JP2021056482A - Toner, developer, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

To provide a toner that is excellent in transferability and in-machine contamination resistance without deteriorating cleanability.SOLUTION: A yellow toner contains at least a binder resin and a colorant. When the intensity of a Raman spectrum at a wavenumber λ of each toner particle obtained within a wavenumber region from 950 cm-1 to 3250 cm-1 in Raman spectroscopy of the toner is normalized to 1, and when the integrated intensity of the spectrum of each toner particle obtained within a wavenumber region from 2750 cm-1 to 3250 cm-1 is In, the average value of the In is Iave, and a value calculated with the following formula (1) is a CH ratio, the number ratio of toner particles having an absolute value of the CH ratio of 25.0% or more with respect to the total toner particles is 1.0 number% or more and 15.0 number% or less. Formula (1): CH ratio (%)=[(In-Iave)/Iave]×100.SELECTED DRAWING: None

Description

The present invention relates to toners, developing agents, process cartridges, image forming apparatus and image forming methods.

In image formation by the electrophotographic method, a statically charged image (latent image) is formed on an electrostatic latent image carrier, the charged toner is conveyed by the developer carrier, and the latent image is developed to obtain a toner image. After the formation, the toner image is transferred onto a recording medium such as paper and fixed by a method such as heating to obtain an output image. Further, there is known a technique in which the toner remaining on the electrostatic latent image carrier after transfer is recovered from the electrostatic latent image carrier by a cleaning member and discharged to a waste toner storage portion.

In the development method, the toner particles supplied into the developing machine have variations in particle size, shape, charging characteristics, etc., and it is very difficult to control all the particles as ideal.
If the mixed state of the toner particles and carriers is uneven and triboelectric charging cannot be obtained, or if the charging performance of the toner particles is low, the toner particles cannot be controlled and scatter, causing contamination inside the machine. ..
Further, if the adhesive force between a part of the toner and the carrier, the photoconductor, or the transfer belt is too strong, the transfer cannot be sufficiently performed, and the consumption of the toner increases.
Even a small amount of variation in the characteristics of the toner particles leads to abnormalities in the image system. Therefore, it is important to narrow the distribution of the characteristic values of each toner particle and improve the uniformity.

Patent Document 1 proposes to narrow the charge distribution and improve the transfer efficiency by using an external additive using the in-flame hydrolysis method.
In Patent Document 2, in addition to selecting a specific release agent, it is proposed to improve the transfer rate by narrowing the shape distribution so that the number of particles that are excessively deformed is reduced.
Patent Document 3 proposes that by selecting a specific resin, the scratch resistance of the fixed image is improved and the toner scattering is improved, and the toner scattering is improved by narrowing the particle size distribution and making it spherical. There is.

In the toner of Patent Document 1, non-uniformity of adhesion amount and burial degree is unavoidable in the mixing step of mixing the toner base and the external additive, so there is a limit to improvement in uniformity, and the charge amount distribution is narrowed. The improvement of the transfer rate by the above has not reached a sufficient level.
Although the transfer rate of the toner of Patent Document 2 is improved by making the shape spherical, it is a problem to achieve both cleanability because the cleaning blade slips through.
Although the toner of Patent Document 3 has a certain effect on reducing scattering due to the narrowing of the particle size distribution, it has not reached a sufficient level because it is unavoidable that non-uniformity of the particle size occurs in the granulation process. .. In addition, since the spheroidization worsens the slip-through of the cleaning blade, it is an issue to improve the toner scattering and to achieve both cleanability.

The present invention has been made in view of the above, and an object of the present invention is to provide a toner having excellent transferability and in-machine contamination resistance without deteriorating the cleaning property.

The present invention that solves the above problems is as described below.
And at least a binder resin, a yellow toner containing a colorant, the Raman spectrum in the wave number λ of the toner particles obtained in the wave number region of 950cm ^-1 ~3250cm ^-1 in the Raman spectroscopy of the yellow toner when normalized strength to ^1, the integrated intensity of the spectrum of each of the toner particles obtained in the wave number region of 2750cm ^-1 ~3250cm -1 and _{I n,} the average value of the _{I n} and _{I ave,} the following formula ( When the value calculated in 1) is taken as the CH ratio, the number ratio of the toner particles whose absolute value of the CH ratio is 25.0% or more to all the toner particles is 1.0 number% or more and 15.0 number% or less. Yellow toner characterized by being.
CH ratio _{(%) = [(I n} -I ave) / I ave] × 100 ··· ( Equation 1)

According to the present invention, it is possible to provide a toner having excellent transferability and in-machine contamination resistance without deteriorating the cleaning property.

It is a figure which shows the calculation method of a wave number λ. It is a figure which shows the normalization method which sets the intensity at a wave number λ to 1. It is a figure which shows the method of calculating the average spectral intensity in 2750cm- ^{1 to} 3250cm- ^1. It is a figure which shows the method of calculating the CH ratio from the difference of 1 particle spectrum with respect to the average spectrum. It is a schematic diagram which shows an example of the image forming apparatus which concerns on this invention. It is a schematic diagram which shows another example of the image forming apparatus which concerns on this invention. It is a schematic diagram which shows another example of the image forming apparatus which concerns on this invention. It is a schematic diagram which shows another example of the image forming apparatus which concerns on this invention.

Hereinafter, embodiments of the toner, developer, process cartridge, image forming apparatus, and image forming method according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments shown below, and can be modified within the range conceivable by those skilled in the art, such as other embodiments, additions, modifications, and deletions. However, as long as the action and effect of the present invention are exhibited, it is included in the scope of the present invention.

(toner)
The present invention is a yellow toner containing a binder resin and a colorant, and the number ratio of toner particles having an absolute value of “CH ratio” described later of 25.0% or more to all toner particles is 1.0. It is a yellow toner characterized by having a number% or more and 15.0 number% or less.
Details will be described below.

<Overview of CH rate>
CH rate is an acronym for Content Heatercentity (content non-uniformity), and is an index defined to evaluate the non-uniformity of the raw material content in toner. Compared with the raw material content ratio at the time of toner preparation, it is evaluated how much the raw material content ratio of each toner grain deviates. Naturally, it is preferable that the raw material content ratio of each toner grain does not deviate from the raw material content ratio at the time of toner preparation.

<Calculation method of CH rate>
The CH ratio is calculated from the Raman spectrum of the toner.
The "CH rate" in the present invention, in the range of ^{950cm -1 ~3250cm} -1 in the Raman spectroscopy of the toner, the total intensity of the sum of the Raman spectrum of the toner particles is defined as the wave number that indicates the maximum value lambda, when normalized to 1 the intensity of the Raman spectrum at a wave number λ of the toner ^particles, the integrated intensity of the spectrum of each of the toner particles obtained in the wave number region of 2750cm ^-1 ~3250cm -1 and _{I n,} the _{I n} When the average value is I _ave , it is a value represented by the following (Equation 1).
CH ratio _{(%) = [(I n} -I ave) / I ave] × 100 ··· ( Equation 1)
The Raman spectrum is measured using a Raman microscope. The apparatus used is not particularly limited, but measurement is performed using, for example, "XproRA PLUS" (manufactured by HORIBA, Ltd.). The Raman spectrum is measured for each toner particle, and after obtaining the spectrum of 500 to 600 particles, the CH ratio is calculated by the above formula (Equation 1).

<Measurement conditions for Raman spectrum>
In the present invention, the Raman spectrum is measured under the following measurement conditions.
(1) Selection of excitation laser A laser having an excitation wavelength of 638 nm is used for the measurement of the Raman spectrum. It is measured by irradiating each particle of toner with a laser, and the laser intensity is adjusted so that the toner does not melt.
(2) Number of particles to be measured The spectral shape of each toner particle is slightly different, and 500 to 600 particles of toner are measured in order to evaluate the variation. By measuring the toner of 500 to 600 particles, the measurement variation converges, and it becomes possible to compare different toners.
(3) Wavenumber region to be measured Since the analysis is ^{performed using the region of 950 cm -1 to} 3250 cm ^-1 , it is necessary to measure the wavenumber region including this range.
Fluorescence spectrum at the Raman spectrum measurement also tends to be measured simultaneously, it is preferable to measure in a wavenumber region of spread in order to facilitate removal of fluorescence spectrum, it is preferable that the measured area of about 200cm ^-1 ~3800cm ^-1.
(4) Focus adjustment conditions Adjust so that the outermost surface of the toner particles is in focus.
(5) Other setting items measurement conditions related to the resolution of other Raman spectrum, the objective lens was measured at 50 times, such as a plot interval of the wave direction of the Raman spectrum is about 3cm ^-1 ~4cm ^-1 Measure by setting the resolution.

<Sample preparation method>
In order to measure the toner particles one by one, a sample is prepared by dispersing the toner on a slide glass.

<Correction of Raman spectrum>
Since the Raman spectrum also includes the effects of fluorescence and noise, it is desirable to perform baseline correction of the spectrum data.
The baseline correction method is not particularly limited, but an example of the correction method is shown below.
For example, the baseline correction of the spectrum is performed using the software "Labspec 6.0" (manufactured by HORIBA, Ltd.).
(1) the wavenumber region of the Raman spectrum measured is extracted with ^{200cm -1 ~3800cm} -1.
(2) The baseline correction is executed in (1) above with "order: 9", "maximum score: 57", and "noise score: 4".
(3) (2) above is extracted again with ^{950cm -1 ~3250cm} -1 wavenumber region of the spectrum.

<Standardization of Raman spectrum>
Since the intensity of the Raman spectrum varies depending on the size and shape of the measurement target, the type of raw material, and the like, it is not possible to simply compare the Raman spectrum intensities of different toners. Therefore, by normalizing the Raman spectrum, different toners can be compared with each other. The normalization process is performed using data editing software (for example, Excel) on the spectrum corrected for the baseline.

Standardization is performed by the following method.
(1) As shown in FIG. 1, the total spectrum obtained by adding all the Raman spectra is calculated, and the wave number λ when the total spectrum shows the maximum intensity is obtained.
(2) As shown in FIG. 2, the correction coefficient X (n) is obtained so that the intensity of the wave number λ becomes 1 with respect to the Raman spectrum of the nth particle, and the correction coefficient X (n) is obtained over the entire wave number region. Multiply to normalize the spectral intensity. Hereinafter, the spectrum obtained by the normalization is referred to as a normalized spectrum.
This is done for the Raman spectra of all the measured particles.

<Exclusion of noise data>
In the measurement of Raman spectrum, there are cases where data that causes noise such as dust is acquired, and if they are added to the CH rate calculation, it may not be possible to evaluate correctly, so noise data is excluded as follows. To do.
The area S (n) of the spectrum is calculated with respect to the normalized spectrum of the nth particle of (2). This is done for all the measured particles.
The standard deviation σ (S) of S (n) of all particles is calculated, and the particles that do not satisfy S (n) -2 × σ (S) ≦ S (n) ≦ S (n) + 2 × σ (S) ( n) is treated as error data and excluded from the calculation target of the CH rate.

<Calculation of CH rate>
FIG. 3 is a diagram showing a region ^{of 2750 cm -1 to} 3250 cm ^{-1 in FIG.}
The average spectrum is obtained using the particles (n) not excluded by the noise data exclusion process.
FIG. 4 shows the average spectrum obtained in FIG. 3 and the spectrum of the particle (n) arranged in the figure.
Calculating the integrated intensity _{I n} at ^{2750cm -1 ~3250cm} -1 particle (n), a material obtained by calculating the average value was _{I ave} with _{I n} of all the particles.
Difference in integral intensity in ^{2750cm -1 ~3250cm} -1 and the average spectrum and particles (n) is the _I n _{-I ave.} As the calculation of the rate of change with respect to the average, the CH rate is calculated using the following (Equation 1).
CH ratio _{(%) = [(I n} -I ave) / I ave] × 100 ··· ( Equation 1)
I _n: integral intensity of ^{2750cm -1 ~3250cm} -1 of the Raman spectrum of the n particles th I _ave: particle average of all _{I n}

Since the intensity of the Raman spectrum differs depending on the type of raw material used, the CH rate is not calculated by the difference between In and Iave, but is calculated as the rate of change as in (Equation 1) based on the same concept as the coefficient of variation (CV). I do.
^{In general, by performing analysis using the range of 2750 cm -1 to} 3250 cm ^-1 , where the colorant spectrum hardly appears, it is possible to accurately evaluate the variation in the content of raw materials other than the colorant.

As a result of diligent studies on the issues of achieving both transferability, in-machine contamination resistance, and cleanability, the present inventors have determined that the CH rate, which indicates the non-uniformity of the resin component content in the toner, is the CH rate. It is important that the proportion of particles having an absolute value of 25.0% or more is 1.0 number% or more and 15.0 number% or less, preferably 5.0 number% or more and 10.0 number% or less. I found.
If the number of particles having an absolute CH ratio of 25.0% or more exceeds 15.0, the effect of suppressing in-flight contamination and the effect of improving transferability due to toner scattering become insufficient, which is not preferable.
On the other hand, if it is less than 1.0% by number, the amount of ground-staining toner is also greatly reduced, but the dam of the cleaning blade portion conventionally formed by the ground-staining toner becomes insufficient, and cleaning defects may occur. ..

The proportion of particles having an absolute value of CH ratio of 50.0% or more is 2.0 number% or less, preferably 1.0 number% or less. The threshold value of the absolute value of CH rate of 50.0% is approximately outside the tail of the distribution, and the particles having the absolute value of CH rate of 50.0% or more are particles having extremely different compositions that deviate from the normal distribution. ..
Such particles can cause transfer defects, but are particularly liable to scatter in the cabin. It is possible to improve the contamination resistance in the machine by reducing the proportion of particles having an absolute value of CH rate of 50.0% or more.

The median CH rate is preferably −3.0% or higher. When the median CH rate is −3.0% or more, toner scattering due to carrier deterioration does not occur, and the stain resistance in the machine does not deteriorate.
Since the CH ratio evaluates the dissociation with respect to the average spectrum, the sum of the CH ratios of all the particles becomes zero. However, when the distribution of components is biased, the median CH ratio is not zero, especially in the presence of some particles with extremely different compositions.

If the median CH ratio is negative, it means that particles with an extremely high CH ratio, that is, particles having a large amount of resin component are present. On the contrary, when the median CH ratio is positive, it means that there are particles having an extremely low CH ratio, that is, particles having an extremely small amount of resin components, for example, particles having an extremely large amount of a colorant.

It is highly possible that the release agent is excessively contained in the particles having a large amount of resin component having a high CH ratio. Particles containing a large amount of release agent are likely to cause carriers to spent, resulting in a decrease in charging ability due to carrier contamination.
Therefore, the lower the median CH rate, the higher the CH rate and the more toner is likely to cause carrier contamination, and it is preferable that the median CH rate does not become a low value.

The method for producing the toner of the present invention is not particularly limited. In the kneading and pulverizing method, it is desirable to pulverize the raw materials in a more uniformly finely dispersed state in the binder resin, such as pre-dispersion of raw materials, increase in strength of the kneading process, and prevention of reaggregation by temperature control.

As an example of the chemical method, the dissolution / suspension method will be described in detail.
A toner composition containing at least a binder resin, a colorant, and a mold release agent is dissolved in an organic solvent, and then the material is refined by a shearing force or a collision force. At this time, by using the shearing force and the collision force together, it is possible to efficiently reduce the non-uniform composition toner having an absolute value of CH ratio of 25.0% or more.

The dispersion method is not particularly limited, but for microdispersion by shearing, a method of pulverizing the material with a high shearing force generated in a narrow gap between the rotor and the stator is preferably used. For microdispersion due to collision, a method is preferably used in which beads such as zirconia are filled in the vessel and rotated, and the material is crushed by collision between the beads or between the beads and the vessel.

Milling by collision is particularly effective for large materials over 1 μm, while milling by shear is effective in further miniaturizing submicron-order materials. Since the main pulverization target areas of the two methods are different, it is possible to improve the uniformity of the material by using them together, so it is particularly preferable to use the two methods together. The order of dispersion by shearing and dispersion by collision is not limited.

In order to efficiently miniaturize the material, it is preferable that the peripheral speed of the rotor exceeds 12 m / s in the microdispersion by shearing. Further, for crushing due to collision, the peripheral speed of the disc is preferably 6 m / s or more, and more preferably 10 m / s to 12 m / s. In crushing by collision, if the peripheral speed of the disk is less than 6 m / s, sufficient crushing energy due to collision cannot be obtained, and beads are biased, so that sufficient dispersion cannot be performed. On the other hand, if the peripheral speed of the disc is increased too much, it will be dispersed excessively, and there is a concern that the cleanability may be deteriorated due to the reduction of the ground stain toner. There is also a risk of reaggregation due to increased liquid temperature and overdispersion.

The media diameter is preferably 0.5 mm or less, more preferably 0.3 mm or less. The smaller the beads, the larger the total surface area of the beads, which increases the chances of dispersion due to collision and improves the dispersion efficiency. If it is too small, it is necessary to narrow the opening of the screen for separating the beads and the process liquid, so there is a risk that the liquid temperature will rise without producing a flow rate and reaggregation will occur.

Further, in order to reduce toner particles having a non-uniform composition in which the absolute value of the CH ratio exceeds 25.0%, an inorganic substance having a hardness higher than that of an organic substance such as a colorant or a release agent is added to the dispersion liquid to disperse the mixture. It is also effective to let them.
The inorganic substance is not particularly limited, and the case where montmorillonite, which is an organically modified layered inorganic mineral, is added as an example will be described below.

After dissolving a toner composition containing at least an organically modified layered inorganic mineral in addition to a binder resin, a colorant, and a mold release agent in an organic solvent, the material is finely divided by a collision force using a media type disperser. To become. When the composition contains the organically modified layered inorganic mineral, the material can be finely dispersed more efficiently than when the composition does not contain the organically modified layered inorganic mineral, and the toner particles having a non-uniform composition can be reduced. Is possible. This makes it possible to effectively disperse low-hardness organic substances because collision opportunities occur between the beads, between the beads and the vessel, as well as between the beads and the inorganic substance, and between the vessel and the inorganic substance.
In the rotor-stator type shear dispersion, the pulverization efficiency does not increase even if an inorganic substance is added, and it is important to utilize the inorganic substance as a pulverizing medium.

The amount of the inorganic substance added is preferably 0.2% by mass to 2.0% by mass, more preferably 0.7% by mass to 1.5% by mass, based on the total solid content. When the addition amount is 0.2% by mass to 2.0% by mass, the function as a pulverized medium is sufficiently exhibited, and the uniformity of the CH ratio is improved.

The shape, size, etc. of the toner are not particularly limited and may be appropriately selected depending on the intended purpose. However, the following average circularity, volume average particle size, volume average particle size and number average are used. It is preferable to have a ratio to the particle size (volume average particle size / number average particle size) and the like.

The average circularity is an average value of circularity, which is a value obtained by dividing the peripheral length of an equivalent circle having the same projected area as the shape of the toner by the peripheral length of the projected image of the toner, and is, for example, 0.950 to 0. .980 is preferable, and 0.960 to 0.975 is more preferable. It is preferable that the number of particles having a circularity of less than 0.950 is 15.0% by number or less.

When the average circularity is 0.950 or more, a high-quality image having satisfactory transferability and no dust can be obtained. Further, since it is 0.980 or less, in an image forming system that employs blade cleaning or the like, there is no occurrence of cleaning defects on the photoconductor and the transfer belt, and stains on the image, for example, a photographic image, etc. In the case of image formation with a high image area ratio, the toner that formed the untransferred image due to poor paper feeding or the like does not become the transfer residual toner on the photoconductor, and the accumulated image is not grounded. Since the charging roller or the like that contact-charges the photoconductor is not contaminated, the original charging ability can be exhibited.

The average circularity is measured using a flow-type particle image analyzer (“FPIA-2100”, manufactured by Sysmex), and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). be able to.

To give a specific example, 0.1 to 0.5 mL of an aqueous solution of a 10 mass% surfactant (alkylbenzenesphonate, Neogen SC-A, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added to a 100 mL beaker made of glass, and each toner was added. Add 0.1 to 0.5 g and stir with microspartel, then add 80 mL of ion-exchanged water. The obtained dispersion is dispersed for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics). The shape and distribution of the toner are measured with the FPIA-2100 of the dispersion until a concentration of 5,000 to 15,000 / μL is obtained.

In this measurement method, it is important that the dispersion liquid concentration is 5,000 to 15,000 pieces / μL from the viewpoint of measurement reproducibility of average circularity. In order to obtain the dispersion liquid concentration, it is necessary to change the conditions of the dispersion liquid, that is, the amount of the surfactant to be added and the amount of the toner. As with the measurement of toner particle size described above, the required amount of surfactant differs depending on the hydrophobicity of the toner. If a large amount is added, noise due to bubbles is generated, and if a small amount is added, the toner cannot be sufficiently wetted, resulting in poor dispersion. Will be enough. The amount of toner added varies depending on the particle size, and is small in the case of a small particle size and needs to be increased in the case of a large particle size. When the toner particle size is 3 μm to 10 μm, the toner amount is 0.1 g to 0. By adding 5 g, the concentration of the dispersion can be adjusted to 5,000 / μL to 15,000 / μL.

The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 3 μm to 10 μm is preferable, and 4 μm to 7 μm is more preferable. If the volume average particle size is less than 3 μm, the toner may be fused to the surface of the carrier in the two-component developer during long-term stirring in the developing apparatus, and the charging ability of the carrier may be lowered. If it exceeds 10 μm. It becomes difficult to obtain a high-resolution and high-quality image, and when the toner in the developing agent is balanced, the particle size of the toner may fluctuate greatly.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) of the toner is preferably 1.00 to 1.25, more preferably 1.00 to 1.15.
The volume average particle size and the ratio of the volume average particle size to the number average particle size (volume average particle size / number average particle size) are determined by using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter). , It can be measured with an aperture diameter of 100 μm and analyzed with analysis software (Beckman CoulterMutilizer 3 Version 3.51).

To give a specific example, 0.5 mL of a 10 mass% surfactant (alkylbenzenesphonate, Neogen SC-A, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added to a glass 100 mL beaker, and 0.5 g of each toner was added. Stir with microspartel, then add 80 mL of ion-exchanged water. The obtained dispersion is dispersed for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics). The dispersion can be measured using the multisizer III and Isoton III (manufactured by Beckman Coulter) as a measurement solution.

In the measurement, the toner sample dispersion is dropped so that the concentration indicated by the apparatus is 8 ± 2%.
In this measurement method, it is important to set the concentration to 8 ± 2% from the viewpoint of measurement reproducibility of the particle size. Within this concentration range, there is no error in the particle size.

<Toner raw material>
In the toner of the present invention, other components such as a mold release agent can be contained in the toner base containing at least the binder resin, if necessary, and an external additive is added as necessary.

<< Bundling resin >>
The binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyester resin, silicone resin, styrene / acrylic resin, styrene resin, acrylic resin, epoxy resin, diene resin, phenol resin, terpene resin, coumarin resin, amidoimide resin, butyral resin, urethane resin, ethylene vinyl acetate resin, etc. Can be mentioned. These may be used alone or in combination of two or more. Among these, a resin in which a polyester resin or a polyester resin and the above-mentioned other binder resin are combined is preferable in that it has excellent low-temperature fixability and sufficient flexibility even when the molecular weight is reduced.

-Polyester resin-
The polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but unmodified polyester resin and modified polyester resin are preferable. These may be used alone or in combination of two or more.

--Unmodified polyester resin ---
The unmodified polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a resin obtained by polyesterifying a polyol represented by the following general formula (1) and a polycarboxylic acid represented by the following general formula (2), a crystalline polyester resin, and the like can be mentioned.

However, in the general formula (1), A represents an aromatic group or a heterocyclic aromatic group which may have an alkyl group, an alkylene group, or a substituent having 1 to 20 carbon atoms, and m is 2 to 2. Represents an integer of 4.
Further, in the general formula (2), B represents an aromatic group or a heterocyclic aromatic group which may have an alkyl group, an alkylene group, or a substituent having 1 to 20 carbon atoms, and n is 2 to 2. Represents an integer of 4.

The polyol represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, Pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, Examples thereof include trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene. These may be used alone or in combination of two or more.

The polycarboxylic acid represented by the general formula (2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid. , Isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2, , 5,7-naphthalentricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl- 2-Methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimeric acid, etc., cyclohexanedicarboxylic acid , Cyclohexene dicarboxylic acid, butane tetracarboxylic acid, diphenylsulfone tetracarboxylic acid, ethylene glycol bis (trimellitic acid) and the like. These may be used alone or in combination of two or more.

--Modified polyester resin ---
The modified polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a resin obtained by an extension reaction and / or a cross-linking reaction of an active hydrogen group-containing compound and a polyester capable of reacting with the active hydrogen group-containing compound (hereinafter, may be referred to as "polyester prepolymer") may be used. Can be mentioned. If necessary, the extension reaction and / or the cross-linking reaction may be stopped by a reaction terminator (such as one in which monoamines such as diethylamine, dibutylamine, butylamine, laurylamine, and ketimine compounds are blocked).

--- Active hydrogen group-containing compound ---
The active hydrogen group-containing compound acts as an extender, a cross-linking agent, or the like when the polyester prepolymer undergoes an extension reaction, a cross-linking reaction, or the like in an aqueous phase.

The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the intended purpose. Among them, when the polyester prepolymer is an isocyanate group-containing polyester prepolymer described later, amines are preferable in that the molecular weight can be increased.

The active hydrogen group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group and the like can be mentioned. These may be contained individually by 1 type, and may contain 2 or more types.

The amines, which are the active hydrogen group-containing compounds, are not particularly limited and may be appropriately selected depending on the intended purpose. For example, diamines, polyamines having a trivalent value or higher, amino alcohols, amino mercaptans, amino acids, and those in which the amino groups of these amines are blocked can be mentioned.

Examples of the diamine include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4'diaminodiphenylmethane, etc.); alicyclic diamines (4,4'-diamino-3,3'dimethyldicyclohexylmethane, diaminecyclohexane, etc.). Isophorone diamine, etc.); Aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like can be mentioned.
Examples of the triamine or higher polyamine include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol include ethanolamine, hydroxyethylaniline and the like.
Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan.

Examples of the amino acid include aminopropionic acid and aminocaproic acid.
Examples of the blocked amino groups of these amines include any of the above amines (diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, etc.) and ketones (acetone, methyl ethyl ketone, etc.). Examples thereof include ketimine compounds and oxazolizone compounds obtained from (methylisobutylketone, etc.).

These may be used alone or in combination of two or more. Among these, the amines are particularly preferably a mixture of diamine, diamine and a small amount of trivalent or higher-valent polyamine.

--- Polymer that can react with active hydrogen group-containing compounds ---
The polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited as long as it is a polymer having at least a group capable of reacting with the active hydrogen group-containing compound, and can be appropriately selected depending on the intended purpose. Among them, urea bond-forming group-containing polyester resin (RMPE) is excellent in high fluidity and transparency at the time of melting, easy to adjust the molecular weight of the polymer component, oilless low temperature fixability in dry toner, and excellent releasability. Is preferable, and an isocyanate group-containing polyester prepolymer is more preferable.

The isocyanate group-containing polyester prepolymer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a polycondensate of a polyol and a polycarboxylic acid, and a polyester resin containing an active hydrogen group reacted with a polyisocyanate.

The polyol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.), alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene, etc.) Glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.), Polyaliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.), trivalent or higher phenols (phenol novolac, cresol novolac, etc.), trivalent or higher polyphenols, alkylene oxide adducts, etc. Diol of trivalent or higher; a mixture of a diol and a polyol of trivalent or higher; and the like.

These may be used alone or in combination of two or more. Among these, the polyol is preferably the diol alone or a mixture of the diol and a small amount of the trivalent or higher valent polyol.

The diol preferably contains alkylene glycol having 2 to 12 carbon atoms and an alkylene oxide adduct of bisphenols (2 mol adduct of bisphenol A ethylene oxide, 3 mol adduct of bisphenol A ethylene oxide) as main components. Further, alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, etc.) may be used for the purpose of adjusting the molecular weight and the motility of the molecular weight.

The content of the polyol in the isocyanate group-containing polyester prepolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 0.5% by mass to 40% by mass is preferable, 1% by mass to 30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable. If the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the storage stability of the toner and the low temperature fixability. If the content exceeds 40% by mass, the temperature is low. Fixability may deteriorate.

The polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkylenedicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.); trivalent or higher. Examples thereof include polycarboxylic acids (aromatic polycarboxylic acids having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid). These may be used alone or in combination of two or more.

Among these, the polycarboxylic acid is preferably an alkenylene dicarboxylic acid having 4 to 20 carbon atoms and an aromatic dicarboxylic acid having 8 to 20 carbon atoms. Instead of the polycarboxylic acid, an anhydride of the polycarboxylic acid, a lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) or the like may be used.

The mixing ratio of the polyol and the polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. The equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] of the polyol to the carboxyl group [COOH] of the polycarboxylic acid is preferably 2/1 to 1/1, preferably 1.5 / 1-1 / 1. Is more preferable, and 1.3 / 1 to 1.02 / 1 is particularly preferable.

The polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane). Diisocyanate, etc.); Alicyclic polyisocyanate (isophorone diisocyanate, cyclohexamethylene diisocyanate, etc.); '-Diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, etc.); aromatic aliphatic diisocyanate (α, α, α', α'- Tetramethylxamethylene diisocyanate, etc.); Isocyanurates (tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, etc.); these phenol derivatives; those blocked with oxime, caprolactam, etc. can be mentioned. These may be used alone or in combination of two or more.

The mixing ratio of the polyisocyanate and the active hydrogen group-containing polyester resin (hydroxyl group-containing polyester resin) is not particularly limited and may be appropriately selected depending on the intended purpose. The equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] of the polyisocyanate to the hydroxyl group [OH] of the hydroxyl group-containing polyester resin is preferably 5/1 to 1/1, preferably 4/1 to 1.2. 1/1 is more preferable, and 3/1 to 1.5 / 1 is particularly preferable. If the equivalent ratio [NCO] / [OH] is less than 1/1, the offset resistance may deteriorate, and if it exceeds 5/1, the low temperature fixability may deteriorate.

The content of the polyisocyanate in the isocyanate group-containing polyester prepolymer is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and particularly preferably 2% by mass to 20% by mass. If the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both storage stability and low-temperature fixability. If it exceeds 40% by mass, low-temperature fixability may be difficult. May get worse.

The average number of isocyanate groups contained in one molecule of the isocyanate group-containing polyester prepolymer is preferably 1 or more, more preferably 1.2 to 5, and even more preferably 1.5 to 4. If the average number is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group may be low, and the hot offset resistance may be deteriorated.

The mixing ratio of the isocyanate group-containing polyester prepolymer and the amines is not particularly limited and may be appropriately selected depending on the intended purpose. The mixed equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the isocyanate group-containing polyester prepolymer and the amino group [NHx] in the amines is preferably 1/3 to 3/1, and 1 / 2 to 2/1 is more preferable, and 1 / 1.5 to 1.5 / 1 is particularly preferable. If the mixed equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may decrease, and if it exceeds 3/1, the molecular weight of the urea-modified polyester resin decreases. Hot offset resistance may deteriorate.

--- Method for synthesizing a polymer that can react with an active hydrogen group-containing compound ---
The method for synthesizing the polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the case of the isocyanate group-containing polyester prepolymer, the polyol and the polycarboxylic acid are required to be heated to 150 ° C. to 280 ° C. in the presence of a known esterification catalyst (titanium tetrabutoxide, dibutyltin oxide, etc.). A method of synthesizing by reacting the polyisocyanate with the hydroxyl group-containing polyester at 40 ° C. to 140 ° C. after distilling water to obtain a hydroxyl group-containing polyester and the like can be mentioned. ..

The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. The molecular weight distribution of the tetrahydrofuran (THF) soluble component by GPC (gel permeation chromatography) is preferably 3,000 to 40,000, more preferably 4,000 to 30,000. If the weight average molecular weight (Mw) is less than 3,000, the storage stability may be deteriorated, and if it exceeds 40,000, the low temperature fixability may be deteriorated.

The weight average molecular weight (Mw) can be measured, for example, as follows. First, the column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was flowed as a column solvent at a flow rate of 1 mL / min at this temperature to adjust the sample concentration to 0.05 to 0.6% by mass. Measure by injecting 50 μL to 200 μL of a tetrahydrofuran sample solution. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number.

As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co., Ltd. Or Toyo Soda Kogyo Co., Ltd. having a molecular weight of ^{6 × 10,2.1 × 10 2, 4} × 10 2, 1.75 × 10 4, 1.1 × 10 5, 3.9 × 10 5, 8.6 × It is preferable to use 10 ⁵ , 2 × 10 ⁶ and 4.48 × 10 ⁶ and use at least 10 standard polystyrene samples. An RI (refractive index) detector can be used as the detector.

<< Release agent >>
The release agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, plant wax (carnauba wax, cotton wax, wood wax, rice wax, etc.), animal wax (honey wax, lanolin, etc.), mineral wax (ozokelite, celsine, etc.), petroleum wax (paraffin, microcrystallin, petrolatum, etc.) ) And other waxes and waxes; synthetic hydrocarbon waxes (Fishertropsh wax, polyethylene wax, etc.), synthetic waxes (esters, ketones, ethers, etc.) and other non-natural waxes; 1,2-hydroxystearic acid amide, Fatty acid amides such as stearate amides, phthalate anhydrides, chlorinated hydrocarbons; homopolymers or copolymers of polyacrylates such as low molecular weight crystalline polymers such as n-stearyl polymethacrylate and n-lauryl polymethacrylate ( Crystalline polymers having a long-chain alkyl group in the side chain, such as n-stearyl-ethyl methacrylate copolymer, etc.).

Among these, Fischer-Tropsch wax, paraffin wax, microcrystalline wax, monoester wax, and rice wax are preferable in that unnecessary volatile organic compounds are less generated during fixing.

As the release agent, a commercially available product can be used. Examples of the microcrystalline wax include "HI-MIC-1045", "HI-MIC-1070", "HI-MIC-1080", "HI-MIC-1090", manufactured by Nippon Seiro Co., Ltd., and Toyo Adre Co., Ltd. Examples include "B-Square 180 White" and "B-Square 195" manufactured by WAX Petrolife, "BARECO C-1035" manufactured by WAX Petrolife, and "CRAY VALLAC WN-1442" manufactured by Cray Valley.

The melting point of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C to 100 ° C, more preferably 65 ° C to 90 ° C. When the melting point is 60 ° C. or higher, the exudation of the release agent from the toner base can be suppressed even during high-temperature storage at about 30 to 50 ° C., and the heat-resistant storage stability can be maintained well. When the temperature is 100 ° C. or lower, cold offset is unlikely to occur during fixing at a low temperature, which is preferable.

The melting point is measured by DSC. For example, TA-60WS and DSC-60 manufactured by Shimadzu Corporation can be used for measurement under the following measurement conditions.
(Measurement condition)
Sample container: Aluminum sample pan (with lid)
Sample amount: 5 mg
Reference: Aluminum sample pan (alumina 10 mg)
Atmosphere: Nitrogen (flow rate 50 mL / min)
Temperature condition 1st. Temperature rise Start temperature: 20 ° C, temperature rise rate: 10 ° C / min, end temperature: 150 ° C, holding time: none 1st. Lowering temperature Lowering temperature: 10 ° C / min, end temperature: 20 ° C, holding time: none 2nd. Temperature rise rate: 10 ° C / min, end temperature: 150 ° C
The measurement results are analyzed using data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation.
The melting point is 2nd. The temperature at the top of the endothermic peak measured by raising the temperature is used.

The release agent preferably exists in a state of being dispersed in the toner matrix particles, and for that purpose, it is preferable that the release agent and the binder resin are incompatible with each other. The method for finely dispersing the mold release agent in the toner matrix particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the release agent is dispersed by applying the shearing force of kneading during toner production. The method etc. can be mentioned.

The dispersed state of the release agent can be confirmed by observing a thin film section of the toner particles with a transmission electron microscope (TEM). The dispersion diameter of the release agent is preferably small, but if it is too small, exudation at the time of fixing may be insufficient. Therefore, if the release agent can be confirmed at a magnification of 10,000 times, the release agent is present in a dispersed state. If the release agent cannot be confirmed at 10,000 times, even if it is finely dispersed, the dyeing at the time of fixing becomes insufficient.

The content of the release agent in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3% by mass to 15% by mass, more preferably 5% by mass to 10% by mass. .. If the content is less than 3% by mass, the hot offset resistance may be deteriorated, which is not preferable. If the content exceeds 15% by mass, the amount of the release agent exuded at the time of fixing tends to be excessive. It is not preferable because the heat-resistant storage property tends to deteriorate.

<< Other ingredients >>
-Colorant-
The colorant used for the toner is not particularly limited, and a known colorant can be appropriately selected depending on the intended purpose.

The color of the toner is yellow, and it contains at least one yellow colorant selected as appropriate.

Examples of the yellow colorant include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; C.I. I. Bat Yellow 1, 3, 20, Orange 36 and the like can be mentioned.

The content of the colorant in the toner is preferably 1% by mass to 15% by mass, more preferably 3% by mass to 10% by mass. If the content is less than 1% by mass, the coloring power of the toner may be lowered, and if it exceeds 15% by mass, poor dispersion of the colorant in the toner occurs, and the coloring power is lowered and the coloring power of the toner is reduced. It may lead to deterioration of electrical characteristics.

The colorant may be used as a masterbatch compounded with a resin. The resin is not particularly limited, but it is preferable to use a binder resin or a resin having a structure similar to that of the binder resin from the viewpoint of compatibility with the binder resin.

The masterbatch can be produced by mixing or kneading a resin and a colorant by applying a high shearing force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Further, the so-called flushing method is also preferable in that the wet cake of the colorant can be used as it is and does not need to be dried. The flushing method is a method in which an aqueous paste containing water as a colorant is mixed or kneaded with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear disperser such as a three-roll mill can be used.

<Organic modified layered inorganic mineral>
The organically modified layered inorganic mineral is an organically modified layered inorganic mineral in which at least a part of the ions existing between the layers of the layered inorganic mineral is modified with organic matter ions. The layered inorganic mineral is a layered inorganic mineral formed by stacking layers having a thickness of several nm. The "modified" is synonymous with the introduction of organic ions into the ions existing between the layers of the layered inorganic mineral, and is broadly defined as intercalation.

It is known that the layered inorganic mineral exerts the greatest effect when it is arranged near the surface, and is easily arranged near the surface. Further, it is desirable that the organically modified layered inorganic mineral in the present invention is contained in the toner particles in a uniform ratio regardless of the size of the toner particle size. Therefore, the organically modified layered inorganic mineral is uniformly arranged in the vicinity of the surface of all the toner particles. As a result, for example, in toner particles having a small particle size, the content of the organically modified layered inorganic mineral becomes small, so that the proportion of the organically modified layered inorganic mineral arranged on the surface decreases, the surface of the toner particle becomes relatively soft, and the toner becomes toner. By facilitating the embedding of the external additive added to the mother body, there is an effect of avoiding a phenomenon in which the removal of the external additive, which is advantageous for imparting the fluidity of the toner, is hindered.

Here, the presence state of the organically modified layered inorganic mineral in the toner is determined by cutting a sample in which toner particles are embedded in an epoxy resin or the like with a micromicrotome or an ultra microtome, and cutting the toner cross section with a scanning electron microscope (SEM) or the like. It can be confirmed by observing. In the case of observation by SEM, it is preferable to confirm by a backscattered electron image, and it is preferable because the presence of the organically modified layered inorganic mineral can be observed with a strong contrast. Alternatively, FIB-STEM (HD-2000, manufactured by Hitachi, Ltd.) may be used to cut a sample in which toner particles are embedded in an epoxy resin or the like with an ion beam, and the cross section of the toner may be observed. Also in this case, it is preferable to confirm with a reflected electron image from the viewpoint of easy visibility.

Further, the vicinity of the toner surface referred to in the present invention is defined as an observation image of a cross section of a toner obtained by cutting a sample in which toner particles are embedded in an epoxy resin or the like with a micromicrotome, an ultra microtome, or FIB-STEM. It is defined as a region of 0 nm to 300 nm from the outermost surface of the toner to the inside of the toner.

The layered inorganic mineral is not particularly limited and may be appropriately selected depending on the intended purpose. For example, smectite group clay minerals (montmorillonite, saponite, hectorite, etc.), kaolin group clay minerals (kaolinite, etc.), bentonite, etc. , Atapargite, Magadiaite, Kaolinite, etc. These may be used alone or in combination of two or more.

The organically modified layered inorganic mineral is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least a part of the ions existing between the layers of the layered inorganic mineral is modified with an organic substance ion. Examples include organically modified layered inorganic minerals. Among these, those in which at least a part of the ions between the layers of the smectite group clay mineral having a smectite-based basic crystal structure are modified with organic cations are preferable from the viewpoint of dispersion stability near the toner surface, and between the layers of montmorillonite. It is particularly preferable that at least a part of the ions is denatured with an organic cation, and at least a part of the ions between the layers of bentonite is denatured with an organic cation.

It can be confirmed by gas chromatography-mass spectrometry (GCMS) that at least a part of the ions existing between the layers of the organically modified layered inorganic mineral is modified with organic matter ions, for example. A preferred method is to filter a solution in which the binder resin in the toner as a sample is dissolved with a solvent, thermally decompose the obtained solid substance with a thermal decomposition device, and identify the structure of the organic substance by GCMS. .. Specifically, a method of using Py-2020D (manufactured by Frontier Lab) as a thermal decomposition apparatus, performing thermal decomposition at 550 ° C., and then identifying with a GCMS apparatus QP5000 (manufactured by Shimadzu Corporation) can be mentioned. Be done.

Further, as the organically modified layered inorganic mineral, a metal anion is introduced by substituting a part of the divalent metal of the layered inorganic mineral with a trivalent metal, and at least a part of the metal anion is an organic anion. Examples thereof include layered inorganic compounds modified with.
Commercially available products can be used as the organically modified layered inorganic mineral. Examples of the commercially available products include Bentone 3, Bentonite 38, Bentone 38V (above, manufactured by Denaturation Specialties), Chixogel VP (manufactured by United catalyst), Clayton 34, Clayton 40, Clayton XL (above, manufactured by Southern Clay). Quantanium 18 bentonite, etc .; Bentone 27 (manufactured by Leox), Tixogel LG (manufactured by BYK Adaptives & Instruments), Clayton AF, Clayton APA (above, BYK Adaptives & Instruments), etc. Quotanium 18 / benzalkonium bentonite such as Clayton PS (manufactured by Southern Clay); organically modified montmorillonite such as Clayton HY (manufactured by Southern Clay); organically modified sukumetite such as Lucentite SPN (manufactured by Corp Chemical) Can be mentioned. Among these, Clayton AF and Clayton APA are particularly preferable.

As the organically modified layered inorganic mineral, DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) contains R ₁ (OR ₂ ) nOSO ₃ M (where R ₁ is an alkyl group having 13 carbon atoms and R ₂ is carbon. It is particularly preferable that the compound is modified with a compound having the organic ion represented by (2 to 6 alkylene groups, n is an integer of 2 to 10 and M represents a monovalent metal element). Examples of the compound having the organic ion represented by R ₁ (OR ₂ ) nOSO ₃ M include Hytenol 330T (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

The organically modified layered inorganic mineral may be mixed with a resin and used as a composite masterbatch. The resin is not particularly limited and may be appropriately selected from known resins depending on the intended purpose.

The content of the organically modified layered inorganic mineral with respect to the toner is preferably 0.1% by mass to 3.0% by mass, and particularly preferably 0.3% by mass to 1.5% by mass. If the content is less than 0.1% by mass, the effect of the layered inorganic mineral is difficult to be exhibited, and if it exceeds 3.0% by mass, the low temperature fixability tends to be impaired.

The organic ion modifier, which is a compound having the organic ion and capable of modifying at least a part of the ions existing between the layers of the layered inorganic mineral to the organic ion, is not particularly limited and may be appropriately selected depending on the intended purpose. Can be, for example, quaternary alkylammonium salt, phosphonium salt, imidazolium salt; branched, non-branched or cyclic alkyl with 1-44 carbon atoms, branched, non-branched or cyclic alkenyl with 1-22 carbon atoms, Sulfates having a skeleton such as branched, non-branched or cyclic alkoxy having 8 to 32 carbon atoms, branched, non-branched or cyclic hydroxyalkyl, ethylene oxide, propylene oxide having 2 to 22 carbon atoms, sulfonate having the skeleton, etc. Examples thereof include a carboxylate having the skeleton and a phosphate having the skeleton. Among these, a quaternary alkylammonium salt and a carboxylic acid having an ethylene oxide skeleton are preferable, and a quaternary alkylammonium salt is particularly preferable. These may be used alone or in combination of two or more.
Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, and oleylbis (2-hydroxyethyl) methylammonium.

-Charge control agent-
It is also possible to add a charge control agent to the toner, if necessary, in order to impart an appropriate chargeability to the toner.
As the charge control agent, any known charge control agent can be used. Since the color tone may change when a colored material is used, a material close to colorless to white is preferable. For example, a triphenylmethane dye, a molybdic chelate pigment, a rhodamine dye, an alkoxy amine, or a quaternary ammonium salt (fluorine). (Including modified quaternary ammonium salts), alkylamides, phosphorus alone or its compounds, tungsten alone or its compounds, fluoroactive agents, salicylic acid metal salts, salicylic acid derivative metal salts and the like. These may be used alone or in combination of two or more.

The content of the charge control agent is determined by the type of the binder resin and the toner manufacturing method including the dispersion method, and is not uniquely limited, but is 0. 01% by mass to 5% by mass is preferable, and 0.02% by mass to 2% by mass is more preferable. If the amount added exceeds 5% by mass, the chargeability of the toner is too large, the effect of the charge control agent is diminished, the electrostatic attraction with the developing roller is increased, the fluidity of the developer is lowered, and the image is displayed. The density may decrease, and if it is less than 0.01% by mass, the charge rising property and the charge amount are not sufficient, and the toner image may be easily affected.

<< External agent >>
The external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica microparticles, hydrophobized silica microparticles, fatty acid metal salts (eg zinc stearate, aluminum stearate, etc.); metal oxides (eg titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized, fluoro. Examples include polymers. Among these, hydrophobicized silica fine particles, titania particles, and hydrophobicized titania fine particles are preferably mentioned.

Examples of the hydrophobized silica fine particles include HDK H2000T, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303VP (all manufactured by Clariant Japan); R972, R974, RX200, RY200, R202, R805, R812, NX90G (both manufactured by Nippon Aerosil Co., Ltd.) and the like can be mentioned.

Examples of the titania fine particles include P-25 (manufactured by Aerosil Japan); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); MT-150W. , MT-500B, MT-600B, MT-150A (all manufactured by TAYCA) and the like.

Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Aerosil Japan Co., Ltd.); STT-30A and STT-65S-S (all manufactured by Titanium Industry Co., Ltd.); TAF-500T and TAF-1500T (all of which are manufactured by Titanium Industry Co., Ltd.). (Made by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by TAYCA Corporation); IT-S (manufactured by Ishihara Sangyo Co., Ltd.) and the like.

The content of the external additive is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.3 parts by mass to 3.0 parts by mass with respect to 100 parts by mass of the toner base particles. , 0.5 parts by mass to 2.0 parts by mass is more preferable.

The total coverage of the external additive with respect to the toner matrix particles is not particularly limited, but is preferably 50% to 90%, more preferably 60% to 80%.

<Toner manufacturing method>
As the method and material for producing the toner in the present invention, all known methods and materials can be used as long as the conditions are satisfied, and the toner particles are not particularly limited. There is a so-called chemical method of granulating.

Examples of the chemical method include a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, and a dispersion polymerization method in which a monomer is used as a starting material; a resin or a resin precursor is dissolved in an organic solvent or the like and placed in an aqueous medium. Dissolution suspension method for dispersing or emulsifying; In the dissolution suspension method, an oil phase composition containing a resin precursor (reactive group-containing prepolymer) having a functional group capable of reacting with an active hydrogen group contains resin fine particles. A method of emulsifying or dispersing in an aqueous medium and reacting the active hydrogen group-containing compound with the reactive group-containing prepolymer in the aqueous medium (ester extension method); from a resin or resin precursor and an appropriate emulsifier. Phase inversion emulsification method in which water is added to the solution to invert the phase; the resin particles obtained by these methods are agglomerated in a dispersed state in an aqueous medium and granulated into particles of a desired size by heat melting or the like. The law etc. can be mentioned. Among these, the toner obtained by the dissolution / suspension method, the ester extension method, and the agglutination method is preferable from the viewpoint of granulation property (particle size distribution control, particle shape control, etc.), and the toner obtained by the ester extension method is preferable. More preferred.
The details of these manufacturing methods will be described below.

The kneading and pulverizing method is a method for producing the base particles of the toner by, for example, melting and kneading a toner material having at least a colorant, a binder resin, and a mold release agent, pulverizing and classifying the toner material.

In the melt-kneading, the toner materials are mixed, and the mixture is charged into a melt-kneader and melt-kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch type kneader using a roll mill can be used. For example, KTK type twin-screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin-screw extruder manufactured by Ktk Inc., PCM type twin-screw extruder manufactured by Ikegai Iron Works, Conider manufactured by Bus Co., Ltd., etc. are suitable. Used. It is preferable that this melt-kneading is performed under appropriate conditions so as not to cause breakage of the molecular chain of the binder resin. Specifically, the melt-kneading temperature is performed with reference to the softening point of the binder resin, and if the temperature is too high above the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded product is first roughly pulverized and then finely pulverized. At this time, a method of colliding with a collision plate in a jet stream to pulverize, colliding particles with each other in a jet stream to pulverize, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification, the pulverized product obtained by the pulverization is classified into particles having a predetermined particle size. The classification can be performed by removing the fine particle portion with, for example, a cyclone, a decanter, a centrifuge, or the like.
After the pulverization is completed, the pulverized product can be classified into an air stream by centrifugal force or the like to produce toner matrix particles having a predetermined particle size.

In the dissolution / suspension method, for example, an oil phase composition obtained by dissolving or dispersing a toner composition containing at least a binder resin or a resin precursor, a colorant, and a mold release agent in an organic solvent is prepared in an aqueous system. This is a method for producing toner matrix particles by dispersing or emulsifying them in a medium.

The organic solvent used when dissolving or dispersing the toner composition is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of facilitating subsequent removal of the solvent.
Examples of the organic solvent include ester-based or ester-ether-based solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate, diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl. Ether solvents such as ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, ketone solvents such as cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2 -Alcohol-based solvents such as ethylhexyl alcohol and benzyl alcohol, and mixed solvents of two or more of these can be mentioned.

In the above-mentioned dissolution / suspension method, an emulsifier or a dispersant may be used, if necessary, when the oil phase composition is dispersed or emulsified in an aqueous medium.
As the emulsifier or dispersant, known surfactants, water-soluble polymers and the like can be used. The surfactant is not particularly limited, and is an anionic surfactant (alkylbenzene sulfonic acid, phosphoric acid ester, etc.), a cationic surfactant (quaternary ammonium salt type, amine salt type, etc.), and an amphoteric surfactant (carboxylic acid). Acid type, sulfate ester salt type, sulfonate type, phosphate ester salt type, etc.), nonionic surfactant (AO addition type, polyhydric alcohol type, etc.) and the like can be mentioned. As the surfactant, one kind alone or two or more kinds of surfactants may be used in combination.

Examples of the water-soluble polymer include cellulose-based compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and their saponified products), gelatin, starch, dextrin, gum arabic, chitin, and chitosan. , Polyvinyl alcohol, Polypolypyrrolidone, Polyethylene glycol, Polyethyleneimine, Polyacrylamide, Acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partial neutralized sodium hydroxide of polyacrylate , Sodium acrylate-acrylic acid ester copolymer), sodium hydroxide (partial) neutralized product of styrene-maleic anhydride copolymer, water-soluble polyurethane (polyethylene glycol, polycaprolactone diol, etc.) and polyisocyanate reaction product Etc.) and so on.
Further, the above-mentioned organic solvent, plasticizer and the like can be used in combination as an auxiliary agent for emulsification or dispersion.

The toner according to the present invention is a binder resin, a binder resin precursor having a functional group capable of reacting with an active hydrogen group (reactive group-containing prepolymer), a colorant, and a mold release agent in the dissolution and suspension method. The oil phase composition containing the above is dispersed or emulsified in an aqueous medium containing resin fine particles, and the active hydrogen group-containing compound contained in the oil phase composition and / or the aqueous medium and the reactive group-containing prepolymer. It is preferable to obtain by granulating the base particles of the toner by a method of reacting with (ester extension method).

The resin fine particles can be formed by using a known polymerization method, but it is preferably obtained as an aqueous dispersion of the resin fine particles. Examples of the method for preparing the aqueous dispersion of the resin fine particles include the methods shown in (a) to (h) below.
(A) A method for directly preparing an aqueous dispersion of resin fine particles by a polymerization reaction of any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method using a vinyl monomer as a starting material.
(B) After dispersing a precursor (monomer, oligomer, etc.) of a heavy addition or condensation resin such as a polyester resin, a polyurethane resin, or an epoxy resin or a solvent solution thereof in an aqueous medium in the presence of an appropriate dispersant, A method of preparing an aqueous dispersion of resin fine particles by heating or adding a curing agent and curing.
(C) In a precursor (monomer, oligomer, etc.) of a heavy addition or condensation resin such as a polyester resin, a polyurethane resin, or an epoxy resin, or a solvent solution thereof (preferably a liquid, which may be liquefied by heating). A method of preparing an aqueous dispersion of resin fine particles by dissolving an appropriate emulsifier in the resin and then adding water for phase inversion emulsification.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-open polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized using a mechanical rotary type or jet type fine pulverizer and classified. A method of preparing an aqueous dispersion of resin fine particles by dispersing the resin fine particles in water in the presence of an appropriate dispersant.
(E) Resin fine particles are formed by spraying a resin solution prepared by dissolving a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent in the form of a mist. After that, the resin fine particles are dispersed in water in the presence of an appropriate dispersant to prepare an aqueous dispersion of the resin fine particles.
(F) A poor solvent is added to a resin solution prepared by dissolving a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, or the solvent is preheated. Resin fine particles are precipitated by cooling the dissolved resin solution, the solvent is removed to form resin fine particles, and then the resin fine particles are dispersed in water in the presence of an appropriate dispersant to carry out aqueous dispersion of the resin fine particles. How to prepare the liquid.
(G) A resin solution prepared by dissolving a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent is used as an aqueous medium in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by dispersing the resin in the resin and then removing the solvent by heating, reducing the pressure, or the like.
(H) A suitable emulsifier is dissolved in a resin solution prepared by dissolving a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, and then water. To prepare an aqueous dispersion of resin fine particles by polycondensation and emulsification.

The volume average particle size of the resin fine particles is preferably 10 nm or more and 300 nm or less, and more preferably 30 nm or more and 120 nm or less. When the volume average particle size of the resin fine particles is less than 10 nm and when it exceeds 300 nm, the particle size distribution of the toner may be deteriorated, which is not preferable.

The solid content concentration of the oil phase is preferably about 40 to 80%. If the concentration is too high, it becomes difficult to dissolve or disperse, and the viscosity becomes high and it is difficult to handle. If the concentration is too low, the manufacturability of the toner is lowered.

Toner compositions other than the binder resin such as the organically modified layered inorganic mineral such as the colorant and the mold release agent, and their master batches and the like are individually dissolved or dispersed in an organic solvent and then dissolved in the binder resin. It may be mixed with a liquid or a dispersion liquid.

As the water-based medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellsolves (methylcellsolve, etc.), lower ketones (acetone, methylethylketone, etc.) and the like.

The method of dispersion or emulsification in the aqueous medium is not particularly limited, but known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Above all, the high-speed shearing method is preferable from the viewpoint of reducing the particle size of the particles. When a high-speed shearing disperser is used, the rotation speed is not particularly limited, but is usually 1000 to 30,000 rpm, preferably 5000 to 20000 rpm. The temperature at the time of dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

In order to remove the organic solvent from the obtained emulsion dispersion, there is no particular limitation, and a known method can be used. For example, the whole system is gradually raised while stirring under normal pressure or reduced pressure. A method of warming and completely evaporating and removing the organic solvent in the droplets can be adopted.

A known technique is used as a method for washing and drying the parent particles of the toner dispersed in the aqueous medium. That is, after solid-liquid separation with a centrifuge, filter press, etc., the obtained toner cake is redistributed in ion-exchanged water at room temperature to about 40 ° C., and the pH is adjusted with an acid or alkali as necessary. Toner powder is obtained by removing impurities and surfactants by repeating the process of solid-liquid separation again several times, and then drying with an air flow dryer, a circulation dryer, a vacuum dryer, a vibration flow dryer, or the like. .. At this time, the fine particle components of the toner may be removed by centrifugation or the like, and after drying, a known classifier can be used to obtain a desired particle size distribution.

In the agglomeration method, for example, a resin fine particle dispersion made of at least a binder resin, a colorant particle dispersion, and a release agent particle dispersion, if necessary, are mixed and agglomerated to produce toner matrix particles. is there. The resin fine particle dispersion liquid is obtained by a known method such as emulsion polymerization, seed polymerization, phase inversion emulsification method, etc., and the colorant particle dispersion liquid and the release agent particle dispersion liquid are known wet dispersion methods. It can be obtained by dispersing a colorant or a mold release agent in an aqueous medium.

For controlling the agglutinated state, methods such as applying heat, adding a metal salt, and adjusting the pH are preferably used.
The metal salt is not particularly limited, and is a monovalent metal constituting a salt such as sodium or potassium; a divalent metal constituting a salt such as calcium or magnesium; a trivalent metal constituting a salt such as aluminum, or the like. Can be mentioned.
Examples of anions constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion, and sulfate ion, and among these, magnesium chloride, aluminum chloride, and a complex or multimer thereof are preferable. ..
Further, it is possible to promote the fusion of the resin fine particles by heating during the aggregation or after the aggregation is completed, which is preferable from the viewpoint of toner uniformity. Further, the shape of the toner can be controlled by heating, and usually, the toner becomes closer to a spherical shape when it is heated more.

As a method for washing and drying the parent particles of the toner dispersed in the aqueous medium, the above-mentioned method or the like can be used.

Further, in order to improve the fluidity, storage stability, developability and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be added and mixed with the toner base particles produced as described above.
A general powder mixer is used for mixing the additives, but it is preferable to equip a jacket or the like to control the internal temperature. In order to change the history of the load applied to the additive, the additive may be added in the middle or gradually. In this case, the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. Further, a strong load may be applied first, and then a relatively weak load may be applied, and vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a locking mixer, a Reedige mixer, a Nauter mixer, a Henschel mixer, and the like. Next, coarse particles and agglomerated particles are removed by passing through a sieve of 250 mesh or more to obtain toner.

(Developer)
The developer of the present invention contains at least the toner and contains other components such as carriers which are appropriately selected. The developer may be a one-component developer or a two-component developer, but when used in a high-speed printer or the like corresponding to an improvement in information processing speed in recent years, the service life is improved. The two-component developer is preferable in terms of the above.

In the case of the one-component developer using the toner, agglomerates of the toner are less likely to be formed over time even under stress caused by the developing means, and the toner is filmed on a developing roller as a developing agent carrier. , Toner is not fused to a layer thickness regulating member such as a blade for thinning the toner, and good and stable image quality can be obtained by maintaining good image density stability and transferability. .. Further, in the case of the two-component developer using the toner, the toner is less likely to agglomerate over time even under agitation stress caused by the developing means, the generation of abnormal images is suppressed, and the image density is stable. Good and stable image quality can be obtained by maintaining good properties and transferability.

<Career>
The carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but those having core particles and a resin layer (coating layer) for coating the core particles are preferable.

<< Core particles >>
The core particles are not particularly limited as long as they are magnetic core particles and can be appropriately selected depending on the intended purpose. For example, ferromagnetic metals such as iron and cobalt; oxidation of magnetite, hematite, ferrite and the like. Iron; Examples thereof include resin particles in which magnetic substances such as various alloys and compounds are dispersed in a resin. Among these, Mn-based ferrite, Mn-Mg-based ferrite, Mn-Mg-Sr-based ferrite and the like are preferable from the viewpoint of consideration for the environment.

-Weight average particle size of core particles Dw-
The weight average particle size Dw of the core particles refers to the particle size at an integrated value of 50% in the particle size distribution of the core particles obtained by a laser diffraction or scattering method. The weight average particle size Dw of the core particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 μm to 80 μm, more preferably 20 μm to 65 μm.

For the measurement of the weight average particle size Dw of the core particles, the particle size distribution (relationship between the number frequency and the particle size) of the particles measured on the basis of the number is measured by using a Microtrack particle size distribution meter (HRA9320-X100, manufactured by Honewell). Use and measure under the conditions described below, and calculate using the following formula (I). Each channel represents a length for dividing the particle size range in the particle size distribution map into measurement width units, and the representative particle size adopts the lower limit of the particle size stored in each channel.

Dw = {1 / Σ (nD3)} × {Σ (nD4)} ・ ・ ・ (I)
However, in the above formula (I), D represents the representative particle size (μm) of the core particles existing in each channel, and n represents the total number of core particles existing in each channel.

[Measurement condition]
[1] Particle size range: 100 μm to 8 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42
<< Coating layer >>
The coating layer contains at least a resin, and may contain other components such as a filler, if necessary.

-Resin-
The resin for forming the coating layer of the carrier is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a crosslinkable copolymer containing polyimide (for example, polyethylene, polypropylene, etc.) and its modified product, polystyrene, acrylic resin, acrylonitrile, vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether, etc.; Silicone resin or modified products thereof (for example, modified products made of alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.); polyamide; polyester; polyurethane; polycarbonate; urea resin; melamine resin; benzoguanamine resin; epoxy resin; ionomer resin; Polyimide resins and derivatives thereof and the like can be mentioned. These may be used alone or in combination of two or more. Among these, silicone resin is preferable.

The silicone resin is not particularly limited and may be appropriately selected from generally known silicone resins according to the purpose. For example, a straight silicone resin consisting only of an organosiloxane bond, and alkyds and polyesters. , Silicone resin modified with epoxy, acrylic, urethane and the like.

Examples of the straight silicone resin include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2405, SR2406 (manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.

Specific examples of the modified silicone resin include epoxy-modified silicone: ES-1001N, acrylic-modified silicone: KR-5208, polyester-modified product: KR-5203, alkyd-modified product: KR-206, and urethane-modified product: KR-. Examples thereof include 305 (all manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy modified product: SR2115, and alkyd modified product: SR2110 (manufactured by Toray Dow Corning Silicone Co., Ltd.).

The silicone resin can be used alone, but it is also possible to use a cross-linking reactive component, a charge amount adjusting component, and the like at the same time. Examples of the cross-linking reactive component include a silane coupling agent and the like. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, aminosilane coupling agent and the like.

-Filler-
The filler is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include conductive fillers and non-conductive fillers. These may be used alone or in combination of two or more. Among these, it is preferable that the coating layer contains a conductive filler and a non-conductive filler.

The conductive filler refers to a filler having a powder resistivity value of 100 Ω · cm or less.
The non-conductive filler refers to a filler having a powder resistivity value of more than 100 Ω · cm.
The powder resistivity value of the filler is measured by a powder resistance measurement system (MCP-PD51, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and a resistivity meter (4-terminal 4-probe method, Loresta-GP, Mitsubishi Chemical Analytech Co., Ltd.). It can be carried out by measuring under the conditions of 1.0 g of sample, 3 mm of electrode spacing, 10.0 mm of sample radius, and 20 kN of load.

--Conductive filler ---
The conductive filler is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a conductive filler formed by forming tin dioxide or indium oxide as a layer on a substrate such as aluminum oxide, titanium oxide, zinc oxide, barium sulfate, silicon oxide, zirconium oxide; or a conductive filler formed by using carbon black. Be done. Among these, a conductive filler containing aluminum oxide, titanium oxide, and barium sulfate is preferable.

--Non-conductive filler ---
The non-conductive filler is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a non-conductive filler formed by using aluminum oxide, titanium oxide, barium sulfate, zinc oxide, silicon dioxide, zirconium oxide or the like can be mentioned. Among these, a non-conductive filler containing aluminum oxide, titanium oxide, and barium sulfate is preferable.

<Manufacturing method of carrier>
The method for producing the carrier is not particularly limited and may be appropriately selected depending on the intended purpose. However, the resin and the filler are contained on the surface of the core particles by using a fluidized bed coating device. A method of producing by applying a coating layer forming solution is preferable. When the coating layer forming solution is applied, the condensation of the resin contained in the coating layer may be promoted, or after the coating layer forming solution is applied, the condensation of the resin contained in the coating layer may be promoted. May proceed.

The method for condensing the resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method in which heat, light or the like is applied to the coating layer forming solution to condense the resin. ..

-Carrier weight average particle size Dw-
The weight average particle size Dw of the carrier refers to the particle size at an integrated value of 50% in the particle size distribution of the core particles obtained by the laser diffraction / scattering method. The weight average particle size Dw of the carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 μm to 80 μm, more preferably 20 μm to 65 μm.

For the measurement of the weight average particle size Dw of the carrier, the particle size distribution (relationship between the number frequency and the particle size) of the particles measured on the basis of the number was used with a Microtrack particle size distribution meter (HRA9320-X100, manufactured by Honewell). Measure under the conditions described below, and calculate using the following formula (II). Each channel represents a length for dividing the particle size range in the particle size distribution map into measurement width units, and the representative particle size adopts the lower limit of the particle size stored in each channel.

Dw = {1 / Σ (nD3)} × {Σ (nD4)} ... (II)
However, in the formula (II), D represents the representative particle size (μm) of the carriers present in each channel, and n represents the total number of carriers present in each channel.

[Measurement condition]
[1] Particle size range: 100 μm to 8 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

When the developer is a two-component developer, the mixing ratio of the toner and the carrier in the two-component developer is preferably 2.0 to 12.0% by mass of the toner to the carrier. It is more preferably 2.5 to 10.0% by mass.

(Process cartridge)
The process cartridge of the present invention includes at least an electrostatic latent image carrier and a developing means for developing an electrostatic latent image formed on the electrostatic latent image carrier with a developer to form a visible image. It is a process cartridge that has and can be attached to and detached from the image forming apparatus main body. The developer is the toner or developer of the present invention. Details of the developing means and the like will be described later.

(Image forming method and image forming device)
In the image forming method of the present invention, the electrostatic latent image is developed by using the electrostatic latent image forming step of forming the electrostatic latent image on the electrostatic latent image carrier and the toner or the developing agent of the present invention. It has a developing step of forming a visible image, a transfer step of transferring the visible image onto a recording medium, and a fixing step of fixing the transferred image transferred on the recording medium. Further, it has other steps appropriately selected as necessary, such as a static elimination step, a cleaning step, a recycling step, a control step and the like.

The image forming apparatus of the present invention uses an electrostatic latent image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and a toner or a developing agent of the present invention. , A developing means for developing the electrostatic latent image to form a visible image, a transfer means for transferring the visible image onto a recording medium, and a fixing means for fixing the transferred image transferred on the recording medium. And have. Further, it has other means appropriately selected as necessary, such as static elimination means, cleaning means, recycling means, control means and the like. Details will be described below.

-Electrostatic latent image forming process and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on an electrostatic latent image carrier.
The material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as "electrophotographic photosensitive member" or "photoreceptor") are not particularly limited, and among known ones. Although it can be appropriately selected, the shape thereof is preferably drum-shaped, and the material thereof is, for example, an inorganic photoconductor such as amorphous silicon or selenium, an organic photoconductor (OPC) such as polysilane or phthalopolymethine, or the like. Can be mentioned. Among these, an organic photoconductor (OPC) is preferable in that a higher-definition image can be obtained.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then exposing it to an image, and by using an electrostatic latent image forming means. Can be done.
The electrostatic latent image forming means includes, for example, a charging means (charger) that uniformly charges the surface of the electrostatic latent image carrier, and an exposure that exposes the surface of the electrostatic latent image carrier in an image manner. It is provided with at least means (exposure device).

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging device.
The charger is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a contact charge known per se including a conductive or semi-conductive roll, brush, film, rubber blade or the like. Examples include non-contact chargers that utilize corona discharge such as vessels, corotrons, and scorotrons.
As the charger, it is preferable that the charger is arranged in contact or non-contact state with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by superimposing and applying DC and AC voltages.
Further, the charger is a charging roller that is non-contactly arranged close to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is supported by superimposing and applying direct current and alternating voltage to the charging roller. Those that charge the body surface are preferable.

The exposure can be performed, for example, by exposing the surface of the electrostatic latent image carrier as an image using the exposure device.
The exposure device is not particularly limited as long as the surface of the electrostatic latent image carrier charged by the charger can be exposed to an image to be formed, and may be appropriately selected depending on the intended purpose. However, examples thereof include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
In the present invention, an optical back surface method may be adopted in which the back surface side of the electrostatic latent image carrier is exposed in an image-like manner.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image with the toner to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image with the toner, and can be performed by the developing means.
The developing means preferably has, for example, a developer that accommodates the toner and is capable of contacting or non-contacting the toner to the electrostatic latent image, and is provided with a container containing the toner. Etc. are more preferable.

The developer may be a monochromatic developer or a multicolor developer, and has, for example, a stirrer for frictionally agitating and charging the toner, and a rotatable magnet roller. Those and the like are preferably mentioned.
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by the friction at that time and is held in a spiked state on the surface of a rotating magnet roller to form a magnetic brush. .. Since the magnet roller is arranged in the vicinity of the electrostatic latent image carrier (photoreceptor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoreceptor) by force. As a result, the electrostatic latent image is developed by the toner, and a visible image by the toner is formed on the surface of the electrostatic latent image carrier (photoreceptor).

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image to a recording medium. After using an intermediate transfer body to primary transfer the visible image onto the intermediate transfer body, the visible image is transferred onto the recording medium. A mode of secondary transfer to the medium is preferable, and a primary transfer step of transferring a visible image onto an intermediate transfer body to form a composite transfer image by using two or more colors, preferably a full-color toner as the toner, and the composite. A mode including a secondary transfer step of transferring the transferred image onto a recording medium is more preferable.
The transfer can be performed, for example, by charging the electrostatic latent image carrier (photoreceptor) with the transfer charger using the transfer charger, and can be performed by the transfer means. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer body to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Aspects are preferred.
The intermediate transfer material is not particularly limited and may be appropriately selected from known transfer materials according to the purpose. For example, a transfer belt or the like is preferably used.

The transfer means (the primary transfer means, the secondary transfer means) transfers and charges the visible image formed on the electrostatic latent image carrier (photoreceptor) to the recording medium side. It is preferable to have at least a vessel. The transfer means may be one or two or more.
Examples of the transfer device include a corona transfer device by corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, an adhesive transfer device, and the like.
The recording medium is not particularly limited, and can be appropriately selected from known recording media (recording paper).

-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium by using a fixing device, and may be performed every time the developer of each color is transferred to the recording medium, or the developer of each color. On the other hand, it may be carried out at the same time in a state where these are laminated.
The fixing device is not particularly limited and may be appropriately selected depending on the intended purpose, but known heating and pressurizing means are suitable. Examples of the heating and pressurizing means include a combination of a heating roller and a pressurizing roller, a combination of a heating roller, a pressurizing roller and an endless belt, and the like.
The fixing device has a heating body including a heating element, a film in contact with the heating body, and a pressure member that presses against the heating body via the film, and the film and the pressure member It is preferable that the means is to heat and fix the film by passing it through a recording medium on which an unfixed image is formed. The heating in the heating and pressurizing means is usually preferably 80 ° C. to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and fixing means, depending on the purpose.

The static electricity elimination step is a step of applying a static electricity elimination bias to the electrostatic latent image carrier to perform static electricity elimination, and can be preferably performed by the static electricity elimination means.
The static eliminating means is not particularly limited as long as it can apply a static eliminating bias to the electrostatic latent image carrier, and can be appropriately selected from known static eliminators, for example, a static eliminating lamp or the like. Preferred.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier, and can be preferably performed by a cleaning means.
The cleaning means is not particularly limited as long as it can remove the toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners, for example, a magnetic brush cleaner. , Electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner and the like are preferable.

The recycling step is a step of causing the developing means to recycle the toner removed by the cleaning step, and can be preferably performed by the recycling means. The recycling means is not particularly limited, and examples thereof include known transportation means.
The control step is a step of controlling each of the steps, and each step can be preferably performed by a control means.
The control means is not particularly limited as long as the movement of each of the means can be controlled, and can be appropriately selected depending on the intended purpose. Examples thereof include devices such as sequencers and computers.

FIG. 5 shows a first example of the image forming apparatus of the present invention. The image forming apparatus 100A includes a photoconductor drum 10, a charging roller 20, an exposure apparatus 30, a developing apparatus 40, an intermediate transfer belt 50, a cleaning apparatus 60 having a cleaning blade, and a static elimination lamp 70.

The intermediate transfer belt 50 is an endless belt stretched by three rollers 51 arranged inside, and can be moved in the direction of the arrow in the drawing. A part of the three rollers 51 also functions as a transfer bias roller capable of applying a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is arranged in the vicinity of the intermediate transfer belt 50. Further, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) for transferring the toner image to the transfer paper 95 is arranged so as to face the intermediate transfer belt 50.

Further, around the intermediate transfer belt 50, a corona charging device 58 for applying an electric charge to the toner image transferred to the intermediate transfer belt 50 is provided with the photoconductor drum 10 in the rotation direction of the intermediate transfer belt 50. It is arranged between the contact portion of the intermediate transfer belt 50 and the contact portion between the intermediate transfer belt 50 and the transfer paper 95.

The developing device 40 includes a developing belt 41, a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C, which are arranged around the developing belt 41. The developing unit 45 for each color includes a developing agent accommodating portion 42, a developing agent supply roller 43, and a developing roller (developer carrier) 44. Further, the developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can be moved in the direction of an arrow in the drawing. Further, a part of the developing belt 41 is in contact with the photoconductor drum 10.

Next, a method of forming an image using the image forming apparatus 100A will be described. First, the surface of the photoconductor drum 10 is uniformly charged using the charging roller 20, and then the exposure light L is exposed to the photosensitive drum 10 using an exposure device (not shown) to obtain an electrostatic latent image. Form. Next, the electrostatic latent image formed on the photosensitive drum 10 is developed with the toner supplied from the developing device 40 to form a toner image. Further, the toner image formed on the photoconductor drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, and then transferred by the transfer bias applied from the transfer roller 80. , Transferred on transfer paper 95 (secondary transfer). On the other hand, the photoconductor drum 10 on which the toner image is transferred to the intermediate transfer belt 50 is statically eliminated by the static elimination lamp 70 after the toner remaining on the surface is removed by the cleaning device 60.

FIG. 6 shows a second example of the image forming apparatus used in the present invention. In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are directly opposed to each other around the photoconductor drum 10 without providing the developing belt 41. Other than that, it has the same configuration as the image forming apparatus 100A.

FIG. 7 shows a third example of the image forming apparatus used in the present invention. The image forming apparatus 100C is a tandem type color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document transporting apparatus (ADF) 400.

The intermediate transfer belt 50 provided in the central portion of the copying apparatus main body 150 is an endless belt stretched on the three rollers 14, 15 and 16, and can be moved in the direction of the arrow in the drawing. In the vicinity of the roller 15, a cleaning device 17 having a cleaning blade for removing the toner remaining on the intermediate transfer belt 50 on which the toner image is transferred to the recording paper is arranged. Along with facing the intermediate transfer belt 50 stretched by the rollers 14 and 15, yellow, cyan, magenta and black image forming units 18Y, 18C, 18M and 18K are juxtaposed to form the tandem unit 120. Is forming.

Further, an exposure device 21 is arranged in the vicinity of the image forming unit 120. Further, the secondary transfer belt 24 is arranged on the side of the intermediate transfer belt 50 opposite to the side on which the image forming unit 120 is arranged. The secondary transfer belt 24 is an endless belt stretched on a pair of rollers 23, and the recording paper and the intermediate transfer belt 50 conveyed on the secondary transfer belt 24 are between the rollers 16 and 23. Can be contacted.

Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 including a fixing belt 26 which is an endless belt stretched on a pair of rollers and a pressure roller 27 which is pressed and arranged by the fixing belt 26. Is placed. A sheet reversing device 28 for reversing the recording paper is arranged in the vicinity of the secondary transfer belt 24 and the fixing device 25 when an image is formed on both sides of the recording paper.

Next, a method of forming a full-color image using the image forming apparatus 100C will be described. First, a color document is set on the platen 130 of the automatic document transfer device (ADF) 400, or the color document is set on the contact glass 32 of the scanner 300 by opening the automatic document transfer device 400 and the document is automatically transferred. Close the device 400. When the start switch is pressed, when the original is set in the automatic document transfer device 400, the original is conveyed and moved onto the contact glass 32, and then the original is set on the contact glass 32. Immediately, the scanner 300 is driven, and the first traveling body 33 including the light source and the second traveling body 34 including the mirror travel. At this time, after the light reflected from the document surface of the light emitted from the first traveling body 33 is reflected by the second traveling body 34, the document is received by the reading sensor 36 via the imaging lens 35, so that the document is formed. It is read and image information of black, yellow, magenta and cyan is obtained.

The image information of each color is transmitted to the image forming unit 120 of each color, and a toner image of each color is formed. As shown in FIG. 8, the image forming unit 120 of each color develops the photoconductor drum 10, the charging roller 160 that uniformly charges the photoconductor drum 10, and the electrostatic latent image with the developer of each color. A developing device 61 for forming a toner image of each color, a transfer roller 62 for transferring the toner image onto the intermediate transfer belt 50, a cleaning device 63 having a cleaning blade, and a static eliminator lamp 64 are provided.

The toner images of each color formed by the image forming unit 120 of each color are sequentially transferred (primary transfer) onto the intermediate transfer body 50 which is stretched and moved by the rollers 14, 15 and 16, and superposed to form a composite toner image. It is formed.

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated, and the recording paper is fed out from one of the paper feed cassettes 144 provided in the paper bank 143 in multiple stages, and the separation rollers 145 are used one by one. It is separated and sent out to the paper feed path 146, conveyed by the transfer roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the resist roller 49 to stop. Alternatively, the paper feed roller is rotated to feed out the recording paper on the manual feed tray 54, the sheets are separated one by one by the separation roller 52, guided to the manual paper feed path 53, and abutted against the resist roller 49 to be stopped.

Although the resist roller 49 is generally grounded and used, it may be used in a state where a bias is applied in order to remove paper dust from the recording paper. Next, by rotating the resist roller 49 in time with the composite toner image formed on the intermediate transfer belt 50, the recording paper is sent out between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is formed. The toner image is transferred (secondary transfer) onto the recording paper. The toner remaining on the intermediate transfer belt 50 on which the composite toner image is transferred is removed by the cleaning device 17.

The recording paper on which the composite toner image is transferred is conveyed by the secondary transfer belt 24, and then the composite toner image is fixed by the fixing device 25. Next, the transport path of the recording paper is switched by the switching claw 55, and the recording paper is discharged onto the paper ejection tray 57 by the ejection roller 56. Alternatively, the transfer path of the recording paper is switched by the switching claw 55, the sheet is inverted by the sheet reversing device 28, an image is formed on the back surface in the same manner, and then the recording paper is ejected onto the output tray 57 by the ejection roller 56. ..

According to the image forming method and the image forming apparatus of the present invention, a high-quality image can be provided for a long period of time.

The present invention relates to the yellow toner of the following (1), and includes the following (2) to (7) as embodiments.
(1) and at least a binder resin, a yellow toner containing a colorant, at a wave number λ of the toner particles obtained in the wave number region of ^{950cm -1 ~3250cm} -1 in the Raman spectroscopy of the yellow toner when normalized intensity of the Raman spectrum ^1, the integrated intensity of the spectrum of each of the toner particles obtained in the wave number region of 2750cm ^-1 ~3250cm -1 and _{I n,} the average value of the _{I n} and _{I ave,} When the value calculated by the following (Equation 1) is taken as the CH ratio, the number ratio of the toner particles having an absolute value of the CH ratio of 25.0% or more to all the toner particles is 1.0 number% or more and 15.0. A yellow toner characterized by being less than a few percent.
CH ratio _{(%) = [(I n} -I ave) / I ave] × 100 ··· ( Equation 1)
(2) The yellow toner according to (1) above, wherein the number ratio of toner particles having an absolute value of CH ratio of 50.0% or more is 2.0 number% or less.
(3) The yellow toner according to (1) or (2) above, wherein the median CH ratio is −3.0% or more.
(4) A developing agent containing the yellow toner according to any one of (1) to (3) above.
(5) The yellow toner according to any one of (1) to (3) above, or the above (5), the electrostatic latent image carrier and the electrostatic latent image formed on the electrostatic latent image carrier. A process cartridge characterized in that a developing means for developing using the developer according to 4) is integrally supported, and the developing means can be attached to and detached from the main body of the image forming apparatus.
(6) Electrostatic latent image carrier and
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier,
With a developing means for developing the electrostatic latent image to form a visible image using the yellow toner according to any one of (1) to (3) above or the developer according to (4) above. ,
A transfer means for transferring the visible image onto a recording medium,
An image forming apparatus comprising a fixing means for fixing a transferred image transferred on the recording medium.
(7) Electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and
A developing step of developing the electrostatic latent image to form a visible image using the yellow toner according to any one of the above (1) to (3) or the developing agent according to the above (4). ,
A transfer step of transferring the visible image onto a recording medium, and
An image forming method comprising a fixing step of fixing a transferred image transferred onto the recording medium.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples. In the description in the example, [%] indicates mass%, and “part” indicates “part by mass”.

(Example 1)
<Manufacturing of toner 1>
-Synthesis of polyester resin-
Reaction 1: Bisphenol A ethylene oxide 3 molar adduct (EO) and 1,2-propylene glycol (PG) in molar ratio 90 in a reaction vessel equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple. / 10, terephthalic acid (TPA) and adipic acid (APA) were charged at a molar ratio of 70/30, charged at OH / COOH = 1.33, and reacted with 500 ppm titanium tetraisopropoxide at 230 ° C. for 10 hours at normal pressure. I let you.
Reaction 2: Then, the reaction was carried out under reduced pressure of 10 mmHg to 15 mmHg for 5 hours.
Reaction 3: Next, 10 parts of trimellitic anhydride (TMA) was placed in a reaction vessel and reacted at 180 ° C. and normal pressure for 3 hours to obtain a [polyester resin].

-Synthesis of prepolymer-
682 parts of bisphenol A ethylene oxide 2 mol adduct, 81 parts of bisphenol A propylene oxide 2 mol adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. A part and 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure, and further reacted under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain a [intermediate polyester resin].
The obtained [intermediate polyester resin] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g. ..
Next, 410 parts of [intermediate polyester resin], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. [Prepolymer] was obtained. The free isocyanate% of the obtained [prepolymer] was 1.53%.

-Preparation of mold release agent dispersion-
70 parts of carnauba wax (WA-05, manufactured by Ceralica Noda), 140 parts of [polyester resin], and 290 parts of ethyl acetate were put in a container in which a stirring rod and a thermometer were set, and the temperature was raised to 75 ° C. under stirring. After holding at 75 ° C. for 1.5 hours, cool to 30 ° C. in 1 hour, and use a bead mill (Ultra Viscomill, manufactured by Imex) to send liquid at a speed of 5 kg / hr, a disk peripheral speed of 6 m / sec, and 0. .5 mm zirconia beads were filled in 80% by volume and dispersed under the conditions of 3 passes to obtain a [release agent dispersion].

-Preparation of masterbatch-
Add 1,000 parts of water, 1,000 parts of Pigment Yellow 185, and 1,000 parts of [polyester resin], mix with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and mix the mixture at 150 ° C. using two rolls. After kneading for 30 minutes, the mixture was rolled and cooled and pulverized with a palperizer to obtain [Masterbatch 1].

-Preparation of oil phase 1-
In a container equipped with a thermometer and a stirrer, 72 parts of [polyester resin], 113 parts of [release agent dispersion], 68 parts of [masterbatch 1], and 122 parts of ethyl acetate were put into a shear disperser (TK homo). After dispersing under the condition of peripheral speed of 12.5 m / sec using a mixer), liquid feeding speed of 5 kg / hr, disk peripheral speed of 6 m / sec, 0. 5 mm zirconia beads were filled in 80% by volume and dispersed under the conditions of 3 passes to obtain [oil phase 1].

-Manufacture of aqueous dispersion of resin particles-
600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, sodium alkylallyl sulfosuccinate (eleminol JS-2, manufactured by Sanyo Kasei Kogyo Co., Ltd.) 10 in a reaction vessel in which a stirring rod and a thermometer are set. A white emulsion was obtained when 1 part of ammonium persulfate was charged and stirred at 400 rpm for 20 minutes. The emulsion was heated to a temperature inside the system of 75 ° C. and reacted for 6 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours to obtain a [aqueous dispersion of resin fine particles]. The volume average particle diameter of the particles contained in this [aqueous dispersion of resin fine particles] was 60 nm, the weight average molecular weight of the resin content was 140,000, and Tg was 73 ° C.

-Preparation of aqueous phase-
990 parts of water, 83 parts of [aqueous dispersion of resin fine particles], 37 parts of 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminor MON-7, manufactured by Sanyo Kasei Kogyo Co., Ltd.), and 90 parts of ethyl acetate were mixed and stirred. , [Aqueous phase] was obtained.

-Emulsification or dispersion-
77 parts of the ethyl acetate solution of the [prepolymer] and 2.5 parts of the 50% ethyl acetate solution of isophorone diamine were added to 374 parts of the [oil phase 1], and a TK homomixer (manufactured by Tokushu Kika) was used. The mixture was stirred at a rotation speed of 5,000 rpm and uniformly dissolved and dispersed to obtain [oil phase 1']. Next, 550 parts of [water phase] was placed in another container in which a stirrer and a thermometer were set, and while stirring at 11,000 rpm with a TK homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.), [oil phase 1] '] Was added and emulsified for 1 minute to obtain [emulsified slurry 1].

-Solvent removal-cleaning-drying-
[Emulsified slurry 1] was put into a container in which a stirrer and a thermometer were set, and the solvent was removed at 30 ° C. for 8 hours under reduced pressure to obtain [Slurry 1]. The obtained [slurry 1] was held at 45 ° C. for 2 hours, filtered under reduced pressure, and the following washing treatment was performed.
(1) 100 parts of ion-exchanged water was added to the filtered cake, mixed with a TK homomixer (rotation speed 6,000 rpm for 5 minutes), and then filtered.
(2) Add 100 parts of ion-exchanged water to the filtered cake of (1) above, mix with a TK homomixer (rotation speed 6,000 rpm for 5 minutes), and then add 1% hydrochloric acid to pH 3.3 under stirring. In that state, stirring was continued for 1 hour, and then filtration was performed.
(3) 300 parts of ion-exchanged water was added to the filtered cake of (2) above, mixed with a TK homomixer (rotation speed: 6,000 rpm for 5 minutes), and then filtered twice to obtain filtered cake 1. ..

The obtained filtered cake 1 was dried at 40 ° C. for 48 hours in a circulation dryer. Then, it was sieved with a mesh having a mesh size of 75 μm to prepare [Toner Maternal Particle 1].

− Mixing −
Add 1.5 parts of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) to 100 parts of the mother particles to the above [toner base particles 1], and use a 20 L Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was mixed at a peripheral speed of 33 m / s for 5 minutes. The above was air sieved with a 500 mesh sieve to obtain [Toner 1].

(Example 2)
In the preparation of [Oil phase 1] in Example 1, [Toner 2] was prepared in the same manner as in Example 1 except that the disk peripheral speed of the bead mill (Ultra Viscomill, manufactured by Imex) was changed to 8 m / sec. ..

(Example 3)
In the preparation of [Oil phase 1] in Example 1, [Toner 3] was prepared in the same manner as in Example 1 except that the disk peripheral speed of the bead mill (Ultra Viscomill, manufactured by Imex) was changed to 9 m / sec. ..

(Example 4)
In the preparation of [Oil phase 1] in Example 1, [Toner 4] was prepared in the same manner as in Example 1 except that the peripheral disk speed of the bead mill (Ultra Viscomill, manufactured by Imex) was changed to 10 m / sec. ..

(Example 5)
In the preparation of [oil phase 1] in Example 4, [toner 5] was prepared in the same manner as in Example 4 except that the peripheral speed of the shear disperser was changed to 13.5 m / sec and pre-dispersion was performed. ..

(Example 6)
In the preparation of [Oil Phase 1] in Example 5, [Toner 6] was prepared in the same manner as in Example 5 except that the bead mill (Ultra Viscomill, manufactured by Imex) was filled with 80% by volume of 0.3 mm zirconia beads. did.

(Example 7)
-Preparation of layered inorganic mineral masterbatch-
[Polyester resin] 100 parts, 100 parts of a montmorillonite compound modified with a quaternary ammonium salt having at least a benzyl group (Clayton APA, manufactured by Southern Clay Products, particle size 500 nm), and 50 parts of ion-exchanged water are often used. The mixture was mixed and kneaded with an open roll type kneader (Kneedex / Mitsui Mine Co., Ltd.). The kneading temperature started from 90 ° C., and then gradually cooled to 50 ° C. to prepare [Layered Inorganic Mineral Masterbatch 1] in which the ratio (mass ratio) of the resin and the layered inorganic mineral was 1: 1.
In the preparation of [Oil Phase 1] in Example 6, [Toner 7] was the same as in Example 6 except that 1.6 parts of 72 parts of [Polyester resin] were replaced with [Layered Inorganic Mineral Masterbatch 1]. ] Was prepared.

(Example 8)
In the preparation of [Oil phase 1] in Example 6, [Toner 8] was the same as in Example 6 except that 0.8 part of 72 parts of [Polyester resin] was replaced with [Layered inorganic mineral masterbatch 1]. ] Was prepared.

(Example 9)
In the preparation of [Oil Phase 1] in Example 8, [Toner 9] was prepared in the same manner as in Example 8 except that the peripheral disk speed of the bead mill (Ultra Viscomill, manufactured by Imex) was changed to 12 m / sec. ..

(Comparative Example 1)
In the preparation of [Oil Phase 1] in Example 5, [Toner 10] was prepared in the same manner as in Example 5 except that dispersion was not performed using a bead mill (Ultra Viscomill, manufactured by Imex).

(Comparative Example 2)
In the production of [Oil Phase 1] in Example 8, [Toner 11] was produced in the same manner as in Example 8 except that the disk peripheral speed of the bead mill (Ultra Viscomill, manufactured by Imex) was changed to 13 m / sec. did.

(Comparative Example 3)
In the preparation of [oil phase 1] in Example 9, [toner 12] was prepared in the same manner as in Example 9 except that the peripheral speed of the shear disperser was changed to 10.0 m / sec for dispersion.

(Comparative Example 4)
In Comparative Example 1, in addition to hydrophobic silica, 1.5 parts of titanium oxide surface-modified by zinc ion treatment was added to [toner matrix particles 1] to a 20 L Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). [Toner 13] was prepared in the same manner as in Comparative Example 1 except that the mixture was mixed at a peripheral speed of 33 m / s for 5 minutes.

(Comparative Example 5)
In Comparative Example 1, [Toner 14] was obtained in the same manner as in Comparative Example 1 except that [Toner matrix particles 1] were obtained and then classified by an airflow type classifier "DS5 type" (manufactured by Nippon Pneumatic Co., Ltd.). ] Was prepared.

(Comparative Example 6)
In Comparative Example 1, 300 parts of ion-exchanged water was added to the washed filtered cake, mixed with a TK homomixer (rotation speed: 6,000 rpm for 5 minutes), and then spherically heat-treated at 55 ° C. for 1 hour. Made [Toner 15] in the same manner as in Comparative Example 1.

Table 1 shows the manufacturing conditions and the like of the toner obtained as described above.

(Measurement)
The following measurements were performed on the toners obtained in the above Examples and Comparative Examples.

<CH rate measurement>
Using a Raman microscope "XproRA PLUS" (manufactured by Horiba Seisakusho Co., Ltd.), a Raman spectrum of 500 to 600 particles was measured for each toner particle with a laser having an excitation wavelength of 638 nm. The CH ratio was calculated from the Raman spectrum, and the proportion of particles having a CH ratio of 25.0% or more, the proportion of particles having a CH ratio of 50.0% or more, and the median CH ratio were obtained.
The results are shown in Table 2.

<X-ray fluorescence elemental analysis (XRF)>
(Quantification of layered inorganic minerals in toner)
The amount of the layered inorganic mineral added was quantified by fluorescent X-rays.
For the calibration curve, a toner in which a predetermined amount of layered inorganic mineral was added to the toner was prepared in advance, and Al contained in the layered inorganic mineral was measured and used as a calibration curve.
Samples were prepared with 3 g of toner obtained after drying, an automatic pressure molding machine (manufactured by T-BRB-32 Maekawa), a load of 6.0 tons, and a pressure time of 60 sec (manufacturer and conditions) to a diameter of 3 mm and a thickness of 2 mm. Pellets were molded, Al in the toner was measured by quantitative analysis with a fluorescent X-ray apparatus (ZSX-100e, manufactured by Rigaku Denki), and the content ratio of layered inorganic minerals was calculated as mass% from the prepared calibration curve.
The measurement results are shown in Table 2.

<Measurement of charge distribution>
The charge amount (μC / g) of the toner is measured by the blow-off powder charge amount measuring device TB-200 (manufactured by Kyocera), and the charge amount distribution is Q / d distribution (manufactured by Hosokawa Micron) by the charge amount distribution measuring device Espart Analyzer (manufactured by Hosokawa Micron). fC / μm) was measured, and the particle ratio in the positively charged region was calculated as the WST rate.
The results are shown in Table 2.

<Measurement of particle size distribution>
The particle size distribution of toner is measured using Coulter Multisizer III (manufactured by Coulter, trade name), connected to a personal computer (manufactured by IBM), and weight average based on volume using dedicated analysis software (manufactured by Coulter). The ratio (Dv / Dn) was determined from the number average particle size (Dn) obtained from the particle size (Dv) and the number distribution.
The results are shown in Table 2.

<Measurement of shape distribution>
The average circularity of 3000 particles or more was measured using a flow-type particle image analyzer FPIA-3000 (manufactured by Sysmex, trade name), and the number ratio of particles having a circularity of 0.850 or less in the measured particles was determined.

<Preparation of developer>
5 parts of the [Toner 1] and 95 parts of the carrier described below were mixed with a turbo shaker mixer (manufactured by Simmal Enterprises) to obtain a developer.
-Creation of carriers-
Silicone resin (organo straight silicone) 100 parts Toluene 100 parts γ- (2-aminoethyl) Aminopropyltrimethoxysilane 5 parts Carbon black 10 parts The above mixture was dispersed with a homomixer for 20 minutes to prepare a coat layer forming solution. This coating layer forming liquid was coated on the surface of 1000 parts of spherical magnetite having a particle size of 50 μm using a fluidized bed coating device to obtain a magnetic carrier.
Using an image forming apparatus using [Developer 1] containing [Toner 1], the transferability, in-machine contamination resistance, and cleaning property of the image were evaluated by the evaluation method described below.

[Evaluation of transferability]
Using a copying machine (Imagio MP 7501) evaluation machine manufactured by Ricoh Co., Ltd., which tuned the linear speed to 162 mm / sec and the transfer time to 40 msec, for the above [Developer 1], A4 size and toner adhesion amount of 0.6 mg / cm ² A running test was conducted in which the solid pattern of was output as a test image. The transfer efficiency in the primary transfer was determined by the following (Equation 2), and the transfer efficiency in the secondary transfer was determined by the following (Equation 3) at the initial stage of the test image and after 100K output. The evaluation criteria are as follows.
Primary transfer efficiency (%) = (amount of toner transferred onto the intermediate transfer body / amount of toner developed on the electrophotographic photosensitive member) x 100 ... (Equation 2)
Secondary transfer efficiency (%) = [(Amount of toner transferred on the intermediate transfer body-Amount of toner remaining on the intermediate transfer body) / Amount of toner transferred on the intermediate transfer body] × 100 ... (Equation) 3)

-Evaluation criteria-
The evaluation criteria were calculated by multiplying the primary transfer rate and the secondary transfer rate, and evaluated according to the following criteria.
Rank: Transfer rate 10: 99.0% or more 9: 98.0% or more and less than 99.0% 8: 96.0% or more and less than 98.0% 7: 94.0% or more and less than 96.0% 6: 92 .0% or more and less than 94.0% 5: 90.0% or more and less than 92.0% 4: 88.0% or more and less than 90.0% 3: 86.0% or more and less than 88.0% 2: 84.0 % Or more and less than 86.0% 1: Less than 84.0%

[Evaluation of internal contamination resistance]
The [Developer 1] of the above example was put into a Ricoh digital color imagio Neo C600 remodeling machine and evaluated. After running 100,000 sheets of an image chart with a 50% image area in a single color mode, the printed matter and the stains around the fixed paper ejection part were visually observed and evaluated by comparing with a 10-step (R1 to R10) step sample. ..
It should be noted that the stains around the printed matter and the fixed paper ejection portion mean that the stains are in ascending order of rank. The evaluation of R1 is a level that cannot be adopted as a product because an unacceptable level of stains are found around the fixing portion and the printed matter.

[Evaluation of blade cleanability]
The blade cleaning property was determined by using a color copier (Ipsio Color8100; manufactured by Ricoh Co., Ltd.) loaded with the developer and the electrostatic latent image carrier (electrophotographic photosensitive member, photoconductor), and the image occupancy rate was 7%. After running 100,000 sheets using 6000 paper (manufactured by Ricoh Co., Ltd.) with a printing rate, 10 images with an image occupancy rate of 50% are continuously output at 10 ° C. in an environment of 15% RH, and the 10th sheet is printed. Was stopped during development. At this time, the toner on the drum before and after the cleaning blade on the photoconductor was transferred to the tape. The transfer tape attached to 6000 paper was subjected to ID measurement using X-Rite eXact (X-Rite Co., Ltd.), and the cleaning rate was determined from the ID by the following (Equation 4).
Cleaning rate [%] = ΔID (Transfer residual ID-ID after cleaning) / Transfer residual ID ... (Equation 4)

-Evaluation criteria-
Rank: Cleaning rate 5: 80% or more 4: 60% or more and less than 80% 3: 40% or more and less than 60% 2: 20% or more and less than 40% 1: 20% or less Note that 2 is equivalent to the conventional product and 1 is as a product. It is a level that cannot be adopted.

<Comprehensive judgment>
The evaluation criteria for the comprehensive judgment are as follows.
All ranks were added to obtain the total rank score, and the toner was evaluated on a 5-point scale from the total rank score.
"☆" is extremely good, "◎" is very good, "○" is good, "△" is equivalent to the conventional product, and "×" is a level that cannot be used practically. "☆", "◎", "○" were accepted, and "△" and "×" were rejected.
If the blade cleaning property rank is "1", the overall judgment is "x" regardless of the total rank score.
Comprehensive judgment: Total rank score ☆: 22 or more ◎: 18-21
○: 14 to 17
Δ: 13 or less ×: Blade cleanability rank is 1

The results obtained as described above are shown in Table 3.

As is clear from the evaluation results in Table 3, in Examples 1 to 9, transferability, in-machine contamination resistance, and cleanability are all compatible at a high level. On the other hand, in Comparative Examples 1 to 6, any of the transfer rate, the stain resistance in the machine, and the cleanability is at a low level, or one of them has a practical problem.

10 Electrostatic latent image carrier (photoreceptor drum)
10K Electrostatic image carrier for black 10Y Electrostatic image carrier for yellow 10M Electrostatic image carrier for magenta 10C Electrostatic image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressurizing roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developer 41 Developer belt 42K Developer storage 42Y Developer housing 42M Developer housing 42C Developer housing 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer Supply roller 44K Development roller 44Y Development roller 44M Development roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Resist roller 50 Intermediate transfer belt 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charging device 60 Cleaning device 61 Developing device 62 Transfer roller 63 Photoreceptor cleaning device 64 Static elimination lamp 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100A, 100B, 100C Image forming device 120 Image forming unit 130 Document stand 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transfer roller 148 Paper feed path 150 Copying device main body 160 Charging device 200 Paper feed table 300 Scanner 400 Document automatic transfer device (ADF)

Japanese Unexamined Patent Publication No. 2003-107783 JP-A-2002-40705 Japanese Unexamined Patent Publication No. 2016-45394

Claims (7)

And at least a binder resin, a yellow toner containing a colorant, the Raman spectrum in the wave number λ of the toner particles obtained in the wave number region of 950cm ^-1 ~3250cm ^-1 in the Raman spectroscopy of the yellow toner when normalized strength to ^1, the integrated intensity of the spectrum of each of the toner particles obtained in the wave number region of 2750cm ^-1 ~3250cm -1 and _{I n,} the average value of the _{I n} and _{I ave,} following (formula When the value calculated in 1) is taken as the CH ratio, the number ratio of the toner particles whose absolute value of the CH ratio is 25.0% or more to all the toner particles is 1.0 number% or more and 15.0 number% or less. Yellow toner characterized by being.
CH ratio _{(%) = [(I n} -I ave) / I ave] × 100 ··· ( Equation 1) The yellow toner according to claim 1, wherein the number ratio of the toner particles having an absolute value of CH ratio of 50.0% or more is 2.0 number% or less. The yellow toner according to claim 1 or 2, wherein the median CH ratio is −3.0% or more. A developer comprising the yellow toner according to any one of claims 1 to 3. The yellow toner according to any one of claims 1 to 3 or the developing agent according to claim 4, the electrostatic latent image carrier and the electrostatic latent image formed on the electrostatic latent image carrier. A process cartridge characterized in that a developing means for developing using toner is integrally supported and can be attached to and detached from the main body of an image forming apparatus. Electrostatic latent image carrier and
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier,
A developing means for developing the electrostatic latent image to form a visible image using the yellow toner according to any one of claims 1 to 3 or the developing agent according to claim 4.
A transfer means for transferring the visible image onto a recording medium,
An image forming apparatus comprising a fixing means for fixing a transferred image transferred on the recording medium. An electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier,
A developing step of developing the electrostatic latent image to form a visible image using the yellow toner according to any one of claims 1 to 3 or the developing agent according to claim 4.
A transfer step of transferring the visible image onto a recording medium, and
An image forming method comprising a fixing step of fixing a transferred image transferred onto the recording medium.

Images