JP2012047777A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner excellent in low temperature fixability as well as excellent in charging stability and environmental stability.SOLUTION: The toner comprises: at least toner particles produced in an aqueous medium; and an inorganic fine powder. The toner particles contain at least a binder resin, a colorant, a release agent, an ionic surfactant and a nonionic surfactant. The binder resin contains a crystalline polyester obtained by condensation polymerization of an aliphatic diol and an aliphatic dicarboxylic acid. The content of the crystalline polyester included in the toner is 2 to 50 parts by mass with respect to 100 parts by mass of the toner particles. The content (A) of the ionic surfactant included in the toner is 10 ppm or more and 1000 ppm or less; and the content (B) of the nonionic surfactant included in the toner is 100 ppm or more and 5000 ppm or less.

Description

  The present invention relates to a toner used in electrophotography, electrostatic recording, and magnetic recording. Specifically, the present invention relates to an electrostatic charge image developing toner (hereinafter abbreviated as toner) used in an image recording apparatus that can be used in a copying machine, a printer, a facsimile, a plotter, and the like.

In recent years, the electrophotographic technology used for copying machines, printers, facsimile receivers, and the like has greatly expanded the market with the development of the apparatus. For this reason, demands from users are becoming stricter year by year, and it is strongly demanded to provide a product with a long life, a small size and a low price while satisfying performance such as high speed and high image quality.
With the reduction in price and size, there is a strong demand for lower power consumption. In particular, in many of the electrophotographic development systems, the toner transferred onto the recording medium is fixed through a fixing process, and thus it is necessary to lower the fixing temperature.
In order to lower the fixing temperature and maintain the durability, a technique for incorporating a crystalline polyester into a binder resin of a toner is disclosed (for example, see Patent Document 1). Crystalline polyester has a sharp melt property and fluidizes in a temperature range exceeding the melting point, and is thus greatly involved in toner fixing properties. Further, sufficient strength can be obtained at a temperature not exceeding the melting point, and good durability can be found.
Furthermore, there is a production method using a specific nonionic surfactant in order to efficiently obtain a toner containing a crystalline polyester (see, for example, Patent Document 2).

JP 2008-191260 A JP 2006-171692 A

However, although the above prior art has excellent low-temperature fixability, there is room for improvement in terms of charging characteristics in order to satisfy the recent demands for higher image quality and higher speed.
For example, in Patent Document 1, there is room for improvement in terms of charging stability by using crystalline polyester as compared with toner using amorphous polyester.
For example, in Patent Document 2, it has been desired to further improve the difference in charge amount depending on the environment by using a nonionic surfactant.
That is, the present invention provides a toner that is excellent in low-temperature fixability and excellent in charging stability and environmental stability.

  The features of the present invention for solving the above-described problems are as follows. A toner containing at least toner particles produced in an aqueous medium and inorganic fine powder, wherein the toner particles are a binder resin, a colorant, a release agent, an ionic surfactant, and a nonionic surfactant. The binder resin contains a crystalline polyester obtained by condensation polymerization of an aliphatic diol and an aliphatic dicarboxylic acid, and the content of the crystalline polyester contained in the toner is 100 parts by mass of the toner particles. The content A of the ionic surfactant contained in the toner is from 10 ppm to 1000 ppm, and the content B of the nonionic surfactant contained in the toner is 100 ppm or more. A toner having a content of 5000 ppm or less.

  According to the invention of the present application, it is possible to provide a toner having excellent low-temperature fixability and excellent charging stability and environmental stability.

The inventors of the present application use a combination of an ionic surfactant and a nonionic surfactant in a toner using a crystalline polyester obtained by condensation polymerization of an aliphatic diol and an aliphatic dicarboxylic acid as a binder resin. In order to obtain a toner with excellent charging characteristics, intensive studies were repeated. As a result, even when a crystalline polyester obtained by polycondensation of an aliphatic diol and an aliphatic dicarboxylic acid is used, the content of the ionic surfactant and the nonionic surfactant is highly controlled. The inventors have obtained a toner having charging characteristics that can satisfy the aforementioned problems.
The present inventors consider these reasons as follows. In the present invention, the crystalline polyester is obtained by condensation polymerization of an aliphatic diol and an aliphatic dicarboxylic acid. And the crystallization site | part is formed because the aliphatic alkyl part in the obtained polyester interacts by van der Waals force. The crystallization index of the crystalline polyester is determined by the ratio of the crystallization sites. The higher the crystallization index, the greater the sharp melt property of the crystalline polyester.
As described above, the sharp melt property of crystalline polyester varies greatly depending on the interaction of aliphatic alkyl. On the other hand, a polyester having an aromatic diol or dicarboxylic acid has less intermolecular interaction because the molecular structure here is more complex than that of a polyester using aliphatic alkyl as a main raw material. However, since there are many π electrons in the aromatic site and easily cause an electron transition, it is easy to retain external electrons generated by friction or the like. Therefore, it is considered that an amorphous polyester having aromatics has a very high charge retention and a good charge rising property as compared with a crystalline polyester mainly composed of aliphatic alkyl.
On the other hand, when crystalline polyester is contained in the toner, it is considered that the charging stability, mainly the rising property of charging is lowered. As a result, the initial image in a high-temperature and high-humidity environment is insufficiently charged, causing density reduction and gradation reproduction. However, when the content of the ionic surfactant and the nonionic surfactant is controlled and contained as in the present invention, good charging characteristics can be obtained even in the toner containing the crystalline polyester. I understood. This is considered that the polyoxyalkylene site | part in a nonionic surfactant etc. has produced the interaction which pi-electrons the electron of the ester site | part in crystalline polyester. For this reason, it is possible to obtain even better charge stability even with toner containing crystalline polyester, and provide high image quality that can be fixed at low temperature through long-term image output (durability) regardless of the environment. A toner that can be obtained is obtained.
Further, it is considered that the interaction between the ester site in the crystalline polyester and the nonionic surfactant is likely to occur in the presence of the ionic surfactant. If the ionic surfactant is not present, the nonionic surfactant is not only in the ester site, but also interacts with the alkyl site, so that π electronization of the ester site is difficult to occur. However, the hydrophobic part of the ionic surfactant has a strong interaction property with the alkyl moiety and selectively interacts with the alkyl moiety. As a result, the nonionic surfactant is likely to selectively interact with the ester site instead of the alkyl site because the ionic surfactant becomes a barrier. As a result, it is considered that sufficient interaction occurs between the nonionic surfactant and the ester moiety, and the π-electronization of the ester moiety proceeds to obtain the effect of the present invention.

The features of the present invention will be described below. The toner of the present invention is a toner containing at least toner particles produced in an aqueous medium and inorganic fine powder, the toner particles comprising a binder resin, a colorant, a release agent, an ionic surfactant, and At least a nonionic surfactant is included, and the binder resin includes a crystalline polyester obtained by polycondensation of an aliphatic diol and an aliphatic dicarboxylic acid, and the content of the crystalline polyester contained in the toner is: It is 2 to 50 parts by mass with respect to 100 parts by mass of toner particles, and the content A of the ionic surfactant contained in the toner is 10 ppm or more and 1000 ppm or less, and the nonionic surfactant contained in the toner Content B is 100 ppm or more and 5000 ppm or less.
In the present invention, the content A of the ionic surfactant contained in the toner is 10 ppm or more and 1000 ppm or less, and the content B of the nonionic surfactant contained in the toner is 100 ppm or more and 5000 ppm or less. When the content A is less than 10 ppm, the interaction with the alkyl group of the crystalline polyester is not sufficient. Therefore, the non-ionic surfactant cannot exhibit the interaction with the ester group, cannot exhibit sufficient charge rising property, and has excellent gradation properties because the initial image is insufficiently charged. Cannot be reproduced. Further, when the content A is more than 1000 ppm, the saturation charge amount is decreased particularly in a high temperature and high humidity environment due to moisture adsorption by the excessively present ionic surfactant, and the image density is decreased. Arise. Further, the content A is more preferably 50 ppm or more and 300 ppm or less. This is because, within the above range, sufficient interaction with the alkyl group occurs, and no excessive ionic surfactant is generated, so that moisture adsorption can be suppressed.
On the other hand, when the content B is less than 100 ppm, the interaction with the ester group of the crystalline polyester is not sufficient, so that sufficient charge rising property cannot be exhibited. Therefore, excellent gradation cannot be reproduced in the initial image, particularly in a high temperature and high humidity environment. When the content B is more than 5000 ppm, the image density decreases due to a significant decrease in the saturated charge amount under high temperature and high humidity due to moisture adsorption by the excessively present nonionic surfactant. Further, the content B is desirably 300 ppm or more and 2000 ppm or less. This is because, within the above range, sufficient interaction with the ester group occurs and no excessive nonionic surfactant is generated, so that moisture adsorption is suppressed.
The content A and the content B are dispersions of a crystalline polyester fine particle dispersion, an amorphous polyester fine particle dispersion, a colorant fine particle dispersion, a release agent fine particle dispersion, a charge control agent particle dispersion, and the like, which will be described later. It is possible to satisfy the above-mentioned range by adding a nonionic surfactant and an ionic surfactant as an agent, and adding it to the mixture of the fine particle dispersion.
It is also possible to add a nonionic surfactant and an ionic surfactant to the toner particle dispersion obtained by subjecting the above mixture to the aggregation step and the heat fusion step. Further, in the toner particle cleaning step, a nonionic surfactant and an ionic surfactant are added to the toner particle cleaning solution, and the addition amount and / or the number of times of toner particle cleaning are changed to satisfy the above range. It is possible. The adjustment by the washing step is preferable in that the content A and the content B can be easily controlled.

In the present invention, the ratio [B / A] of the content B of the nonionic surfactant to the content A of the ionic surfactant [B / A] is preferably 1.0 or more and 20.0 or less, and 3.0 or more. It is more preferable that it is 10.0 or less.
If it is the said range, interaction with crystalline polyester, an ionic surfactant, and a nonionic surfactant will arise effectively, and a charging start property and environmental stability will further improve. This is because the nonionic surfactant interacts with the highly polar site of the ionic surfactant that is exposed when interacting, thereby reducing the water adsorption of the ionic surfactant. I believe that.

The ionic surfactant used in the present invention is not particularly limited, and may be any of an ionic surfactant selected from an anionic surfactant, a cationic surfactant and an amphoteric surfactant. You may use the above together. Of these, an anionic surfactant is preferably used.
If it is an anionic surfactant, since the hydrophilic site | part in surfactant is negative polarity, it becomes easy to interact with an alkyl site | part more selectively than the ester site | part of crystalline polyester.
For this reason, the nonionic surfactant and the ester portion of the crystalline polyester are likely to interact with each other, and the charging characteristics are more effectively stabilized.
The anionic surfactant is not particularly limited, and examples thereof include sulfate ester-based, sulfonate-based, phosphate ester-based, and soap-based anionic surfactants.
Specific examples of the anionic surfactant include sodium dodecyl sulfate, sodium alkyl naphthalene sulfonate, sodium dodecyl benzene sulfonate, sodium dialkyl sulfosuccinate and the like. These may be used individually by 1 type and may use 2 or more types together.
On the other hand, the cationic surfactant is not particularly limited, and specific examples thereof include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.

The nonionic surfactant used in the present invention is not particularly limited, and any fatty acid, higher alcohol, or alkylphenol nonionic surfactant can be used. The nonionic surfactant specifically refers to a substance belonging to a nonionic (nonionic) surfactant classified according to the miscellaneous goods quality display regulations by the Ministry of Economy, Trade and Industry.
In the present invention, the nonionic surfactant preferably has a polyoxyalkylene chain. Moreover, it is also one of the preferable aspects that the said nonionic surfactant is sugar esters, such as sucrose fatty acid ester.
Among these, polyoxyalkylene alkyl ether or polyoxyalkylene alkyl ester is more preferable, and specifically, a compound represented by the following formula (3) or formula (4) is preferable.

Ｒ：水素または炭素数が１乃至３０であるアルキル基
ＡＯ：オキシアルキレン
ｎ：平均付加モル数

R: hydrogen or an alkyl group having 1 to 30 carbon atoms AO: oxyalkylene n: average number of moles added

The average added mole number of oxyalkylene in the polyoxyalkylene chain is preferably 5 or more and 50 or less, more preferably 5 or more and 20 or less, further preferably 5 or more and 15 or less, and more preferably 8 or more and 12 or less. It is particularly preferred that
R is more preferably hydrogen or an alkyl group having 1 to 30 carbon atoms, and still more preferably 8 to 20 carbon atoms.
It was found that when the average added mole number of oxyalkylene in the polyoxyalkylene chain is in the above range, the charge rising property is further improved. This is because the nonionic surfactant expresses a hydrophilic part and a hydrophobic part by changing the state of polarization in the molecule. In the case of having a polyoxyalkylene chain, since various orientation states are obtained, it is easy to form a polarization state necessary for interaction. And when the average added mole number of oxyalkylene is in the above range, it is considered that the orientation state is optimized and the interaction is effectively generated.
The polyoxyalkylene chain is preferably a polyoxyalkylene chain obtained by addition polymerization of ethylene oxide and / or propylene oxide (that is, ethylene oxide, propylene oxide, or ethylene oxide and propylene oxide).
In the present invention, the nonionic surfactant is particularly preferably a polyoxyalkylene alkyl ether represented by the following formula (5).

Ｒ：水素または炭素数が１乃至３０であるアルキル基

R: hydrogen or an alkyl group having 1 to 30 carbon atoms

In the above formula (5), r represents the total number of added moles of oxyethylene groups, and s represents the total number of added moles of oxypropylene groups. The nonionic surfactant used in the present invention may have a structure in which polyoxyethylene and polyoxypropylene blocks are alternately present. To express. For example, when the compound represented by the following formula (6) is represented by the above formula (5), r = 10 and s = 7.
The average added mole number n is determined by n = r + s, and is preferably within the above range. Also, either r or s may be 0. Further, R is the same as described above.

In the present invention, the content A of the ionic surfactant and the content B of the nonionic surfactant contained in the toner are determined by the method described below.
In a sample bottle, 120 ml of methanol and 10 g of toner are accurately weighed and mixed well. Irradiate with sound waves for 30 minutes. Thereafter, filtration is performed using a solvent-resistant membrane filter “Maeshori Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm. Thereafter, the filtrate is trapped in order on a cation exchanger and an anion exchanger. Further, each ion exchanger is sufficiently washed away with a 0.1N HCl methanol solution to obtain a methanol solution containing a cationic surfactant and a methanol solution containing an anionic surfactant. Moreover, what passed through the ion exchanger in sequence is collected to obtain a methanol solution containing a nonionic surfactant. Collect exactly 100 ml of each solution and concentrate to about 5 ml under reduced pressure.
<Quantitative determination of cationic surfactant>
A buffer solution having a pH of 3.5 is prepared by mixing 160 ml of 0.1N acetic acid and 10 ml of 0.1M sodium acetate. On the other hand, 0.1 g of orange 2 is dissolved in pure water to make 100 ml of orange 2 solution.
A methanol solution containing the cationic surfactant, 10 ml of pH 3.5 buffer, 3 ml of sodium chloride and orange 2 solution are mixed, and 20 ml of chloroform is added and mixed well. Thereafter, the chloroform layer is extracted by centrifugation. Centrifugation is performed with a centrifuge H-9R (manufactured by Kokusan Co., Ltd.) using an angle rotor LN at 5 ° C. and 3000 rpm for 10 minutes. To the aqueous layer, 20 ml of chloroform is added again and the same operation is performed, and the chloroform layer is further extracted.
The volume of the extracted chloroform layer is adjusted to 50 ml with a volumetric flask, and then the absorbance near 485 nm is measured with an ultraviolet-visible spectrophotometer V-500V (manufactured by JASCO Corporation). The measurement uses a quartz cell having an optical path length of 10 mm and measures the absorbance of the solution in the wavelength range of 350 nm to 800 nm.
On the other hand, 0.1 mg, 0.3 mg, and 0.5 mg of cationic surfactant were precisely weighed and dissolved in 5 ml of methanol solution. The content of the cationic surfactant is determined by a calibration curve.
<Quantification of anionic surfactant>
A basic sodium borate solution is prepared by mixing 100 ml of 0.05 M sodium borate solution and 100 ml of 0.10 M sodium hydroxide solution. On the other hand, 0.25 g of methylene blue is dissolved in 1 L of pure water to prepare a methylene blue solution.
A methanol solution containing the anionic surfactant, 50 ml of pure water, 15 ml of an alkaline boric acid solution, and 5 ml of a methylene blue solution were mixed. To this was added 15 ml of chloroform, and the mixture was shaken for 1 minute and then centrifuged to extract the chloroform layer. This was mixed with 100 ml of pure water, 15 ml of alkaline boric acid solution, 5 ml of methylene blue solution, and 3 ml of 1M sulfuric acid. This is centrifuged again to recover only the chloroform layer. Centrifugation is performed with a centrifuge H-9R (manufactured by Kokusan Co., Ltd.) using an angle rotor LN at 5 ° C. and 3000 rpm for 10 minutes.
The volume of the extracted chloroform layer is adjusted to 50 ml with a volumetric flask, and then the absorbance near 650 nm is measured with an ultraviolet-visible spectrophotometer V-500V (manufactured by JASCO Corporation). The measurement uses a quartz cell having an optical path length of 10 mm and measures the absorbance of the solution in the wavelength range of 350 nm to 800 nm.
On the other hand, 0.1 mg, 0.3 mg, and 0.5 mg of an anionic surfactant were precisely weighed and dissolved in 5 ml of a methanol solution. The content of the anionic surfactant is determined from a calibration curve.
<Quantification of nonionic surfactant>
310 g of ammonium thiocyanate and 140 g of cobalt nitrate hexahydrate are dissolved in pure water to obtain 500 ml of an ammonium tetrathiocyanocobaltate solution.
The methanol solution containing the nonionic surfactant is diluted to 100 ml with pure water. To this, 15 ml of an ammonium tetrathiocyanocobaltate solution and 35 g of sodium chloride are added and vigorously stirred. Thereafter, 25 ml of benzene is accurately measured and added, and then mixed thoroughly. Thereafter, the benzene layer is extracted by centrifugation. Centrifugation is performed with a centrifuge H-9R (manufactured by Kokusan Co., Ltd.) using an angle rotor LN at 5 ° C. and 3000 rpm for 10 minutes.
Absorbance near 322 nm is measured for the extracted benzene layer with an ultraviolet-visible spectrophotometer V-500 V (manufactured by JASCO Corporation). The measurement uses a quartz cell having an optical path length of 10 mm and measures the absorbance of the solution in the wavelength range of 350 nm to 800 nm.
On the other hand, 0.1 mg, 0.5 mg, and 1.0 mg of a nonionic surfactant were precisely weighed and measured in advance for a solution dissolved in 10 ml of methanol solution, and the obtained calibration curve was used to measure the nonionic interface. Determine the activator content.

The composition of the nonionic surfactant, for example, the presence and composition of the polyoxyalkylene chain constituting the nonionic surfactant, and the average number of moles of oxyalkylene added in the polyoxyalkylene chain are as follows: Can be specified.
First, mass analysis of a methanol solution containing the nonionic surfactant was performed under the following conditions. The mass spectrometer addition thermal desorption gas chromatography (ThermoQuest TRACE2000CG / MS) is used for the measurement.
Extraction condition 120.0 ℃
Sample amount 1.0g
Column 0.32 mm (capillary column)
About each peak in the obtained analysis result, the component derived from the polyoxyalkylene chain in a nonionic surfactant is analyzed and identified from a mass spectrum.
Next, the solvent is removed from the methanol solution containing the nonionic surfactant by an evaporator. In addition to deuterated chloroform, ¹ H-NMR (nuclear magnetic resonance) measurement was performed, and the above identified peak intensity derived from 3.4 to 3.8 ppm hydrogen derived from polyoxyethylene chain and derived from alkyl carbon. The ratio of hydrogen-derived peaks of 0.5 ppm to 2.5 ppm is determined.
The measurement apparatus and measurement conditions are as follows.
Apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 1024 times Measurement temperature: 40 ° C
The molecular weight of the nonionic surfactant is measured by gel permeation chromatography (GPC).
First, the solvent is removed from the methanol solution containing the nonionic surfactant by an evaporator. This is dissolved in tetrahydrofuran (THF). The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used. The measured average molecular weight is divided by the unit molecular weight of the alkylene constituting the polyoxyalkylene chain, and the value obtained by rounding down the decimal point is defined as the average added mole number.
As described above, the average number of added moles can be specified by calculating from the ratio of the obtained alkyl moiety to the polyoxyalkylene chain and the molecular weight.

The toner of the present invention contains a crystalline polyester obtained by condensation polymerization of an aliphatic diol and an aliphatic dicarboxylic acid in a binder resin. Hereinafter, the crystalline polyester will be described.
Here, the crystalline polyester refers to a polyester that uses a modulated mode in differential scanning calorimetry (DSC) measurement, has an endothermic peak when the temperature is raised, and has an exothermic peak when the temperature is lowered.
In the present invention, in the endothermic curve obtained by differential scanning calorimetry (DSC) measurement, the crystalline polyester preferably has a peak top of the endothermic peak in the range of 50 to 130 ° C. More preferably, it is 55 to 120 ° C., and further preferably 60 to 110 ° C. When the temperature at the peak top of the endothermic peak of the crystalline polyester is less than 50 ° C., the storage stability of the toner tends to be inferior. On the other hand, when the temperature is higher than 130 ° C., the rapid fixing property tends to be lowered. The temperature at the peak top of the endothermic peak in the differential scanning calorimetry (DSC) measurement of the crystalline polyester can be adjusted, for example, by appropriately selecting the type and molecular weight of the monomer used.
The DSC measurement is performed according to ASTM D 3417-99. For example, it is measured using DSC-7 manufactured by PerkinElmer, DSC2920 manufactured by TA Instruments, and Q1000 manufactured by TA Instruments. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. A measurement sample (polyester) is placed in an aluminum pan for measurement, and an empty pan is set as a control for measurement.
When heated, the crystalline polyester contained in the toner of the present invention may be compatible with other resins contained in the binder resin. In the normal DSC measurement mode, the peak top temperature is obtained from the DSC curve at the time of the second temperature increase, including the process of temperature increase, temperature decrease and temperature increase. At that time, if it is slowly heated to 180 ° C. at the first temperature raising stage, a part of the crystalline polyester may be compatible with other resins contained in the binder resin. For this reason, it is not preferable to perform DSC measurement of the crystalline polyester contained in the toner of the present invention in the normal measurement mode.
Therefore, the DSC measurement of the crystalline polyester contained in the toner of the present invention is measured using the modulated mode shown below. The peak top temperature of the endothermic peak is determined from the obtained DSC curve at the time of temperature increase.
<Measurement conditions using the modulated mode>
• Equilibrate at 20 ° C for 1 minute.
・ Turn the temperature up to 180 ° C. at 2 ° C./min while applying modulation of amplitude 1.5 ° C. and frequency 1 / min
• Equilibrate at 180 ° C for 10 minutes.
・ The temperature is lowered to 20 ° C. at 2 ° C./min while applying modulation of amplitude 1.5 ° C. and frequency 1 / min.

In the toner of the present invention, the content of the crystalline polyester contained in the toner is 2 to 50 parts by mass, preferably 5 to 30 parts by mass with respect to 100 parts by mass of the toner particles. When the content of the crystalline polyester is less than 2 parts by mass, the effect of the present invention described above is lowered. Further, since the crystalline polyester easily absorbs moisture, if the content is more than 50 parts by mass with respect to 100 parts by mass of the toner particles, the uniformity of charging of the toner is impaired, which causes an increase in fog.
The crystalline polyester is obtained by polycondensation of an aliphatic diol (alcohol component) and an aliphatic dicarboxylic acid (carboxylic acid component). The crystalline polyester is preferable because it has a high degree of crystallinity and excellent sharp melt properties.
In the present invention, the aliphatic diol having 2 to 22 carbon atoms (more preferably 2 to 12 carbon atoms) and the carbon number sandwiched between two carboxy groups is 2 to 22 (more preferably 4 to 14 carbon atoms). A crystalline polyester obtained by polycondensation with an aliphatic dicarboxylic acid is preferred. More preferably, the alcohol component containing 80 to 100 mol% of an aliphatic diol having 2 to 22 carbon atoms and 80 to 100 mol% of an aliphatic dicarboxylic acid compound having 2 to 22 carbon atoms sandwiched between two carboxy groups are contained. It is a crystalline polyester obtained by condensation polymerization of the carboxylic acid component. Particularly preferably, the alcohol component containing 80 to 100 mol% of an aliphatic diol having 2 to 12 carbon atoms and 80 to 100 mol% of an aliphatic dicarboxylic acid compound having 4 to 14 carbon atoms sandwiched between two carboxy groups are contained. It is a crystalline polyester obtained by condensation polymerization of the carboxylic acid component.
By combining the aliphatic diol and the aliphatic dicarboxylic acid, it is considered that the order of the molecular arrangement of the obtained crystalline polyester can be increased, and thus the degree of crystallinity can be increased.
The ratio (molar basis) between the carboxylic acid component and the alcohol component is preferably carboxylic acid component: alcohol component = 60: 40 to 40:60.
The aliphatic diol having 2 to 22 carbon atoms is not particularly limited, but a chain (more preferably linear) aliphatic diol is preferable. Examples of chain aliphatic diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, Examples include methylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol and the like. Among these, linear aliphatic α, ω-diols such as ethylene glycol, diethylene glycol and 1,4-butanediol are particularly preferred.
Also, among the alcohol components, preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 80 to 100 mol%, particularly preferably 100 mol% is selected from aliphatic diols having 2 to 22 carbon atoms. Alcohol.
Polyhydric alcohol monomers other than the aliphatic diols can be used to the extent that the characteristics of the crystalline polyester in the present invention are not impaired. Examples of the dihydric alcohol monomer among the polyhydric alcohol monomers include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like. . Examples of the trihydric or higher polyhydric alcohol monomer among the polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tritriol. Pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, etc. Of aliphatic alcohols.
Furthermore, you may use a monovalent alcohol to such an extent that the characteristic of the crystalline polyester in this invention is not impaired. Examples of the monohydric alcohol include 1 such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, dodecyl alcohol and the like. Functional monomers and the like are included.
On the other hand, the aliphatic dicarboxylic acid having 2 to 22 carbon atoms sandwiched between two carboxy groups is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. Specific examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid , Dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, and anhydrides thereof. Further, the lower alkyl ester can be hydrolyzed and used as the aliphatic dicarboxylic acid.
Of the carboxylic acid components, the number of carbon atoms sandwiched between two carboxy groups is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 to 100 mol%, and particularly preferably 100 mol%. A carboxylic acid selected from 2 to 22 aliphatic dicarboxylic acids.
A polyvalent carboxylic acid other than the aliphatic dicarboxylic acid may be included to the extent that the characteristics of the crystalline polyester in the present invention are not impaired. Examples of divalent carboxylic acids among other polyvalent carboxylic acid monomers include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. Anhydrides are also included. Further, the lower alkyl ester may be hydrolyzed and used as a divalent carboxylic acid. In addition, among other carboxylic acid monomers, examples of trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, Aromatic carboxylic acids such as 1,2,4-naphthalenetricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl Aliphatic carboxylic acids such as 2-methylenecarboxypropane and the like, and these acid anhydrides are also included. Further, the lower alkyl ester may be hydrolyzed and used as a polyvalent carboxylic acid.
Furthermore, you may contain monovalent carboxylic acid to such an extent that the characteristic of crystalline polyester in this invention is not impaired. Examples of monovalent carboxylic acids include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid Monocarboxylic acids such as dodecanoic acid and stearic acid.

The crystalline polyester in the present invention can be produced according to an ordinary polyester synthesis method. For example, the above-mentioned carboxylic acid monomer and alcohol monomer are esterified or transesterified, and then subjected to a polycondensation reaction in accordance with a conventional method under reduced pressure or by introducing nitrogen gas. Crystalline polyester can be obtained.
The esterification or transesterification reaction can be performed using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, and magnesium acetate, if necessary.
The polycondensation reaction can be performed using a conventional polymerization catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. The polymerization temperature and the catalyst amount are not particularly limited, and may be determined appropriately.
In the esterification or transesterification reaction or polycondensation reaction, all monomers are charged together to increase the strength of the resulting polyester component; or divalent to reduce the low molecular weight component of the resulting polyester component After the monomer is first reacted, a monomer having a valence of 3 or more can be added and reacted.
The number average molecular weight of the crystalline polyester used in the toner of the present invention is preferably 2,000 to 10,000, more preferably 2,000 to 6,000. When the number average molecular weight of the crystalline polyester is less than 2,000, it tends to cause compatibility with other resins contained in the binder resin during the production of the toner particles, and the intended effect of the present invention tends to be reduced. The storage stability and durability of the toner also tend to decrease.
On the other hand, if the number average molecular weight of the crystalline polyester is larger than 10,000, the dispersibility tends to be lowered, and the response to heat is likely to be lowered (it takes time to melt) and fixing at a low temperature. Tend to decrease.
The number average molecular weight of the crystalline polyester is determined by the GPC method. As a specific measurement procedure, 0.03 g of the polyester to be measured is dispersed in 10 ml of o-dichlorobenzene and dissolved; the obtained solution is shaken at 135 ° C. for 24 hours with a shaker; The solution is filtered through a 0.2 μm filter; the obtained filtrate is used as a sample and measured under the following analysis conditions.
[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene mobile phase flow rate: 1.0 ml / min.
Sample concentration: about 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71
Further, in calculating the molecular weight of the sample, a molecular weight calibration curve prepared with a standard polystyrene resin is used. Examples of the standard polystyrene resin include TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, manufactured by Tosoh Corporation. F-2, F-1, A-5000, A-2500, A-1000, A-500 are included.

In the present invention, in order to further improve the charging stability, the ester group concentration defined by the following formula of the crystalline polyester is preferably 3.50 mmol / g or more and 10.00 mmol / g or less, preferably 4.00 mmol. / G to 7.80 mmol / g is more preferable.
If it is the said range, it is thought that the ratio of the alkyl part and ester part of crystalline polyester is suitable, and the negative polarity density of an ester part can be relieve | moderated effectively by nonionic surfactant, a gradation A toner with excellent properties can be obtained without environmental differences.
The ester group concentration M indicates the ratio of ester groups in the crystalline polyester, and is defined by the following formula.
[Ester group concentration M (mmol / g)] = [Mole number of ester group in repeating structural unit of crystalline polyester] / [Molecular weight of repeating structural unit of crystalline polyester]
The polyester resin is generally obtained by a reaction of a polyvalent carboxylic acid and a polyhydric alcohol, and forms an ester bond by dehydration condensation between a carboxy group in the polyvalent carboxylic acid and a hydroxyl group of the polyhydric alcohol group. The number of moles of the ester group in the repeating structural unit of the crystalline polyester of the above formula and the molecular weight of the repeating structural unit of the crystalline polyester are the carboxy group of the polycarboxylic acid and the hydroxyl of the polyhydric alcohol when the crystalline polyester was synthesized. It is determined by the number of moles of the group.
Specifically, if the polyvalent carboxylic acid is a divalent carboxylic acid represented by the formula (1) and the polyhydric alcohol is a divalent alcohol represented by the formula (2), the formula (1) And the crystalline polyester obtained by the formula (2) becomes the formula (3).
_HOOC-R 1 -COOH formula (1)
HO—R ₂ —OH Formula (2)
— (— OCO—R ₁ —COO—R ₂ —) n— Formula (3)
The number of moles of the ester group in the above formula (3) is an average of the number of moles of the carboxy group of the carboxylic acid of the above formula (1) and the number of moles of the hydroxyl group of the above formula (2).
The molecular weight _{m 3} of _{m 1} the molecular weight of the above formula (1), the molecular weight _{m 2} in the formula (2), when in the above formula _(3), and the number of moles of m _{1 +} m 2 -18 × (carboxy group The average number of moles of hydroxyl groups) = m ₃ .
Therefore, the ester group concentration M in the above formula (3) is [ester group concentration M] = (average of the number of moles of carboxy groups and the number of moles of hydroxyl groups) / m ₃ .
In addition, when two or more polycarboxylic acids or two or more polyhydric alcohols are used in combination, the average of the carboxy group and molecular weight of each polycarboxylic acid and the average of the hydroxyl group and molecular weight of the polyhydric alcohol Become.
Further, the ester group concentration M can be obtained from crystalline polyester by, for example, ¹ H-NMR (nuclear magnetic resonance) measurement using deuterated chloroform. Specifically, the ester group concentration is calculated from the ratio of the peak of the hydrogen atom derived from carbon at the alkyl site and the peak of the hydrogen atom derived from carbon adjacent to the ester group.

In order to measure the temperature at the top of the endothermic peak, the ester group concentration, the content, and the like from the crystalline polyester contained in the toner, it is necessary to extract the crystalline polyester from the toner. Specifically, the crystalline polyester can be extracted from the toner as follows.
First, the toner is dissolved in methyl ethyl ketone (MEK) at room temperature (20 ° C. or more and 25 ° C. or less). This is because when the crystalline polyester and the amorphous resin are contained in the toner, only the amorphous resin is dissolved in the MEK at room temperature. Therefore, since the MEK-soluble component contains an amorphous resin, the amorphous resin can be obtained from the supernatant separated by centrifugation after the dissolution. On the other hand, the solid content after centrifugation is heated at 65 ° C. for 60 minutes and dissolved in tetrahydrofuran (THF), and this is filtered with a glass filter at 60 ° C., whereby a crystalline polyester is obtained from the filtrate. In addition, since crystalline polyester will precipitate if temperature falls during filtration by this operation, it operates in the state kept warm.
By conducting various analyzes on the crystalline polyester thus obtained, the melting point, ester group concentration, content and the like can be determined.

Next, the toner of the present invention will be described in detail. The toner of the present invention is a toner containing at least toner particles produced in an aqueous medium and inorganic fine powder, and the toner particles include a binder resin, a colorant, a release agent, and an ionic surfactant. And at least a nonionic surfactant. The method for producing the toner particles is not particularly limited as long as it is produced at least in an aqueous medium. Specific examples of the method for producing toner particles in an aqueous medium include an emulsion aggregation method, a solution suspension method, and a suspension polymerization method. Among them, a crystalline polyester, an ionic surfactant, and a nonionic interface are mentioned. The emulsion aggregation method is also preferred in order to allow the active agent to interact uniformly. Specifically, the toner particles used in the present invention are in a mixed solution containing at least binder resin fine particles, colorant fine particles, release agent fine particles, an ionic surfactant and a nonionic surfactant. The toner particles are preferably obtained by forming agglomerated particles containing at least fine particles of a binder resin, fine particles of a colorant, and fine particles of a release agent, and then heating and aggregating the agglomerated particles. The toner particles obtained by using the above method can uniformly interact the ionic surfactant and the nonionic surfactant with the crystalline polyester in the binder resin particles. Is optimally expressed. The fine particles of the binder resin are crystalline polyester fine particles and fine particles of a binder resin other than the crystalline polyester, so that the crystalline polyester, the ionic surfactant, and the nonionic surfactant are uniformly mixed. It is preferable from the viewpoint of action.
In addition, the toner particles used in the present invention preferably have a nearly spherical shape so that the toner particles can be satisfactorily charged up to the saturation charge amount. Specifically, the average circularity of the toner particles used is preferably 0.960 or more. Further, the ratio of toner particles having a circularity of 0.950 or more is preferably 75% or more of all particles. Furthermore, the standard deviation of circularity is less than 0.030, more preferably less than 0.025.
If the toner particles have such a high average circularity and a sharp circularity distribution, the friction between the toner carrier and the toner regulating member and the frictional charging due to the friction between the toner and the carrier are uniform and efficient. Therefore, the charge rising property is improved. In addition, the uniformity of the charge amount distribution is improved, and stable charging characteristics can be obtained through durability.
As described above, as a method for obtaining toner particles having a high average circularity and a sharp circularity distribution, production in an aqueous medium can be mentioned. In recent years, a technique for increasing the average circularity of a toner has been developed by, for example, thermal spheronization treatment of a toner obtained by a dry method such as a melt-kneading pulverization method. However, it is difficult to improve the average circularity and sharpen the circularity distribution of the toner obtained by this method.
The average circularity of the toner particles and the standard deviation of the circularity are measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.
A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
For the measurement, the flow type particle image analyzer equipped with “UPlanApro” (magnification: 10 ×, numerical aperture: 0.40) as an objective lens is used. Is used. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity and standard deviation of the circularity of the toner particles are obtained.
In the measurement, before starting the measurement, standard latex particles (for example, Duke Science)
Automatic focusing is performed using “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by tific. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement is performed under the measurement and analysis conditions when the calibration certificate is received, except that the analysis particle diameter is limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

Hereinafter, the toner particles obtained by the emulsion aggregation method will be described in detail, but the production method is not limited to the method.
As described above, the fine particles of the binder resin are composed of crystalline polyester fine particles and fine particles of a binder resin other than the crystalline polyester. Examples of binder resins other than the crystalline polyester include conventionally known thermoplastic binder resins. Specifically, homopolymers or copolymers of styrenes such as styrene, parachlorostyrene, α-methylstyrene (styrene resin); methyl acrylate, n-butyl acrylate, lauryl acrylate, acrylic acid 2 -Ethylhexyl, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, homopolymers or copolymers of vinyl groups such as 2-ethylhexyl methacrylate (vinyl resin); acrylonitrile, methacrylonitrile, etc. Homopolymers or copolymers of vinyl nitriles (vinyl resins); Homopolymers or copolymers of vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether (vinyl resins); Vinyl methyl ketone, vinyl isopropenyl Homopolymers or copolymers of vinyl ketones such as ketones Polymer (vinyl resin); homopolymer or copolymer of olefins such as ethylene, propylene, butadiene, isoprene (olefin resin); epoxy resin, amorphous polyester resin, polyurethane resin, polyamide resin, cellulose resin, Examples thereof include non-vinyl condensation resins such as polyether resins, and graft polymers of these non-vinyl condensation resins and vinyl monomers. These resins may be used alone or in combination of two or more.
Among these resins, vinyl resins and amorphous polyester resins are particularly preferable.
In the case of a vinyl resin, it is advantageous in that a resin particle dispersion can be easily prepared by emulsion polymerization or seed polymerization using an ionic surfactant or the like. Examples of the monomer constituting the vinyl resin include, for example, vinyl polymer acids such as acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, ethyleneimine, vinyl pyridine, and vinyl amine, and vinyl resins. Examples include monomers that are raw materials for polymer bases.
In the present invention, among these vinyl monomers, vinyl polymer acids are more preferable in terms of ease of formation reaction of vinyl resins, and specifically, acrylic acid, methacrylic acid, maleic acid, cinnamon A dissociable vinyl monomer having a carboxy group as a dissociating group such as acid and fumaric acid is particularly preferable in terms of controlling the degree of polymerization and the glass transition point. Furthermore, at this time, in order to adjust the molecular weight, a chain transfer agent, a crosslinking agent, or the like can be used in combination. The chain transfer agent is not particularly limited, and for example, mercaptans such as octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, halogen compounds such as carbon tetrabromide, disulfides and the like are used. On the other hand, examples of the crosslinking agent include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, hexanediol diacrylate, and diallyl phthalate. In particular, divinylbenzene is preferably used.
In the present invention, the binder resin other than the crystalline polyester preferably contains a vinyl resin produced using the vinyl monomer as a monomer component, and changes in the charge amount of the toner in a high temperature and high humidity or low temperature and low humidity environment It is more preferable to contain a small amount of styrene-acrylic resin. In the present invention, the radical polymerization initiator used for producing the polymer can be appropriately used as long as it is water-soluble. For example, persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds [4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis (2-amidinopropane) salts, etc.], Examples thereof include peroxide compounds such as hydrogen oxide and benzoyl peroxide. Furthermore, the radical polymerization initiator can be combined with a reducing agent as necessary to form a redox initiator. By using a redox initiator, the polymerization activity is increased, the polymerization temperature can be lowered, and the polymerization time can be further shortened.
The polymerization temperature may be any temperature as long as it is equal to or higher than the minimum radical generation temperature of the polymerization initiator. Further, polymerization can be performed at a temperature equal to or higher than the boiling point of the dispersion (usually an aqueous medium) under pressurized conditions. On the other hand, surfactants that can be used for polymerization include sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino- Sodium 8-naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfone Acid salts), sulfate salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate) Potassium, potassium stearate, calcium oleate), and the like.

On the other hand, in this invention, it is also a preferable form that the binder resin other than the crystalline polyester is an amorphous polyester resin. When an amorphous polyester resin is used, a resin particle dispersion can be prepared by emulsification and dispersion described later, as with the crystalline polyester resin. The amorphous polyester resin refers to a polyester resin other than the crystalline polyester.
The amorphous polyester can be obtained by a reaction between a divalent or higher polyvalent carboxylic acid and a polyhydric alcohol. Although it does not specifically limit as polyvalent carboxylic acid, Aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid, maleic anhydride, fumaric acid, succinic acid Examples thereof include aliphatic carboxylic acids such as acid, alkenyl succinic anhydride and adipic acid, and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These polyvalent carboxylic acids can be used alone or in combination. Of these polycarboxylic acids, aromatic carboxylic acids are preferably used. In addition, in order to ensure good fixability, a dicarboxylic acid or a trivalent or higher carboxylic acid (trimellitic acid or acid anhydride thereof) capable of forming a crosslinked structure or a branched structure may be used in combination. preferable. On the other hand, the polyhydric alcohol is not particularly limited, and examples of the dihydric alcohol include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like. . Examples of the trihydric or higher polyhydric alcohol include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1, Examples include aliphatic alcohols such as 2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.
The ratio (molar basis) between the carboxylic acid component and the alcohol component is preferably carboxylic acid component: alcohol component = 60: 40 to 40:60.
Further, the amorphous polyester may contain a monovalent carboxylic acid. Examples of monovalent carboxylic acids include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid Monocarboxylic acids such as dodecanoic acid and stearic acid.
The amorphous polyester in the present invention can be produced in accordance with a normal polyester synthesis method in the same manner as the crystalline polyester. The preferred range of the number average molecular weight of the amorphous polyester used in the toner of the present invention and the method for measuring the number average molecular weight are the same as those for the crystalline polyester.

The average particle diameter of the fine particles of the binder resin is usually 1.00 μm or less, and preferably 0.01 to 1.00 μm. When the average particle size exceeds 1.00 μm, the particle size distribution of the finally obtained toner is broadened, free particles are generated, and performance and reliability are liable to be lowered. On the other hand, when the average particle size is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toners is improved, and the variation in performance and reliability is advantageous.
(Dispersion preparation process)
The fine particle dispersion of the binder resin is prepared, for example, as follows. That is, when the resin is a homopolymer or copolymer (vinyl resin) of vinyl monomers such as esters having a vinyl group, vinyl nitriles, vinyl ethers, vinyl ketones, etc. By subjecting the monomer to emulsion polymerization or seed polymerization in an ionic surfactant, a dispersion liquid in which fine particles of resin are dispersed in the ionic surfactant is prepared.
On the other hand, when the resin is a resin other than a vinyl resin, the resin is mixed in an aqueous medium in which an ionic surfactant or a polymer electrolyte is dissolved. Thereafter, the solution is heated to a melting point or a softening point or higher to be dissolved, and a dispersion liquid is prepared by dispersing fine particles of the resin in an ionic surfactant using a dispersing machine having a strong shearing force such as a homogenizer. The
The dispersion means is not particularly limited, and examples thereof include known dispersion apparatuses such as a rotary shear type homogenizer and a ball mill having a medium, a sand mill, and a dyno mill.
The fine particle dispersion of the colorant is obtained by dispersing at least colorant fine particles in a dispersant. Examples of the colorant include phthalocyanine pigments, monoazo pigments, bisazo pigments, and quinacridone pigments. Specific examples thereof include carbon black, chrome yellow, hansa yellow, benzidine yellow, slen yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, brilliantamine 6B, Dupont oil red, pyrazolone red, resol red, rhodamine B rake, lake red C, rose bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate Pigment: Acridine, xanthene, azo, benzoquinone, azine, anthraquinone, dioxazine Thiazine, azomethine, indigo, thioindigo, phthalocyanine, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, thiazole type, various dyes such as xanthene; and the like. These colorants may be used alone or in combination of two or more.
The average particle diameter of the fine particles of the colorant is preferably 0.5 μm or less, and more preferably 0.2 μm or less. When the average particle size exceeds 0.5 μm, it is difficult to prevent irregular reflection of visible light, and when coarse particles are present, coloring power, color reproducibility, and OHP permeability are easily affected. Further, even if the binder resin fine particles and the colorant fine particles are aggregated in the aggregation step described later, they tend to be detached during fusion, and the quality of the obtained toner tends to be lowered. On the other hand, when the average particle size is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toner is good, and the variation in performance and reliability is advantageous. .
The amount of the colorant used is preferably 0.1 parts by mass or more and 30 parts by mass with respect to 100 parts by mass of the binder resin.
It is not more than part by mass, more preferably not less than 0.5 part by mass and not more than 20 parts by mass.
The release agent fine particle dispersion is obtained by dispersing at least release agent fine particles in a dispersant. As the mold release agent, those having a melting point of 150 ° C. or less measured by a conventional method are used, and those having a temperature of 45 ° C. to 130 ° C. can preferably achieve both durability and mold release properties.
For example, low molecular weight polyolefins such as polyethylene, silicones having a melting point (softening point) upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, and ester waxes such as stearyl stearate Plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc. And particles such as mineral / petroleum wax; and modified products thereof. Of these, ester waxes are preferably used from the viewpoints of stability when a fine particle dispersion of a release agent, environmental resistance when toner is formed, image stability, and the like.
As an optimal release agent that can achieve a good balance between low temperature fixability and durability by matching with the physical properties of the binder resin of the present invention, a low melting point ester wax having a melting point of 45 ° C. or higher and 75 ° C. or lower is obtained. preferable.
Further, in order to widen the latitude of the fixable temperature, in addition to the low melting point wax, a high melting point wax having a melting point higher than 70 ° C. and not higher than 130 ° C. can be used to impart a function suitably.
The average particle size of the release agent fine particles is preferably 2.0 μm or less, and more preferably 1.0 μm or less. When the average particle diameter exceeds 2.0 μm, the toner content tends to be generated between the toners, affecting the stability of the image over a long period of time. On the other hand, when the average particle size is within the above range, uneven distribution between toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are reduced.
The amount of the release agent to be used is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.
The combination of the colorant fine particles, the binder resin fine particles, and the release agent fine particles is not particularly limited and may be appropriately selected depending on the purpose.
In the present invention, in addition to the binder resin fine particle dispersion, the colorant fine particle dispersion, and the release agent fine particle dispersion, if necessary, a fine particle dispersion obtained by dispersing appropriately selected fine particles in the dispersant is further mixed. May be.
The fine particles contained in the fine particle dispersion are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include internal additive fine particles, charge control agent fine particles, inorganic fine particles, and abrasive fine particles. In the present invention, these fine particles may be dispersed in the binder resin fine particle dispersion or the colorant particle dispersion.
Examples of the charge control agent fine particles include fine particles of a quaternary ammonium salt compound, a nigrosine compound, a compound composed of a complex such as aluminum, iron, chromium, zinc, and zirconium. In addition, as the charge control agent fine particles in the present invention, a material that is difficult to dissolve in water is preferable from the viewpoint of controlling ionic strength that affects stability at the time of aggregation and fusion and recycling of wastewater.
The average particle size of each of the above-mentioned fine particles is usually 1.00 μm or less, and preferably 0.01 to 1.00 μm. When the average particle size exceeds 1.00 μm, the particle size distribution of the finally obtained toner is widened, and performance and reliability are likely to be lowered. On the other hand, when the average particle size is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toners is improved, and the variation in performance and reliability is advantageous.
Examples of the dispersant contained in the binder resin fine particle dispersion, the colorant fine particle dispersion, the release agent fine particle dispersion, the other fine particle dispersion, and the like include an aqueous medium containing a polar surfactant. Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together. The content of the polar surfactant cannot be generally defined and can be appropriately selected according to the purpose. Examples of the polar surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type Is mentioned. Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like. Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. These may be used individually by 1 type and may use 2 or more types together.

The content of the binder resin fine particles in 100 parts by mass of the binder resin fine particle dispersion is preferably 5 to 60 parts by mass. The content of the binder resin fine particles in 100 parts by mass of the aggregated particle dispersion when the aggregated particles are formed is preferably 50 parts by mass or less.
The content of the colorant fine particles is preferably about 1 to 10 parts by mass with respect to 100 parts by mass of the binder resin in the aggregated particle dispersion when the aggregated particles are formed.
The content of the release agent fine particles is about 1 to 25 parts by mass with respect to 100 parts by mass of the binder resin in the aggregated particle dispersion when the aggregated particles are formed, and 5 to 20 parts by mass. The degree is preferred. When the content is less than 5 parts by mass, the releasing effect is lowered and the low-temperature fixability tends to be lowered. On the other hand, if the content exceeds 20 parts by mass, the amount of surface release agent or the amount of precipitation increases with the endurance deterioration of the toner, so that the fog characteristic tends to deteriorate. Moreover, when the said content is larger than 20 mass parts, a particle size distribution may spread depending on the kind of mold release agent, and a characteristic may deteriorate. In this case, for example, when the resin particles are produced, the above problem can be solved by performing seed polymerization on the release agent.
Further, in order to control the chargeability of the obtained toner, the charge control fine particles and the binder resin fine particles may be added after the aggregated particles are formed.
The particle size of the fine particles such as binder resin fine particles, colorant fine particles, and release agent fine particles was measured using a laser diffraction / scattering type particle size distribution measuring apparatus LA-920 manufactured by Horiba. The average particle diameter is a 50% particle diameter (median diameter) based on volume distribution.

(Aggregation process)
The agglomeration step for forming the agglomerated particles is to form agglomerated particles in a mixed solution containing at least the fine particles of the binder resin, the fine particles of the colorant, and the fine particles of the release agent to prepare an agglomerated particle dispersion. The agglomerated particles can be formed in the mixed solution by adding, for example, a pH adjusting agent, a flocculant, and a stabilizer to the mixed solution and mixing them, and appropriately adding temperature, mechanical power and the like.
Examples of the pH adjuster include alkalis such as ammonia and sodium hydroxide, and acids such as nitric acid and citric acid. Examples of the flocculant include monovalent metal salts such as sodium and potassium; divalent metal salts such as calcium and magnesium; trivalent metal salts such as iron and aluminum; and alcohols such as methanol, ethanol and propanol. It is done.
Examples of the stabilizer mainly include the polar surfactant itself or an aqueous medium containing the same. For example, when the polar surfactant contained in the fine particle dispersion is anionic, a cationic one can be selected as the stabilizer.
The addition / mixing of the flocculant and the like is preferably performed at a temperature below the glass transition point of the resin contained in the mixed solution. When mixing is performed under this temperature condition, aggregation proceeds in a stable state. Mixing can be performed using, for example, a known mixing device, a homogenizer, a mixer and the like.
Further, in the aggregation step, the second binder resin fine particles are adhered to the surface of the aggregated particles using the binder resin fine particle dispersion containing the second binder resin fine particles, and the coating layer (shell layer) is formed. It is possible to obtain aggregated particles having a core / shell structure in which a shell layer is formed on the surface of the core aggregated particles. The second binder resin fine particles used at this time may be the same as or different from the binder resin fine particles constituting the core aggregated particles. The aggregating step may be repeatedly performed in a plurality of steps.

(Aging process)
The aging step is a step of heating and fusing the obtained aggregated particles. Before entering the ripening step, the pH adjuster, the polar surfactant, the nonpolar surfactant, and the like can be appropriately added in order to prevent fusion between toner particles.
The heating temperature may be the glass transition temperature of the resin contained in the aggregated particles (the glass transition temperature of the resin having the highest glass transition temperature when there are two or more types of resin) or the decomposition temperature of the resin. That's fine. Therefore, the temperature of the heating varies depending on the type of resin of the binder resin fine particles and cannot be generally defined, but is generally the glass transition temperature of the resin contained in the aggregated particles to 140 ° C. . In addition, the said heating can be performed using a publicly known heating apparatus and instrument.
As the 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 fusion time depends on the temperature of heating and cannot be defined in general, but is generally 30 minutes to 10 hours.
The toner particles obtained through the above steps can be solid-liquid separated according to a known method, the toner particles can be collected, and then washed, dried, and the like under appropriate conditions.
In addition, in order to bring the content of ionic surfactant and nonionic surfactant to the values specified in the present application, it is also possible to surface-treat toner particles with ionic surfactant and nonionic surfactant. It is. The surface treatment operation can be added in the washing step before the solid-liquid separation step, and even after the drying step, the surfactant is dissolved in a solvent such as methanol that is highly volatile and difficult to dissolve the toner particles. The surface treatment is also possible by spraying the solution with a spraying device or the like.

(External addition process)
The toner of the present invention contains inorganic fine powder as an external additive on the toner particle surface.
The inorganic fine particles used in the present invention are not particularly limited, but are preferably hydrophobized silica fine particles in order to further improve charging stability, developability, fluidity and cleaning properties. Hydrophobized silica fine particles are used for the purpose of hydrophobization and chargeability control, etc. Silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organic silicon It is desirable to treat with a treating agent such as a compound or an organic titanium compound, or a combination of these treating agents. Typical examples of the silane coupling agent include dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltriethoxysilane, and γ-methacrylic. Examples thereof include oxypropyltrimethoxysilane, vinyltriacetoxysilane, and divinylchlorosilane.
In addition, a well-known method can be used for the processing method containing the addition amount of a processing agent.

Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this does not limit the present invention in any way. In the following formulation, “part” and “%” are based on mass unless otherwise specified.
<Production Example of Crystalline Polyester 1>
In a reaction apparatus equipped with a stirrer, a thermometer and an outflow cooler, 230.3 parts by mass (1.0 mol part) of 1,10-decanedicarboxylic acid and 118.2 parts by mass of 1,6-octanediol (1 0.0 mol part) and 0.50 part by mass of tetrabutyl titanate were added, and an esterification reaction was carried out at 190 ° C. Thereafter, the temperature was raised to 220 ° C. and the pressure inside the system was gradually reduced, and a polycondensation reaction was performed at 150 Pa to obtain crystalline polyester 1. The temperature at the peak top of the endothermic peak of the crystalline polyester 1 (hereinafter also referred to as the melting point) was 72 ° C., and the number average molecular weight was 4,500. The characteristics of the crystalline polyester 1 are shown in Table 1.

<Production Example of Crystalline Polyester 2>
In the production of crystalline polyester 1, the above-mentioned crystal was changed except that 118.2 parts by mass (1.0 mol part) of 1,6-octanediol was changed to 62.1 parts by mass (1.0 mol part) of ethylene glycol. Crystalline polyester 2 was obtained in the same manner as in the production of crystalline polyester 1. The crystalline polyester 2 had a melting point of 68 ° C. and a number average molecular weight of 4200. The characteristics of the crystalline polyester 2 are shown in Table 1.

<Production Example of Crystalline Polyester 3>
A reactor equipped with a stirrer, a thermometer, and an outflow cooler was added with 174.2 parts by mass (1.0 mol) of sebacic acid, 62.1 parts by mass (1.0 mol) of ethylene glycol, and tetrabutyl titanate 0. 50 parts by mass were added, and the esterification reaction was carried out at 190 ° C. Thereafter, the temperature was raised to 220 ° C. and the pressure inside the system was gradually reduced, and a polycondensation reaction was performed at 150 Pa to obtain crystalline polyester 3. The crystalline polyester 3 had a melting point of 84 ° C. and a number average molecular weight of 3000. The characteristics of the crystalline polyester 3 are shown in Table 1.

<Production example of crystalline polyester 4>
Manufacture of crystalline polyester 3 except that sebacic acid 174.2 parts by mass (1.0 mol part) was changed to glutaric acid 160.2 parts by mass (1.0 mol part). In the same manner, crystalline polyester 4 was obtained. The crystalline polyester 4 had a melting point of 87 ° C. and a number average molecular weight of 4100. The characteristics of the crystalline polyester 4 are shown in Table 1.

<Production Example of Crystalline Polyester 5>
In the production of the crystalline polyester 3, except that 174.2 parts by mass (1.0 mol) of sebacic acid was changed to 342.6 parts by mass (1.0 mol) of 1,18-octadecadicarboxylic acid. Crystalline polyester 5 was obtained in the same manner as in the production of crystalline polyester 3. The crystalline polyester 5 had a melting point of 62 ° C. and a number average molecular weight of 4800. The characteristics of the crystalline polyester 5 are shown in Table 1.

<Production example of crystalline polyester 6>
In a reaction apparatus equipped with a stirrer, a thermometer, and an outflow cooler, 342.6 parts by mass (1.0 mol part) of 1,18-octadecadicarboxylic acid and 258.5 parts by mass of 1,16-hexadecanediol (1 0.0 mol part) and 0.50 part by mass of tetrabutyl titanate were added, and an esterification reaction was carried out at 190 ° C. Thereafter, the temperature was raised to 220 ° C. and the pressure inside the system was gradually reduced, and a polycondensation reaction was performed at 150 Pa to obtain crystalline polyester 6. The crystalline polyester 6 had a melting point of 78 ° C. and a number average molecular weight of 6300. The characteristics of the crystalline polyester 6 are shown in Table 1.

<Production example of crystalline polyester 7>
In the production of the crystalline polyester 6, except that 258.5 parts by mass (1.0 mol part) of 1,16-hexadecanediol was changed to 174.3 parts by mass (1.0 mol part) of 1,10-decanediol. In the same manner as in the production of the crystalline polyester 6, the crystalline polyester 7 was obtained. The crystalline polyester 7 had a melting point of 71 ° C. and a number average molecular weight of 5700. The characteristics of the crystalline polyester 7 are shown in Table 1.

<Production example of crystalline polyester 8>
In a reaction apparatus equipped with a stirrer, a thermometer, and an outflow cooler, 370.6 parts by mass of 1,20-eicosanedicarboxylic acid (1.0 mol part), 286.6 parts by mass of 1,18-octadecanediol (1 0.0 mol part) and 0.50 part by mass of tetrabutyl titanate were added, and an esterification reaction was carried out at 190 ° C. Thereafter, the temperature was raised to 220 ° C. and the pressure inside the system was gradually reduced, and a polycondensation reaction was performed at 150 Pa to obtain crystalline polyester 8. Crystalline polyester 8 had a melting point of 74 ° C. and a number average molecular weight of 5900. The properties of the crystalline polyester 8 are shown in Table 1.

(Preparation of crystalline polyester fine particle dispersion 1)
-Crystalline polyester 1 200 parts by mass-Ion-exchanged water 500 parts by mass The above materials are put in a stainless steel container, heated and melted to 95 ° C in a warm bath, and using a homogenizer (manufactured by IKA: Ultra Turrax T50) at 7800 rpm. While stirring well, add 0.1N sodium bicarbonate to increase the pH above 7.0. Thereafter, a mixed solution of 3 parts by mass of sodium dodecylbenzenesulfonate and 297 parts by mass of ion-exchanged water was gradually added dropwise and emulsified and dispersed to obtain a crystalline polyester fine particle dispersion 1. When the particle size distribution of the crystalline polyester fine particles contained in the crystalline polyester fine particle dispersion 1 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the average particle size of the crystalline polyester fine particles contained was , 0.21 μm, and coarse particles exceeding 1 μm were not observed.

(Preparation of crystalline polyester fine particle dispersions 2 to 8)
In the preparation of the crystalline polyester fine particle dispersion 1, the crystalline polyester fine particle dispersion 2 to the same as the preparation of the crystalline polyester fine particle dispersion 1 except that the crystalline polyester 1 is changed to the crystalline polyester 2 to 8. 8 was obtained. The particle size distribution of the crystalline polyester fine particles contained in the crystalline polyester fine particle dispersions 2 to 8 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.). The diameters were 0.27 μm, 0.30 μm, 0.25 μm, 0.26 μm, 0.22 μm, 0.22 μm, and 0.24 μm, respectively, and no coarse particles exceeding 1 μm were observed.

(Preparation of amorphous polyester resin fine particle dispersion)
Amorphous polyester resin 200 parts by mass (terephthalic acid: isophthalic acid: propylene oxide modified bisphenol A (2 mol adduct): ethylene oxide modified bisphenol A (2 mol adduct) = 30: 30: 30: 10 (mass basis ), Glass transition temperature (Tg): 47 ° C., weight average molecular weight (Mw): 9800, number average molecular weight (Mn): 3800, acid value: 12 mgKOH / g)
-Ion-exchanged water 500 parts by mass The above material is put in a stainless steel vessel, heated and melted to 95 ° C in a warm bath, and 0.1 N while sufficiently stirring at 7800 rpm using a homogenizer (manufactured by IKA: Ultra Turrax T50). Add sodium bicarbonate to increase pH above 7.0. Thereafter, a mixed solution of 3 parts by mass of sodium dodecylbenzenesulfonate and 297 parts by mass of ion-exchanged water was gradually added dropwise to carry out emulsification dispersion. When the particle size distribution of the amorphous polyester resin fine particles contained in the amorphous polyester resin fine particle dispersion was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the amorphous polyester resin fine particles contained therein were measured. The average particle size of was 0.29 μm, and coarse particles exceeding 1 μm were not observed.

(Preparation of release agent fine particle dispersion)
Ion-exchanged water 500 parts by mass release agent (ester compound mainly composed of behenyl behenate) 200 parts by mass (Unistar M-2222SL, manufactured by NOF Corporation)
Put the above materials in a stainless steel container, heat and melt to 95 ° C. in a warm bath, add 0.1N sodium hydrogen carbonate with sufficient stirring at 7800 rpm using a homogenizer (IKA: Ultra Tarrax T50) to adjust the pH. Make it larger than 7.0. Thereafter, a mixed solution of 5 parts by mass of sodium dodecylbenzenesulfonate and 295 parts by mass of ion-exchanged water was gradually added dropwise to carry out emulsification dispersion. When the particle size distribution of the release agent fine particles contained in this release agent fine particle dispersion was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the average particle size of the release agent fine particles contained was: Coarse particles of 0.35 μm and exceeding 1 μm were not observed.

(Preparation of colorant fine particle dispersion)
C. I. Pigment Blue 15: 3 25 parts by mass Sodium dodecylbenzenesulfonate 1 part by mass Ion-exchanged water 74 parts by mass The above was mixed and dispersed using a sand grinder mill. When the particle size distribution of the colorant fine particles contained in the colorant fine particle dispersion was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the average particle size of the colorant fine particles contained was 0.2 μm. In addition, coarse particles exceeding 1 μm were not observed.

(Preparation of charge control agent fine particle dispersion)
20 parts by mass of a metal compound of di-alkyl-salicylic acid (charge control agent, Bontron E-84, manufactured by Orient Chemical Industries)
Sodium dodecylbenzenesulfonate 0.3 parts by mass Ion exchange water 79.7 parts by mass The above was mixed and dispersed using a sand grinder mill. When the particle size distribution of the charge control agent fine particles contained in this charge control agent fine particle dispersion was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the average particle size of the charge control agent fine particles contained was: Coarse particles of 0.2 μm and exceeding 1 μm were not observed.

  In the present invention, the nonionic surfactants listed in Table 2 below were used.

<Method for Manufacturing Toner 1>
-Crystalline polyester fine particle dispersion 1 400 parts by mass-Amorphous polyester fine particle dispersion 1350 parts by mass-Release agent fine particle dispersion 140 parts by mass-Colorant fine particle dispersion 80 parts by mass-Charge control agent fine particle dispersion 10 parts by mass Parts / nonionic surfactant 1 20 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
Into a reactor (1 liter flask, anchor blade with baffle), crystalline polyester fine particle dispersion 1, amorphous polyester fine particle dispersion, release agent fine particle dispersion and nonionic surfactant 1 are charged uniformly. Mix. On the other hand, the colorant fine particle dispersion and the charge control agent fine particle dispersion are uniformly mixed in a 500 mL beaker, and this is gradually added to the reactor while stirring to obtain a mixed dispersion. While stirring the obtained mixed dispersion, 20 parts by mass of 5.0% by mass aluminum sulfate aqueous solution was dropped (aggregation step).
After completion of the dropwise addition, the system was replaced with nitrogen, and the system was maintained at 50 ° C. for 1 hour and further at 55 ° C. for 1 hour. Thereafter, the temperature was raised and maintained at 90 ° C. for 30 minutes (thermal fusion process). The reaction at this time was performed in a nitrogen atmosphere. After completion of the predetermined time, cooling was performed until the temperature reached room temperature at a rate of 0.5 ° C. per minute. After cooling, the reaction product was subjected to solid-liquid separation with a 10 L pressure filter under a pressure of 0.4 Mpa to obtain a toner cake. Thereafter, ion-exchanged water was added to the pressure filter until the water became full, and washing was performed at a pressure of 0.4 Mpa. After washing twice in the same manner, fluidized bed drying was performed at 45 ° C. to obtain toner particles.
Toner 100 was obtained by stirring and mixing 100 parts by mass of the toner particles with 1.8 parts by mass of hydrophobic silica having a BET specific surface area of 130 (m ² / g). The production conditions of toner 1 are shown in Table 3.

<Method for Manufacturing Toner 2>
After the toner was washed three times with ion-exchanged water in the production method of toner 1, the toner cake was washed with ion-exchanged water four times, and then the toner cake was nonionic with a concentration of 0.5% by mass of a 50/50 mixed solvent of methanol / water. It was re-dispersed in an aqueous solution of surfactant 1 and allowed to stand for 24 hours to allow the nonionic surfactant to penetrate into the toner particles. Thereafter, solid-liquid separation was performed again with a 10 L capacity pressure filter under a pressure of 0.4 Mpa to obtain a toner cake, followed by fluidized bed drying at 45 ° C. to obtain toner particles. Toner 2 was obtained by mixing 1.8 parts by mass of hydrophobic silica having a BET specific surface area of 130 (m ² / g) with 100 parts by mass of the toner particles. The production conditions of toner 2 are shown in Table 3.

<Method for Manufacturing Toner 3>
-Crystalline polyester fine particle dispersion 1 1000 parts by weight-Amorphous polyester fine particle dispersion 750 parts by weight-Release agent fine particle dispersion 140 parts by weight-Colorant fine particle dispersion 80 parts by weight-Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 3 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
・ Anionic surfactant 3.5 parts by mass (sodium dodecylbenzenesulfonate)
Using the above materials, toner 3 was obtained in the same manner as toner 1 except that the number of washings was 3 in the manufacturing method of toner 1. The production conditions of the toner 3 are shown in Table 3.

<Method for Manufacturing Toner 4>
-Crystalline polyester fine particle dispersion 1 400 parts by mass-Amorphous polyester fine particle dispersion 1350 parts by mass-Release agent fine particle dispersion 140 parts by mass-Colorant fine particle dispersion 80 parts by mass-Charge control agent fine particle dispersion 10 parts by mass Parts / nonionic surfactant 1 5 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
・ Anionic surfactant 3.5 parts by mass (sodium dodecylbenzenesulfonate)
Using the above materials, Toner 4 was obtained in the same manner as Toner 1. The production conditions of the toner 4 are shown in Table 3.

<Method for Manufacturing Toner 5>
-Crystalline polyester fine particle dispersion 1 400 parts by mass-Amorphous polyester fine particle dispersion 1350 parts by mass-Release agent fine particle dispersion 140 parts by mass-Colorant fine particle dispersion 80 parts by mass-Charge control agent fine particle dispersion 10 parts by mass Parts / anionic surfactant 5 parts by weight (sodium dodecylbenzenesulfonate)
Using the above materials, the toner 2 was washed four times with ion-exchanged water and washed twice with ion-exchanged water. Furthermore, when it was re-dispersed in a 0.5% by mass nonionic surfactant 1 in a 50:50 mixed solvent of methanol / water, an aqueous solution of the nonionic surfactant 1 having a concentration of 4% by mass was obtained. A toner 5 was obtained in the same manner as the toner 2 except that it was redispersed. The manufacturing conditions of the toner 5 are shown in Table 3.

<Method for Manufacturing Toner 6>
Crystalline polyester fine particle dispersion 3 100 parts by mass Amorphous polyester fine particle dispersion 1650 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 5 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
・ Anionic surfactant 1.5 parts by weight (sodium dodecylbenzenesulfonate)
A toner 6 was obtained in the same manner as in the toner 1 except that the above material was used and the toner 1 was washed three times with ion-exchanged water and then washed twice with ion-exchanged water. The production conditions of the toner 6 are shown in Table 3.

<Method for Manufacturing Toner 7>
Crystalline polyester fine particle dispersion 4 600 parts by mass Amorphous polyester fine particle dispersion 1150 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 20 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
Using the above materials, the toner 2 was washed four times with ion-exchanged water and washed twice with ion-exchanged water. Furthermore, when it was re-dispersed in a 0.5% by weight nonionic surfactant 1 in a 50:50 mixed solvent of methanol / water, a 0.1% by weight nonionic surfactant 1 Toner 7 was obtained in the same manner as toner 2 except that it was redispersed in an aqueous solution. The manufacturing conditions of the toner 7 are shown in Table 3.

<Method for Manufacturing Toner 8>
Crystalline polyester fine particle dispersion 8 600 parts by mass Amorphous polyester fine particle dispersion 1150 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 20 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
Toner 8 was obtained in the same manner as Toner 2 except that the above material was used and the toner 2 was washed four times with ion-exchanged water and washed twice with ion-exchanged water. The manufacturing conditions of the toner 8 are shown in Table 3.

<Method for Manufacturing Toner 9>
Crystalline polyester fine particle dispersion 6 600 parts by mass Amorphous polyester fine particle dispersion 1150 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 5 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
・ 2.5 parts by weight of anionic surfactant (sodium dodecylbenzenesulfonate)
The toner 2 was washed with ion exchange water four times and then washed twice with ion exchange water. Furthermore, when it was re-dispersed in a 0.5% by mass nonionic surfactant 1 of a 50:50 mixed solvent of methanol / water, an aqueous solution of the nonionic surfactant 1 having a concentration of 1% by mass was obtained. A toner 9 was obtained in the same manner as the toner 2 except that it was redispersed. The manufacturing conditions of the toner 9 are shown in Table 3.

<Method for Manufacturing Toner 10>
-Crystalline polyester fine particle dispersion 1 400 parts by mass-Amorphous polyester fine particle dispersion 1350 parts by mass-Release agent fine particle dispersion 140 parts by mass-Colorant fine particle dispersion 80 parts by mass-Charge control agent fine particle dispersion 10 parts by mass Parts / nonionic surfactant 1 5 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
・ Anionic surfactant 5 parts by weight (sodium dodecylbenzenesulfonate)
Using the above materials, Toner 10 was obtained in the same manner as Toner 1. The manufacturing conditions of the toner 10 are shown in Table 3.

<Method for Manufacturing Toner 11>
Crystalline polyester fine particle dispersion 1 100 parts by mass Amorphous polyester fine particle dispersion 1650 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / anionic surfactant 5 parts by weight (sodium dodecylbenzenesulfonate)
The toner 2 was washed with ion exchanged water four times and then washed with ion exchanged water three times. Furthermore, when it was re-dispersed in a 0.5% by mass nonionic surfactant 1 of a 50:50 mixed solvent of methanol / water, a 0.05% by mass nonionic surfactant 2 was obtained. Toner 11 was obtained in the same manner as Toner 2 except that it was redispersed in an aqueous solution. The manufacturing conditions of the toner 11 are shown in Table 3.

<Method for Manufacturing Toner 12>
Crystalline polyester fine particle dispersion 1 100 parts by mass Amorphous polyester fine particle dispersion 1650 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / anionic surfactant 5 parts by weight (sodium dodecylbenzenesulfonate)
The toner 2 was washed with ion exchanged water four times and then washed with ion exchanged water three times. Furthermore, when it was re-dispersed in a nonionic surfactant 1 having a concentration of 0.5% by mass in a 50:50 mixed solvent of methanol / water, the nonionic surfactant 2 having a concentration of 0.07% by mass was obtained. Toner 12 was obtained in the same manner as Toner 2 except that it was redispersed in an aqueous solution. The production conditions of the toner 12 are shown in Table 3.

<Method for Manufacturing Toner 13>
-Crystalline polyester fine particle dispersion 1 400 parts by mass-Amorphous polyester fine particle dispersion 1350 parts by mass-Release agent fine particle dispersion 140 parts by mass-Colorant fine particle dispersion 80 parts by mass-Charge control agent fine particle dispersion 10 parts by mass Parts / anionic surfactant 5 parts by weight (sodium dodecylbenzenesulfonate)
The toner 2 was washed with ion exchanged water four times and then washed with ion exchanged water three times. Furthermore, when it was re-dispersed in a 0.5% by mass nonionic surfactant 1 in a 50:50 mixed solvent of methanol / water, a 0.3% by mass nonionic surfactant 3 was obtained. A toner 13 was obtained in the same manner as the toner 2 except that it was redispersed in an aqueous solution. The manufacturing conditions of the toner 13 are shown in Table 3.

<Method for Manufacturing Toner 14>
Crystalline polyester fine particle dispersion 5 400 parts by mass Amorphous polyester fine particle dispersion 1350 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / anionic surfactant 1.5 parts by weight (sodium dodecylbenzenesulfonate)
Using the above-mentioned materials, the toner 2 was washed with ion-exchanged water four times in the method for producing toner 2, but was not washed. Further, it was re-dispersed in a nonionic surfactant 1 having a concentration of 0.5% by mass in a 50/50 mixed solvent of methanol / water to obtain a nonionic surfactant 4 having a concentration of 0.3% by mass. A toner 14 was obtained in the same manner as the toner 2 except that it was redispersed in an aqueous solution. The manufacturing conditions of the toner 14 are shown in Table 3.

<Method for Manufacturing Toner 15>
Crystalline polyester fine particle dispersion 5 400 parts by mass Amorphous polyester fine particle dispersion 1350 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / anionic surfactant 1.5 parts by weight (sodium dodecylbenzenesulfonate)
Using the above-mentioned materials, the toner 2 was washed with ion-exchanged water four times in the method for producing toner 2, but was not washed. Furthermore, when it was re-dispersed in a 0.5% by mass nonionic surfactant 1 in a 50:50 mixed solvent of methanol / water, a 0.3% by mass nonionic surfactant 5 was obtained. A toner 14 was obtained in the same manner as the toner 2 except that it was redispersed in an aqueous solution. The manufacturing conditions of the toner 14 are shown in Table 3.

<Method for Manufacturing Toner 16>
Crystalline polyester fine particle dispersion 5 400 parts by mass Amorphous polyester fine particle dispersion 1350 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / anionic surfactant 1.5 parts by weight (sodium dodecylbenzenesulfonate)
Using the above materials, the toner 2 was washed four times with ion-exchanged water and then washed three times with ion-exchanged water. Further, it was re-dispersed in a nonionic surfactant 1 having a concentration of 0.5% by mass in a 50/50 mixed solvent of methanol / water to obtain a nonionic surfactant 6 having a concentration of 0.3% by mass. Toner 16 was obtained in the same manner as toner 2 except that it was redispersed in an aqueous solution. The manufacturing conditions of the toner 16 are shown in Table 3.

<Method for Manufacturing Toner 17>
Crystalline polyester fine particle dispersion 7 400 parts by mass Amorphous polyester fine particle dispersion 1350 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control particle dispersion 10 parts by weight・ Anionic surfactant 1.5 parts by mass (sodium dodecylbenzenesulfonate)
Using the above materials, the toner 2 was washed four times with ion-exchanged water and then washed three times with ion-exchanged water. Furthermore, when it was re-dispersed in a 0.5% by mass nonionic surfactant 1 in a 50:50 mixed solvent of methanol / water, a 0.3% by mass nonionic surfactant 7 was obtained. Toner 17 was obtained in the same manner as toner 2 except that it was redispersed in an aqueous solution. The manufacturing conditions of the toner 17 are shown in Table 3.

<Method for Manufacturing Toner 18>
Crystalline polyester fine particle dispersion 7 400 parts by mass Amorphous polyester fine particle dispersion 1350 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / anionic surfactant 1.5 parts by weight (sodium dodecylbenzenesulfonate)
Using the above materials, the toner 2 was washed four times with ion-exchanged water and then washed three times with ion-exchanged water. Furthermore, when it was re-dispersed in a 0.5% by weight nonionic surfactant 1 of a 50:50 mixed solvent of methanol / water, a 0.1% by weight nonionic surfactant 8 was obtained. A toner 18 was obtained in the same manner as the toner 2 except that it was redispersed in an aqueous solution. The manufacturing conditions of the toner 18 are shown in Table 3.

<Method for Producing Toner 19>
Crystalline polyester fine particle dispersion 2 400 parts by mass Amorphous polyester fine particle dispersion 1350 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 9 5 parts by mass / anionic surfactant 1.5 parts by mass (sodium dodecylbenzenesulfonate)
Using the above materials, Toner 19 was obtained in the same manner as Toner 1. The manufacturing conditions of the toner 19 are shown in Table 3.

<Method for Manufacturing Toner 20>
Crystalline polyester fine particle dispersion 2 400 parts by mass Amorphous polyester fine particle dispersion 1350 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 5 parts by mass / cationic surfactant 2.5 parts by mass (cetyl tertiary butyl ammonium bromide)
Using the above materials, the toner 1 was produced three times with ion-exchanged water and then re-dispersed in an aqueous solution of 0.1% by weight cationic surfactant (cetyl tertiary butyl ammonium bromide) for 24 hours. The cationic surfactant was allowed to permeate into the toner particles. Thereafter, after further washing with ion-exchanged water twice, it is re-dispersed in 0.3% by weight nonionic surfactant 1 of a 50:50 mixed solvent of methanol / water and left for 24 hours in the toner particles. Nonionic surfactant 1 was infiltrated into the surface. Thereafter, solid-liquid separation was performed again with a 10 L capacity pressure filter under a pressure of 0.4 Mpa to obtain a toner cake, followed by fluidized bed drying at 45 ° C. to obtain toner particles. Toner 20 was obtained by stirring and mixing 1.8 parts by mass of hydrophobic silica having a BET specific surface area of 130 (m ² / g) with 100 parts by mass of the toner particles. The manufacturing conditions of the toner 20 are shown in Table 3.

<Method for Manufacturing Toner 21>
Crystalline polyester 2 5 parts by mass Amorphous polyester 74 parts by mass (terephthalic acid: isophthalic acid: propylene oxide modified bisphenol A (2 mol adduct): ethylene oxide modified bisphenol A (2 mol adduct) = 30: 30 : 30:10 (mass basis) polycondensate, glass transition temperature (Tg): 47 ° C., weight average molecular weight (Mw): 9800, number average molecular weight (Mn): 3800, acid value: 12 mgKOH / g)
-80 parts by weight of methyl ethyl ketone-80 parts by weight of ethyl acetate-15 parts by weight of ester wax (melting point: 73 ° C) I. Pigment Blue 15: 3 5 parts by mass / metal compound of di-alkyl salicylic acid 1 part by mass (charge control agent, Bontron E-84, manufactured by Orient Chemical Industries)
The mixture consisting of was dispersed for 3 hours using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.) to prepare a dispersion. In a 2 liter four-necked flask equipped with a high-speed stirring device TK-homomixer, 350 parts by mass of ion-exchanged water and 225 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution were added. Was adjusted to 10,000 rpm and heated to 65 ° C. To this, 34 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a minute hardly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ .
272 parts by mass of the dispersion was charged into a high-speed agitator, and granulated for 15 minutes at 65 ° C. with stirring while maintaining a rotational speed of 10,000 rpm. Thereafter, the high-speed stirrer is changed to a normal propeller stirrer, the rotation speed of the stirrer is maintained at 150 rpm, the internal temperature is raised to 95 ° C. and held for 3 hours to remove the solvent from the dispersion, and the toner A dispersion of particles was prepared.
The toner particle dispersion was subjected to solid-liquid separation with a 10 L pressure filter under a pressure of 0.4 Mpa to obtain a toner cake. Thereafter, ion-exchanged water was added to the pressure filter until the water became full, and washing was performed at a pressure of 0.4 Mpa. This was redispersed in an aqueous solution in which 0.5 parts by mass of an anionic surfactant (sodium dodecylbenzenesulfonate) and 0.1 parts by mass of the nonionic surfactant 1 were dissolved in 1000 parts by mass of ion-exchanged water. did. The toner particles were allowed to stand for 24 hours to allow the anionic surfactant and nonionic surfactant to penetrate into the toner particles.
The dispersion was again subjected to solid-liquid separation under a pressure of 0.4 Mpa using a 10 L capacity pressure filter, and then fluidized-bed dried at 45 ° C. to obtain toner particles.
Toner 21 was obtained by stirring and mixing 1.8 parts by mass of hydrophobic silica having a BET specific surface area of 130 (m ² / g) with 100 parts by mass of the toner particles. The manufacturing conditions of the toner 21 are shown in Table 3.

<Method for Manufacturing Toner 22>
500 parts by mass of 0.1 M Na ₃ PO ₄ aqueous solution is added to 720 parts by mass of ion-exchanged water and heated to 60 ° C., and then 72 parts by mass of 1.0 M CaCl ₂ aqueous solution is added to contain a dispersion stabilizer. An aqueous medium was obtained.
-Styrene 60 mass parts-n-butyl acrylate 23 mass parts-C.I. I. Pigment Blue 15: 3 5 parts by mass / metal compound of di-alkylsalicylic acid 0.75 parts by mass (charge control agent, Bontron E-84, manufactured by Orient Chemical Industries)
・ Divinylbenzene 0.5 mass part ・ Crystalline polyester 1 5 mass part ・ Crystal nucleating agent ・ Adekastab NA-11 (Asahi Denka Kogyo) 0.25 mass part (methylenebis (2,4-di-tBu-phenyl) phosphate Sodium salt)
The above formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.) to obtain a monomer composition. This monomer composition was heated to 60 ° C., and 5.5 parts by mass of paraffin wax (melting point: 63 ° C.) was added and mixed and dissolved. Then, the polymerization initiator 2,2′-azobis (2,4 -Dimethylvaleronitrile) 5.5 parts by mass was dissolved.
The monomer composition was put into the aqueous medium and stirred at 12,000 rpm using a TK homomixer in a nitrogen atmosphere at 60 ° C. for granulation. Thereafter, the reaction was carried out at 70 ° C. for 5 hours while stirring with a paddle stirring blade, then the temperature was raised to 90 ° C. and the mixture was stirred as it was for 2 hours. After completion of the reaction, the suspension was cooled and washed with acid by adding hydrochloric acid.
The toner particle dispersion was subjected to solid-liquid separation with a 10 L pressure filter under a pressure of 0.4 Mpa to obtain a toner cake. Thereafter, ion-exchanged water was added to the pressure filter until the water became full, and washing was performed at a pressure of 0.4 Mpa. This was redispersed in an aqueous solution in which 0.1 part by weight of an anionic surfactant (sodium dodecylbenzenesulfonate) and 0.1 part by weight of a nonionic surfactant 1 were dissolved in 1000 parts by weight of ion-exchanged water. did. The toner particles were allowed to stand for 24 hours to allow the anionic surfactant and nonionic surfactant to penetrate into the toner particles.
The dispersion was again subjected to solid-liquid separation under a pressure of 0.4 Mpa using a 10 L capacity pressure filter, and then fluidized-bed dried at 45 ° C. to obtain toner particles.
To 100 parts by mass of the toner particles, 1.8 parts by mass of hydrophobic silica having a BET specific surface area of 130 (m ² / g) was stirred and mixed to obtain toner 22. The manufacturing conditions of the toner 22 are shown in Table 3.

<Method for Manufacturing Toner 23>
-Crystalline polyester fine particle dispersion 1 1000 parts by weight-Amorphous polyester fine particle dispersion 750 parts by weight-Release agent fine particle dispersion 140 parts by weight-Colorant fine particle dispersion 80 parts by weight-Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 7.5 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
・ Anionic surfactant 3.5 parts by mass (sodium dodecylbenzenesulfonate)
A toner 23 was obtained in the same manner as the toner 1 except that the above material was used and the manufacturing method of the toner 1 was changed from one washing to three times. The manufacturing conditions of the toner 23 are shown in Table 3.

<Method for Manufacturing Toner 24>
-Crystalline polyester fine particle dispersion 1 400 parts by mass-Amorphous polyester fine particle dispersion 1350 parts by mass-Release agent fine particle dispersion 140 parts by mass-Colorant fine particle dispersion 80 parts by mass-Charge control agent fine particle dispersion 10 parts by mass Parts / anionic surfactant 3.5 parts by mass (sodium dodecylbenzenesulfonate)
Using the above-mentioned materials, the number of washings was 4 in the method for producing toner 2, and the nonionic surfactant 1 having a concentration of 0.5% by mass in a 50/50 mixed solvent of methanol / water was used. A toner 24 was obtained in the same manner as in the toner 2 except that it was redispersed in an aqueous solution of the nonionic surfactant 1 having a concentration of 4% by mass. The production conditions of the toner 24 are shown in Table 3.

<Method for Manufacturing Toner 25>
-Crystalline polyester fine particle dispersion 1 1000 parts by weight-Amorphous polyester fine particle dispersion 750 parts by weight-Release agent fine particle dispersion 140 parts by weight-Colorant fine particle dispersion 80 parts by weight-Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 25 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries, Ltd.); oxyalkylene average added mole number 10)
・ 4 parts by weight of anionic surfactant (sodium dodecylbenzenesulfonate)
A toner 25 was obtained in the same manner as the toner 1 except that the above material was used and the toner 1 was produced by the method for producing the toner 1 except that the washing was performed 3 times. Table 3 shows the manufacturing conditions of the toner 25.

<Method for Manufacturing Toner 26>
-Crystalline polyester fine particle dispersion 1 50 parts by weight-Amorphous polyester fine particle dispersion 1700 parts by weight-Release agent fine particle dispersion 140 parts by weight-Colorant fine particle dispersion 80 parts by weight-Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 20 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
Toner 26 was obtained in the same manner as toner 1 using the above materials. The production conditions of the toner 26 are shown in Table 3.

<Method for Manufacturing Toner 27>
A toner 27 was obtained in the same manner as in the toner 2 except that the toner 2 was washed 4 times with ion exchange water and washed 5 times with ion exchange water. The production conditions of the toner 27 are shown in Table 3.

<Method for Manufacturing Toner 28>
Toner 3 in the same manner as in Toner 3 except that the amount of the anionic surfactant (sodium dodecylbenzenesulfonate) added was 3.5 parts by mass in the production method of Toner 3. 28 was obtained. The manufacturing conditions of the toner 28 are shown in Table 3.

<Method for Manufacturing Toner 29>
Crystalline polyester fine particle dispersion 6 400 parts by weight Amorphous polyester fine particle dispersion 1350 parts by weight Release agent fine particle dispersion 140 parts by weight Colorant fine particle dispersion 80 parts by weight Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 3 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
・ Anionic surfactant 5 parts by weight (sodium dodecylbenzenesulfonate)
Using the above materials, Toner 29 was obtained in the same manner as Toner 1. The manufacturing conditions of the toner 29 are shown in Table 3.

<Method for Manufacturing Toner 30>
-Crystalline polyester fine particle dispersion 3 400 parts-Amorphous polyester fine particle dispersion 1350 parts-Release agent fine particle dispersion 140 parts-Colorant fine particle dispersion 80 parts-Charge control agent fine particle dispersion 10 parts Parts / nonionic surfactant 1 10 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries, Ltd.); oxyalkylene average added mole number 10)
Using the above materials, the toner 1 was washed three times with ion-exchanged water and then washed twice with ion-exchanged water. Thereafter, the dispersion is re-dispersed in 5.0% by mass nonionic surfactant 1 in a 50/50 mixed solvent of methanol / water and left for 24 hours to allow the nonionic surfactant 1 to penetrate into the toner particles. It was. This was again subjected to solid-liquid separation with a 10 L capacity pressure filter under a pressure of 0.4 Mpa to obtain a toner cake, followed by fluidized bed drying at 45 ° C. to obtain toner particles.
Toner 30 was obtained by stirring and mixing 1.8 parts by mass of hydrophobic silica having a BET specific surface area of 130 (m ² / g) with 100 parts by mass of the toner particles. The manufacturing conditions of the toner 30 are shown in Table 3.

<Method for Manufacturing Toner 31>
-Crystalline polyester fine particle dispersion 1 1000 parts by weight-Amorphous polyester fine particle dispersion 750 parts by weight-Release agent fine particle dispersion 140 parts by weight-Colorant fine particle dispersion 80 parts by weight-Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 25 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries, Ltd.); oxyalkylene average added mole number 10)
・ Anionic surfactant 5 parts by weight (sodium dodecylbenzenesulfonate)
Toner 31 was obtained in the same manner as toner 1 except that the above material was used and the toner 1 was produced by the method for producing toner 1 except that it was not washed. The manufacturing conditions of the toner 31 are shown in Table 3.

<Method for Manufacturing Toner 32>
-Crystalline polyester fine particle dispersion 1 1000 parts by weight-Amorphous polyester fine particle dispersion 750 parts by weight-Release agent fine particle dispersion 140 parts by weight-Colorant fine particle dispersion 80 parts by weight-Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 30 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries, Ltd.); oxyalkylene average added mole number 10)
・ 4 parts by weight of anionic surfactant (sodium dodecylbenzenesulfonate)
Toner 32 was obtained in the same manner as Toner 1 except that the above material was used and the method for producing Toner 1 was not cleaned where the number of cleaning was 3 times. The manufacturing conditions of the toner 32 are shown in Table 3.

<Method for Manufacturing Toner 33>
-Crystalline polyester fine particle dispersion 1 30 parts by weight-Amorphous polyester fine particle dispersion 1720 parts by weight-Release agent fine particle dispersion 140 parts by weight-Colorant fine particle dispersion 80 parts by weight-Charge control agent fine particle dispersion 10 parts by weight Parts / nonionic surfactant 1 20 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
Toner 33 was obtained in the same manner as toner 1 using the above materials. The manufacturing conditions of the toner 33 are shown in Table 3.

<Method for Manufacturing Toner 34>
-Crystalline polyester fine particle dispersion 1 1200 parts by mass-Amorphous polyester fine particle dispersion 550 parts by mass-Release agent fine particle dispersion 140 parts by mass-Colorant fine particle dispersion 80 parts by mass-Charge control agent fine particle dispersion 10 parts by mass Parts / nonionic surfactant 1 20 parts by mass (polyoxyethylene (10) lauryl ether (manufactured by Wako Pure Chemical Industries); oxyalkylene average added mole number 10)
Toner 34 was obtained in the same manner as toner 1 using the above materials. The production conditions of the toner 34 are shown in Table 3.

Using the above method, the content A of the ionic surfactant and the content B of the nonionic surfactant in the toners 1 to 26 were measured. Table 4 shows the measured ionic surfactant content A, nonionic surfactant content B, toner particle size, average circularity, and standard deviation of the circularity of the toners 1 to 26.
The toner particle diameter means a weight average particle diameter (D4), and the measurement method is as follows.
<Measurement method of toner particle size>
The particle size [weight average particle size (D4)] of the toner was calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement was performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software was set as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter The value obtained using the product was set. The threshold value and the noise level were automatically set by pressing the “threshold / noise level measurement button”. Further, the current was set to 1600 μA, the gain was set to 2, the electrolyte was set to ISOTON II, and the “aperture tube flush after measurement” was checked.
In the “pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

The following items were evaluated for the toners 1 to 26.
The image evaluation was performed by partially modifying a commercially available color laser printer HP Color LaserJet 3525dn (manufactured by HP). In the modification, the process speed was changed to 240 mm / sec. Furthermore, it has been modified to work even when only one color process cartridge is installed.
After removing toner contained in a commercially available black cartridge and cleaning the inside by air blow, the test toner (300 g) and a toner carrier were mounted on the cartridge for evaluation. The environmental stability and the charging stability were evaluated in a high temperature and high humidity environment (HH: 30 ° C., 80% RH) and in a low temperature and low humidity environment (LL: 15 ° C., 10% RH).
In addition, the image evaluation items and methods are as follows. For the evaluation of environmental stability and charging stability, an original image that has a printing rate of 1% in the horizontal line is the initial (first sheet), 15000 sheets. And after printing 30000 sheets. As the transfer material, XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) of LETTER size was used.
(1) Evaluation of low-temperature fixability For the evaluation, a modified fixing device in which the fixing unit was modified so that the fixing temperature can be adjusted was used. Evaluation was performed in a room temperature and normal humidity (NN: 23.5 ° C., 60% RH) environment. After adjusting the toner amount of the unfixed image to be 0.6 mg / cm ² , a solid image of 5 cm square in the paper at a fixing temperature set in the temperature range of 80 to 150 ° C. at intervals of 5 ° C. 9 points were output. The image was reciprocated five times with sylbon paper loaded with a load of 4.9 kPa, and the temperature at which the density reduction rate measured with “Macbeth reflection densitometer RD918” (manufactured by Macbeth) was 20% or more was minimized. The fixing temperature was evaluated.
(2) Environmental stability evaluation After printing 15,000 sheets of the original image in a high temperature and high humidity environment (HH: 30 ° C., 80% RH) and a low temperature and low humidity environment (LL: 15 ° C., 10% RH), respectively. A sample image in which a solid black image of 20 mm square was printed at the four corners and the center of the paper surface was output, and the average density of the five points was measured. And the difference of the average density | concentration in a high temperature / humidity environment (HH: 30 degreeC, 80% RH) and a low temperature / humidity environment (LL: 15 degreeC, 10% RH) was calculated | required. With respect to the concentration difference, environmental stability was evaluated based on the following criteria.
The image density was measured as a relative density using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) when the white background portion was 0.00.
A: Very good Less than 0.05 B: Good 0.05 or more, less than 0.15 C: No practical problem 0.15 or more, less than 0.25 D: Practical problem 0.25 or more (3) Charging Stability evaluation Initial and after printing 15,000 sheets and 30,000 sheets, each halftone of 10H, 20H, 30H, 40H, 50H, 60H, 70H, 80H, 90H, A0H with respect to the transfer paper conveyance direction An original chart on which images of vertical bands (20 mm in width) were arranged was output, and charging stability was evaluated based on the following criteria.
The 10H halftone image is a value in which 256 gradations are displayed in hexadecimal, and 00H is solid white and FFH is solid black.
The image density was measured as a relative density using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) when the white background portion was 0.00.
A: Through durability, it is possible to obtain an image that reproduces the gradation very well in which the density change of the adjacent halftone vertical band image changes between 0.05 and less than 0.10, and is excellent in charging stability. . B: Although the density change of the adjacent halftone vertical band image changes between 0.10 and less than 0.15 through endurance, an image having a well-reproduced gradation is obtained, and the charging stability is good.
C: Through endurance, the density change of the adjacent halftone vertical band image changes between 0.15 and less than 0.20, but an image in which gradation can be reproduced is obtained, and charging stability is practical. No problem.
D: Through endurance, the density change of the adjacent halftone vertical band image changes at 0.20 or more, and an image in which gradation cannot be reproduced is obtained, and there is a problem in charging stability practically.

[Example 1]
Evaluation was performed using toner 1. As a result, good results were obtained for each item. The evaluation results are shown in Table 5.

[Examples 2 to 26]
Evaluation was performed in the same manner as in Example 1 using toners 2 to 26. In either case, the results were satisfactory for practical use. Table 5 shows the evaluation results of toners 2 to 26.

[Comparative Examples 1 to 8]
Evaluation was performed in the same manner as in Example 1 using toners 27 to 34. The toner 27 was inferior in charging stability in the initial image in a high temperature and high humidity environment, and the gradation could not be reproduced. The toner 28 was inferior in environmental stability, and the density under high temperature and high humidity was very low. For this reason, a sufficient charge amount cannot be obtained through durability under high temperature and high humidity, and gradation cannot be reproduced. The toner 29 was inferior in charging stability under low temperature and low humidity, and gradation could not be reproduced from the middle of the durability. The toner 30 was inferior in environmental stability, and the density under high temperature and high humidity was very low. The toners 31 and 32 have low concentrations in a high-temperature and high-humidity environment, and the gradation cannot be reproduced through durability. The toner 33 could not be fixed in the temperature range of 80 to 150 ° C. and was not evaluated for durability. The tone of the toner 34 deteriorated for the first time after the durability evaluation under low temperature and low humidity. It worsened further when durability was advanced at a level that was already a problem in the middle of durability. Table 5 shows the evaluation results of the toners 27 to 34.

Claims (6)

A toner containing at least toner particles produced in an aqueous medium and inorganic fine powder,
The toner particles include at least a binder resin, a colorant, a release agent, an ionic surfactant, and a nonionic surfactant,
The binder resin includes a crystalline polyester obtained by condensation polymerization of an aliphatic diol and an aliphatic dicarboxylic acid,
The content of the crystalline polyester contained in the toner is 2 to 50 parts by mass with respect to 100 parts by mass of the toner particles.
The content A of the ionic surfactant contained in the toner is 10 ppm or more and 1000 ppm or less,
The toner according to claim 1, wherein the content B of the nonionic surfactant contained in the toner is 100 ppm or more and 5000 ppm or less. 2. The toner according to claim 1, wherein the crystalline polyester has an ester group concentration defined by the following formula of 3.50 mmol / g or more and 10.00 mmol / g or less.
[Ester group concentration (mmol / g)] = [Mole number of ester groups in the repeating structural unit of the crystalline polyester] / [Molecular weight of the repeating structural unit of the crystalline polyester]   The toner according to claim 1, wherein a ratio [B / A] of the content B to the content A is 1.0 or more and 20.0 or less. The nonionic surfactant includes a polyoxyalkylene chain obtained by addition polymerization of ethylene oxide and / or propylene oxide,
4. The toner according to claim 1, wherein an average added mole number of ethylene oxide and / or propylene oxide in the polyoxyalkylene chain is 5 or more and 50 or less. 5.   The toner according to claim 1, wherein the ionic surfactant is an anionic surfactant.   The toner particles include the binder resin in a mixed liquid containing at least the fine particles of the binder resin, the fine particles of the colorant, the fine particles of the release agent, the ionic surfactant, and the nonionic surfactant. The toner according to claim 1, which is obtained by forming aggregated particles including at least resin fine particles, colorant fine particles, and release agent fine particles, and then fusing the aggregated particles by heating.