrease in chargeability.

That is, the present invention
A method for producing a toner having toner particles containing a resin having an acid group and a release agent,
A method for producing a toner comprising a step of ion-exchanging the cation of the acid group with lithium ion and ammonium ion in an aqueous medium.

  According to the present invention, it is possible to provide a toner manufacturing method capable of achieving both high chargeability and low adhesion.

  In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.

The resin having an acid group constitutes a binder resin for toner particles. The binder resin for the toner particles can contain a conventionally known resin for toner in addition to the resin having an acid group to the extent that the effects of the present invention are not impaired.
The acid group means a hydrogen atom that can be ionized as a hydrogen ion (that is, a cation) or a remaining atom or atomic group obtained by removing one or more metal atoms that can be ionized as a cation.
The resin having an acid group is a resin having an acid group such as a carboxy group, a sulfonic acid group, or a sulfate group at the end of the main chain of a molecular chain or the end of a side chain.
The acid group-containing resin can be selected from known resins used as toner binder resins.

Specific examples of the resin having an acid group include vinyl polymers such as styrene-acrylic copolymers; non-vinyl polymers such as polyester resins, epoxy resins, polycarbonate resins, and polyurethane resins; Examples thereof include graft polymers of non-vinyl polymers and other polymers.
Among these, from the viewpoint of chargeability and compatibility with other toner materials such as a colorant, the resin having an acid group contains a polyester resin having an acid value or a modified polyester resin having an acid value. Is preferred.
The resin having an acid value preferably contains a crystalline resin having an acid value from the viewpoint of fixability.
Resins having an acid group may be used alone or in combination of two or more.
When the resin having an acid group includes a polyester resin having an acid group, the polyester resin may be either a crystalline resin or an amorphous resin.
In the present invention, the crystalline resin is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).

When the resin having an acid group is an amorphous resin, the glass transition temperature of the resin having an acid group is preferably 30 ° C. or higher and 80 ° C. or lower. When the glass transition temperature is in the above range, the chargeability and fixability are further improved.
The glass transition temperature (Tg) can be measured using a differential scanning calorimeter (DSC).
Specifically, 0.01 g to 0.02 g of a sample is precisely weighed in an aluminum pan, and the temperature is increased from 0 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min.
Subsequently, the temperature is decreased from 200 ° C. to −100 ° C. at a temperature decrease rate of 10 ° C./min, and then again increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min to obtain a DSC curve.
In the obtained DSC curve, the temperature at the intersection of the straight line obtained by extending the base line on the low temperature side to the high temperature side and the tangent line drawn at the point where the gradient of the step-like change portion of the glass transition is maximized is glass. Let it be a transition temperature (Tg; unit ° C.).

When the resin having an acid group is an amorphous resin, the softening point (Tm) of the resin having an acid group is preferably 70 ° C. or higher and 150 ° C. or lower, and 80 ° C. or higher and 140 ° C. or lower. More preferably, it is 80 degreeC or more and 130 degrees C or less.
If the softening point (Tm) is in the above range, both blocking resistance and offset resistance can be achieved well. Further, in the fixing at a high temperature, the toner melting component permeates into the paper appropriately, and good surface smoothness can be obtained.
The softening point (Tm) of the amorphous resin can be measured using a constant-load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation).
The CFT-500D melts while heating the measurement sample filled in the cylinder while applying a constant load by the piston from the top, and pushes it out from the narrow tube hole at the bottom of the cylinder. This is a device capable of graphing a flow curve from (° C.).
In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point (Tm).
The melting temperature in the 1/2 method is calculated as follows.
First, ½ of the difference between the piston descent amount (outflow end point, Smax) when the outflow is completed and the piston descent amount (lowest point, Smin) when the outflow starts is obtained. (This is X. X = (Smax−Smin) / 2). Then, the temperature of the flow curve when the piston lowering amount is the sum of X and Smin is defined as “melting temperature in the 1/2 method”.
As a measurement sample, 1.2 g of an amorphous resin was used at a pressure of 10 MPa using a tablet molding compressor (for example, a standard manual Newton press NT-100H, manufactured by NPA Corporation) in an environment of 25 ° C., 60 A cylinder having a diameter of 8 mm and compression-molded for 2 seconds is used.
The specific operation in the measurement is performed according to the manual attached to the device.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 40 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 5.0 kgf
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

When the resin having an acid group is a crystalline resin, the melting point of the resin having an acid group is preferably 30 ° C. or higher and 100 ° C. or lower. When the melting point is in the above range, the chargeability and fixability can be further improved.
Note that the melting point of the crystalline resin can be measured using a differential scanning calorimeter (DSC).
Specifically, 0.01 g to 0.02 g of sample is precisely weighed in an aluminum pan, and the temperature is raised from 0 ° C. to 200 ° C. at a rate of temperature rise of 10 ° C./min to obtain a DSC curve. In the obtained DSC curve, the peak temperature of the melting endothermic peak is defined as the melting point (° C.).

The acid value of the resin having an acid group is preferably 5.0 mgKOH / g or more and 40.0 mgKOH / g or less, and more preferably 10.0 mgKOH / g or more and 20.0 mgKOH / g or less.
When the acid value of the resin having an acid group is in the above range, the granulation property and charging property of the toner particles can be further improved.
The acid value is defined as the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of the sample, and can be measured as follows according to JIS-K0070.
(1) Reagent <Solvent>
The tetrahydrofuran-ethyl alcohol mixture (2: 1) is neutralized with a 0.1 mol / L potassium hydroxide ethyl alcohol solution using phenolphthalein as an indicator immediately before use.
<Phenolphthalein solution>
1 g of phenolphthalein is dissolved in 100 mL of ethyl alcohol (95% by volume).
<0.1 mol / L potassium hydroxide ethyl alcohol solution>
Dissolve 7.0 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95% by volume) to 1 liter, leave it for 2 to 3 days, and filter. The standardization is performed according to JIS K 8006 (basic matters concerning titration during the reagent content test).
(2) Operation Correctly weigh 1 to 20 g of resin as a sample, add 100 mL of the solvent and a few drops of the phenolphthalein solution (indicator) to this, and shake well until the sample is completely dissolved to obtain a sample solution.
The sample solution is titrated with the above 0.1 mol / L potassium hydroxide ethyl alcohol solution, and the end point of neutralization is when the indicator is slightly red for 30 seconds.
(3) Calculation The acid value is calculated by the following formula.
A = B × f × 5.661 / S
A: Acid value (mgKOH / g)
B: Amount of use of 0.1 mol / L potassium hydroxide ethyl alcohol solution (mL)
f: Factor of 0.1 mol / L potassium hydroxide ethyl alcohol solution S: Mass of sample (g)
In addition, when resin which has an acid group consists of 2 or more types of resin, the acid value of the resin which has an acid group uses the following average acid value.
The average acid value is calculated from the acid value (A1, A2,..., An) and the mass ratio (W1, W2,..., Wn: where W1 + W2 +... + Wn = 1) of each resin as follows. .
Average acid value of resin having acid group (mgKOH / g) = A1 × W1 + A2 × W2 +... + An × Wn

Examples of the release agent (wax) include the following.
Low molecular weight polyolefins such as polyethylene; silicones having a melting point upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; ester waxes such as stearyl stearate; carnauba wax, rice Plant waxes such as wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; minerals and petroleum such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, ester wax Waxes; and their modified products.
The content of the releasing agent is preferably 2.0 parts by mass or more and 20.0 parts by mass or less, and 5.0 parts by mass or more and 15.0 parts by mass with respect to 100 parts by mass of the resin having an acid group. The following is more preferable.
When the content of the release agent is in the above range, fixability and adhesion can be further improved.
The melting point of the release agent is preferably 40.0 ° C. or higher and 150.0 ° C. or lower, more preferably 40.0 ° C. or higher and 130.0 ° C. or lower, more preferably 40.0 ° C. or higher and 110.0 ° C. More preferably, it is as follows.

Examples of the lithium ion supply source include lithium compounds.
The lithium compound is added to exchange ions of acid group-derived cations (hydrogen ions and other metal ions) contained in the acid group-containing resin with lithium ions derived from the lithium compound in an aqueous medium. May be.
The lithium compound can be selected from known compounds as long as it contains a lithium atom and is water-soluble. Among these, a basic lithium compound is preferable from the viewpoint of ion exchange properties.
Specifically, inorganic salts such as lithium hydroxide and lithium carbonate; organic acid salts such as lithium formate, lithium acetate, lithium succinate, lithium citrate and lithium salt of ethylenediaminetetraacetic acid; lithium polyacrylate Such a polymer electrolyte is mentioned.
The lithium compound may be used alone or in combination of two or more.
The total amount of lithium ions supplied by the lithium compound is preferably 0.50 mmol / g or more and 3.00 mmol / g or less, and 0.70 mmol / g or more and 2.80 mmol / g with respect to the resin having an acid group. More preferably, it is g or less.
When the total amount of the lithium ions is within the above range, the amount of lithium ions is appropriate and the chargeability is further improved. Further, the exposure of the wax can be further suppressed, and the effect of reducing the adhesion of the toner is further increased.

The supply source of ammonium ions can be exemplified by ammonia or an ammonium compound.
The ammonia or ammonium compound ion-exchanges an acid group-derived cation (hydrogen ion or other metal ion) contained in the acid group-containing resin with an ammonium ion derived from the ammonia or ammonium compound in an aqueous medium. You may add in order to make it.
The ammonium compound can be selected from known compounds that contain ammonium ions and are water-soluble.
Specific examples include inorganic salts such as ammonium hydroxide (ammonia water) and ammonium carbonate; organic acid salts such as ammonium formate, ammonium acetate, ammonium succinate, and ammonium citrate.
The ammonia or ammonium compound may be used alone or in combination of two or more.
The total amount of ammonia or ammonium compound that can supply the ammonium ions is preferably 1.0 equivalent or more and 15.0 equivalents or less, and 2.0 equivalents or more and 13.35 equivalents or less with respect to the acid value of the resin having an acid group. More preferably, it is 0 equivalent or less.
When the total amount of ammonia or ammonium compound that can supply the ammonium ions is in the above range, the dispersion stability of the emulsified particles is further improved, and the granulation property of the toner particles is improved. Moreover, since the ion exchange by the said lithium ion is not inhibited, charging property improves more.
Here, the applicable amount means the molar ratio of the amount of ammonium ions to be supplied to the acid group amount of the resin having an acid group, and the calculation method is included in the total amount of ammonia or ammonium compound supplied during production. In this method, the total number of moles of ammonium ions is divided by the total number of moles of acid groups contained in the total amount of resin having acid groups supplied during production.

The total number of moles of ammonium ions supplied by ammonia or an ammonium compound is N,
When the total number of moles of lithium ions supplied by the lithium compound is L,
The N and L preferably satisfy the following formula (1), and more preferably satisfy the following formula (1) ′.
0.5 ≦ N / L ≦ 5.0 (1)
1.0 ≦ N / L ≦ 3.0 (1) ′
When the N / L is in the above range, the amount of ion exchange by lithium ions becomes an appropriate amount, the chargeability is further improved, and the effect of reducing adhesion is further improved.

Hereinafter, the toner production method of the present invention will be described in detail, but the present invention is not limited thereto.
The method for producing the toner of the present invention includes:
A method for producing a toner having toner particles containing a resin having an acid group and a release agent,
It includes a step of ion-exchange of the cation derived from the acid group with lithium ion and ammonium ion in an aqueous medium.

Except for the step of ion exchange in an aqueous medium, a known toner production method can be used.
Specifically, an emulsion aggregation method, a suspension polymerization method, a dissolution suspension method, or the like can be used.
As described above, the ion exchange refers to exchanging a cation component (hydrogen ion or other metal ion) derived from an acid group contained in a resin having an acid group with another cation in an aqueous medium. Means. In the present invention, the lithium ion and the ammonium ion are exchanged.
In the emulsion aggregation method, a dispersion of resin fine particles and a dispersion of release agent fine particles that are sufficiently small with respect to the target particle diameter are prepared, and the resin fine particles and the release agent fine particles are aggregated in an aqueous medium. And a toner manufacturing method including the step of:
In the emulsion aggregation method, a step of preparing resin fine particles and release agent fine particles, a step of aggregating the resin fine particles and release agent fine particles, a step of stopping the aggregation and preparing an aggregate, and fusing the aggregates Thus, the toner is manufactured through a step of preparing the fusion body and a step of cooling the fusion body.
Further, if necessary, a toner having a core-shell structure can be obtained by adding a step for forming a shell layer.

Hereinafter, the toner production method using the emulsion aggregation method will be specifically described, but the present invention is not limited thereto.
For example, the toner manufacturing method is:
A method for producing the toner includes:
(A) Dispersing the resin having an acid group in an aqueous medium to prepare a dispersion of resin fine particles,
(B) Dispersing the release agent in an aqueous medium to prepare a dispersion of release agent fine particles;
(C) mixing the resin fine particle dispersion and the release agent fine particle dispersion, and aggregating the resin fine particles and the release agent fine particles using an aggregating agent;
(D) a step of stopping aggregation using an aggregation stopper and preparing an aggregate;
(E) heating and fusing the aggregate to prepare a fusion;
(F) It is good to include the process of cooling this fusion body.

(A) A step of preparing a dispersion of resin fine particles A step of preparing a dispersion of resin fine particles by dispersing a resin having an acid group in an aqueous medium.
The dispersion can be prepared by the following known methods (phase inversion emulsification method, forced emulsification method, emulsion polymerization method, self-emulsification method, etc.), but is not limited to these methods.
In the case of the phase inversion emulsification method, first, a resin, if necessary, a surfactant is dissolved in an amphiphilic organic solvent alone or in a mixed solvent. A basic substance is dropped while stirring the obtained resin solution using a known stirrer, emulsifier, disperser, and the like, and then an aqueous medium is dropped while further stirring.
At a certain point in time, the oil phase and the aqueous phase are reversed, and the oil phase becomes oil droplets. Thereafter, a water-based dispersion in which the resin is dispersed is obtained through a solvent removal step under reduced pressure.
The amphiphilic organic solvent preferably has a solubility in water at 20 ° C. of 5 g / L or more, more preferably 10 g / L or more.
The basic substance is a compound that neutralizes an acid group in a resin having an acid group and improves dispersibility. The basic substance preferably contains the lithium compound and / or the ammonium compound.
A known surfactant can be used as the surfactant.
For example, anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; addition of polyethylene glycol and alkylphenol ethylene oxide Nonionic surfactants such as physical and polyhydric alcohols can be mentioned. Among these, an anionic surfactant is preferable.

(B) Step of preparing a dispersion of release agent fine particles In this step, a release agent fine particle dispersion is prepared by dispersing a release agent in an aqueous medium.
The release agent may be dispersed by a known method. For example, a media type dispersing machine such as a rotary shearing homogenizer, a ball mill, a sand mill, or an attritor, or a high pressure opposed collision type dispersing machine may be used. Further, a surfactant or a polymer dispersant that imparts dispersion stability can be added as necessary.

(C) Aggregation step In this step, the resin fine particle dispersion and the release agent fine particle dispersion are mixed, and the resin fine particles and the release agent fine particles are aggregated using an aggregating agent.
Examples of the method of aggregating the fine particles include a method of adding and mixing the aggregating agent and appropriately adding temperature, mechanical power and the like. At that time, if necessary, other toner components such as a dispersion of colorant fine particles may be mixed.
Examples of the flocculant include metal salts of monovalent metals such as sodium and potassium; metal salts of divalent metals such as calcium and magnesium; metal salts of trivalent metals such as iron and aluminum.
The addition and mixing of the flocculant is preferably performed at a temperature not higher than the glass transition temperature (Tg) of the resin fine particles. When addition and mixing are performed under this temperature condition, aggregation proceeds in a stable state.
The mixing can be performed using a known mixing apparatus, homogenizer, mixer, or the like.
The volume average particle size of the aggregate formed in the aggregation step is not particularly limited, but is usually controlled to be about the same as the volume average particle size of the toner particles to be obtained (about 4.0 to 7.0 μm). Good.
This control can be easily performed, for example, by appropriately setting / changing the temperature at the time of addition / mixing of the flocculant and the like and the conditions of stirring and mixing. The volume average particle size may be measured using a particle size distribution analyzer by Coulter method (Coulter Multisizer III: manufactured by Coulter).
A shell adhering step of adhering resin fine particles to the surface of the aggregate particles by adding resin fine particles for forming a shell phase to the aggregate dispersion obtained in the aggregation step;
In addition, toner particles having a core-shell structure can be produced by aggregating the aggregate particles having resin fine particles attached to the surface through a fusion process described later.
The resin fine particles for forming the shell phase added here may be resin fine particles having the same structure as the resin contained in the aggregate particles, or may be resin fine particles having a different structure.

(D) Step of stopping aggregation using an aggregation terminator and preparing an aggregate This is a step of adding an aggregation terminator for stopping aggregation and suppressing a change in particle size in the fusion step described later. As the aggregation terminator, a chelating agent that chelates the aggregating agent added in the aggregation step, a pH adjuster, a surfactant, and the like can be used.
In the present invention, the aggregation terminator preferably contains the lithium compound and / or the ammonium compound.
The addition amount of the aggregation terminator is preferably adjusted to a range in which aggregation is stopped and the aggregate is not deagglomerated. Further, the addition amount may be appropriately adjusted depending on the type of the aggregation terminator.

(E) Fusion process After aggregation is stopped, the obtained aggregate is heated and fused to prepare a fusion.
The heating temperature may be between the glass transition temperature (Tg) of the resin contained in the aggregate and the temperature at which the resin is thermally decomposed.
In addition, as the heat fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low. That is, the time for heat fusion depends on the temperature of heating and cannot be defined unconditionally, but is generally about 10 minutes to 10 hours.

(F) Cooling process In the cooling process, the obtained fusion body is cooled. Specifically, the temperature of the dispersion containing the fusion may be cooled to a temperature lower than the glass transition temperature (Tg) of the resin contained in the aggregate.
By performing the cooling to a temperature lower than the glass transition temperature (Tg) of the resin contained in the aggregate, the generation of coarse particles can be suppressed. The cooling rate is preferably about 0.1 to 50 ° C./min.

(G) Washing / Drying Steps The resin particles produced through the above steps may be washed, filtered, dried, etc. to obtain emulsion aggregation toner particles.
Further, if necessary, the following inorganic fine particles, resin fine particles and the like may be added to the emulsion aggregation toner particles by applying a shearing force in a dry state.
Examples of the inorganic fine particles include silica fine particles, alumina fine particles, titania fine particles, and calcium carbonate fine particles.
Examples of the resin fine particles include fine particles such as vinyl resin, polyester resin, and silicone resin.
These inorganic fine particles and resin fine particles function as external additives such as fluidity aids and cleaning aids.

In at least one of the steps (A) and (C) to (F),
Adding a lithium compound capable of supplying the lithium ion, and ammonia or an ammonium compound capable of supplying the ammonium ion;
The cation derived from the acid group may be ion exchanged with the lithium ion and the ammonium ion.
For example, in the at least one step, the lithium compound or the ammonium compound may be added alone, or both may be added.

  Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, the aspect of this invention is not limited to these. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.

<Example of production of dispersion of resin fine particles 1>
-Tetrahydrofuran (manufactured by Wako Pure Chemical Industries) 200 parts-Polyester resin A 120 parts [composition (mole parts) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: isophthalic acid: terephthalic acid = 100: 50: 50], number average molecular weight (Mn) = 4,600, weight average molecular weight (Mw) = 16,500, peak molecular weight (Mp) = 10,400, Mw / Mn = 3.6, softening point (Tm) = 122 ° C., glass transition temperature (Tg) = 70 ° C., acid value = 11.0 mgKOH / g]
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 0.6 part After mixing the said material, it stirred for 12 hours and dissolved the polyester resin A in tetrahydrofuran.
Subsequently, 21.4 parts of 1 mol / L aqueous ammonia was added, and an ultra-high speed stirring device T.I. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primemics).
Furthermore, 360 parts of ion exchange water was added at a rate of 1 part / min to precipitate resin fine particles. Thereafter, tetrahydrofuran was removed using an evaporator to obtain a dispersion of resin fine particles 1.
The 50% particle size (d50) based on the volume distribution of the resin fine particles 1 in the dispersion was measured using a dynamic light scattering particle size distribution meter (Nanotrack: Nikkiso Co., Ltd.) and found to be 0.13 μm. .

<Example of production of dispersion of resin fine particles 2>
Resin fine particles 2 and dispersions thereof were obtained in the same manner as in the production example of resin fine particles 1 except that 21.4 parts of 1 mol / L aqueous ammonia was changed to 21.4 parts of 1 mol / L lithium hydroxide aqueous solution. . The resin fine particle 2 obtained had a 50% particle size (d50) based on volume distribution of 0.12 μm.

<Example of production of dispersion of resin fine particles 3>
Resin fine particles 3 and a dispersion thereof were obtained in the same manner as in the production example of resin fine particles 1 except that 21.4 parts of 1 mol / L aqueous ammonia were changed to 21.4 parts of 1 mol / L aqueous sodium hydroxide solution. . The obtained resin fine particles 3 had a 50% particle size (d50) based on volume distribution of 0.12 μm.

<Example of production of dispersion of resin fine particles 4>
-Tetrahydrofuran (manufactured by Wako Pure Chemical Industries) 200 parts-Polyester resin B 120 parts [composition (mole parts) [1,9-nonanediol: sebacic acid = 100: 100], number average molecular weight (Mn) = 5,500, weight Average molecular weight (Mw) = 15,500, peak molecular weight (Mp) = 11,400, Mw / Mn = 2.8, melting point = 78 ° C, acid value = 11.0 mgKOH / g]
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 0.6 part After mixing the said material, it heated at 50 degreeC and stirred for 3 hours, and dissolved the polyester resin B in tetrahydrofuran.
Subsequently, 21.4 parts of a 1 mol / L lithium hydroxide aqueous solution was added, and an ultra-high speed stirring device T.I. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primemics).
Furthermore, 360 parts of ion exchange water was added at a rate of 1 part / min to precipitate resin fine particles. Thereafter, tetrahydrofuran was removed using an evaporator to obtain resin fine particles 4 and a dispersion thereof.
The 50% particle size (d50) based on the volume distribution of the resin fine particles 4 (crystalline resin) was measured using a dynamic light scattering particle size distribution meter (Nanotrack: Nikkiso Co., Ltd.) and found to be 0.30 μm. It was.

<Example of production of dispersion of resin fine particles 5>
The resin fine particles 5 and the dispersion thereof were prepared in the same manner as in the production example of the resin fine particles 4 except that 21.4 parts of the 1 mol / L lithium hydroxide aqueous solution was changed to 21.4 parts of the 1 mol / L sodium hydroxide aqueous solution. Obtained. The obtained resin fine particles 5 had a 50% particle size (d50) based on volume distribution of 0.29 μm.

<Example of production of dispersion of resin fine particles 6>
・ Tetrahydrofuran (manufactured by Wako Pure Chemical Industries) 200 parts ・ Polyester resin A 96 parts ・ Polyester resin B 24 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 0.6 parts The mixture was heated and stirred for 3 hours to dissolve polyester resins A and B in tetrahydrofuran.
Subsequently, 21.4 parts of 1 mol / L aqueous ammonia was added, and an ultra-high speed stirring device T.I. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primemics).
Furthermore, 360 parts of ion exchange water was added at a rate of 1 part / min to precipitate resin fine particles. Thereafter, tetrahydrofuran was removed using an evaporator to obtain resin fine particles 5 and a dispersion thereof.
The 50% particle size (d50) based on the volume distribution of the resin fine particles 6 was measured using a dynamic light scattering particle size distribution meter (Nanotrack: Nikkiso Co., Ltd.) and found to be 0.35 μm.

<Example of production of dispersion of release agent fine particles>
・ Mold release agent (HNP-51, melting point 78 ° C., Nippon Seiwa) 20 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 1 part ・ Ion-exchanged water 79 parts After being charged into the mixing vessel, heated to 90 ° C. and circulating to Claremix W Motion (M Technique), the rotor rotation speed was 19000 rpm at a shearing stirring site with a rotor outer diameter of 3 cm and clearance of 0.3 mm. The mixture was stirred under the condition of a screen rotation speed of 19000 rpm and dispersed for 60 minutes.
Thereafter, a dispersion of release agent fine particles was obtained by cooling to 40 ° C. under cooling treatment conditions of a rotor rotation speed of 1000 rpm, a screen rotation speed of 0 rpm, and a cooling rate of 10 ° C./min.
The 50% particle size (d50) based on the volume distribution of the release agent fine particles in the dispersion was measured using a dynamic light scattering particle size distribution meter (Nanotrack: manufactured by Nikkiso), and was 0.15 μm.

<Production Example of Dispersion of Colorant Fine Particles>
Colorant 10.0 parts (Cyan pigment, manufactured by Dainichi Seika: Pigment Blue 15: 3)
・ Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 1.5 parts ・ Ion-exchanged water 88.5 parts Mix and dissolve the above, and use high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) A dispersion of colorant fine particles was prepared by dispersing the colorant for about 1 hour.
The volume distribution standard 50% particle size (d50) of the obtained colorant fine particles was measured using a dynamic light scattering particle size distribution meter (Nanotrack: Nikkiso Co., Ltd.) and found to be 0.20 μm.

<Example 1>
(Production example of toner 1)
-Resin fine particle 1 dispersion 320 parts-Resin fine particle 4 dispersion 80 parts-Colorant fine particle dispersion 50 parts-Release agent fine particle dispersion 50 parts-Ion exchange water 400 parts After putting into a stainless steel flask and mixing, an aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 98 parts of ion-exchanged water, and the mixture was added at 5000 rpm using a homogenizer (IKA: Ultra Turrax T50). Dispersed for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 58 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 5.8 μm were obtained.
9 parts of trilithium citrate was dissolved in an aqueous solution in which 20 parts of triammonium citrate was dissolved in 190 parts of ion-exchanged water and 166 parts of ion-exchanged water in the dispersion containing the aggregated particles. After adding 100 parts of aqueous solution and 1 mol / L ammonia water, it heated to 85 degreeC.
Holding at 85 ° C. for 2 hours, toner particles having a volume average particle diameter of about 5.8 μm and an average circularity of 0.965 were obtained.
The volume average particle diameter of the toner particles was measured using a Coulter Multisizer III (manufactured by Coulter) according to the operation manual of the apparatus. Further, the average circularity was calculated by performing measurement according to an operation manual of the apparatus using a flow type particle image measuring apparatus “FPIA-3000” (manufactured by Sysmex Corporation).
The obtained aqueous dispersion of toner particles is cooled to 25 ° C. while maintaining stirring, filtered and solid-liquid separated, and then the filtrate is sufficiently washed with ion-exchanged water and dried to obtain a volume average particle size. A toner 1 having a diameter of 5.7 μm was obtained.

<Example 2>
(Production example of toner 2)
-Resin fine particle 1 dispersion 320 parts-Resin fine particle 4 dispersion 80 parts-Colorant fine particle dispersion 50 parts-Release agent fine particle dispersion 50 parts-Ion exchange water 400 parts After putting into a stainless steel flask and mixing, an aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 98 parts of ion-exchanged water, and the mixture was added at 5000 rpm using a homogenizer (IKA: Ultra Turrax T50). Dispersed for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 58 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 5.9 μm were obtained.
An aqueous solution in which 18 parts of trilithium citrate was dissolved in 332 parts of ion exchange water and 30 parts of 1 mol / L aqueous ammonia were added to the dispersion containing the aggregated particles, and then heated to 85 ° C. Thereafter, in the same manner as in Example 1, a toner 2 having a volume average particle diameter of 5.8 μm was obtained.

<Example 3>
(Production example of toner 3)
-Resin fine particle 1 dispersion 320 parts-Resin fine particle 4 dispersion 80 parts-Colorant fine particle dispersion 50 parts-Release agent fine particle dispersion 50 parts-Ion exchange water 400 parts After putting into a stainless steel flask and mixing, an aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 98 parts of ion-exchanged water, and the mixture was added at 5000 rpm using a homogenizer (IKA: Ultra Turrax T50). Dispersed for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 58 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 5.8 μm were obtained.
An aqueous solution in which 5 parts of trilithium citrate was dissolved in 180 parts of ion-exchanged water and 180 parts of 1 mol / L aqueous ammonia were added to the dispersion containing the aggregated particles, and then heated to 85 ° C. Thereafter, in the same manner as in Example 1, a toner 3 having a volume average particle diameter of 5.7 μm was obtained.

<Example 4>
(Production example of toner 4)
-Resin fine particle 2 dispersion 320 parts-Resin fine particle 4 dispersion 80 parts-Colorant fine particle dispersion 50 parts-Release agent fine particle dispersion 50 parts-Ion-exchanged water 400 parts After putting into a stainless steel flask and mixing, an aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 98 parts of ion-exchanged water, and the mixture was added at 5000 rpm using a homogenizer (IKA: Ultra Turrax T50). Dispersed for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 58 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 5.8 μm were obtained.
8 parts of trilithium citrate was dissolved in an aqueous solution in which 12 parts of triammonium citrate was dissolved in 218 parts of ion-exchanged water and 142 parts of ion-exchanged water in the dispersion containing the aggregated particles. After adding 100 parts of aqueous solution and 1 mol / L ammonia water, it heated to 85 degreeC. Thereafter, in the same manner as in Example 1, a toner 4 having a volume average particle diameter of 5.7 μm was obtained.

<Example 5>
(Production example of toner 5)
-Resin fine particle 1 dispersion 320 parts-Resin fine particle 4 dispersion 80 parts-Colorant fine particle dispersion 50 parts-Release agent fine particle dispersion 50 parts-Ion exchange water 400 parts After putting into a stainless steel flask and mixing, an aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 98 parts of ion-exchanged water, and the mixture was added at 5000 rpm using a homogenizer (IKA: Ultra Turrax T50). Dispersed for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 58 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 5.7 μm were obtained.
An aqueous solution in which 13 parts of triammonium citrate was dissolved in 237 parts of ion-exchanged water and 100 parts of 1 mol / L ammonia water were added to the dispersion containing the aggregated particles, and then heated to 85 ° C. Thereafter, in the same manner as in Example 1, a toner 5 having a volume average particle size of 5.6 μm was obtained.

<Example 6>
(Production example of toner 6)
-Resin fine particle 1 dispersion 320 parts-Resin fine particle 4 dispersion 80 parts-Colorant fine particle dispersion 50 parts-Release agent fine particle dispersion 50 parts-Ion exchange water 400 parts After putting into a stainless steel flask and mixing, an aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 98 parts of ion-exchanged water, and the mixture was added at 5000 rpm using a homogenizer (IKA: Ultra Turrax T50). Dispersed for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 58 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 5.8 μm were obtained.
An aqueous solution in which 5 parts of trilithium citrate was dissolved in 95 parts of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 85 ° C.
Holding at 85 ° C. for 2 hours, toner particles having a volume average particle diameter of about 7.0 μm and an average circularity of 0.965 were obtained. Thereafter, a toner 6 having a volume average particle diameter of 6.9 μm was obtained in the same manner as in Example 1.

<Example 7>
(Production example of toner 7)
-Resin fine particle 1 dispersion 320 parts-Resin fine particle 4 dispersion 80 parts-Colorant fine particle dispersion 50 parts-Release agent fine particle dispersion 15 parts-Ion exchange water 400 parts After putting into a stainless steel flask and mixing, an aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 98 parts of ion-exchanged water, and the mixture was added at 5000 rpm using a homogenizer (IKA: Ultra Turrax T50). Dispersed for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 58 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 5.8 μm were obtained.
9 parts of trilithium citrate was dissolved in an aqueous solution in which 20 parts of triammonium citrate was dissolved in 190 parts of ion-exchanged water and 166 parts of ion-exchanged water in the dispersion containing the aggregated particles. After adding 100 parts of aqueous solution and 1 mol / L ammonia water, it heated to 85 degreeC. Thereafter, in the same manner as in Example 1, a toner 7 having a volume average particle diameter of 5.7 μm was obtained.

<Comparative Example 1>
(Production example of comparative toner 1)
-Resin fine particle 6 dispersion 400 parts-Colorant fine particle dispersion 50 parts-Release agent fine particle dispersion 50 parts-Ion-exchanged water 400 parts After the above materials are charged into a round stainless steel flask and mixed Then, an aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 98 parts of ion-exchanged water, and dispersed at 5000 rpm for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50).
Thereafter, the mixture was heated to 45 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 45 ° C. for 1 hour, aggregated particles having a volume average particle size of about 5.5 μm were obtained.
An aqueous solution in which 13 parts of triammonium citrate was dissolved in 237 parts of ion-exchanged water and 100 parts of 1 mol / L ammonia water were added to the dispersion containing the aggregated particles, and then heated to 85 ° C. Thereafter, in the same manner as in Example 1, Comparative Toner 1 having a volume average particle size of 5.4 μm was obtained.

<Comparative example 2>
(Production example of comparative toner 2)
-Resin fine particle 2 dispersion 320 parts-Resin fine particle 4 dispersion 80 parts-Colorant fine particle dispersion 50 parts-Release agent fine particle dispersion 50 parts-Ion-exchanged water 400 parts After putting into a stainless steel flask and mixing, an aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 98 parts of ion-exchanged water, and the mixture was added at 5000 rpm using a homogenizer (IKA: Ultra Turrax T50). Dispersed for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 58 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 5.5 μm were obtained.
An aqueous solution in which 18 parts of trilithium citrate is dissolved in 342 parts of ion exchange water and 30 parts of a 1 mol / L lithium hydroxide aqueous solution are added to the dispersion containing the aggregated particles, and then heated to 85 ° C. did. Thereafter, in the same manner as in Example 1, Comparative Toner 2 having a volume average particle size of 5.4 μm was obtained.

<Comparative Example 3>
(Production example of comparative toner 3)
-Resin fine particle 1 dispersion 320 parts-Resin fine particle 5 dispersion 80 parts-Colorant fine particle dispersion 50 parts-Release agent fine particle dispersion 50 parts-Ion-exchanged water 400 parts After putting into a stainless steel flask and mixing, an aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 98 parts of ion-exchanged water, and the mixture was added at 5000 rpm using a homogenizer (IKA: Ultra Turrax T50). Dispersed for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 58 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 5.5 μm were obtained.
In the dispersion liquid containing the aggregated particles, an aqueous solution in which 20 parts of triammonium citrate was dissolved in 190 parts of ion-exchanged water and 9 parts of trisodium citrate in 166 parts of ion-exchanged water were dissolved. After adding 100 parts of aqueous solution and 1 mol / L ammonia water, it heated to 85 degreeC. Thereafter, a comparative toner 3 having a volume average particle size of 5.5 μm was obtained in the same manner as in Example 1.

<Evaluation of toner>
(Preparation of external toner)
In 100 parts of toner, the number average particle diameter of primary particles is 100 nm, 2.5 parts of silica fine particles hydrophobized with silicone oil, and the number average particle diameter of primary particles is 20 nm. 0.5 parts of the treated silica fine particles were dry-mixed with a Henschel mixer (manufactured by Mitsui Mining) to prepare an externally added toner to which an external additive was added.

(Evaluation of chargeability)
1 part of the externally added toner and 9 parts of a ferrite carrier (volume average particle size 42 μm) surface-coated with a silicone resin are weighed into a plastic bottle and allowed to stand still for 24 hours in an environment of temperature 30 ° C. and humidity 80% RH. I put it.
Then, using a shaker (YS-LD, manufactured by Yayoi Co., Ltd.), the mixture was shaken for 30 minutes at a speed of 150 reciprocations per minute in an environment of temperature 30 ° C. and humidity 80% RH. A two-component developer composed of a carrier was prepared, and the externally added toner was charged.
The charge amount of the external toner was measured with an Espart analyzer manufactured by Hosokawa Micron Corporation. The Espart analyzer is a device that measures the particle size and the charge amount by introducing sample particles into a detection unit (measurement unit) in which an electric field and an acoustic field are simultaneously formed, and measuring the moving speed of the particles by a laser Doppler method. .
The sample particles entering the measuring unit of the apparatus are affected by the acoustic field and the electric field, fall while being biased in the horizontal direction, and the beat frequency of the horizontal speed is counted. The count value is input by interruption to the computer, and the particle size distribution or the charge amount distribution per unit particle size is shown on the computer screen in real time.
The screen stops when a predetermined number of charge amounts are measured, and then the three-dimensional distribution of charge amount and particle diameter, charge amount distribution by particle size, average charge amount (coulomb / weight), etc. are displayed on the screen. Is displayed.
By introducing the two-component developer as sample particles into the measurement part of the Espart analyzer, the triboelectric charge amount of the toner was measured and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: The charge amount of the externally added toner is −35 μC / g or less B: The charge amount of the externally added toner is greater than −35 μC / g, and −25 μC / g or less C: The charge amount of the externally added toner is greater than −25 μC / g

(Evaluation of adhesion)
Adhesion was evaluated according to the operation manual using a centrifuge adhesion force measuring device (centrifuge CS150NX (manufactured by Hitachi Koki Co., Ltd.), analyzer NS-C300-HK (manufactured by Nano Seeds)).
The rotor was an S110AT rotor for ultracentrifugation, and the substrate was a stainless steel plate.
After the toner was applied on the substrate, the number was recorded with an analyzer.
Next, the substrate was set on a rotor, centrifugal force (300000 G) was applied, and the number of toners remaining on the substrate was recorded. The residual rate was calculated from the number before and after centrifugation and evaluated according to the following evaluation criteria. The lower the residual rate, the lower the toner adhesion.
(Evaluation criteria)
A: Residual rate is 30% or less B: Residual rate is greater than 30%, 40% or less C: Residual rate is greater than 40%

(Evaluation of fixability)
The external additive toner and a ferrite carrier (volume average particle size 42 μm) surface-coated with a silicone resin were mixed so that the toner concentration was 8% by mass to prepare a two-component developer. The two-component developer was filled in a commercially available full-color digital copying machine (CLC1100, manufactured by Canon Inc.) to form an unfixed toner image (0.6 mg / cm ² ) on the image receiving paper (64 g / m ² ).
On the other hand, a fixing unit removed from a commercially available full-color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon) was modified so that the fixing temperature could be adjusted, and a fixing test of an unfixed toner image was performed using the fixing unit.
Under normal temperature and humidity, the process speed was set to 246 mm / second, and the appearance when the unfixed toner image was fixed was visually evaluated. Fixing was performed nine times while changing the set temperature of the fixing unit every 10 ° C. within the range of 120 to 200 ° C., and the state of offset in the fixed image was visually evaluated and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: Fixed image with no occurrence of offset 7 times or more B: Fixed image with no occurrence of offset 5 times or 6 times C: Fixed image with no occurrence of offset 4 times or less

(Evaluation of granulation)
The ratio (Dv / Dn) of the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner was used as the particle size distribution, and the granulation property was evaluated according to the following evaluation criteria. The number average particle size was measured in the same manner as the volume average particle size using a Coulter Multisizer III (manufactured by Coulter) according to the operation manual of the apparatus.
(Evaluation criteria)
A: Particle size distribution is 1.15 or less B: Particle size distribution is greater than 1.15, 1.20 or less C: Particle size distribution is greater than 1.20

Claims (9)

A method for producing a toner having toner particles containing a resin having an acid group and a release agent,
A method for producing a toner comprising a step of ion-exchanging a cation derived from an acid group with lithium ions and ammonium ions in an aqueous medium. A method for producing the toner includes:
(A) Dispersing the resin having an acid group in an aqueous medium to prepare a dispersion of resin fine particles,
(B) Dispersing the release agent in an aqueous medium to prepare a dispersion of release agent fine particles;
(C) mixing the resin fine particle dispersion and the release agent fine particle dispersion, and aggregating the resin fine particles and the release agent fine particles using an aggregating agent;
(D) a step of stopping aggregation using an aggregation stopper and preparing an aggregate;
(E) heating and fusing the aggregate to prepare a fusion;
(F) cooling the fusion,
In at least one of the steps (A) and (C) to (F),
Adding a lithium compound capable of supplying the lithium ion, and ammonia or an ammonium compound capable of supplying the ammonium ion;
The method for producing a toner according to claim 1, wherein the cation derived from the acid group is ion-exchanged with the lithium ion and the ammonium ion.   The method for producing a toner according to claim 1, wherein a total amount of the lithium ions is 0.50 mmol / g or more and 3.00 mmol / g or less with respect to the resin having an acid group.   The toner production according to claim 2, wherein a total amount of ammonia or an ammonium compound capable of supplying the ammonium ion is 1.0 equivalent or more and 15.0 equivalent or less with respect to an acid value of the resin having an acid group. Method. The total number of moles of ammonium ions is N,
When the total number of moles of lithium ions is L,
The method for producing a toner according to claim 1, wherein the N and the L satisfy the following formula (1).
0.5 ≦ N / L ≦ 5.0 Formula (1)   The content of the release agent is 5.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the resin having an acid group, according to any one of claims 1 to 5. Toner manufacturing method.   The method for producing a toner according to claim 1, wherein the acid value of the resin having an acid group is 5.0 mgKOH / g or more and 40.0 mgKOH / g or less.   The method for producing a toner according to claim 1, wherein the resin having an acid value contains a crystalline resin having an acid value.   The toner manufacturing method according to claim 1, wherein the resin having an acid value contains a polyester resin having an acid value or a modified polyester resin having an acid value.