JP2010091755A - Magenta toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a magenta toner having high durability for continuously outputting images of high definition and high picture quality even for a long period of printing, while keeping favorable fixability at a low temperature, high gloss and transparency for an OHP. <P>SOLUTION: The toner includes toner particles containing a binder resin, a colorant and a polar resin. The toner particles are prepared in an aqueous medium, a cyclohexane (CHX) insoluble content in a tetrahydrofuran (THF) soluble content of the toner has a glass transition temperature (Tg) existing in a range from 80°C to 120°C, the cyclohexane (CHX) insoluble content has an acidic number of 5 to 40 mgKOH/g, and the colorant is a specific monoazo pigment. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a magenta toner used in a recording method such as an electrophotographic method, an electrostatic recording method, and a toner jet method.

In recent years, electrophotographic devices such as printer devices have
(1) High definition, high image quality (2) While achieving energy savings more than ever,
(3) High-speed printing (4) Development of an apparatus capable of achieving low running cost is strongly desired. Furthermore, these (1) to (4) are also desired to have (5) high reliability that can continue to output the same level as the initial image even if printed over a long period of time.

  Along with this, the properties required for toners have become more advanced and diverse than conventional ones, and development has been carried out from various viewpoints.

  From the viewpoint of high definition and high image quality, fine particles are desired as the toner in accordance with the higher resolution of the electrophotographic apparatus such as 1200 and 2400 dpi. As one method for producing such a toner, a production method using a polymerization method has been proposed. The toner obtained by such a polymerization method includes a toner obtained by agglomerating and fusing emulsion-aggregated (aggregated) resin particles and colorant particles (emulsion-aggregated (aggregated) toner), radically polymerizable, and the like. There are toner particles (suspension polymerization toner) obtained by dispersing a monomer and a colorant, then dispersing the droplets in an aqueous medium or the like so as to obtain a desired toner particle size, and suspension polymerization.

  In particular, the suspension-polymerized toner not only makes it easy to make fine particles, but also has a sharp particle size distribution, high sphericity, and can form particles with a substantially uniform surface material. A toner having properties can be obtained. Such a toner can have high developability and high transferability and is preferably used. In addition, as described above, since the sharp particle size distribution is obtained, the classification process can be simplified. Therefore, energy saving, shortening of manufacturing time, improvement of process yield, and cost reduction effect are great, which is also preferable from the viewpoint of low running cost.

  On the other hand, colorization is rapidly progressing in the field of electrophotography. In general, a color image is formed by appropriately overlapping and developing four color toners of yellow, magenta, cyan, and black. Therefore, each color toner is required to have higher development characteristics than a single color toner. That is, there is a need for a toner that can faithfully develop an electrostatic charge image formed on a photoreceptor, reliably transferred to a transfer material without scattering, and easily fixed on a transfer material such as paper. The toner produced by the suspension polymerization method as described above is also preferably used from such a viewpoint.

  From the viewpoint of energy saving, it is desired to develop a toner that can be easily fixed on a transfer material such as paper at a low temperature. At the same time, as the resolution of the image increases, the glossiness of the image must be controlled and, in the case of a color machine, good color mixing and a wide range of color reproducibility are required in order to approach the image quality of photographs and prints. ing.

  For example, (6) obtaining an image with high glossiness close to photographic quality, (7) enabling high image density output, (8) excellent OHP transparency, (9) excellent light resistance It is that.

  As one of means for achieving the requirements (6) to (9) while achieving the requirements (1) to (5), an approach from a colorant has been made.

  In particular, as an example focusing on magenta pigments, by defining the average particle size of monoazo pigments, proposals have been made for magenta toners that have excellent light resistance, triboelectric chargeability, dispersibility, and excellent transparency. (See Patent Document 1).

  In addition, by specifying the content of β-naphthol derivatives and aromatic amines contained in monoazo pigments, a magenta toner with excellent color reproducibility, gradation, light resistance, and excellent charging characteristics is proposed. (See Patent Document 2).

  However, further improvements are required for the ever-changing market demands (1) to (9).

  Specifically, while maintaining good fixability at low temperatures, high glossiness, and OHP transparency, it is possible to continue outputting high-definition and high-quality images even when printing over a long period of time. Magenta toner is awaited.

JP-A-11-272014 JP 2003-149869 A

  The present invention is to solve the above-mentioned problems of the prior art.

  That is, the object of the present invention is to maintain high fixability at low temperature, high glossiness and OHP transparency, and continue to output high-definition and high-quality images even when printing over a long period of time. The object is to provide a magenta toner having durability.

  As a result of intensive studies, the present inventors have found that the above-described problems can be solved by the following configuration, and have reached the present invention.

  That is, the present invention relates to a toner having toner particles containing at least a binder resin, a colorant, and a polar resin, wherein the toner particles are produced in an aqueous medium and are soluble in tetrahydrofuran (THF) of the toner. The cyclohexane (CHX) insoluble matter in the minute has a glass transition temperature (Tg) measured by a differential scanning calorimeter of at least 80 ° C. to 120 ° C., and the acid value of the cyclohexane (CHX) insoluble matter is 5 mgKOH. The magenta colorant (A) is a monoazo pigment represented by the following (formula 1), wherein the magenta colorant (A) is at least 40 mgKOH / g.

から選ばれる置換基を示し、Ｒ₄及びＲ₅は、水素原子、ハロゲン原子、もしくはアルキル基、アルコキシ基、ニトロ基から選ばれる置換基を示す。）

R ₄ and R _{5 each} represents a hydrogen atom, a halogen atom, or a substituent selected from an alkyl group, an alkoxy group, and a nitro group. )

  According to the present invention, while maintaining good fixability at low temperature, high glossiness and OHP transparency, high durability that can continue to output high-definition and high-quality images even when printing over a long period of time. A magenta toner having the following can be obtained.

  Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention.

  The magenta toner of the present invention is a toner having toner particles containing at least a binder resin, a colorant, and a polar resin, wherein the toner particles are produced in an aqueous medium, and the toner tetrahydrofuran (THF) The cyclohexane (CHX) insoluble matter in the soluble matter has a glass transition temperature (Tg) measured by a differential scanning calorimeter of at least 80 ° C. to 120 ° C., and the acid value (Avx) of the cyclohexane (CHX) insoluble matter. ) Is 5 mg KOH / g or more and 40 mg KOH / g or less, and the colorant is a monoazo pigment represented by the following (formula 1).

から選ばれる置換基を示し、Ｒ₄及びＲ₅は、水素原子、ハロゲン原子、もしくはアルキル基、アルコキシ基、ニトロ基から選ばれる置換基を示す。）

R ₄ and R _{5 each} represents a hydrogen atom, a halogen atom, or a substituent selected from an alkyl group, an alkoxy group, and a nitro group. )

  In order to enable both low-temperature fixability and high durability, a toner having toner particles having a core / shell structure has been proposed.

  Some types of toner particles having such a core / shell structure are separated into an inner layer and an outer layer. This is mainly intended to protect the inner layer components by the outer layer and has an excellent function. However, since the adhesion between the inner layer and the outer layer is weak, if the toner continues to be stressed as in continuous print output, the outer layer peels off or scrapes, and the toner particle surface composition changes rapidly at a certain point. There is a possibility, and it becomes difficult to obtain high reliability with respect to developability and transferability.

  In order to improve the above-described problems, the magenta toner of the present invention is a resin having a polarity and a compatibility with a binder resin as a core binder at the same time when producing toner particles in an aqueous medium ( It is considered that it is important to form the outer layer while ensuring sufficient adhesion with the inner layer by using a polar resin) as a shell binder.

  Cyclohexane (hereinafter also referred to as CHX) has a property of being hardly soluble in a polar solvent and has a high solubility for dissolving a polymer having no polarity, but has a low solubility for dissolving a polymer having polarity. Therefore, it is one of the most excellent solvents for separating non-polar polymers and polar resins.

  From this, it is considered that the cyclohexane insoluble component in the tetrahydrofuran (hereinafter also referred to as THF) soluble component of the toner of the present invention refers to the polar resin.

  In addition, since the polar resin has polarity and compatibility with the binder resin at the same time, in the toner particles, the layers having the inner layer and the outer layer are not completely separated. thinking. That is, the present inventors consider that a concentration gradient is generated such that the concentration of the polar resin is high on the surface of the toner particles and gradually decreases toward the inside.

  For example, it is assumed that a suspension polymerization method is used as a toner production method.

  When a general polar resin is added, the amount of the polymerizable monomer is decreased with the polymerization reaction after being dissolved in the polymerizable monomer, so that the solubility is decreased and the layers are separated. Similarly, the polar resin thus separated is easily compatible with highly polar water and is localized on the surface of the toner particles.

  However, since the polar resin used in the present invention has good compatibility with the binder resin at the same time, it is estimated that the polar resin does not completely separate in toner particles but has a concentration gradient.

  Thus, it is expected that the outer layer having high toughness can be formed while sufficiently securing the adhesion with the inner layer.

  As a result, the initial surface state of the toner particles can be easily maintained, so that the charging stability is excellent, and there is little change in developability and transferability through durability, which leads to high durability.

  In fixing, a specific internal structure in which the polar resin has a concentration gradient in the toner particles is considered to have an effect on fixing characteristics.

  In other words, the property that the polar resin is easily compatible with the binder resin is expected to facilitate the rapid movement of the wax contained in the toner particles to the toner particle surface when the toner is heated.

  In the magenta toner of the present invention, it is considered important that the magenta colorant (A) is a monoazo pigment represented by the following (formula 1) (hereinafter also simply referred to as a monoazo pigment).

から選ばれる置換基を示し、Ｒ₄及びＲ₅は、水素原子、ハロゲン原子、もしくはアルキル基、アルコキシ基、ニトロ基から選ばれる置換基を示す。）

R ₄ and R _{5 each} represents a hydrogen atom, a halogen atom, or a substituent selected from an alkyl group, an alkoxy group, and a nitro group. )

  The monoazo pigment is conventionally used preferably as a pigment for magenta toner having excellent light resistance, high brightness and saturation, and good color reproducibility.

  However, when toner particles are produced in an aqueous medium, there is a possibility that the toner particles lack stability and the particle size distribution becomes wide. As a result, the rise of charge and the broadening of the charge amount distribution may be caused, and the developability and transferability may be deteriorated.

  The reason for this is not clear, but one of the causes is that when the toner particles are produced in an aqueous medium, the dispersibility of the monoazo pigment is deteriorated and a part of the pigment component is localized on the toner particle surface layer. I expect that.

  Such a deterioration of the dispersibility of the monoazo pigment may possibly cause a reduction in coloring power, a deterioration in transparency in an OHP image, and a fixing problem.

  The magenta toner of the present invention uses, as a magenta colorant (A), a monoazo pigment represented by the above formula 1 and a resin (polar resin) having polarity and compatibility with the binder resin at the same time. This led to the improvement of the above problem. The reason is not clear, but the present inventors consider as follows.

  A general polar resin is likely to be localized on the surface of toner particles when toner particles are produced in an aqueous medium. At that time, the monoazo pigment having a highly polar functional group such as a hydroxyl group or a carbonyl group interacts with the polar resin and easily moves to the toner particle surface layer. As a result, it is expected that the dispersibility of the monoazo pigment is deteriorated.

  However, as described above, the magenta toner of the present invention uses a resin (polar resin) having polarity and compatibility with the binder resin at the same time, and the concentration gradient of the polar resin in the toner particles is It is thought that it has occurred. That is, it is considered that the degree of phase separation occurs more slowly than in the conventional toner, and as a result, the dispersibility of the monoazo pigment in the toner particles is considered to be improved.

  On the other hand, the magenta colorant (A) of the present invention has a characteristic that it is easily adapted to both polar resins and nonpolar resins, although the reason is not clear. In other words, it means that both the polar resin and the binder resin can be easily used, and it is expected that the pigment dispersibility during the phase separation is easily maintained.

  Furthermore, the polar resin used in the magenta toner of the present invention has a possibility that the developability may be deteriorated due to charge-up particularly in a low humidity environment, although the reason is not clear. However, it was found that a stable charge amount can be maintained by combining with the monoazo pigment represented by the above (Formula 1) as the magenta colorant (A). The reason is that the carboxyl group or hydroxyl group present in the polar resin and the hydroxyl group or carbonyl group present in the monoazo pigment represented by the above (formula 1) are electrostatically bonded to stabilize the charge. I'm expecting that it is planned.

  In the magenta toner of the present invention, the glass transition temperature (Tg) measured by a differential scanning calorimeter of the CHX insoluble component in the THF soluble component is at least 80 ° C. or higher and 120 ° C. or lower. Preferably, it is 85 degreeC or more and 110 degrees C or less.

  In order to improve the low-temperature fixability, it is preferable to design the glass transition temperature (Tg) of the binder resin as the core binder to be low. When the binder resin is designed with a low glass transition temperature (Tg), the heat resistance (blocking resistance) tends to decrease, but the measurement was made with a differential scanning calorimeter of the CHX insoluble content in the THF soluble content. When the glass transition temperature (Tg) is within the above range, a decrease in heat resistance can be suppressed. In addition, it is possible to obtain a toner having high toughness and high stress resistance. As a result, improvement in developability, transferability and fixability can be achieved even in long-term image output, and better characteristics than before can be obtained.

  The glass transition temperature (Tg) is influenced by the polar resin used as the toner raw material, and can be adjusted by the monomer composition ratio at the time of manufacturing the polar resin.

  In the magenta toner of the present invention, the acid value of the CHX insoluble component in the THF soluble component of the toner is 5 mgKOH / g or more and 40 mgKOH / g or less. Preferably, they are 10 mgKOH / g or more and 25 mgKOH / g or less.

  When the acid value of the CHX-insoluble component in the THF-soluble component of the toner is in the above range, the binder resin as the core binder is appropriately separated from the polar resin as the shell binder, and the heat resistance Improves stress resistance. Further, the charge-up can be suppressed by the interaction between the polar resin and the magenta colorant (A). Further, the dispersibility of the magenta colorant (A) in the toner particles becomes good, the localization to the toner particle surface layer is suppressed, and the particle size distribution becomes good. As a result, improvement in developability and transferability can be achieved, and better characteristics than before can be obtained.

  Since the acid value is affected by the polar resin used as the toner raw material, it can be adjusted by the type and amount of the monomer when the polar resin is produced.

  In the magenta toner of the present invention, the magenta colorant (A) of the toner has a transmittance of 15.0% or less, preferably 10.0% or less after 5 minutes of dispersion of the aqueous dispersion at a wavelength of 800 nm. A monoazo pigment represented by the formula 1) is preferred.

  Further, in the magenta toner of the present invention, the magenta colorant (A) of the toner simultaneously satisfies that the transmittance after 5 minutes of dispersion of the toluene dispersion at a wavelength of 800 nm is 5.0% or less (Formula 1 A monoazo pigment represented by

  The transmittance after 5 minutes of dispersion of the aqueous dispersion at a wavelength of 800 nm is considered to monitor the ease with which the polar resin and the monoazo pigment are used. In other words, water is one of highly polar solvents, so if the transmittance of the dispersion liquid is low, it is considered that the pigment is highly dispersible in polar resins, leading to improved pigment dispersibility as toner particles. .

  On the other hand, the transmittance after 5 minutes of dispersion of the toluene dispersion at a wavelength of 800 nm is considered to monitor the ease of familiarization of the binder resin and the monoazo pigment. In other words, since toluene is one of solvents with low polarity, if the transmittance of the dispersion liquid is low, it is considered that the pigment is highly dispersible in a nonpolar resin (= binder resin). It leads to improvement of pigment dispersibility.

  Thus, as the magenta colorant (A), it is possible to use the monoazo pigment represented by (Formula 1) that exhibits good dispersibility in both the polar resin and the binder resin. It improves the pigment dispersibility and leads to obtaining toner particles with a sharp particle size distribution. As a result, it is considered that the rise of charge is improved, the charge amount distribution is sharpened, and the developability and transferability are improved.

  In the magenta toner of the present invention, the magenta colorant (A) of the toner has a transmittance of 50.0% or more in the aqueous layer after 5 minutes of dispersion of the water-toluene dispersion at a wavelength of 800 nm (Formula 1). It is preferable that it is the monoazo pigment shown by these. The transmittance after 5 minutes of dispersion of the water-toluene dispersion is considered to monitor whether the monoazo pigment is more familiar to the polar resin or the binder resin.

  When the transmittance in the aqueous layer after 5 minutes of dispersion of the water-toluene dispersion is 50.0% or more, it means that the monoazo pigment is more familiar to the binder resin. Yes. In other words, the present inventors consider that the concentration of the colorant in the toner particles is opposite to that of the polar resin, and the concentration of the colorant is low on the surface of the toner particles and gradually increases toward the inside. ing.

  As a result, it is considered that there is an effect of suppressing the exposure of the monoazo pigment to the surface of the toner particles while the monoazo pigment is dispersed throughout the toner particles.

  As an example of obtaining the magenta colorant (A) having the above-mentioned characteristics, the monoazo pigment represented by (formula 1) which is the magenta colorant (A) is mixed with stearic acid, abietic acid, pimaric acid, parastoline. Examples of the surface treatment include a fatty acid such as an acid or a rosin that is a resin acid.

  In the magenta toner of the present invention, the main peak molecular weight (Mp) in the gel permeation chromatography (GPC) of the CHX insoluble component in the THF soluble component of the toner is preferably 10,000 to 250,000. More preferably, it is 15,000 or more and 100,000.

  By maintaining the main peak molecular weight (Mp) in the gel permeation chromatography (GPC) of the CHX insoluble content in the THF soluble content of the toner within the above range, it has an appropriate strength while maintaining the low temperature fixing property. Toner can be obtained, and the development property, transfer property and fixing property can be improved, and better characteristics than before can be obtained.

  The molecular weight (Mp) is determined by polymerization conditions (temperature, polymerization initiator species, polymerization initiator amount, etc.) during the production of the polar resin and polymerization conditions (temperature, polymerization initiator species, polymerization initiator amount) during the production of the toner particles. Etc.) and the like can be adjusted.

  In the magenta toner of the present invention, the CHX insoluble content in the THF soluble content is preferably 3% by mass or more and 30% by mass or less, more preferably 10% by solid content obtained as the CHX insoluble content. The content is from 30% by mass to 30% by mass, and more preferably from 15% by mass to 30% by mass.

  The CHX-insoluble component in the THF-soluble component is a toner having an appropriate particle size distribution and an appropriate strength while maintaining a low-temperature fixability when the solid component obtained as the CHX-insoluble component is within the above range. As a result, improvement in developability, transferability and fixability can be achieved, and better characteristics than before can be obtained.

  Since the cyclohexane insoluble content is affected by the amount of the polar resin in the toner raw material, the content of the cyclohexane insoluble content can be adjusted by the amount of the polar resin charged at the time of toner production.

  The physical properties (content, main peak molecular weight (Mp), glass transition temperature (Tg), and acid value) of the CHX insoluble matter in the THF soluble content of the magenta toner of the present invention are measured by the following methods.

<Preparation method of CHX insoluble content in THF soluble content of toner>
The measurement sample is prepared as follows.

  Mix the toner to be measured and tetrahydrofuran (THF) at a concentration of 450 mg / ml, shake well at room temperature for 10 hours until the sample is no longer united, and mix the THF and sample well. Put.

  Thereafter, the lysate is centrifuged at 15000 r / min for 60 minutes in a 10 ° C. environment using a cooling high-speed centrifuge (H-9R (manufactured by Kokusan Co., Ltd.), thereby separating the supernatant into a supernatant and a sediment. Collect the liquid. Further, the supernatant is reduced by 50% while bubbling the supernatant with nitrogen gas to prepare a concentrated solution.

  Thereafter, 5 ml of the concentrated solution is added to 100 ml of cyclohexane (CHX) to form a CHX insoluble matter. The liquid in which the CHX insoluble matter is generated is centrifuged for 60 minutes at 15000 r / min in a 10 ° C. environment using a cooling high-speed centrifuge (H-9R (manufactured by Kokusan Co., Ltd.)). And the supernatant liquid is removed.

  After the removed precipitate was allowed to stand at room temperature for 24 hours, the solvent was removed in a vacuum dryer (40 ° C.) for 24 hours to remove THF, and CHX insoluble matter in THF soluble matter (A) Collect.

<Content of CHX insoluble content in THF soluble content of toner>
Using the CHX insoluble content (A) as a measurement sample, the content (% by mass) of the CHX insoluble content in the THF soluble content of the toner is calculated as follows.

<Main peak molecular weight (Mp) of CHX insoluble matter in THF soluble content of toner>
The molecular weight (Mp) of the main peak measured by gel permeation chromatography (hereinafter also referred to as GPC) of the CHX insoluble component in the THF soluble component of the toner is measured by the following method.

  The CHX insoluble matter (A) is the measurement target.

  CHX insoluble matter (A) to be measured and THF are mixed at a concentration of 5 mg / ml, and allowed to stand at room temperature for 5 hours, and then thoroughly shaken to mix the THF and sample well (until the sample is no longer integrated) ), And further left at room temperature for 24 hours. Then, what passed the sample processing filter (Maishori disk H-25-2 manufactured by Tosoh Corporation) is prepared as a measurement sample used for GPC.

  The molecular weight distribution of the prepared sample and the molecular weight (Mp) of the main peak are measured under the following measurement conditions using a GPC measurement device (HLC-8120 GPC manufactured by Tosoh Corporation) according to the operation manual of the GPC measurement device.

<Measurement conditions>
Equipment: High-speed GPC “HLC8120 GPC” (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: THF
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  Moreover, in calculating the molecular weight of the measurement sample, a calibration curve is obtained using standard polystyrene resin (TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F, manufactured by Tosoh Corporation). -20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500) are used.

<Glass transition temperature (Tg) of CHX insoluble matter in THF soluble content of toner>
Using the CHX insoluble matter (A) as a measurement sample, the glass transition temperature (Tg) of the CHX insoluble matter in the THF soluble content of the toner is measured under the following conditions.

A differential scanning calorimeter (DSC measuring apparatus) can be measured as follows according to ASTM D3418-82 using DSC-7 (manufactured by Perkin Elmer), DSC2920 (manufactured by TA Instruments Japan) and the like. In the present invention, DSC-7 (manufactured by PerkinElmer) was used as a DSC measuring apparatus. The measurement sample is precisely weighed in an amount of 2 to 5 mg, preferably 3 mg. It is put in an aluminum pan, and an empty aluminum pan is used as a control, and measurement is performed at a temperature rising rate of 1 ° C./min within a measurement range of 20 to 140 ° C.
Detailed measurement conditions are as follows.

(Measurement condition)
・ Equilibrium at 20 ° C. for 5 minutes ・ Modulation of 1.0 ° C./min is applied and the temperature is raised to 140 ° C. at 1 ° C./min. ・ Equilibrium is maintained at 140 ° C. for 5 minutes.

  Tg is determined by the midpoint method from the peak position of the obtained DSC curve at the first temperature increase.

<Acid value of the CHX insoluble component in the THF soluble component of the toner>
Using the CHX insoluble matter (A) as a measurement target, the acid value (mgKOH / g) of the CHX insoluble matter in the THF soluble content of the toner is measured by the following method.

(Sample preparation)
In a 200 ml beaker, 1.0 g of CHX insoluble matter (A) to be measured was precisely weighed, dissolved in 120 ml of toluene while stirring with a stirrer, and further 30 ml of ethanol was added to obtain a measurement sample.

(apparatus)
For example, a potentiometric automatic titrator AT-400WIN (manufactured by Kyoto Electronics Industry Co., Ltd.) is used as the measuring device.

  The setting of the measuring device is intended for a sample dissolved in an organic solvent. The glass electrode and the comparative electrode to be used should be compatible with organic solvents.

  For example, product code # 100-H112 is used as the pH glass electrode. The tip should not be dried. Cork type reference electrode uses product code # 100-R115. The tip should not be dried. Check if the internal liquid is filled up to the internal liquid replenishment port. As the internal solution, a 3.3 mol / KCl solution is used.

(procedure)
The adjusted measurement sample is set on the autosampler of the measurement apparatus, and the glass electrode is immersed in the measurement sample solution.

  Next, a titrant (1/10 N KOH (ethanol solution)) is set on the sample solution, and 0.05 ml is added dropwise by automatic intermittent titration to calculate the acid value.

The acid value is obtained from the following calculation formula. The mass unit of the measurement sample at this time is g.
(Acid value) = [{(sample end point) − (blank end point)} × f × 56 × 0.1] / (mass of measurement sample)

  Here, f is a factor of the potassium hydroxide solution, and f = 1.09.

<Measurement method of transmittance of water of colorant, toluene, water-toluene dispersion>
20 mg of colorant is charged into 10 g of each dispersion medium in a 30 ml glass bottle. Here, the water dispersion is prepared by adjusting ion-exchanged water to pH = 5 with acetic acid and NaOH. In the case of a toluene dispersion, 10 g is used as it is, and in the case of a water-toluene dispersion, water: It is assumed that toluene = 7: 3.

  Next, shake with a shaker KM-Shaker V-SX (manufactured by Iwaki) at a speed of 250 times / minute for 1 minute. Let stand for 5 minutes, then sample with a dropper. When sampling the aqueous layer from the water-toluene dispersion, it is performed gently with a dropper in contact with the bottom of the glass bottle so that toluene is not mixed.

  Each sampled sample is measured for transmittance (% T) from a wavelength of 900 nm to 400 nm using a Shimadzu spectrophotometer UV-3100 (manufactured by Shimadzu Corporation), and the transmittance at 800 nm is read.

  In the magenta toner of the present invention, the magenta colorant (A) of the toner preferably has an acid value (Ava) of 10 (mgKOH / g) to 20 (mgKOH / g).

  When the acid value (Ava) of the magenta colorant (A) is within the above range, the magenta colorant (A) is well dispersed in the polar resin and the binder resin. Therefore, it is possible to obtain a toner having an appropriate particle size distribution and better characteristics than the conventional ones with improved developability, transferability and fixability.

  The acid value (Ava) measurement method of the magenta colorant (A) is in accordance with the acid value measurement method of the CHX insoluble component in the THF soluble component of the toner described above.

  In the magenta toner of the present invention, the magenta colorant (A) of the toner is preferably a monoazo pigment represented by (Formula 1) having a transmittance of 15% or less after 24 hours of dispersion of the methanol dispersion. .

  The transmittance after 24 hours of dispersion of the methanol dispersion at a wavelength of 800 nm is considered to monitor the familiarity of the polar resin and the monoazo pigment, similar to the transmittance after 5 minutes of dispersion of the aqueous dispersion. .

  The measurement method is in accordance with the above-described method for measuring the transmittance of water, toluene, and a water-toluene dispersion of the colorant.

  In the magenta toner of the present invention, the magenta colorant (A) of the toner is C.I. I. Pigment Red185 is more preferable from the viewpoint that it is a monoazo pigment that is easily compatible with both the binder resin and the polar resin.

  The magenta pigment used in the magenta toner of the present invention is used in combination with other magenta pigments or dyes from the viewpoint of excellent light resistance, high brightness and saturation, wide color reproducibility, and pigment dispersibility. It is also preferable. Particularly preferred is the combined use with a quinacridone pigment represented by the following formula, and most preferred is C.I. I. pigment Red122.

［Ｘ₁及びＸ₂は、それぞれ独立して水素原子、ハロゲン原子、炭素数１乃至３のアルキル基及び炭素数１乃至３のアルコキシ基からなる群より選ばれる置換基を示す。］

[X ₁ and X ₂ each independently represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. ]

  The magenta toner of the present invention preferably contains a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group. This is because, in particular, the toner coat amount in the longitudinal direction of the toner carrier becomes uniform, and it is excellent in faithful development on the photoreceptor and high in-page uniformity. In addition to this, even with a transfer material with low smoothness, transfer uniformity similar to that with a transfer material with high smoothness can be obtained.

  As a monomer having a sulfonic acid group for producing the polymer, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamide-2-methylpropane sulfonic acid, vinyl sulfonic acid, and And methacrylsulfonic acid.

  The polymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group used in the present invention may be a homopolymer of the monomer, but the monomer and other monomers It may be a copolymer of As a monomer that forms a copolymer with the above monomer, there is a vinyl polymerizable monomer, and a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p A styrenic polymerizable monomer such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n -Hexyl acrylate, 2-ethylhexyl acrylate Acrylic polymerizable monomers such as relate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Body; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n- Octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl Methacrylic polymerizable monomers such as tacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl methyl ether; Examples thereof include vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, 2,2′-bis (4-methacryloxy / polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, and the like.

  The polymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group preferably contains 0.01 to 5.0 parts by mass, more preferably 0 to 100 parts by mass of the binder resin. .1 to 3.0 parts by mass.

  When the polymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group is 0.01 to 5.00 mass with respect to 100 mass parts of the binder resin, sufficient chargeability is obtained and uniform transferability is obtained. Obtainable. Furthermore, in the granulation step in an aqueous medium using a dispersion stabilizer having a positive component, a sharp distribution of toner particle size can be obtained in order to enhance the formation of an electric double layer.

The magenta toner of the present invention preferably has a toner viscosity (Pa · s) at 100 ° C. of 1.00 × 10 ⁴ (Pa · s) or more and 3.50 × 10 ⁴ (Pa · s) or less. More preferably, it is 1.00 × 10 ⁴ (Pa · s) or more and 3.00 × 10 ⁴ (Pa · s) or less.

  When the viscosity of the toner at 100 ° C. is within the above range, it is possible to obtain a toner having good low-temperature fixability and better characteristics than the conventional one having both developability and transferability.

  The viscosity of the toner at 100 ° C. can be adjusted by adjusting the molecular weight and glass transition temperature of the binder resin or adjusting the type and content of the wax component. It is also possible to adjust the polymerization conditions (temperature, polymerization initiator type and polymerization initiator amount).

<Measurement Method of Toner Viscosity at 100 ° C.>
The viscosity of the toner at 100 ° C. is measured using a constant-load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the apparatus. In this device, while applying a constant load from the top of the measurement sample by the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is extruded from the die at the bottom of the cylinder, and the temperature at this time And measure the relationship between the amount of piston descent.

  In the present invention, measurement is performed from 50 ° C. to 200 ° C., and the apparent viscosity calculated at 100 ° C. is defined as the viscosity (Pa · s) of the toner at 100 ° C.

The apparent viscosity η (Pa · s) at 100 ° C. is calculated as follows. First, the flow rate Q (cm3 / s) is calculated from the following equation (1). In the formula, the sectional area of the piston is A (cm 2), and the time required for the piston to descend between 0.10 mm up and down (0.20 mm as the interval) with respect to the position of the piston at 100 ° C. is Δt ( Seconds).
Q = (0.20 × A) / (10 × Δt) (1)

And the apparent viscosity (eta) in 100 degreeC is computed from the following formula (2) using the obtained flow rate Q. In the formula, the piston load is P (Pa), the diameter of the hole of the die is B (mm), and the length of the die is L (mm).
η = (π × B4 × P) / (128000 × L × Q) (2)

As a measurement sample, about 1.0 g of toner is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used. The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

  In the present invention, the average circularity of the toner measured by a flow particle image analyzer is preferably 0.960 or more and 0.995 or less, more preferably 0.970 or more and 0.995 or less.

  When the average circularity of the toner is within the above range, it is possible to obtain a toner having higher transfer efficiency and development efficiency and better characteristics than conventional ones.

  The average circularity of the toner can satisfy the condition by adjusting the temperature during the production of the toner. In the case of a polymerized toner, it can be adjusted by adjusting the amount of the dispersion stabilizer charged.

<Measuring method of average circularity of toner>
In the present invention, a flow type particle image measuring device “FPIA-3000 type” (manufactured by Sysmex Corporation) is used as a measuring device in order to measure the average circularity of the toner.

  The measurement principle of the flow type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) is to capture the flowing particles as a still image and perform image analysis. The sample (toner) added to the sample chamber is sent to the flat sheath flow cell by the sample suction syringe. The sample fed into the flat sheath flow cell is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is subjected to image processing at an image processing resolution of 512 × 512 (0.37 μm × 0.37 μm per pixel), and the contour of each particle image is extracted, Projected area, perimeter, etc. are measured.

  The image signal is A / D converted by the image processing unit, captured as image data, and image processing for determining the presence or absence of particles is performed on the stored image data.

  Next, contour enhancement processing is performed as preprocessing for accurately extracting the contour of the particle image. Then, the image data is binarized at an appropriate threshold level. When the image data is binarized at an appropriate threshold level, each particle image becomes a binarized image as shown in FIG. Next, it is determined whether each of the binarized particle images is an edge point (contour pixel representing a contour), and in which direction there is an edge point adjacent to the target edge point. Information, that is, chain code is generated.

Next, the projected area S and the perimeter L of each particle image are obtained. Using the area S and the perimeter L, the equivalent circle diameter and the circularity are obtained. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image. The circularity (C) is obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. And is calculated by the following formula.
C = 2 × (πS) ^1/2 / L

  When the particle image is circular, the degree of circularity is 1, and the degree of unevenness on the outer periphery of the particle image increases, and the degree of circularity decreases. After calculating the circularity of each particle, the range of the circularity of 0.2 to 1.0 is divided into 800, and the average circularity is calculated using the center value of the dividing points and the number of measured particles.

  As a specific measurement method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a dispersion means, an ultrasonic disperser UH-50 type (manufactured by SMT Co., Ltd.) equipped with a titanium alloy chip having a diameter of 5 mm as a vibrator is used and subjected to a dispersion treatment for 5 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not become 40 degree | times or more.

  For the measurement, the above-mentioned flow type particle image analyzer equipped with a standard objective lens (10 times) was used, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion liquid prepared according to the above procedure is introduced into the flow type particle image analyzer, 3000 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is 85%. The analysis particle diameter was limited to a circle equivalent diameter of 2.00 μm to 200.00 μm, and the average circularity of the toner was determined.

  In the measurement, automatic focus adjustment is performed using standard latex particles (for example, Duke Scientific 5200A diluted with ion-exchanged water) before the measurement is started. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In this embodiment, a flow type particle image analyzer which has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, has an analysis particle diameter of 2.00 μm in equivalent circle diameter. The measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that it was limited to 200.00 μm or less.

  The weight average particle diameter (D4) of the toner in the present invention is preferably 4.0 μm or more and 9 μm or less, more preferably 4.5 μm or more and 8.5 μm or less from the viewpoint of obtaining a high-definition and high-quality image. is there.

  When the weight average particle diameter (D4) of the toner is within the above range, contamination of the member can be suppressed more favorably, and good dot reproducibility can be obtained.

<Method for measuring weight average particle diameter of toner>
The weight average particle diameter (D4) of the toner is determined based on the precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting and analyzing the measurement data, the measurement data is measured with 25,000 effective channels. Analysis was performed and calculated.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used. Prior to measurement and analysis, dedicated software was set up as follows.

  In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked. In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

  <1> About 200 ml of the electrolytic solution is placed in a glass-made 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.

  <2> About 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat bottom beaker made of glass, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder consisting of organic builder) is used as a dispersant. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion exchange water is added.

  <3> Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic disperser “Ultrasonic Dissipation System Tetora150” (manufactured by Nikkiki Bios) with an electrical output of 120 W. A fixed amount of ion-exchanged water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  <4> The beaker of <2> is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  <5> About 10 mg of toner is added to the electrolytic aqueous solution little by little in a state where the electrolytic aqueous solution in the beaker of <4> is irradiated with ultrasonic waves, and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  <6> The electrolyte solution of <5> in which the toner is dispersed with a pipette is dropped into the round bottom beaker of <1> installed in the sample stand, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.

  <7> The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

  The main peak molecular weight in GPC of the toner soluble matter in the present invention is preferably from 10,000 to 40,000, more preferably from 15,000 to 35,000.

  When the main peak molecular weight in GPC of the THF soluble content of the toner is within the above range, it is possible to obtain a toner having a high offset resistance that can be fixed at a low temperature and has good exudation of wax. Moreover, since it has moderate strength, good developability and transferability can be obtained.

  The main peak molecular weight of the toner can be adjusted by adjusting the temperature and polymerization conditions (temperature, polymerization initiator species and polymerization initiator amount) at the time of toner production.

  The main peak molecular weight of the THF soluble part of the toner in the present invention is the THF soluble part of the toner before being added to the cyclohexane solvent in the above <Method for preparing CHX insoluble part in THF soluble part of the toner> as a measurement sample. The molecular weight (Mp) of the main peak measured by gel permeation chromatography (GPC) of the CHX insoluble matter in the THF soluble content of the magenta toner is measured by the same measurement method except that it is used.

  The glass transition temperature measured by the differential thermal analysis measuring apparatus for toner in the present invention is preferably 30 ° C. or more and 58 ° C. or less from the viewpoint of achieving both low temperature fixability and developability, more preferably 35 ° C. or more and 55 ° C. or less. .

  The toner glass transition temperature in the present invention is measured by measuring the THF soluble content of the toner before being added to the cyclohexane solvent in the above <Method for preparing CHX insoluble content in the THF soluble content of the toner> as a measurement sample. Except for the above, it can be obtained by the same measurement method as the Tg of the CHX insoluble matter in the THF soluble matter of the magenta toner.

  It is preferable that the glass transition temperature (Tg) of the binder resin as the core binder is such that the Tg rises as the polar resin as the shell binder dissolves and becomes the measured Tg of the present invention. As a result, the design with a low theoretical Tg has greatly improved the heat resistance that has been lowered. In addition to this, the development property, transfer property, and fixing property described in the present invention can be improved, and toner characteristics that cannot be achieved by the prior art can be obtained.

  In the present invention, the glass transition temperature (Tg) of the binder resin as the core binder is preferably 10 ° C. or higher and 45 ° C. or lower, more preferably 15 ° C. or higher and 40 ° C. or lower from the viewpoint of low-temperature fixability. Since it is difficult to isolate only the binder resin from the toner particles, the glass transition temperature (Tg) of the binder resin as the core binder is calculated based on the theoretical Tg calculated from the formulation. It may be regarded as (Tg).

  The materials used for the toner of the present invention will be described below.

  Examples of the binder resin used in the present invention include polystyrene; a styrene-substituted homopolymer such as poly-p-chlorostyrene and polyvinyltoluene; a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer, Styrene-vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacrylic acid methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether Styrene copolymer such as copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Coalescence; acrylic resin; methacrylic tree ; Polyvinyl acetate; silicone resins; polyester resins; polyamide resin; furan resins, epoxy resins, xylene resins. These resins are used alone or in combination.

  The comonomer for the styrene monomer of the styrene copolymer includes acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, doditer acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methacrylic acid. Monocarboxylic acid having a double bond such as methyl acid, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof; maleic acid, butyl maleate, methyl maleate, maleate Dicarboxylic acids having a double bond such as dimethyl acid and its substitutes; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene and butylene; Sulfonyl methyl ketone, vinyl ketones such as vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

  As the polymerizable monomer used when the toner of the present invention is produced by the polymerization method, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p A styrene derivative such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl accelerator Acrylic polymerizable monomers such as N-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Body; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n- Octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl meta Methacrylic polymerizable monomers such as relate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinylmethyl And vinyl ethers such as ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, Examples include 2,2′-bis (4- (methacryloxy / polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  In the present invention, the above-described monofunctional polymerizable monomers are used alone or in combination of two or more, or the above-mentioned monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. . The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

  Examples of polar resins used in the present invention include polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, or copolymers of nitrogen-containing monomers and styrene-unsaturated carboxylic acid esters; acrylonitrile Nitrile monomers such as: Halogen-containing monomers such as vinyl chloride; Unsaturated carboxylic acids such as acrylic acid and methacrylic acid; Unsaturated dibasic acids; Unsaturated dibasic acid anhydrides; Nitro monomers Or a styrene monomer such as a styrene monomer, a styrene-acrylic acid ester copolymer, and a styrene-methacrylic acid ester copolymer; a polyester; an epoxy resin.

  The polar resin (shell binder) of the present invention preferably contains the same composition as that of the binder resin from the viewpoint of adhesion to the binder resin (core binder). When a vinyl polymer such as polystyrene, a styrene-substituted homopolymer, or a styrene copolymer is used as the binder resin, a vinyl copolymer is preferably used as the polar resin.

  In the case of using a styrene copolymer, the residual styrene is preferably in the range of 0 to 300 ppm in order to improve the familiarity between the polar resin and the binder resin.

  The polar resin has a GPC peak molecular weight Mp of 8,000 to 250,000, a weight average molecular weight Mw of 8,000 to 260,000, and a ratio of the number average molecular weight to the weight average molecular weight (Mw / Mn) is 1. Those of .05 to 5.00 are preferred. More preferably, the peak molecular weight Mp is 10,000 to 250,000 and the weight average molecular weight Mw is 11,000 to 260,000, and still more preferably, the peak molecular weight Mp is 15,000 to 100,000. Mw is 16,000 to 110,000. The glass transition temperature Tg is preferably 80 to 120 ° C. Furthermore, the acid value is preferably 5 to 40 mgKOH / g.

  In order to obtain a good fixed image, the toner of the present invention preferably contains 0.5 to 50 parts by mass, more preferably 3 to 30 parts by mass of the wax component with respect to 100 parts by mass of the binder resin. More preferably, it is 5 to 20 parts by mass. If the wax is less than 0.5 parts by mass with respect to 100 parts by mass of the binder resin, the effect of suppressing the low temperature offset is poor, and if it exceeds 50 parts by mass, the long-term storage stability decreases and the dispersion of other toner materials This leads to a decrease in toner fluidity and image characteristics.

  Examples of the wax used in the present invention include the following. Petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax, petrolactam; montan wax and derivatives thereof; hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method; polyolefin waxes and derivatives thereof such as polyethylene wax and polypropylene wax; carnauba wax Natural waxes such as candelilla wax and derivatives thereof. Examples of the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, the following are mentioned. Higher fatty alcohols; fatty acids such as stearic acid and palmitic acid; acid amide waxes; ester waxes; hardened castor oil and its derivatives; plant waxes; Among these, ester wax and hydrocarbon wax are preferable from the viewpoint of excellent releasability. In addition, a wax containing 50 to 95% by mass of a compound having the same total carbon number is preferable because of its high wax purity and easy development of the effects of the present invention.

  The wax preferably contains 1 to 40 parts by mass with respect to 100 parts by mass of the binder resin. More preferably, it is 3 to 25 parts by mass.

  When the amount of the wax is 1 to 40 parts by mass, the winding resistance at a high temperature is improved by having an appropriate wax bleeding property when the toner is heated and pressurized. Further, even when subjected to stress on the toner during development or transfer, the exposure of the wax to the toner surface is small, and uniform chargeability of each toner can be obtained.

  Among these waxes, those having a maximum endothermic peak of the DSC curve measured by a differential scanning calorimeter are preferably in the range of 40 ° C. to 110 ° C., and more preferably in the range of 45 ° C. to 90 ° C. More preferred. Moreover, it is preferable that the half value width of an endothermic peak is 2 degreeC or more and 15 degrees C or less, More preferably, it is 2 degreeC or more and 10 degrees C or less. The half-value width of the endothermic peak is the temperature width of the endothermic chart at a portion showing a value half the peak height from the base line in the endothermic peak.

  When the full width at half maximum is less than 2 ° C., the productivity of toner particles tends to decrease due to the high purity wax.

  When the full width at half maximum exceeds 15 ° C., the wax crystallinity is not high, so the hardness of the wax is soft, and there is a risk of contamination of the photoreceptor and the charging member. Along with this, developability and transferability tend to deteriorate.

  The toner of the present invention preferably has a maximum endothermic peak due to the melting point of the wax in the range of 70 ° C. to 120 ° C. of the DSC curve measured by a differential scanning calorimeter.

  The above-mentioned DSC curve was obtained by using the THF-soluble component of the toner except that the THF-soluble component of the toner before being added to the cyclohexane solvent in the above <Method for preparing the CHX-insoluble component in the THF-soluble component of the toner> was used as a measurement sample. It is obtained in the temperature rising process when measured by the same measurement method as Tg of CHX insoluble matter in the solution.

  In the present invention, toner particles are produced in an aqueous medium.

  Examples of the method for producing toner particles in an aqueous medium include the following methods. An emulsion aggregation method in which an emulsion composed of essential toner components is aggregated in an aqueous medium; a suspension granulation method in which the essential toner components are dissolved in an organic solvent and then the organic solvent is volatilized after granulation in the aqueous medium. A suspension polymerization method or an emulsion polymerization method in which a polymerizable monomer in which an essential toner component is dissolved is directly granulated in an aqueous medium and then polymerized; a method in which an outer layer is then formed on the toner by using seed polymerization; A microcapsule method represented by drying in liquid.

  Among these, the suspension polymerization method is particularly preferable as the one that easily exhibits the effects of the present invention. In this suspension polymerization method, a polymerizable monomer is uniformly dissolved or dispersed with a wax and a colorant (and a polymerization initiator, a crosslinking agent, a charge control agent, and other additives as necessary) to achieve polymerization. A monomer composition is used. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using a suitable stirrer, and a polymerization reaction is performed to obtain toner particles having a desired particle size. is there. After the polymerization, the toner particles are filtered, washed and dried by a known method, and if necessary, a fluidity improver is mixed and adhered to the surface to obtain the toner of the present invention.

  For the purpose of efficiently proceeding the polymerization reaction, it is preferable to manage the dissolved oxygen in the reaction vessel. If there is little dissolved oxygen, the polymerization reaction will be more efficient. As a result, low molecular weight components that adversely affect developability and transferability can be suppressed, and excellent high development efficiency, high transfer efficiency, and uniformity can be obtained.

  When the toner is produced by this suspension polymerization method, since the individual toner particle shapes are substantially spherical, the charge amount distribution is relatively uniform and a toner having satisfactory development characteristics can be easily obtained. Further, it is easy to obtain a toner that maintains a high transferability with little dependence on external additives.

  Examples of the polymerizable monomer for producing the toner by the suspension polymerization method include the monofunctional polymerizable monomer and the polyfunctional polymerizable monomer.

  As the crosslinking agent, a compound having two or more polymerizable double bonds is mainly used. The following aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline And divinyl compounds such as divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups. These can be used alone or in combination. A preferable addition amount is 0.001 to 15 parts by mass with respect to 100 parts by mass of the binder resin.

  As the polymerization initiator used in the present invention, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. When the polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 10,000 and 100,000 is usually obtained. A toner having strength and melting characteristics can be obtained.

  As polymerization initiators, the following 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbohydrate) were used. Nitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2- Ethyl hexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4- Peroxidation such as dichlorobenzoyl peroxide and lauroyl peroxide System polymerization initiators, and the like.

  Particularly preferred is a polymerization initiator that produces an ether compound upon decomposition during the polymerization reaction.

  The ether compound produced at the time of decomposition during the polymerization reaction is preferably a compound having an ether bond represented by the following formula (2) or (3).

〔式（２）及び（３）中、Ｒ₁乃至Ｒ₁₁は、炭素数１乃至６までのアルキル基であり、互いに同じであっても、異なっていても良い。〕

[In the formulas (2) and (3), R _{1 to} R ₁₁ are alkyl groups having 1 to 6 carbon atoms and may be the same or different. ]

  Since the ether compound is excellent in compatibility with the binder resin, it is considered that when the ether compound is contained in the toner, it is dispersed in a nearly uniform state. Further, since oxygen atoms are elements having high electronegativity, the negative charges generated in the toner are delocalized. Since the ether compound has these two characteristics, the presence of the ether compound stabilizes the negative charge of the toner. Therefore, the effect of containing the ether compound is particularly remarkable when the toner of the present invention is a negative triboelectrically chargeable toner. In addition, it has the effect of suppressing overcharging even in the case of positive tribocharging.

  The ether compound has tertiary carbon and has a bulky structure. Since the functional group centered on tertiary carbon functions as a steric hindrance, it is hardly affected by water and charge leakage is suppressed. However, since the carbon bonded to the oxygen atom rotates, the functional group that can become steric hindrance can move, and the water molecule involved in the leakage of triboelectric charge is a small molecule. Must not. As a result, the functional group centered on the tertiary carbon functions as an appropriate steric hindrance.

  Therefore, by combining the polar resin and the ether compound, what has conventionally contributed to the charge stabilization effect of the entire inner layer resin can also contribute to the charge stabilization effect in the outer layer resin. Therefore, the balance of triboelectric charge as a whole toner is excellent in a high temperature and high humidity environment and a low temperature and low humidity environment.

  Therefore, it is considered that the rise of charge is improved, the charge amount distribution is sharpened, and the developing property is improved, such as the improvement of the coat uniformity of the toner on the toner carrier and the improvement of the development efficiency.

  Furthermore, it is considered that the transfer efficiency is maintained at a high level, leading to an improvement in transferability such as transfer uniformity within the same page and easy transfer onto a transfer material having low smoothness.

  Eventually, it is considered that such improvement in developability and transferability leads to improvement in durability.

  The ether compound is preferably contained in the toner in the range of 5 to 1,000 ppm, more preferably 10 to 800 ppm, and still more preferably 10 to 500 ppm, in order to sufficiently exhibit the above effects. It is. The ether compound preferably contains at least one compound having the above structure, and may contain an ether compound having another structure. The content at that time is the total amount of the ether compounds contained.

  When the content of the ether compound in the toner is 5 to 1000 ppm, a good triboelectric charge amount can be obtained. Further, uniform toner charging can be obtained. As a result, the uniformity of toner coating on the toner carrier and the transfer efficiency can be maintained at a high level, a uniform transfer property within the same page can be obtained, and a uniform transfer to a low smoothness transfer material can be achieved. Sex can be obtained.

  Examples of the structure of the ether compound include the following structures.

  In the present invention, in order to control the degree of polymerization of the polymerizable monomer, a known chain transfer agent, polymerization inhibitor or the like can be further added and used.

  In addition to the polymer having a sulfonic acid group in the side chain, a charge control agent may be added to the toner of the present invention in order to stabilize charging characteristics. As the charge control agent, known ones can be used, and in particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable. Specific compounds include metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, metal salts or metal complexes of azo dyes or azo pigments, boron compounds as negative charge control agents , Silicon compounds, calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, a nigrosine compound, and an imidazole compound.

  The amount of these charge control agents to be used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. When added internally, it is preferably used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin. Further, when added externally, the amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.3 part by mass with respect to 100 parts by mass of the toner.

  It is preferable to add an appropriate stabilizer to the aqueous medium used in the present invention.

  A dispersion stabilizer is added to the aqueous medium. Examples of inorganic compounds used as a dispersion stabilizer include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, Examples include barium sulfate, bentonite, silica, and alumina.

  Examples of the organic compound used as the dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, polyacrylic acid and its salt, starch and the like. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Further, 0.001 to 0.1 parts by mass of a surfactant may be used for fine dispersion of these dispersion stabilizers. This is to promote the intended action of the dispersion stabilizer. Specific examples include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like.

  When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain finer particles, the inorganic compound may be generated and used in an aqueous medium. For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high stirring.

  Furthermore, in the toner of the present invention, a fluidity improver may be added to the toner particles for the purpose of improving the fluidity of the toner particles. As the fluidity improver, the following fluororesin powders such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fatty acid metal salts such as zinc stearate, calcium stearate and lead stearate; titanium oxide powder, oxidation Metal powder such as aluminum powder and zinc oxide powder, or powder obtained by hydrophobizing the above metal oxide; and silica fine powder such as wet process silica and dry process silica, or silica with silane coupling agent and titanium coupling And surface-treated silica fine powder that has been surface-treated with a treating agent such as an agent and silicone oil.

  The fluidity improver is preferably used in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the toner particles.

  Next, an image forming method using the toner of the present invention will be described.

  The conditions of the development step in the image forming method to which the toner of the present invention can be applied may be that the toner carrier and the surface of the photosensitive body as the electrostatic latent image carrier are in contact or non-contact. . Here, the case where it contacts is demonstrated.

<Process cartridge>
FIG. 2 is a schematic cross-sectional view of a process cartridge 7 (hereinafter also referred to as “cartridge”) that can be suitably used in an image forming apparatus to which the image forming method of the present invention is applied.

  The cartridge 7 includes a photosensitive drum 1, a cleaner unit 50 including a charging unit 2 and a cleaning unit 6, and a developing unit 4A having a developing unit 4 that develops an electrostatic latent image formed on the photosensitive drum 1. Have. The photosensitive drum 1 is rotatably attached to the cleaning frame 31 constituting the cleaner unit 50 via a bearing member (not shown).

  The photosensitive drum 1 has a charging roller 2 for uniformly charging the photosensitive layer provided on the outer peripheral surface of the photosensitive drum 1, and a developer (residual toner) remaining on the photosensitive drum 1 after transfer is removed. The cleaning blade 60 for making contact is in contact. The toner (removed toner) removed from the surface of the photosensitive drum 1 by the cleaning blade 60 is stored in a removed toner storage chamber 35 provided in the cleaning frame 31.

  The developing unit 4A has a developing frame body 45 (45a, 45b, 45e) that accommodates toner, and the developing roller 40 (rotated in the direction of arrow Y) is rotatably attached to the developing frame body 45 via a bearing member. It is supported. Further, a toner supply roller 43 (rotated in the arrow Z direction) and a toner regulating member 44 are provided in contact with the developing roller 40. Further, the developing frame body 45 is provided with a toner transport mechanism 42 for stirring the toner contained therein and transporting the toner to the toner supply roller 43.

  The developing unit 4A is supported so as to be swingable with respect to the cleaner unit 50. That is, the coupling holes 47, 48 provided at both ends of the developing device frame 45 and the support holes (not shown) provided at both ends of the cleaning frame 31 of the cleaner unit 50 are aligned, and pins (not shown) are inserted from both ends of the cleaner unit 50. It is out.

  Further, the developing unit 4A is always urged by a pressure spring (not shown) so that the developing roller 40 contacts the photosensitive drum 1 with the support hole as the rotation axis.

  At the time of development, the toner stored in the toner container 41 is conveyed to the toner supply roller 43 by the toner stirring mechanism 42. The toner supply roller 43 supplies toner to the developing roller 40 by rubbing with the developing roller 40, and causes the toner to adhere on the developing roller 40. The toner adhered on the developing roller 40 reaches the toner regulating member 44 as the developing roller 40 rotates. Then, the toner regulating member 44 regulates the toner to form a predetermined toner thin layer, and gives a desired charge amount. The toner thinned on the developing roller 40 is conveyed to the developing unit in which the photosensitive drum 1 and the developing roller 40 come close as the developing roller 40 rotates. Then, in the developing unit, the latent image is developed by attaching to the electrostatic latent image formed on the surface of the photosensitive drum 1 by a developing bias applied to the developing roller 40 from a power source (not shown). The toner remaining on the surface of the developing roller 40 without contributing to the development of the electrostatic latent image is returned into the developing frame 45 as the developing roller 40 rotates. Then, it is peeled off and collected from the developing roller 40 at the rubbing portion with the toner supply roller 43. The collected toner is stirred and mixed with the remaining toner by the toner stirring mechanism 42.

  Here, an elastic roller is used as the developing roller 40, and a method of bringing the roller into contact with the surface of the photosensitive drum 1 can be used. In general, in a developing method in which a toner carrier and a photoreceptor are in contact with each other, toner is easily damaged or deformed. However, when the toner described in the present invention is used, such a change can be effectively suppressed. preferable.

In the developing method in which the toner carrying member and the photosensitive member are in contact with each other, development is performed by an electric field acting between the photosensitive member and the elastic roller facing the surface of the photosensitive member through the toner. Therefore, the surface of the elastic roller or the vicinity of the surface has a potential, and it is necessary to have an electric field in a narrow gap between the surface of the photosensitive member and the surface of the toner carrying member. Therefore, it is possible to use a method in which the elastic rubber of the elastic roller is resistance-controlled in the middle resistance region to keep the electric field while preventing conduction with the surface of the photoreceptor, or a method of providing a thin insulating layer on the surface layer of the conductive roller. . Further, a conductive resin sleeve in which the side facing the surface of the photoconductor is coated with an insulating material on the conductive roller, or a conductive layer is provided on the side not facing the photoconductor with an insulating sleeve is also possible. . Further, it is possible to employ a configuration in which a rigid roller is used as the toner carrying member and the photosensitive member is a flexible material such as a belt. The resistance value of the roller as the toner carrier is preferably in the range of 10 ^{2 to} 10 ⁹ Ω · cm.

  As the surface shape of the toner carrier, when the surface roughness Ra (μm) is set to 0.1 to 3.0 μm, both high image quality and high durability can be achieved. The surface roughness Ra correlates with the toner conveying ability and the toner charging ability. When the surface roughness Ra of the toner carrier exceeds 3.0 μm, it is difficult not only to make the toner layer on the toner carrier thin, but also the chargeability of the toner is not improved, so that improvement in image quality cannot be expected. . By suppressing the toner carrying capacity on the surface of the toner carrying body to 3.0 μm or less, the toner layer on the toner carrying body is thinned, and the number of contact between the toner carrying body and the toner increases. Since the chargeability of the toner is also improved, the image quality is synergistically improved. On the other hand, when the surface roughness Ra is smaller than 0.1 μm, it becomes difficult to control the toner coat amount.

  In the present invention, the surface roughness Ra of the toner carrier is in accordance with Japanese Industrial Standard (JIS) B06014.2.1 (revision date January 20, 2001, confirmation date July 20, 2005). Arithmetic mean roughness determined. In the present invention, a surface roughness measuring device (Surfcoder SE3500 manufactured by Kosaka Laboratory Co., Ltd.) was used to measure from an arbitrary point on the surface of the toner carrier in a direction parallel to the rotation axis of the toner carrier. The cut-off value was 0.8 mm, the measurement length was 2.5 mm, and the measurement speed was 0.1 mm / second.

  In the image forming method of FIG. 2, the toner carrier rotates in the same direction as the peripheral speed of the photosensitive member, but may rotate in the opposite direction. When the rotation is in the same direction, it is preferable to set the peripheral speed of the toner carrying member to be 1.05 to 3.0 times the peripheral speed of the photosensitive member.

  When the peripheral speed of the toner carrier is less than 1.05 times the peripheral speed of the photoreceptor, the stirring effect received by the toner on the photoreceptor is insufficient, and good image quality cannot be expected. On the other hand, when the peripheral speed ratio exceeds 3.0 times, toner deterioration due to mechanical stress and toner adhesion to the toner carrier are generated and promoted, which is not preferable.

  When the toner carrier is an elastic roller, a structure having an elastic layer on the surface is preferably used. The hardness of the material of the elastic layer used for the elastic roller is preferably 30 to 60 degrees (ASKER-C / load 1 kg).

  Further, the toner coating amount is controlled by the toner regulating member 44, and the toner regulating member 44 is in contact with the developing roller 40 through the toner layer. At this time, the contact pressure between the toner regulating member 44 and the developing roller 40 is preferably in a range of 0.05 N / cm to 0.5 N / cm as a linear pressure.

  The linear pressure is a load applied per length of the toner regulating member. For example, when a 1.2 N load is applied to the toner regulating member having a contact length of 1 m and brought into contact with the developing roller. The linear pressure is 1.2 N / m. If the linear pressure is less than 0.05 N / cm, it is difficult to control the toner coating amount and uniform triboelectric charging, resulting in fogging. On the other hand, if the linear pressure is higher than 0.5 N / cm, the toner particles are subjected to an excessive load, and therefore, deformation of the particles and adhesion of the toner to the toner regulating member or the developing roller are likely to occur.

  The free end portion of the toner regulating member 44 may have any shape. For example, in addition to a linear cross-sectional shape, an L-shape that is bent near the tip, or a shape that bulges in the vicinity of the tip. Etc. are preferably used.

  As the toner regulating member, a material in which a metal elastic body such as stainless steel, steel, phosphor bronze or the like is used as a base material and a resin is adhered or coated on a portion that contacts the sleeve contact portion is preferably used.

  Furthermore, by applying a DC electric field and / or an AC electric field to the toner regulating member, the uniform thin layer coating property and the uniform charging property are further improved due to the loosening action on the toner, and sufficient image density is achieved. A good quality image can be obtained.

<Image forming apparatus>
FIG. 3 is a schematic cross-sectional view showing an example of an image forming apparatus to which the toner of the present invention is applied. The image forming apparatus main body 100 has four image forming stations Pa, Pb, Pc, and Pd arranged in parallel in the vertical direction. The process cartridges 7 (7a, 7b, 7c, 7d) are detachably attached to the image forming stations Pa, Pb, Pc, Pd by attachment means (not shown). The magenta, cyan, yellow, and black cartridges 7a, 7b, 7c, and 7d have the same configuration.

  In this schematic diagram, the image forming stations Pa, Pb, Pc, and Pd are arranged side by side with a slight inclination in the vertical direction, but they may be arranged in the vertical direction without being inclined. Further, the process cartridge 7 may be the same as that illustrated in FIG. 1 or may be different.

  Each cartridge 7 (7a, 7b, 7c, 7d) includes a photosensitive drum 1 (1a, 1b, 1c, 1d). The photosensitive drum 1 is driven to rotate counterclockwise in the drawing by a driving means (not shown). Around the photosensitive drum 1, the following means are provided in order according to the rotation direction. (A) Charging means 2 (2a, 2b, 2c, 2d) for uniformly charging the surface of the photosensitive drum 1. (B) A scanner unit 3 (3a, 3b, 3c, 3d) that irradiates a laser beam based on image information to form an electrostatic latent image on the photosensitive drum 1. (C) Developing means 4 (4a, 4b, 4c, 4d) for developing a toner image by attaching a developer (hereinafter also referred to as “toner”) to the electrostatic latent image. (D) A transfer device 5 that transfers the toner image on the photosensitive drum 1 to the recording medium S. (E) Cleaning means 6 (6a, 6b, 6c, 6d) for removing the toner remaining on the surface of the photosensitive drum 1 after transfer.

  Here, the photosensitive drum 1 and the charging means 2, the developing means 4, and the cleaning means 6, which are process means, are integrally constituted by a cartridge frame to form a cartridge to constitute a cartridge 7.

  The photosensitive drum 1 (1a, 1b, 1c, 1d) is configured by providing a photosensitive layer on the outer peripheral surface of a cylinder. Both ends of the photosensitive drum 1 are rotatably supported by support members. Then, when a driving force from a driving motor (not shown) is transmitted to one end portion, it is rotationally driven counterclockwise.

As the photoconductor, a photoconductor drum having a photoconductive insulating material layer such as a-Se, CdS, ZnO ₂ , OPC, or a-Si is preferably used. Further, the binder resin of the organic photosensitive layer in the OPC photoreceptor is not particularly limited. Among them, polycarbonate resin, polyester resin, and acrylic resin are particularly preferable because they are excellent in transferability and hardly cause toner fusion to the photoreceptor and filming of external additives.

  As the charging means 2 (2a, 2b, 2c, 2d), a contact charging type is used. The charging means 2 is a conductive roller formed in a roller shape. The roller is brought into contact with the surface of the photosensitive drum 1 and a charging bias voltage is applied to the roller. As a result, the surface of the photosensitive drum 1 is uniformly charged.

  As a preferable process condition when the charging roller is used, the contact pressure of the roller is 0.05 to 5 N / cm as a linear pressure. As the applied voltage, a DC voltage or a DC voltage superimposed with an AC voltage is preferably used. When a DC voltage superimposed with an AC voltage is used, it is preferable that AC voltage = 0.5 to 5 dVpp, AC frequency = 50 Hz to 5 kHz, and DC voltage = ± 0.2 to ± 1.5 kV. When a DC voltage is used, the DC voltage is preferably ± 0.2 to ± 5 kV.

  As charging means other than the charging roller, there are a method using a charging blade and a method using a conductive brush. These contact charging means have an effect that a high voltage is unnecessary and generation of ozone is reduced as compared with non-contact corona charging. The material of the charging roller and charging blade as the contact charging means is preferably conductive rubber, and a release coating may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), and the like are applicable.

  In the scanner unit 3 (3a, 3b, 3c, 3d), a laser diode (not shown) passes image light corresponding to an image signal through a polygon mirror (not shown) and an imaging lens (not shown) rotated at high speed. Then, the surface of the charged photosensitive drum 1 is exposed according to image information. As a result, an electrostatic latent image is formed on the photosensitive drum.

  The developing means 4 (4a, 4b, 4c, 4d) is composed of a toner container 41 containing magenta, cyan, yellow, and black toners, respectively, and a toner transport mechanism 42 in the toner container 41 is used. The toner is fed into the toner supply roller 43.

  The toner supply roller 43 rotates in the clockwise direction in the figure, and does not contribute to supply of toner to the developing roller 40 (40a, 40b, 40c, 40d) as a toner carrier and development of an electrostatic latent image. The toner remaining on the developing roller 40 is removed.

  The toner supplied to the developing roller 40 is applied to the outer periphery of the developing roller 40 (rotated clockwise) by the toner regulating member 44 pressed against the outer periphery of the developing roller 40, and is given an electric charge. Then, a developing bias is applied to the developing roller 40 facing the photosensitive drum 1 on which the latent image is formed. Then, toner development is performed on the photosensitive drum 1 in accordance with the latent image.

  The transfer device 5 is provided with a transfer belt 11 that circulates and moves so as to face and contact all the photosensitive drums 1 (1a, 1b, 1c, 1d). The transfer belt 11 is stretched around a driving roller 13, driven rollers 14a and 14b, and a tension roller 15, and electrostatically attracts the recording medium S to the outer peripheral surface on the left side in the drawing. The transfer belt 11 circulates so that the recording medium S is brought into contact with the photosensitive drum 1. As a result, the recording medium S is conveyed to the transfer position by the transfer belt 11 and the toner image on the photosensitive drum 1 is transferred.

  The transfer roller 12 (12a, 12b, 12c, 12d) is arranged in parallel at a position in contact with the inside of the transfer belt 11 and facing the four photosensitive drums 1 (1a, 1b, 1c, 1d). A bias is applied to the transfer rollers 12 at the time of transfer, and electric charges are applied to the recording medium S via the transfer belt 11. The toner image on the photosensitive drum 1 is transferred to the recording medium S in contact with the photosensitive drum 1 by the electric field generated at this time.

  The feeding unit 16 feeds and transports the recording medium S to the image forming stations Pa, Pb, Pc, and Pd. A plurality of recording media S are stored in the cassette 17 in the feeding unit 16. At the time of image formation, the feeding roller 18 (half-moon roller) and the registration roller 19 are driven and rotated according to the image forming operation. The feeding roller 18 separates and feeds the recording medium S in the cassette 17 one by one, and then stops the recording medium S by abutting against the registration roller 19. Thereafter, the registration roller 19 feeds the recording medium S to the transfer belt 11 in synchronization with the rotation of the transfer belt 11 and the image writing position.

  The fixing unit 20 fixes the toner images of a plurality of colors transferred to the recording medium S. The fixing unit 20 includes a heating roller 21a and a pressure roller 21b that presses against the heating roller 21a and applies heat and pressure to the recording medium S. That is, the recording medium S to which the toner image formed on the photosensitive drum 1 has been transferred is conveyed by the pressure roller 21b and applied with heat and pressure by the heating roller 21a when passing through the fixing unit 20. As a result, a plurality of color toner images are fixed on the surface of the recording medium S.

  As an image forming operation, the cartridges 7 (7a, 7b, 7c, 7d) are sequentially driven in accordance with the image forming timing. In response to the driving, the photosensitive drums 1a, 1b, 1c, and 1d are rotationally driven in the counterclockwise direction. Then, the scanner units 3 corresponding to the respective cartridges 7 are sequentially driven. By this driving, the charging roller 2 applies a uniform charge to the peripheral surface of the photosensitive drum 1. The scanner unit 3 exposes the circumferential surface of the photosensitive drum in accordance with the image signal to form an electrostatic latent image on the circumferential surface of the photosensitive drum. The developing roller 40 in the developing unit 4 forms (develops) a toner image on the circumferential surface of the photosensitive drum 1 by transferring the toner to the low potential portion of the electrostatic latent image.

  At the timing when the leading edge of the toner image formed on the circumferential surface of the most upstream photosensitive drum 1 is rotated and conveyed to the point facing the transfer belt 11, the print start position of the recording medium S coincides with the point facing the transfer belt 11. Thus, the registration roller 19 rotates to feed the recording medium S to the transfer belt 11.

  The recording medium S is pressed against the outer periphery of the transfer belt 11 so as to be sandwiched between the suction roller 22 and the transfer belt 11. A voltage is applied between the transfer belt 11 and the suction roller 22. Electric charges are induced in the recording medium S that is a dielectric and the dielectric layer of the transfer belt 11, and the recording medium S is electrostatically adsorbed on the outer periphery of the transfer belt 11. As a result, the recording medium S is stably adsorbed to the transfer belt 11 and conveyed to the most downstream transfer unit.

  While being conveyed in this manner, the toner image on each photosensitive drum 1 is sequentially transferred to the recording medium S by an electric field formed between each photosensitive drum 1 and the transfer roller 12.

  The recording medium S to which the four color toner images are transferred is separated from the transfer belt 11 by the curvature of the belt driving roller 13 and is carried into the fixing unit 20. After the toner image is heat-fixed by the fixing unit 20, the recording medium S is discharged out of the main body by the paper discharge roller 23 with the image surface facing down from the paper discharge unit 24.

  Although FIG. 3 illustrates a method using a heating roller for the fixing unit 20, other fixing methods can be suitably used for the image forming method of the present invention. 4 and 5 show an apparatus for fixing a toner image by heating a heat-resistant film using a heating element.

FIG. 4 shows a fixing device having a structure in which a tension is always applied to the heat resistant film 55.
In the present invention, the heating element 53 has a small heat capacity and has a linear or planar heating section, and the maximum temperature of the heating section is preferably 100 to 300 ° C.

  The heat-resistant film is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. As these heat-resistant sheets, polyester, PET (polyethylene terephthalate), PFA (tetrafluoroethylene-perfluoro) having high heat resistance are preferable. In addition to polymer sheets such as alkyl vinyl ether copolymer), PTFE (polytetrafluoroethylene), polyimide, and polyamide, a metal sheet such as aluminum and a laminate sheet composed of a metal sheet and a polymer sheet are used.

  As a more preferable structure of the heat resistant film, these heat resistant sheets have a release layer and / or a low resistance layer.

  Reference numeral 51 denotes a heating body fixedly supported by the apparatus, and includes a heater substrate 52, a temperature detecting element 54, and the like.

  The heater substrate 52 is a member having heat resistance, insulation, low heat capacity, and high heat conductivity, and is, for example, an alumina substrate having a thickness of 1 mm, a width of 10 mm, and a length of 240 mm.

The heating element 53 is screen-printed in an approximately 10 μm thickness and a width of 1 to 3 mm in the form of a line or a thin strip of an electric resistance material along the longitudinal center of the lower surface of the heater substrate 52 (on the side facing the heat resistant film 55). Etc. are applied by, for example. As the electrical resistance material, for example, Ag / Pd (silver palladium), Ta ₂ N, RuO ₂ or the like is used.

  The temperature measuring element 54 is, for example, a temperature measuring resistor having a low heat capacity, such as a Pt film, which is provided by applying screen printing or the like on the substantially central portion of the upper surface of the heater substrate 52 (the side opposite to the surface on which the heating element 53 is provided). Is the body. A thermistor with a low heat capacity can also be used.

  In the case of the heating element 51 of this example, the heating element 53 having a linear or planar shape is energized at a predetermined timing by an image formation start signal to cause the heating element 53 to generate heat over substantially the entire length. The energization is AC 100 V, and the supplied power is controlled by controlling the phase angle of energization by an energization control circuit (not shown) including a triac according to the temperature detected by the temperature sensing element 54.

  When the heating element 51 is energized to the heating element 53, since the heat capacity of the heater substrate 52 and the heating element 53 is small, the surface of the heating element rapidly rises to a required fixing temperature (for example, 140 to 200 ° C.).

  The heat resistant film 55 is in contact with the heating body 51.

  In order to reduce the heat capacity and improve the quick start performance, the heat resistant film 55 has a total thickness of 100 μm or less, a heat resistance / release property of 20 μm or more, a single layer or a composite layer film having strength / durability. Can be used.

  For example, polyimide, polyetherimide (PEI), polyethersulfone (PES), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), polyetheretherketone (PEEK), polyparabanic acid (PPA), Alternatively, a composite layer film such as a polyimide film having a thickness of 20 μm, on at least the image contact surface side, PTFE (tetrafluoroethylene resin), fluororesin such as PAF / FEP, silicon resin, etc., and further, a conductive material (carbon black, graphite, And a releasable coat layer to which conductive whiskers and the like are added is applied to a thickness of 10 μm.

  The support roller 58, which is a rotating body, is made of a rubber elastic body having good releasability such as silicon rubber, and is pressed against the heating body 51 via a heat resistant film 55 to form a nip portion, and the heat resistant film 55 is preliminarily provided. Drive moving to speed. When a recording material sheet as a material to be heated is introduced between the heat resistant film 55 and the recording material sheet, the recording material sheet is brought into close contact with the surface of the heat resistant film 55 and pressed against the heating body 51. Let

  Another embodiment of an apparatus for fixing a toner image by heating a heat resistant film using a heating element will be described.

  FIG. 5 shows a fixing device having a structure in which no tension is applied to the heat resistant film (tension-free type).

  In the present invention, the heating element has a small heat capacity and has a linear or planar heating section, and the maximum temperature of the heating section is preferably 100 to 300 ° C.

  The heat-resistant film is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. As these heat-resistant sheets, polyester, PET (polyethylene terephthalate), PFA (tetrafluoroethylene-perfluoro) having high heat resistance are preferable. In addition to polymer sheets such as alkyl vinyl ether copolymer), PTFE (polytetrafluoroethylene), polyimide, and polyamide, a metal sheet such as aluminum and a laminate sheet composed of a metal sheet and a polymer sheet are used.

  As a more preferable structure of the heat resistant film, these heat resistant sheets have a release layer and / or a low resistance layer.

  Reference numeral 64 denotes a low heat capacity linear heating element fixedly supported by the apparatus, and includes a heater substrate 64a, an energization heating resistor (heating element) 64b, a surface protection layer 64c, a temperature detecting element 64d, and the like.

  The heater substrate 64a is a member having heat resistance, insulation, low heat capacity, and high heat conductivity, and is, for example, an alumina substrate having a thickness of 1 mm, a width of 10 mm, and a length of 240 mm.

The heating element 64b is coated with an electric resistance material in a linear or narrow strip shape having a thickness of about 10 μm and a width of 1 to 3 mm along the longitudinal center of the lower surface of the heater substrate 64a (the side facing the heat resistant film 65). The surface protective layer 64c is coated with about 10 μm of heat-resistant glass. As the electrical resistance material, for example, Ag / Pd (silver palladium), Ta ₂ N, RuO ₂ or the like is used. Moreover, as a coating method of the electrical resistance material, a screen printing method or the like is used.

  The temperature measuring element 64d is, for example, a low-temperature-capacitance resistance measuring resistor such as a Pt film that is applied by screen printing or the like on the substantially central portion of the upper surface of the heater substrate 64a (the side opposite to the surface on which the heating element 64b is provided). Is the body. A thermistor with a low heat capacity can also be used.

In the case of the heating element 64 of this example, the heating element 64b having a linear or planar shape is energized at a predetermined timing by an image formation start signal to cause the heating element 64b to generate heat over substantially the entire length.
The energization is AC 100 V, and the supplied power is controlled by controlling the phase angle of energization by an energization control circuit (not shown) including a triac according to the temperature detected by the temperature sensing element 64d.

  When the heating element 64 is energized to the heating element 64b, the heat capacity of the heater substrate 64a, the heating element 64b, and the surface protective layer 64c is small, so the surface of the heating element rapidly rises to the required fixing temperature (for example, 140 to 200 ° C.). To do.

  The heat resistant film 65 is in contact with the heating body 64.

  In order to improve the quick start performance by reducing the heat capacity, the heat resistant film 65 has a total thickness of 100 μm or less, a heat resistance / releasability of 20 μm or more, and a single layer or composite film having strength and durability. Can be used.

  For example, polyimide, polyetherimide (PEI), polyethersulfone (PES), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), polyetheretherketone (PEEK), polyparabanic acid (PPA), Alternatively, a composite layer film such as a polyimide film having a thickness of 20 μm, on at least the image contact surface side, PTFE (tetrafluoroethylene resin), fluororesin such as PAF / FEP, silicon resin, etc., and further, a conductive material (carbon black, graphite, And a releasable coat layer to which conductive whiskers and the like are added is applied to a thickness of 10 μm.

  The support roller 62, which is a rotating body, is made of a rubber elastic body having good releasability, such as silicon rubber, and is pressed against the heating body 64 via a heat resistant film 65 to form a nip portion, and the heat resistant film 65 is predetermined. Drive moving to speed. When a recording material sheet as a material to be heated is introduced between the heat resistant film 65 and the recording material sheet, the recording material sheet is brought into close contact with the surface of the heat resistant film 65 and pressed against the heating body 64, and is moved and driven together with the heat resistant film 65. Let

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In addition, all “parts” described in the examples indicate parts by mass.

<Example 1>
(Preparation of aqueous dispersion medium)
Water 350 parts Trisodium phosphate 15 parts The above mixture was kept at 60 ° C while stirring at a speed of 12,000 rpm with a high-speed stirring device TK-homomixer. Next, 9 parts of calcium chloride was added to prepare an aqueous dispersion medium containing a fine hardly water-soluble stabilizer Ca ₃ (PO ₄ ) ₂ .

(Preparation of polymerizable monomer composition 1)
Styrene 50 parts Magenta Colorant (A) (CI Pigment Red 185. Abietic acid is mixed with Colorant (A) and adjusted to an acid value of 16) 8 parts The polymerizable monomer composition 1 was obtained by dispersing for 5 hours at room temperature with a lighter.

(Preparation of polymerizable monomer composition 2)
Styrene 18 parts n-butyl acrylate 32 parts sulfonic acid group-containing polymer (FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.)) 1 part di-t-butyl ether (ether compound 1) 0.1 part negative charge control agent (3,5- Aluminum compound of jettery butylsalicylic acid)
1 part polar resin (styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 15500, Tg = 90 ° C., acid value = 21, Mw / Mn = 2.1) 25 parts The above mixture was placed in a stirring vessel capable of adjusting the temperature, heated to 60 ° C., and stirred for 5 hours.

Furthermore,
10 parts of Fischer-Tropsch wax (melting point = 75 ° C.) was put into the stirring tank, and stirring was continued for 1 hour to obtain a polymerizable monomer composition 2.

(Granulation / polymerization process)
The temperature of the polymerizable monomer composition 2 was raised to 70 ° C., and the polymerizable monomer composition 1 was added thereto, followed by stirring for 5 minutes. The obtained mixture of the polymerizable monomer compositions 1 and 2 was put into the aqueous dispersion medium. Furthermore, 8.0 parts of 2,2′-azobis-isobutyrovaleronitrile, which is a polymerization initiator, was added to the dispersion in the aqueous medium, and granulated for 30 minutes while maintaining the rotational speed of the stirrer at 12000 rpm. . Thereafter, the high-speed stirrer was transferred to a propeller-type stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring. Next, the temperature inside the container was raised to 80 ° C. and maintained for 5 hours. Thereafter, the mixture was cooled to obtain a polymer fine particle dispersion.

(Washing / Solid-liquid separation / Drying process / External addition process)
Diluted hydrochloric acid was added to the obtained polymer fine particle dispersion to adjust the pH to 1.4, and the stabilizer Ca ₃ (PO ₄ ) ₂ was dissolved. Further, after filtration and washing, the particles were vacuum-dried at a temperature of 40 ° C., and the particle diameter was adjusted by classification using a sieve to obtain nonmagnetic magenta toner particles.

Hydrophobic silica having a specific surface area by the BET method of 200 m ² / g with respect to 100 parts of the obtained magenta toner particles (10 parts treated with silicone oil for 100 parts of silica, average primary particle diameter 13 nm) 2.0 Part of the inorganic fine powder was externally added by stirring for 10 minutes with a Henschel mixer, and non-magnetic magenta toner No. 1 was added. 1 was obtained. The physical properties of the toner are shown in Table 1, and the evaluation results are shown in Table 2.

  This magenta toner No. 1 was evaluated using the image forming apparatus for the following [1] to [10].

As the image forming apparatus, a modified machine of LBP-5400 (manufactured by Canon), which is a commercially available laser printer, was used. The remodeling points of this evaluation machine are as follows.
(1) The process speed was set to 190 mm / sec by changing the gear and software of the evaluation machine main body.
(2) The cartridge used for evaluation was a magenta cartridge. That is, the product toner was extracted from a commercially available magenta cartridge, the interior was cleaned by air blow, and then 200 g of the toner according to the present invention was filled for evaluation. In addition, the product toner was extracted from each of the magenta, yellow, and black stations, and evaluation was performed by inserting magenta, yellow, and black cartridges in which the toner remaining amount detection mechanism was disabled.
(3) The software of the fixing device was changed so that the heating temperature could be controlled to 150 ° C. ± 20 ° C.

  Under the above conditions, magenta toner No. 1 was used under a low temperature and low humidity environment (15 ° C., 5% RH). After the process cartridge packed with 1 was left for 48 hours, an image having a printing ratio of 1% was continuously printed up to 3000 sheets, and the following items [1] to [10] were evaluated. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

[1] Image density Using an A4 Canon color laser copier paper (81.4 g / m ² ), a solid image was output after printing 3000 sheets in an image output test, and the density was measured. The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co.) according to the attached instruction manual to measure the relative density with respect to an image of a white background portion having a document density of 0.00.
A: Very good 1.40 or more B: Good 1.35 or more and less than 1.40 C: Average 1.00 or more and less than 1.35 D: Somewhat difficult Less than 1.00

[2] Glossiness The solid image output at [1] was measured according to the attached instruction manual using a gloss meter PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.).
A: Very good 20 or more B: Good 15 or more and less than 20 C: Average 10 or more and less than 15 D: Somewhat difficult Less than 10

[3] Line in the circumferential direction [1] After outputting a solid image, the developing container was disassembled, and the surface and end of the toner carrier were visually observed. The criteria are shown below.
A: Very good The surface and edges of the toner carrier have no circumferential streak due to foreign matter sandwiched between the toner regulating member and the toner carrier due to toner destruction or fusion.
B: Good Some foreign matter is caught between the toner carrier and the toner end seal.
C: One to four streaks in the circumferential direction are seen at the end.
D: Somewhat difficult There are 5 or more circumferential streaks in the entire area.

[4] Image Coverage In the gloss paper mode (1/2 speed), an image with a printing ratio of 1% is printed on the Letter size HP Color Laser Photo Paper, glossy (220 g / m ² ), and the “REFECTRECTER MODEL TC- 6DS "(manufactured by Tokyo Denshoku Co., Ltd.) was used to calculate the fog density (%) from the difference between the whiteness of the white portion of the measured printout image and the whiteness of the transfer paper, and image fogging after printing 3000 sheets. Evaluated. A green filter was used as the filter.
A: Very good Less than 0.5% B: Good 0.5% or more and less than 1.0% C: Average 1.0% or more and less than 1.5% D: Somewhat difficult 1.5% or more

[5] Contamination of main body and cartridge due to scattering of toner In order to evaluate the balance between chargeability and fluidity of toner, the degree of contamination by toner around the cartridge after printing 3000 sheets and the cartridge in the main body was observed.
A: Very good No contamination by toner around the cartridge and the cartridge in the main body is observed.
B: Good Dirt due to a small amount of toner is observed on the cartridge.
C: Normal: Contamination due to toner around the cartridge and the cartridge in the main body is observed, but does not affect the attachment / detachment of the image / cartridge.
D: Somewhat difficult The cartridge and the cartridge in the main body are markedly soiled by toner, and the image / cartridge attachment / detachment is also adversely affected.

[6] Charging Rise The toner charge rise was determined based on the following criteria based on the density change (measured with a Macbeth reflection densitometer) of the solid patch images from the first sheet to the 20th sheet of the print.
A: Very good Number of sheets up to density 1.4 is 5 or less B: Good Number of sheets up to density 1.4 is 6 to 10 sheets C: Average number of sheets up to density 1.4 is 11 20 sheets D: Somewhat difficult Even at the 20th sheet, the density does not reach 1.4.

[7] Transfer uniformity The halftone images after printing 100 sheets and 3000 sheets were transferred to Fox River Bond paper (90 g / m ² ) and evaluated. The criteria are shown below.
A: Very good Even at 3000 sheets, good transfer uniformity is exhibited.
B: Good When the number of samples is 3000, some of transfer uniformity is slightly inferior.
C: Somewhat inferior in the case of 100 sheets and 3000 sheets sample.
D: Somewhat difficult. When 100 sheets and 3000 sheets are sampled, the transfer uniformity is greatly inferior.

[8] Low-temperature fixability In the image forming apparatus of the contact one-component development system shown in FIGS. The process cartridge filled with 1 is left for 48 hours in a normal temperature and humidity environment (23 ° C./50% RH). Thereafter, an unfixed image of an image pattern in which 9 points of 10 mm × 10 mm square images are evenly arranged on the entire transfer paper is output. The amount of toner loaded on the transfer paper was 0.35 mg / cm ² and the fixing start temperature was evaluated. The transfer material used was Fox River Bond (90 g / m ² ). The fixing device used was an external fixing device in which the fixing device of LBP-5400 (manufactured by Canon) was removed to the outside so as to operate even outside the laser beam printer. For the external fixing device, the fixing temperature can be arbitrarily set, and the process speed was measured under fixing conditions of 190 mm / sec.

Further, the determination of the start of fixing is performed by rubbing a fixed image (including a low-temperature offset image) with a load of 50 g / cm ² on a sylbon [Lenz Cleaning Paper “dasper (R)” (Ozu Paper Co. Ltd)] The temperature at which the density reduction rate before and after rubbing was less than 20% was defined as the fixing start point.

[9] Resistance to wrapping at low temperature The wrapping resistance to the fixing roller was visually confirmed during the evaluation of [8], and the temperature at which paper passed without winding was defined as the winding start point.

[10] Full-color projection image color reproducibility and OHP transparency Non-magnetic one-component developer No. 1 as shown in FIG. The process cartridge filled with 1 is left for 48 hours in a normal temperature and humidity environment (23 ° C./50% RH). Thereafter, in the image forming apparatus (Canon: LBP-5400) of the contact one-component developing system as shown in FIG. 2, the loading amount of each toner on the OHP sheet “CG3700” (manufactured by 3M) is 0.6 mg / A full-color image adjusted to cm ² was output.

  OHP “95550” (manufactured by 3M) was used as a transmission image, and the image projected on the white wall surface was visually evaluated and measured with a spectral radiance meter “PR650” (manufactured by Photo Research), and the CIELAB color system The volume of the color space solid determined by lightness L *, a * representing the degree of red or green, and b * representing the degree of yellow or blue was determined. A larger value means a wider color space, and a smaller value means poor color reproducibility.

  The toner other than magenta for outputting a full color image was manufactured according to the following method.

  For the cyan toner, magenta colorant (A) is added to C.I. I. Except for changing Pigment Blue 15: 3 to 7 parts, the above magenta toner No. 1 was produced by the same production method.

  For yellow toner, magenta colorant (A) is added to C.I. I. Except for changing the pigment yellow 93 to 7 parts, the above magenta toner No. A yellow toner was produced by the same production method as in No. 1.

  The black toner is the same as the magenta toner No. 1 except that the magenta colorant (A) is changed to 8 parts of carbon black. A black toner was produced by the same production method as in No. 1.

(Color space volume)
A: Very good 2.5 million or more B: Good 2 million or more and less than 2.5 million C: Average 1.5 million or more and less than 2 million D: Somewhat difficult Less than 1.5 million

(Visual evaluation)
A: Very good Vivid and excellent in transparency B: Good Transparency is good and magenta color reproducibility is excellent, but secondary colors (red and blue) are slightly inferior C: Normal transparency is slightly inferior , Magenta and secondary colors (red and blue) are slightly inferior in color reproducibility D: somewhat difficult and dull, and magenta and secondary colors (red and blue) are inferior in color reproducibility

<Example 2>
In Example 1, the magenta colorant (A) (CI Pigment Red 185. Abietic acid was mixed with the colorant (A) and adjusted to have an acid value of 16) was changed to 4 parts. In the same manner as in Example 1, except that 4 parts of magenta colorant (CI Pigment Red 122. Abietic acid was mixed and adjusted to have an acid value of 16) was added. . 2 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 3.

<Example 3>
In Example 1, the same procedure as in Example 1 was performed except that the addition amount of the polymerizable monomer was changed to 4 parts of styrene and 46 parts of n-butyl acrylate at the time of preparing the polymerizable monomer composition 2. Magenta toner no. 3 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 3.

<Example 4>
In Example 1, the same procedure as in Example 1 was performed except that the addition amount of the polymerizable monomer was changed to 5 parts of styrene and 45 parts of n-butyl acrylate when preparing the polymerizable monomer composition 2. Magenta toner no. 4 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 3.

<Example 5>
In Example 1, the same procedure as in Example 1 was performed except that the addition amount of the polymerizable monomer was changed to 7 parts of styrene and 43 parts of n-butyl acrylate at the time of preparing the polymerizable monomer composition 2. Magenta toner no. 5 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 3.

<Example 6>
In Example 1, the same procedure as in Example 1 was performed except that the addition amount of the polymerizable monomer was changed to 8 parts of styrene and 42 parts of n-butyl acrylate when preparing the polymerizable monomer composition 2. Magenta toner no. 6 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 3.

<Example 7>
Example 1 is the same as Example 1 except that the addition amount of the polymerizable monomer is changed to 22 parts of styrene and 28 parts of n-butyl acrylate at the time of preparing the polymerizable monomer composition 2. Magenta toner no. 7 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 3.

<Example 8>
In Example 1, the same procedure as in Example 1 was performed except that the addition amount of the polymerizable monomer was changed to 23 parts of styrene and 27 parts of n-butyl acrylate when preparing the polymerizable monomer composition 2. Magenta toner no. 8 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 3.

<Example 9>
In Example 1, the same procedure as in Example 1 was performed except that the addition amount of the polymerizable monomer was changed to 25 parts of styrene and 25 parts of n-butyl acrylate at the time of preparing the polymerizable monomer composition 2. Magenta toner no. 9 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 3.

<Example 10>
In Example 1, the same procedure as in Example 1 was performed except that the addition amount of the polymerizable monomer was changed to 26 parts of styrene and 24 parts of n-butyl acrylate when preparing the polymerizable monomer composition 2. Magenta toner no. 10 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 3.

<Example 11>
Polar resin is styrene-n-butyl acrylate-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 80.0: 14.0: 3.5: 2.5 Mp = 13500, Tg = 80 ° C. , Acid value = 21, Mw / Mn = 1.9) Magenta toner No. 1 was changed in the same manner as in Example 1 except that it was changed to 25 parts. 11 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 12>
Polar resin is styrene-n-butyl acrylate-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 82.0: 12.0: 3.5: 2.5 Mp = 15000, Tg = 84 ° C. , Acid value = 21, Mw / Mn = 2.3) Magenta toner No. 1 was changed in the same manner as in Example 1 except that the amount was changed to 25 parts. 12 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 13>
Polar resin is styrene-n-butyl acrylate-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 83.0: 11.0: 3.5: 2.5 Mp = 16500, Tg = 85 ° C. , Acid value = 20, Mw / Mn = 2.3) Magenta toner no. 13 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 14>
A polar resin is a styrene-α-methylstyrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio 75.0: 19.0: 3.5: 2.5, Mp = 21000, Tg = 110 ° C., acid value = 25, Mw / Mn = 2.0) Magenta toner no. 14 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 15>
Polar resin is styrene-α-methylstyrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio 74.0: 20.0: 3.5: 2.5, Mp = 21000, Tg = 111 ° C., acid value = 22, Mw / Mn = 2.0) Magenta toner no. 15 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 16>
Polar resin is styrene-α-methylstyrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio 69.0: 25.0: 3.5: 2.5, Mp = 25000, Tg = 120 ° C., acid value = 21, Mw / Mn = 2.2) Magenta Toner No. 2 was changed in the same manner as in Example 1 except that it was changed to 25 parts. 16 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 17>
Polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 0.3: 5.7, Mp = 15000, Tg = 89 ° C., acid value = 5, Mw / Mn = 2.4) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 17 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 18>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 1.8: 4.2, Mp = 15500, Tg = 89 ° C., acid value = 9, Mw / Mn = 2.4) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 18 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 19>
A polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 1.9: 4.1, Mp = 15500, Tg = 89 ° C., acid value = 10, Mw / Mn = 2.4) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 19 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 20>
Polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.7: 2.3, Mp = 15000, Tg = 91 ° C., acid value = 25, Mw / Mn = 2.4) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 20 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 21>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.8: 2.2, Mp = 15300, Tg = 91 ° C., acid value = 26, Mw / Mn = 2.4) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 21 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 22>
A polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 5.0: 1.0, Mp = 14500, Tg = 90 ° C., acid value = 39, Mw / Mn = 2.4) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 22 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 23>
The magenta colorant (A) is C.I. I. Pigment Red 146 (mixed with abietic acid to colorant (A) and adjusted to have an acid value of 11) was changed to 8 parts in the same manner as in Example 1 and magenta Toner No. 23 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 24>
The magenta colorant (A) is C.I. I. Pigment Red 185 (admixed with abietic acid to colorant (A) and adjusted to have an acid value of 20) was changed to 8 parts in the same manner as in Example 1 and magenta Toner No. 24 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 25>
The magenta colorant (A) is C.I. I. Pigment Red 185 (mixed with abietic acid to colorant (A) and adjusted to have an acid value of 23) was changed to 8 parts in the same manner as in Example 1 and magenta Toner No. 25 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 26>
The magenta colorant (A) is C.I. I. Pigment Red 185 (mixed with abietic acid to colorant (A) and adjusted to have an acid value of 28) was changed to 8 parts in the same manner as in Example 1 and magenta Toner No. 26 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 27>
The magenta colorant (A) is C.I. I. Pigment Red 185 (mixed with abietic acid to colorant (A) and adjusted to have an acid value of 32) was changed to 8 parts in the same manner as in Example 1 and magenta Toner No. 27 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 28>
The magenta colorant (A) is C.I. I. Pigment Red 185 (admixed with abietic acid to colorant (A) and adjusted to have an acid value of 5) was changed to 8 parts in the same manner as in Example 1 and magenta Toner No. 28 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 29>
The magenta colorant (A) is C.I. I. Pigment Red 185 (mixed with abietic acid to colorant (A) and adjusted to have an acid value of 4) was changed to 8 parts in the same manner as in Example 1 and magenta Toner No. 29 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 30>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 9900, Tg = 87 ° C., acid value = 21, Mw / Mn = 1.9) Magenta toner No. was changed in the same manner as in Example 1 except for changing to 25 parts. 30 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 31>
Polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 10000, Tg = 88 ° C., acid value = 21, Mw / Mn = 2.0) Magenta toner No. 2 was changed in the same manner as in Example 1 except that it was changed to 25 parts. 31 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 32>
Polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 100000, Tg = 95 ° C., acid value = 21, Mw / Mn = 2.4) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 32 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 33>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 15000, Tg = 97 ° C., acid value = 21, Mw / Mn = 2.4) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 33 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 34>
Polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 248000, Tg = 100 ° C., acid value = 22, Mw / Mn = 2.4) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 34 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 35>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 251000, Tg = 105 ° C., acid value = 21, Mw / Mn = 2.6) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 35 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 36>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 15500, Tg = 90 ° C., acid value = 21, Mw / Mn = 2.1) Magenta toner No. 1 was changed in the same manner as in Example 1 except for changing to 3 parts. 36 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 37>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 15500, Tg = 90 ° C., acid value = 21, Mw / Mn = 2.1) Magenta toner No. 4 was changed in the same manner as in Example 1 except for changing to 4 parts. 37 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 38>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 15500, Tg = 90 ° C., acid value = 21, Mw / Mn = 2.1) Magenta toner No. 1 was changed in the same manner as in Example 1 except for changing to 12 parts. 38 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 39>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 15500, Tg = 90 ° C., acid value = 21, Mw / Mn = 2.1) Magenta toner No. 1 was changed in the same manner as in Example 1 except for changing to 15 parts. 39 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 40>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 15500, Tg = 90 ° C., acid value = 21, Mw / Mn = 2.1) In the same manner as in Example 1 except that 18 parts were changed, the magenta toner No. 40 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 41>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 15500, Tg = 90 ° C., acid value = 21, Mw / Mn = 2.1) In the same manner as in Example 1, except for changing to 21 parts, magenta toner No. 41 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 42>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 15500, Tg = 90 ° C., acid value = 21, Mw / Mn = 2.1) In the same manner as in Example 1 except that 50 parts are changed, the magenta toner No. 42 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 43>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 15500, Tg = 90 ° C., acid value = 21, Mw / Mn = 2.1) Magenta toner No. was changed in the same manner as in Example 1 except for changing to 51 parts. 43 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 44>
In the same manner as in Example 1 except that di-t-butyl ether (ether compound 1) is changed to 0.1 part of t-butyl isobutyl ether (ether compound 4) in Example 1, magenta toner No. 44 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 45>
Magenta toner No. 1 was prepared in the same manner as in Example 1 except that di-t-butyl ether (ether compound 1) was not added. 45 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 46>
A magenta toner No. 1 was prepared in the same manner as in Example 1 except that a sulfonic acid group-containing polymer (FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.)) was not added. 46 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 47>
In the same manner as in Example 1, except that the sulfonic acid group-containing polymer (FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.)) was changed to the sulfur-containing polymer 1 synthesized as described below, magenta toner No. 47 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

(Example of adjustment of sulfur-containing polymer 1)
Styrene 100 parts o-Methyl styrenesulfonate 10 parts 2,2'-azobisisobutyronitrile 1.3 parts dimethylformamide 110 parts Styrene in a reactor equipped with a condenser, stirrer, thermometer and nitrogen inlet Then, methyl o-styrenesulfonate and 2,2′-azobisisobutyronitrile were added and dissolved in dimethylformamide, and then polymerized at 70 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, it was recovered by reprecipitation in 500 parts of methanol. The obtained polymer was washed twice with 500 parts of water and dried under reduced pressure, whereby a sulfur-containing polymer 1 containing a sulfonic acid methyl unit represented by chemical formula (1) (Mw: 13200, Mw / Mn = 2). .6) was obtained.

<Example 48>
(Preparation of release agent fine particle dispersion 1)
78.33 parts of demineralized water, 10 parts of Fischer-Tropsch wax (melting point = 75 ° C.) and 1.7 parts of sodium dodecylbenzenesulfonate are mixed, emulsified by applying high-pressure shear at 90 ° C., and release agent fine particle dispersion 1 Got.

(Preparation of resin fine particle dispersion 1)
In a reactor (with a high-shear stirrer, volume 1 liter flask), 150 parts of ion-exchanged water, 1.5 parts of a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) and an anionic surfactant ( Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 3.5 parts was added.

Styrene 65 parts nbutyl acrylate 35 parts sulfonic acid group-containing polymer (FCA1001NS (Fujikura Kasei Co., Ltd.)) 1 part polar resin (styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass) Ratio) 94.0: 3.5: 2.5, Mp = 13500, Tg = 90 ° C., acid value = 24, Mw / Mn = 2.1) 25 parts. Octanethiol 0.35 part. Carbon tetrabromide A mixture of 0.7 part or more and dissolved was added to the reactor, and slowly mixed with 10 parts of ion-exchanged water in which 5 parts of ammonium persulfate was dissolved, over 10 minutes. Thereafter, the contents were heated in an oil bath while stirring the contents until the temperature reached 75 ° C., and after 1 hour, the temperature was further raised to 70 ° C. and emulsion polymerization was continued in a nitrogen atmosphere for 4 hours. 2 ° C per minute Cooling was performed until the temperature reached room temperature at a temperature lowering rate, and thus a resin particle dispersion 1 in which resin particles having an average particle diameter of 0.07 μm were dispersed was prepared.

(Preparation of colorant fine particle dispersion 1)
Coloring agent (A) used in Example 1 8 partsAnionic surfactant 2 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 parts or more were mixed and dispersed using a sand grinder mill.

(Preparation of charge control fine particle dispersion 1)
-Aluminum compound of di-alkyl-salicylic acid 15 parts-Di-t-butyl ether (ether compound 1) 0.1 part-Anionic surfactant 2 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 parts or more were mixed and dispersed using a sand grinder mill.

(Example of toner production)
-Resin fine particle dispersion 1 360 parts-Colorant fine particle dispersion 1 40 parts-Release agent fine particle dispersion 1 70 parts-Charge control particle dispersion 1 7 parts-Anionic surfactant 2 parts (Daiichi Kogyo Seiyaku ( Co., Ltd .: Neogen SC)
Using each of the above components, a toner was produced by the following procedure. The resin fine particle dispersion 1 and the anionic surfactant were charged into a reactor (volume 1 liter flask, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, 0.6 part by mass of an aqueous aluminum sulfate solution as a solid content was dropped (aggregation step).

  After completion of the dropwise addition, the system was replaced with nitrogen, and the system was maintained at 50 ° C. for 1 hour and further at 55 ° C. for 1 hour.

  After completion of the predetermined time, the charge control fine particle dispersion, the release agent fine particle dispersion 1, and the aluminum sulfate aqueous solution (0.6 parts by mass as a solid content) were added, and then 1 hour at 60 ° C., 30 minutes at 90 ° C. Retained (thermal fusion process). Finally, the temperature was raised to 100 ° C. and held for 1 hour. The reaction at this time was performed in a nitrogen atmosphere.

After the predetermined time, magenta toner particles were obtained by adjusting the particle size by classification after filtering, washing and drying. Hydrophobic silica having a specific surface area by the BET method of 200 m ² / g with respect to 100 parts of the obtained magenta toner particles (10 parts treated with silicone oil for 100 parts of silica, average primary particle diameter 13 nm) 2.0 Part of the inorganic fine powder was externally added by stirring for 10 minutes with a Henschel mixer, and non-magnetic magenta toner No. 1 was added. 48 was obtained. The physical properties of the toner are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 49>
(Toner binder synthesis)
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 230 ° C. for 8 hours at normal pressure. Then, the reaction was allowed to proceed for 5 hours under a reduced pressure of 10 to 15 mmHg. This was cooled to 160 ° C., 32 parts of phthalic anhydride was added and reacted for 2 hours. Further, this was cooled to 80 ° C. and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate-containing prepolymer (1). Next, 267 parts of this prepolymer (1) and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a urea-modified polyester (1) having a weight average molecular weight of 64,000.

  In the same manner as above, 724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. An unfinished polyester (a) was obtained.

  200 parts of urea-modified polyester (1) and 800 parts of unmodified polyester (a) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / ethyl methyl ketone (MEK) (1/1), and the toner binder ethyl acetate / A MEK solution was obtained.

(Production of toner particles)
In a beaker, 300 parts of the above-mentioned toner binder in ethyl acetate / MEK solution, 10 parts of Fischer-Tropsch wax (melting point = 75 ° C.), 1 part of a sulfonic acid group-containing polymer (FCA1001NS (manufactured by Fujikura Kasei)), 1 part, polar resin ( Styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 3.5: 2.5, Mp = 13500, Tg = 90 ° C., acid value = 24, Mw / Mn = 2 .1) 25 parts-Colorant used in Example 1 (A) 8 parts-Aluminum compound of di-alkyl-salicylic acid 15 parts-Di-tert-butyl ether (ether compound 1) 0.1 part is added, TK formula The mixture was stirred at 60 ° C. and 12,000 rpm with a homomixer, and uniformly dissolved and dispersed.

  In a beaker, 706 parts of ion-exchanged water, 294 parts of hydroxyapatite 10% suspension (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.2 part of sodium dodecylbenzenesulfonate were uniformly dissolved. Next, the temperature was raised to 60 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 12000 rpm with a TK homomixer. The mixture is then transferred to a Kolben equipped with a stir bar and a thermometer, heated to 98 ° C. to remove the solvent, filtered, washed, dried, further filtered, washed, dried, and then classified. The particle diameter was adjusted to obtain magenta toner particles.

Hydrophobic silica having a specific surface area by the BET method of 200 m ² / g with respect to 100 parts of the obtained magenta toner particles (10 parts treated with silicone oil for 100 parts of silica, average primary particle diameter 13 nm) 2.0 Part of the inorganic fine powder was externally added by stirring for 10 minutes with a Henschel mixer, and non-magnetic magenta toner No. 1 was added. 49 was obtained. The physical properties of the toner are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 50>
The magenta colorant (A) is C.I. I. Pigment Red 185 (stearic acid mixed with colorant (A) and adjusted to have an acid value of 16) was changed to 8 parts in the same manner as in Example 1, magenta Toner No. 50 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Comparative Example 1>
Polar resin is styrene-n-butyl acrylate-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 79.0: 15.0: 3.5: 2.5 Mp = 11500, Tg = 79 ° C. , Acid value = 20, Mw / Mn = 1.9) Magenta toner no. 51 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Comparative example 2>
A polar resin is a styrene-α-methylstyrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio 68.0: 26.0: 3.5: 2.5, Mp = 25700, Tg = 121 ° C., acid value = 21, Mw / Mn = 2.2) Magenta Toner No. 2 was changed in the same manner as in Example 1 except that it was changed to 25 parts. 52 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Comparative Example 3>
The polar resin was a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 0.2: 5.8, Mp = 15000, Tg = 90 ° C., acid value = 4, Mw / Mn = 2.4) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 53 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Comparative example 4>
The polar resin is a styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization ratio (mass ratio) 94.0: 5.3: 0.7, Mp = 14500, Tg = 90 ° C., acid value = 42, Mw / Mn = 2.6) Magenta toner No. was changed in the same manner as in Example 1 except that it was changed to 25 parts. 54 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Comparative Example 5>
The magenta colorant (A) is C.I. I. Pigment Red 57: 1 (Same as Example 1 except that the colorant (A) was mixed with abietic acid and adjusted to have an acid value of 16). , Magenta toner no. 55 was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

It is a figure which shows an example of the binarized image of the particle | grains measured by FPIA-3000. FIG. 4 is a cross-sectional explanatory view of a process cartridge in which the toner of the present invention is used. 1 is a schematic configuration diagram of an example of an image forming apparatus in which a toner of the present invention is used. FIG. 5 is a schematic configuration diagram of another fixing device used for the toner of the present invention. FIG. 5 is a schematic configuration diagram of another fixing device used for the toner of the present invention.

Explanation of symbols

Pa, Pb, Pc, Pd Image forming station 1 (1a to 1d) Photosensitive drum (image carrier)
2 (2a to 2d) Charging roller (charging means)
3 (3a to 3d) Scanner unit 4 (4a to 4d) Developing means 4A Developing unit 5 Transfer device 6 (6a to 6d) Cleaning means 7 (7a to 7d) Process cartridge 11 Transfer belt 12 (12a to 12d) Transfer roller 13 Belt drive rollers 14a and 14b Follower roller 15 Tension roller 16 Feed unit 17 Cassette 18 Feed roller 19 Registration roller 20 Fixing unit 21a Heating roller 21b Pressure roller 22 Adsorption roller 23 Paper discharge roller 24 Paper discharge unit 31 Cleaning frame ( Cartridge frame)
35 Removal toner storage chamber 40 (40a to 40d) Developing roller (toner carrier)
41 Toner container (developer storage part)
42 Toner transport mechanism 43 Toner supply roller 44 Toner regulating member (blade)
45 (45a, 45b, 45e) Development frame (cartridge frame)
47, 48 Coupling hole 50 Cleaner unit 51, 64 Heating body 52, 64a Heater substrate 53, 64b Energizing heating resistor (heating element)
54, 64d Temperature detecting element 55, 65 Heat resistant film 56, 57 Belt support roller 58 Support roller 60 Cleaning blade 62 Support roller (rotating body)
63 Belt support 64c Surface protective layer 100 Image forming apparatus main body S Recording medium (recording material sheet)

Claims (13)

A magenta toner having magenta toner particles containing at least a binder resin, a magenta colorant (A), and a polar resin,
The magenta toner particles are produced in an aqueous medium, and the cyclohexane (CHX) insoluble content in the tetrahydrofuran (THF) soluble content of the magenta toner has at least a glass transition temperature (Tg) measured by a differential scanning calorimeter. It exists in 80 degreeC or more and 120 degrees C or less, The acid value (Avx) of the said cyclohexane (CHX) insoluble matter is 5 mgKOH / g or more and 40 mgKOH / g or less,
The magenta toner, wherein the magenta colorant (A) is a monoazo pigment represented by the following (formula 1).

R ₄ and R _{5 each} represents a hydrogen atom, a halogen atom, or a substituent selected from an alkyl group, an alkoxy group, and a nitro group. )   The magenta colorant (A) has a transmittance of 15.0% or less after 5 minutes of dispersion of the aqueous dispersion at a wavelength of 800 nm, and a transmittance of 5% or less after 5 minutes of dispersion of the toluene dispersion. The magenta toner according to claim 1, wherein the magenta toner is present.   3. The magenta toner according to claim 1, wherein the magenta colorant (A) has a transmittance of 10.0% or less after 5 minutes of dispersion of the aqueous dispersion at a wavelength of 800 nm.   The magenta colorant (A) has a water layer transmittance of 50.0% or more at a wavelength of 800 nm after 5 minutes of dispersion of the water-toluene dispersion. The magenta toner according to item.   The main peak molecular weight (Mp) in the gel permeation chromatography (GPC) of the cyclohexane (CHX) insoluble matter in the tetrahydrofuran (THF) soluble matter of the magenta toner is 10,000 or more and 250,000 or less. The magenta toner according to claim 1, wherein:   6. The cyclohexane (CHX) insoluble component in the tetrahydrofuran (THF) soluble component of the magenta toner is present in an amount of 3% by mass to 30% by mass with respect to the magenta toner. The magenta toner according to claim 1.   7. The cyclohexane (CHX) insoluble component in the tetrahydrofuran (THF) soluble component of the magenta toner is present in an amount of 10% by mass to 30% by mass with respect to the magenta toner. The magenta toner according to claim 1.   The magenta toner particles are magenta toner particles produced by polymerizing a polymerizable monomer composition containing at least a polymerizable monomer, a magenta colorant (A), and a polar resin in an aqueous medium. The magenta toner according to any one of claims 1 to 7, wherein the toner is a magenta toner.   The magenta colorant (A) has an acid value (Ava) of 5 (mgKOH / g) or more and 20 (mgKOH / g) or less, according to any one of claims 1 to 8. Magenta toner.   The magenta toner according to claim 1, wherein the magenta colorant (A) has a transmittance of 15.0% or less after 24 hours of dispersion of the methanol dispersion.   The magenta colorant (A) is C.I. I. The magenta toner according to claim 1, wherein the magenta toner is a pigment Red185.   The magenta toner according to claim 1, wherein the magenta toner contains a compound having an ether bond.   The magenta toner according to any one of claims 1 to 12, wherein the magenta toner contains a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group.

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