JP4700500B2 - Toner and method for producing the same, developer, toner container, process cartridge, image forming apparatus, and image forming method - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, and the like, a method for producing the same, a developer using the toner, a container containing the toner, a process cartridge, an image forming apparatus, and The present invention relates to an image forming method.

  In recent years, office automation and colorization have further progressed in offices, and in addition to copying originals consisting only of conventional characters, originals including graphs created with a personal computer are output by a printer and used as presentation materials. Opportunities to copy sheets are increasing. Many of these printer output images are solid images, line images, and halftone images. Accordingly, market demands for image quality are changing, and demands for high reliability and the like are further increased. .

  In general, a developer used in electrophotography, electrostatic recording, electrostatic printing or the like is, for example, an electrostatic latent image carrier (hereinafter referred to as “electrophotographic photosensitive member”) in which an electrostatic charge image is formed. In the fixing process, after being temporarily transferred to the recording medium such as transfer paper in the transfer process. Fixed on paper. At that time, as a developer for developing an electrostatic charge image formed on the electrostatic latent image carrier, a two-component developer composed of a carrier and a toner, and a toner composed only of a toner without requiring a carrier. Component developers (magnetic toner or non-magnetic toner) are known. In the two-component development method, the developer deteriorates due to the toner particles adhering to the carrier surface. Further, since only the toner is consumed, the toner concentration in the developer is lowered, so that the mixing ratio of the carrier and the toner has to be maintained at a constant ratio, and there is a disadvantage that the developing device is increased in size. On the other hand, the one-component development method has no such disadvantages and the apparatus has advantages such as downsizing, and is therefore becoming the mainstream of the development method.

By the way, the one-component developing method using the one-component developer is classified into a magnetic one-component developing method using magnetic toner and a non-magnetic one-component developing method using non-magnetic toner. The magnetic one-component development method uses a developing sleeve provided with a magnetic field generating means such as a magnet inside to hold magnetic toner containing a magnetic material such as magnetite, and develops it by thinning it with a layer thickness regulating member. In recent years, a large number of small printers have been put to practical use.
On the other hand, in the non-magnetic one-component developing method, since the toner does not have a magnetic force, the toner supply roller or the like is pressed against the developing sleeve to supply the toner onto the developing sleeve, and the toner is electrostatically held. The regulating member is developed with a thin layer, and since it does not contain a colored magnetic substance, there is an advantage that it can cope with colorization. Further, since no magnet is used for the developing sleeve, the apparatus can be made lighter and lower in cost, and in recent years, it has been put to practical use in a small full-color printer or the like.

  However, in the one-component development system, there are still many problems to be improved. On the other hand, in the two-component development system, a carrier is used as a means for charging and transporting toner, and the toner and the carrier are sufficiently agitated and mixed in the inside of the developing device and then transported to the developing sleeve for development. It is possible to maintain stable charging and conveyance even in the use of the above. It is also easy to deal with high-speed developing devices. Compared to this, the one-component development method does not have a stable charging / conveying means such as a carrier, and therefore, charging and conveyance defects are likely to occur due to long-term use and high speed. That is, in the one-component development method, after the toner is transported onto the developing sleeve, the toner is thinned by the layer thickness regulating member and developed, but the toner and the developing sleeve or the friction charging member such as the layer thickness regulating member are used. Since the contact time and frictional charging time are extremely short, the amount of low-charge and reverse-charged toner tends to increase more than in the two-component development method using a carrier. In particular, in the non-magnetic one-component developing method, usually, means for conveying toner by at least one toner conveying member and developing an electrostatic charge image formed on the latent image carrier by the conveyed toner is adopted. . At that time, the toner layer thickness on the surface of the toner conveying member is supposed to be as thin as possible. This is because if the toner layer is thick, only the surface of the toner layer is charged, and the entire toner layer is difficult to be uniformly charged. For this reason, the non-magnetic one-component toner is required to be given a quicker charging speed and maintain an appropriate charge amount.

Further, in the non-magnetic one-component developing method, it is necessary to sufficiently consider the selection of materials for the toner supply member, the layer thickness regulating member, the developing sleeve, and the like so that the toner can be charged with a high charge. At that time, the toner is forcibly rubbed (pressure) to the supply member, the layer thickness regulating member or the like to some extent. Therefore, in order to ensure a reliable image quality over a long period of time, the binder resin that is the main component of the toner must be able to withstand a mechanical impact force. However, under such conditions, the toner generates heat due to friction, so that so-called filming that is fused to the charging member is likely to occur, the life of the developing sleeve is shortened, and the chargeability of the toner is unstable during long-term use. There is a problem of becoming. In addition, the toner is pulverized in the developing machine and becomes easy to be finely divided, and these cause a decrease in image density and obstruction of conveyance, thereby generating a white image.
For this reason, the non-magnetic one-component development system cannot withstand long-term use, and therefore has a drawback that the process cartridge must be replaced at an early stage after copying several thousand sheets.

  Several methods have been proposed for such conventional problems. For example, in Patent Document 1 and Patent Document 2, the type of additive, the prescription amount, the surface treatment agent of the additive, and the like are changed between the initial toner and the replenishment toner, and the charge amounts of the initial toner and the replenishment toner are set differently. There has been proposed a method for reducing the difference in charge amount of toner in the developer during use and maintaining image stability. However, in these methods, there is no problem if the replenishment is performed once, but the charge amount cannot be adjusted by the replenishment of several times. Furthermore, the durability such as filming has not been improved.

  On the other hand, it is known that the thermal characteristics of the binder resin, which is the main component of the toner, are also important for the fixing process. In the fixing step, a pressure heating method using a heating roller or the like is usually used. In this pressure heating method, the toner image on the transfer body is brought into contact with the surface of a heating roller or the like on the surface of the toner under pressure while passing the transfer body to fix the toner image. According to this method, the surface of the heating roller or the like and the toner image on the transfer body come into contact with each other under pressure, so that the thermal efficiency when the toner image is fused on the transfer body is good and fixing is performed quickly. It is possible to increase the speed of a printer or the like. Further, when high-speed fixing is performed by such a pressure heating method, the toner is required to have good low-temperature fixability (low fixing minimum temperature). For this reason, as the binder resin, one having a low softening point temperature is used. However, in this method, when the heating roller and the toner surface come into contact with each other, a so-called offset phenomenon that the molten toner adheres to the heating roller and moves to a recording medium such as paper fed from the rear is likely to occur. For this reason, in order to prevent offset, a heating roller having a surface made of a releasable material is used, or a liquid release agent such as silicone oil is applied to the surface to prevent offset. However, these are effective in offset resistance, but have a problem that they do not contribute to low-temperature fixability, peelability, storage stability, and the like.

  In general, the factor that governs the fixing characteristics of the toner is the physical properties of the binder resin that is the main component of the toner. Typical binder resins for toner include styrene-acrylic resins, polyester resins, and polyol resins. However, the styrene-acrylic resin generally has a high softening point temperature and is suitable for obtaining an output image having low gloss, but is generally inferior to a polyester resin or a polyol resin in terms of low-temperature fixability and image strength. Are known. For this reason, polyester resins and polyol resins tend to be widely used as binder resins for toners from the recent environmental viewpoint.

  Moreover, it is known that the polyester resin generally has a higher acid value and is excellent in chargeability (particularly negative chargeability). However, as described above, an apparatus using a non-magnetic one-component development system that can reduce the size of an image forming apparatus is often placed in various environments because of its small size, and is subject to high temperature and high humidity. Sometimes used in. When placed in such a poor environment, if a polyester resin having a high acid value is used, there is a problem that the chargeability is lowered, the background stain is increased, and image defects are caused.

  With respect to such a problem, Patent Document 3 improves environmental fluctuations by providing a toner having a water content of 1,000 to 5,000 ppm using a resin having a relatively low acid value. However, in non-magnetic one-component development that must be sufficiently charged at one time using a doctor blade or the like, there is a problem that the amount of charge is often insufficient, and background stains increase to cause image defects.

  In order to improve such a problem, a method of simply increasing the charge control agent can be considered, but the toner cohesiveness is increased. In particular, in the case of a one-component development method, a toner thin layer is formed by a layer thickness regulating member such as a doctor blade, and if toner cohesion is increased, the toner aggregate is clogged by the layer thickness regulating member, resulting in poor thin layer formation. White streaks (hereinafter sometimes referred to as “white streaks”) are generated on the image.

On the other hand, in order to reduce the cost, the predetermined outer particles (toner fine particles) generated in the toner manufacturing process are reused, and the toner fine particles are usually added in an amount of 25 to 30% by mass in the kneading process. Yes. However, the addition of the toner fine particles further increases the cohesiveness of the toner and eventually causes white streaks.
In order to reduce the cohesiveness of the toner, the amount of the external additive is increased. However, in this case, the initial characteristics cannot be maintained, for example, the external additive is detached from the toner surface or embedded in the toner particles due to long-term stirring in the developing unit. Also, if the cohesiveness is too low, problems such as in-machine contamination due to toner scattering occur.

  Therefore, although the image forming apparatus based on the non-magnetic one-component development system has an excellent aspect in that the entire apparatus can be reduced in size, it can be used in various environments. In addition, the related art using the toner has not yet been provided.

JP-A-2-205858 Japanese Patent Laid-Open No. 2-198456 JP 2000-305318 A

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention has a stable chargeability even when a specific binder resin and a large amount of charge control agent are used, and does not generate background stains, white stripes, filming, etc., and has sufficient durability. An object of the present invention is to provide a toner production method excellent in productivity such as toner and cost, a developer using the toner, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method.

Means for solving the problems are as follows. That is,
<1> A kneading step of kneading a toner material containing at least a binder resin, a colorant, and a charge control agent, a pulverizing step of pulverizing the obtained kneaded product, and classifying the obtained pulverized product to obtain predetermined particles A method for producing a toner comprising a classification step of adjusting to particles having a diameter,
The binder resin includes a polyester resin having an acid value of 20 KOHmg / g or less, the content of the charge control agent in the toner material is 2% by mass or more, and at least one of the pulverization step and the classification step in advance In the toner production method, 1 to 20% by mass of the finely powdered toner that is the collected non-specified particles is added to the toner material in the kneading step.
<2> The polyester resin does not contain a tetrahydrofuran (THF) insoluble component, and in the molecular weight distribution in gel permeation chromatography (GPC), the content of the component having a molecular weight of 500 or less is 4% by mass or less, and the molecular weight is 3 The method for producing a toner according to <1>, wherein the toner has one peak in the region of 000 to 9,000.
<3> The method for producing a toner according to any one of <1> to <2>, wherein the charge control agent is a metal salt of salicylic acid.
<4> The method for producing a toner according to any one of <1> to <3>, further including at least two additives.
<5> The toner production method according to <4>, wherein the additive includes silica fine particles hydrophobized with at least one selected from silicone oil and hexamethyldisilazane.
<6> The additive according to any one of <4> to <5>, wherein the additive has a coating film of any one of aluminum and Al ₂ O ₃ and further includes titanium oxide fine particles surface-treated with an organic treatment agent. A toner manufacturing method.
<7> The method for producing a toner according to any one of <4> to <6>, wherein the additive is added in an amount of 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the toner base.
<8> A toner manufactured by the toner manufacturing method according to any one of <1> to <7>.
<9> A developer comprising the toner according to <8>.
<10> The developer according to <9>, wherein the developer is a nonmagnetic one-component developer.
<11> A toner-containing container filled with the toner according to <8>.
<12> An electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to <8> to form a visible image. It is a process cartridge characterized by having at least.
<13> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the toner according to <8>. And developing means for forming a visible image by development, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. The image forming apparatus.
<14> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to <8> to form a visible image. An image forming method comprising: a developing step for forming; a transferring step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium.

  The toner production method of the present invention includes a kneading step of kneading a toner material containing at least a binder resin, a colorant, and a charge control agent, a pulverizing step of pulverizing the obtained kneaded product, and an obtained pulverized product And a classification step of adjusting the particles to particles having a predetermined particle size, wherein the binder resin contains a polyester resin having an acid value of 20 KOHmg / g or less, and the content of the charge control agent in the toner material is 2% by mass In addition, 1 to 20% by mass of fine powder toner, which is the predetermined outer particles collected in advance in at least one of the pulverization step and the classification step, is added to the toner material in the kneading step. As a result, even if a specific binder resin and a large amount of charge control agent are used, the toner has stable chargeability, does not cause background stains, white streaks, filming, etc., and has low durability. It can be manufactured efficiently and efficiently at low cost.

  The toner of the present invention is manufactured by the toner manufacturing method of the present invention. As a result, even if a specific binder resin and a large amount of charge control agent are used, the toner has stable chargeability, does not cause background stains, white streaks, filming, etc., and has sufficient durability. it can.

  The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, even if a specific binder resin and a large amount of a charge control agent are used, stable chargeability is obtained, and background stains, white stripes, film There is no occurrence of ming, etc., sufficient durability, and high image quality can be obtained.

  The toner-containing container of the present invention contains the toner of the present invention in a container. For this reason, when an image is formed by electrophotography using the toner contained in the toner-containing container, as a result, even if a specific binder resin and a large amount of charge control agent are used, stable chargeability is obtained. In addition, there is no occurrence of background stains, white streaks, filming, etc., sufficient durability and high image quality can be obtained.

  The process cartridge of the present invention comprises an electrostatic latent image carrier and developing means for developing a latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge is detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention. As a result, even if a specific binder resin and a large amount of charge control agent are used, the process cartridge is stable. Therefore, there is no generation of background stains, white streaks, filming, etc., sufficient durability and high image quality can be obtained.

  The image forming apparatus of the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. The image forming apparatus includes at least a developing unit that forms a visible image by developing with toner, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, even if a specific binder resin and a large amount of charge control agent are used, it has stable chargeability, does not cause background stains, white streaks, filming, etc., has sufficient durability, and has high durability. A high-quality electrophotographic image can be formed.

  The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and the electrostatic latent image is developed using the toner of the present invention to be visible. It includes at least a developing step for forming an image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming method, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, even if a specific binder resin and a large amount of charge control agent are used, it has stable chargeability, does not cause background stains, white streaks, filming, etc., has sufficient durability, and has high durability. A high-quality electrophotographic image can be formed.

  According to the present invention, conventional problems can be solved, and even when a specific binder resin and a large amount of charge control agent are used, stable chargeability is generated and background stains, white stripes, filming, etc. occur. Providing a toner having sufficient durability and a toner having excellent productivity such as cost, and a developer, a container containing the toner, a process cartridge, an image forming apparatus, and an image forming method using the toner can do.

(Toner and toner production method)
The toner production method of the present invention includes a kneading step, a pulverizing step, and a classification step, and further includes other steps as necessary.
The toner of the present invention is manufactured by the toner manufacturing method of the present invention.
Hereinafter, the details of the toner of the present invention will be clarified through the description of the toner production method of the present invention.

-Kneading process-
The kneading step is a step of kneading a toner material containing at least a binder resin, a colorant, and a charge control agent.

  As the binder resin, a polyester resin that is suitable as a binder resin for full-color toners from the viewpoint of color developability and image strength is used. In a color image, several types of toner layers are stacked several times, so that the toner layer becomes thick, and cracks and defects of the image due to insufficient strength of the toner layer occur, or an appropriate gloss is lost. For this reason, a polyester resin is used to maintain an appropriate gloss and excellent strength. The polyester resin can be generally obtained by an esterification reaction of a polyhydric alcohol and a polycarboxylic acid.

  Among the monomers constituting the polyester resin, the alcohol monomer includes a trifunctional or higher polyfunctional monomer, for example, ethylene glycol, diethylene glycol triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol. Diols such as 1,4-butadieneol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol; bisphenol A, hydrogenated bisphenol A, polyoxypropylenated bisphenol Bisphenol A alkylene oxide adducts such as A; other dihydric alcohols, or sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripe Taerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, tri Examples include methylolpropane, 1,3,5-trihydroxybenzene, and other trihydric or higher polyhydric alcohols.

  Among these monomers, those using a bisphenol A alkylene oxide adduct as a main component monomer are particularly preferably used. When the bisphenol A alkylene oxide adduct is used as a constituent monomer, a polyester having a relatively high glass transition point is obtained due to the nature of the bisphenol A skeleton, and the copy blocking resistance and heat resistant storage stability are good. In addition, the presence of alkyl groups on both sides of the bisphenol A skeleton acts as a soft segment in the polymer, and the color developability and image strength during toner fixing are improved. Of the bisphenol A alkylene oxide adducts, those having an ethylene group or a propylene group are preferably used.

  Among the monomers constituting the polyester resin, acid monomers include, for example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipine Alkenyl succinic acids or alkyl succinic acids such as acids, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, n-dodecyl succinic acid, anhydrides, alkyl esters of these acids, or other divalent carboxylic acids; 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxylic acid Lu-2-methyl-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, empole trimer acid, or anhydrides thereof, alkyl ester, alkenyl ester, aryl ester Or other trivalent or higher carboxylic acids.

  Specific examples of the alkyl group, alkenyl group or aryl ester include 1,2,4-benzenetricarboxylic acid, trimethyl 1,2,4-benzenetricarboxylate, triethyl 1,2,4-benzenetricarboxylate, 1,2 , 4-benzenetricarboxylic acid tri-n-butyl, 1,2,4-benzenetricarboxylic acid isobutyl, 1,2,4-benzenetricarboxylic acid tri-n-octyl, 1,2,4-benzenetricarboxylic acid tri-2-ethylhexyl, 1,2,4-benzenetricarboxylic acid tribenzyl, 1,2,4-benzenetricarboxylic acid tris (4-isopropylbenzyl), and the like.

  It is known that the chargeability and acid value of the polyester resin are in a substantially proportional relationship, and it is known that the higher the acid value, the greater the negative chargeability of the resin, and at the same time affects the environmental stability of charging. That is, when the acid value is high, the charge amount is high under low temperature and low humidity, and the charge amount is low under high temperature and high humidity, resulting in large changes in background stains, image density, and color reproducibility, and maintaining high image quality. difficult. Therefore, the acid value of the polyester resin is 20 KOHmg / g or less, and more preferably 5 KOHmg / g or less.

Here, the acid value (AV) in the present invention is specifically determined by the following procedure.
Measuring device: potentiometric automatic titrator DL-53 Titrator (manufactured by METTLER TOLEDO)
Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
Analysis software: LabX Light Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 mL of toluene and 30 mL of ethanol.
Measurement temperature: 23 ° C
Measurement conditions: As shown below
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1)
Sensor DG115
Unit of measurement mV
Predispensing to Volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steppes jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potentialial 2 No
Stop for revaluation No
(Measurement method of acid value)
Measurement is performed under the following conditions in accordance with the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) is added to 120 mL of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 mL of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation is performed as follows.
Titrate with a standardized N / 10 KOH-alcohol standard solution, and determine the acid value from the consumption of the standard solution by the following calculation.
Acid value = KOH (mL) × N × 56.1 / weight of sample (where N is a factor of N / 10 KOH)

  Furthermore, the polyester resin is particularly free of tetrahydrofuran (THF), and in the molecular weight distribution in gel permeation chromatography (GPC), the content of components having a molecular weight of 500 or less is preferably 4% by mass or less. The mass% is more preferable. Moreover, it has one peak in the area | region of molecular weight 3,000-9,000. When THF-insoluble matter enters, the glossiness is lowered and the transparency is lowered, and a high-quality image cannot be obtained when an OHP sheet is used. Further, when the component having a molecular weight of 500 or less is 4% by mass, a brittle component as a resin can be reduced, and so-called filming components to be fused and fine particles in a developing machine can be suppressed. As a result, the non-magnetic one-component development system can withstand long-term use, and can be used in the toner replenishment system. From the viewpoint of ease of production, the proportion of components having a molecular weight of 500 or less is preferably 1% by mass or more.

The molecular weight distribution of the polyester resin is measured by GPC as follows. A toner base THF sample in which the column is stabilized in a heat chamber at 40 ° C., THF as a solvent is flowed through the column at this temperature at a flow rate of 1 mL / min, and the sample concentration is adjusted to 0.05 to 0.6% by mass. 200 μL of the solution is injected and measured. The THF sample solution is removed with a 0.45 μm liquid chromatograph filter prior to injection to remove THF insoluble components. In measuring the molecular weight of a toner sample, the molecular weight distribution of the sample can be calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.
As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Alternatively, the molecular weights manufactured by Toyo Soda Industry Co., Ltd. are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3. It is preferable to use 9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. Further, it is preferable to use an RI (refractive index) detector as the detector. The presence or absence of the THF-insoluble matter in the binder resin is determined when preparing the THF sample solution for molecular weight distribution measurement. That is, when a 0.45 μm filter unit is attached to the tip of the syringe and the liquid is pushed out of the syringe, it is determined that there is no THF-insoluble matter unless the filter is clogged.

The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used individually by 1 type and may use 2 or more types together.
The content of the colorant in the toner material is preferably 0.1 to 50% by mass, and more preferably 1 to 10% by mass.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin, and the like. These may be used individually by 1 type and may use 2 or more types together.

The charge control agent is not particularly limited, and a positive or negative charge control agent can be appropriately selected and used depending on whether the charge charged on the photoconductor is positive or negative.
As the negative charge control agent, for example, a resin or compound having an electron donating functional group, an azo dye, a metal complex of an organic acid, or the like can be used. Specifically, Bontron (product numbers: S-31, S-32, S-34, S-36, S-37, S-39, S-40, S-44, E-81, E-82, E -84, E-86, E-88, A, 1-A, 2-A, 3-A) (above, manufactured by Orient Chemical Industry Co., Ltd.)), Kaya Charge (part numbers: N-1, N-2), Kaya Set Black (Part No .: T-2, 004) (Nippon Kayaku Co., Ltd.), Eisenspiron Black (T-37, T-77, T-95, TRH, TNS-2) FCA-1001-N, FCA-1001-NB, FCA-1001-NZ (manufactured by Fujikura Kasei Co., Ltd.), and the like.
Examples of the positive charge control agent include basic compounds such as nigrosine dyes, cationic compounds such as quaternary ammonium salts, and metal salts of higher fatty acids. Specifically, Bontron (part numbers: N-01, N-02, N-03, N-04, N-05, N-07, N-09, N-10, N-11, N-13, P -51, P-52, AFP-B) (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415, TP-4040 (above, manufactured by Hodogaya Chemical Co., Ltd.), Copy Blue PR, Copy Charge ( Product number: PX-VP-435, NX-VP-434) (manufactured by Hoechst), FCA (Product number: 201, 201-B-1, 201-B-2, 201-B-3, 201-PB, 201-PZ, 301) (above, manufactured by Fujikura Kasei Co., Ltd.), PLZ (product numbers: 1001, 2001, 6001, 7001) (above, manufactured by Shikoku Kasei Kogyo Co., Ltd.), and the like.
Among these, the salicylic acid metal salt is used because of the quick charge rise of the toner replenished by the replenishment mechanism and the sharp charge distribution even under the usage environment where the stress on the toner is applied over a long period of time. It is particularly preferable to use it.

  The content of the charge control agent in the toner material is 2% by mass or more, and more preferably 2.5 to 3.5% by mass. When the content is less than 2% by mass, the charge rising property and the charge amount are not sufficient, and the image may be easily affected, particularly when a low acid value binder resin is used. It is.

  In addition to the binder resin, colorant, and charge control agent, additives, wax, fluidity improver, cleaning improver, magnetic material, metal soap, etc. are added to the toner material as necessary. be able to.

As the inorganic fine particles as the additive, for example, silica, titania, alumina, cerium oxide, strontium titanate, calcium carbonate, magnesium carbonate, calcium phosphate, etc. can be used, and hydrophobized with silicone oil, hexamethyldisilazane, etc. It is more preferable to use treated silica fine particles or titanium oxide subjected to a specific surface treatment.
Examples of the silica fine particles include, for example, Aerosil (product numbers: 130, 200 V, 200 CF, 300, 300 CF, 380, OX50, TT600, MOX80, MOX170, COK84, RX200, RY200, R972, R974, R976, R805, R811, R812, T805, R202, VT222, RX170, RXC, RA200, RA200H, RA200HS, RM50, RY200, REA200 (above, manufactured by Nippon Aerosil Co., Ltd.), HDK (Part No .: H20, H2000, H3004, H2000 / 4, H2050EP, H2015EP, H3050EP) , KHD50), HVK2150 (above, manufactured by Wacker Chemical Co., Ltd.), Cabogil (Part No .: L-90, LM-130, LM-150, M-5, PTG, MS-55, H-5) HS-5, EH-5, LM-150D, M-7D, MS-75D, TS-720, TS-610, TS-530) (or, can be used Cabot Corp.).

The titanium oxide subjected to the special surface treatment is a titanium oxide particle having an aluminum or Al ₂ O ₃ coating and further subjected to a surface treatment with an organic treatment agent, and is formed in at least one of the titanium oxide particles. The aluminum or alumina coating is preferably 0.1 to 2.0% by mass in terms of Al ₂ O ₃ . When the amount is less than 0.1% by mass in terms of Al ₂ O ₃ , the effect is weakened. When the amount exceeds 2.0% by mass in terms of Al ₂ O ₃ , the positive chargeability of aluminum functions and the negative polarity toner Chargeability may be reduced.

  Further, at least one particle surface of the titanium oxide fine particles on which the aluminum or alumina coating is formed is further at least one of an anionic surfactant, zwitterionic surfactant, silane coupling agent, silicone oil, fatty acid, and fatty acid ester. The surface treatment is preferably performed with a kind of organic treatment agent. Thereby, peeling of the surface treatment agent in the titanium oxide fine particles does not occur even under long-term stress, and a stable negative charging performance can be obtained.

  The mechanism by which peeling of the treatment agent is suppressed by forming an aluminum or alumina coating on the titanium oxide fine particles is not clear, but is presumed as follows. When an aluminum or alumina film is first formed on the surface of the titanium oxide fine particles, the surface charge is + near neutrality because the isoelectric point of alumina is relatively high. When an anionic surfactant, a zwitterionic surfactant, a silane coupling agent, a silicone oil, a fatty acid, or a fatty acid ester is added to the compound in that state, these compounds are oriented and adsorbed to form titanium oxide. The fine particle surface becomes lipophilic. Further, it is presumed that by applying heat, the bonding and the like become stronger, and peeling of the surface treatment agent is suppressed.

  Among these, it is preferable to contain two or more different additives, two or more different average particle sizes are more preferable, and an external additive having an average particle size difference of about 2 to 5 times is included. More preferably. When two or more types of external additives having different particle diameters are not contained, the external additive is rapidly embedded in the toner base material over time, and toner fluidity is rapidly deteriorated. Image unevenness due to a decrease in toner fluidity is likely to occur, and the adhesion to the toner is difficult to increase, so that the toner is easily detached from the toner, causing a photosensitive material scratch and an image blur. If two or more types of external additives with different particle sizes are contained, the large particle size external additive acts as a spacer, preventing the embedding of the small particle size external additive effective in toner fluidity in the toner base Thus, toner fluidity can be maintained. Moreover, although the cause is unknown, the thin layer of the developing carrier over time becomes uniform.

  The addition amount of the additive is preferably 0.1 to 5.0 parts by mass, and more preferably 0.8 to 3.2 parts by mass with respect to 100 parts by mass of the toner base. When the addition amount is less than 0.1 parts by mass, a necessary charge amount may not be obtained. When the addition amount exceeds 5.0 parts by mass, the toner of the external additive is caused by long-term stirring in the developing device. The initial characteristics may not be maintained due to separation from the surface or embedding in the toner particles.

The wax is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include animal and plant waxes such as rice wax, candelilla wax, carnauba wax, lanolin; paraffin wax, microcrystalline wax, petrolatum Petroleum wax such as: low density polyethylene, high density polyethylene, polyethylene copolymer, polypropylene, polypropylene copolymer, acid value modified polyethylene, acid modified polyethylene, graft modified polyethylene with aromatic monomers, pyrolytic low density Examples thereof include olefinic waxes such as polyethylene and pyrolytic polypropylene.
Specific examples of the wax include HNP (product numbers: 1, 3, 9, 10, 11, 12), SP (product numbers: 0145, 1035, 3040, 3035, 0110), Hi-Mic (product numbers: 2095, 1080, 3080, 1070, 2065, 1045, 2045), POLYCOAT (part numbers: 1025, 1455, 2255, 3030, 3155), NEOPALAX (part numbers: 2545, 3240), PALVAX (part numbers: 1230, 1335, 1430), CARTOWAX- 3025, BONTEX (product number: 0011, 2266), S-0750, OX (product number: 261BN, 0550, 2251, 1949), NSP-8070, NPS (product number: L-70, 6010, 9210), HAD (product number: 5080) 5670), WEISSEN- 453, JP-1500, LUVAX (part numbers: 1266, 2191, 1151, 0321), EMUSTAR (part numbers: 0001, 042X, 0135, 0136, 0164, 358) (manufactured by Nippon Wax Co., Ltd.), high wax (part number: 800P, 400P, 200p, 100P, 720P, 410P, 420P, 320P, 210P, 220P, 110P, 405MP, 310MP, 320MP, 210MP, 220MP, 4051E, 4052E, 4202E, 1105A, 2203A, 1120H, 1140H, 1160H, NL100, NL200, NL500, NL800, NP055, NP105, NP505, NP805) (the above, Mitsui Petrochemical Co., Ltd.) etc. can be used.
The content of the wax in the toner material is preferably 0.1 to 30% by mass, and more preferably 1 to 10% by mass.

  The above toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay Co., Ltd. Preferably used. It is important that this melt-kneading is performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

-Crushing process-
The pulverization step is a step of pulverizing the kneaded product obtained in the kneading step.
In this pulverization step, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. In this case, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

-Classification process-
The classification step is a step of classifying the pulverized product obtained in the pulverization step to adjust the particles to a predetermined particle size.
The classification can be performed, for example, by removing the fine particle portion by a cyclone, a decanter, centrifugation, or the like.
After the pulverization step is completed, the pulverized product is classified in an air stream by centrifugal force or the like, thereby producing a toner having a predetermined particle size, for example, an average particle size of 5 to 20 μm.

  When the above pulverization and classification steps are completed, powder (fine powder toner) other than the particles obtained as products obtained in those steps is collected, and a predetermined amount is added to the toner material in the mixing step and the melt-kneading step. It is preferable to repeat the above operation.

Here, the powder (fine powder toner) other than the particles used as the product is generated in the fine particle other than the component used as the product having a desired particle size obtained in the pulverization process after the melt-kneading process and the subsequent classification process. It means fine particles other than the components that become a product having a desired particle size.
The content of the fine toner is 1 to 20% by mass with respect to the toner material, and more preferably 5 to 15 parts by mass. If the amount of the fine toner is less than 1% by mass, the amount of fine powder toner consumed may be reduced, so that it may not be possible to contribute to cost reduction. If the amount exceeds 20% by mass, the cause is not clarified. The agglomeration property of the ink becomes high, which may cause a problem that white streaks are generated.

  In order to improve the fluidity, storage stability, developability, and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner manufactured as described above. For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Also, a strong load may be given first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

  The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

  The toner manufactured by the toner manufacturing method of the present invention may be filled in a toner-containing container described later and mounted on the image forming apparatus as it is. Also, the carrier and toner may be filled in the same container and mounted on the image forming apparatus, but the toner of the present invention is preferable for a non-magnetic one-component replenishment type developing unit that does not use a carrier. Used.

(Developer)
The developer of the present invention comprises the toner of the present invention.
The developer may be a one-component developer or a two-component developer. Further, although it may be magnetic or non-magnetic, a non-magnetic one-component developer is most preferable because the apparatus can be reduced in size and can be easily colored.

(Toner container)
The toner-containing container of the present invention comprises the toner or the developer of the present invention contained in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a toner container main body and a cap etc. are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral unevenness is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Particularly preferred.
The material of the toner container main body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polychlorinated resin Preferred examples include vinyl resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. A developing means for forming the image forming apparatus, and further having other means such as a charging means, an exposure means, a developing means, a transfer means, a cleaning means, and a static elimination means, which are appropriately selected as necessary. .
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably provided in the image forming apparatus of the present invention described later.

Here, for example, as shown in FIG. 1, the process cartridge includes a photosensitive member 101, and further includes a charging unit 102, a developing unit 104, and a cleaning unit 107, and further includes other members as necessary. Do it.
As the photoreceptor 101, the above-described one can be used.
As the exposure means 103, a light source capable of writing with high resolution is used.
As the charging means 102, an arbitrary charging member is used.

  In the image forming apparatus of the present invention, the electrostatic latent image carrier (photosensitive member 101), the developing device (developing unit 104), the cleaning unit (cleaning unit 107), and the like are integrally combined as a process cartridge. The unit may be configured to be detachable from the apparatus main body. Further, at least one of a charging device (charging means 102), an exposure device (exposure means 103), a developing device (developing means 104), a transfer device (transfer means 108) or a separator, and a cleaning device (cleaning means 107) is provided. A process cartridge is formed by supporting it together with the electrostatic latent image carrier (photosensitive member 101) to form a single unit that can be attached to and detached from the apparatus main body, and is configured to be removable using guide means such as a rail of the apparatus main body. Also good.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The material, shape, structure, size, etc. of the electrostatic latent image carrier (photosensitive member) are not particularly limited, and can be appropriately selected from known ones. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon or the like is preferable in terms of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

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

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 4 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 4. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full color image (color copy) using the tandem image forming apparatus will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem image forming apparatus. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem image forming apparatus is respectively photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image-corresponding image (L in FIG. 5), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner, and the toner image is an intermediate transfer member. The image forming apparatus includes a transfer charger 62 for transferring the image onto 0, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotated by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual sheet feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming apparatus and the image forming method of the present invention, even when a specific binder resin and a large amount of charge control agent are used, stable chargeability is obtained, and there is no occurrence of background stains, white stripes, filming, etc. Since the toner of the present invention having sufficient durability is used, a clear high-quality image can be formed.

Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Synthesis Example 1)
-Synthesis of polyester resin a-
In a 4-neck separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, a flow-down condenser, and a condenser tube, 740 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 300 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 466 g of dimethyl terephthalate, 80 g of isododecenyl succinic anhydride, and 114 g of tri-n-butyl 1,2,4-benzenetricarboxylate It was added along with the esterification catalyst.
Subsequently, it was made to react at 210 degreeC under nitrogen atmosphere for 8 hours, and then it was made to react for 5 hours, stirring at 210 degreeC pressure reduction. As a result, the molecular weight is 500 or less, the content is 3.5%, the molecular weight peak is 7,500, the glass transition temperature (Tg) is 62 ° C., the Mw / Mn ratio is 5.1, the acid value is 2.3 KOHmg / g, and the apparent viscosity is 103 Pa by a flow tester A polyester resin a having s (temperature of 112 ° C.) was synthesized. Moreover, THF insoluble matter was not contained.

(Synthesis Example 2)
-Synthesis of polyester resin b-
In Synthesis Example 1, 650 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 650 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane , Except that 515 g of isophthalic acid, 70 g of isooctenyl succinic acid and 80 g of 1,2,4-benzenetricarboxylic acid were added to the flask together with the esterification catalyst, the reaction was carried out in the same apparatus and the same formulation as in Synthesis Example 1. Polyester resin b was synthesized by shortening the reaction time.
The obtained polyester resin b has a molecular weight of 500 or less, a content of 3.8%, a molecular weight peak of 3,500, a glass transition temperature (Tg) of 61 ° C., an Mw / Mn ratio of 2.7, an acid value of 9.0 KOHmg / g, The apparent viscosity by a flow tester was 103 Pa · s (temperature 117 ° C.). No THF-insoluble matter was contained.

(Synthesis Example 3)
-Synthesis of polyester resin c-
A polyester resin c was synthesized in the same manner as in Synthesis Example 1 with the same formulation as in Synthesis Example 2.
The obtained polyester resin c has a molecular weight of 500 or less, a content of 2.1%, a molecular weight peak of 9,200, a glass transition temperature (Tg) of 61 ° C., an Mw / Mn ratio of 4.6, an acid value of 10.0 KOH mg / g, The apparent viscosity by a flow tester was 103 Pa · s (temperature 117 ° C.). No THF-insoluble matter was contained.

(Synthesis Example 4)
-Synthesis of polyester resin d-
In Synthesis Example 1, 714 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 663 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane Polyester resin d was synthesized by reacting in the same apparatus and the same formulation as in Synthesis Example 1 except that 648 g of isophthalic acid and 150 g of isooctenyl succinic acid were added to the flask together with the esterification catalyst.
The obtained polyester resin d has a molecular weight of 4.8% or less, a molecular weight peak of 8,500, a glass transition temperature (Tg) of 67 ° C., an Mw / Mn ratio of 8.5, an acid value of 23.2 KOHmg / g, The apparent viscosity by a flow tester was 103 Pa · s (temperature 126 ° C.). No THF-insoluble matter was contained.

(Synthesis Example 5)
-Synthesis of polyester resin e-
In Synthesis Example 1, 680 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 720 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane Polyester resin e was synthesized by reacting in the same apparatus and the same formulation as in Synthesis Example 1 except that 570 g of isophthalic acid and 180 g of isooctenyl succinic acid were added to the flask together with the esterification catalyst.
The obtained polyester resin e has a molecular weight of 3.8% or less, a molecular weight peak of 7,500, a glass transition temperature (Tg) of 67 ° C., an Mw / Mn ratio of 8.5, an acid value of 21.6 KOHmg / g, The apparent viscosity by a flow tester was 103 Pa · s (temperature 126 ° C.). The THF-insoluble content was 3.1%.

(Synthesis Example 6)
-Preparation of surface-treated titanium oxide-
Titanium oxide was produced by a wet precipitation method in which ilmenite was used as an ore, dissolved in sulfuric acid to separate iron, and TiOSO ₄ was hydrolyzed to produce titanium oxide. Next, after the titanium oxide fine particles were fired, wet pulverization was performed to cut coarse particles, followed by filtration, washing with water, and drying.
Subsequently, the surface treatment was performed under the surface treatment conditions shown in Table 1. T1 was added with SiO ₂ solution, and T2 was added with hydrous alumina dilute solution, filtered and dried to obtain SiO ₂ coated titanium oxide and alumina coated titanium oxide, respectively.
Next, wet pulverization is performed again in an aqueous solution, coarse particles are cut, treated with the organic treatment agent shown in Table 1, filtered, washed with water, dried, and pulverized in a dry manner to obtain surface-treated titanium oxide. Manufactured.
As raw material titanium oxide, untreated titanium oxide having a primary particle size of 0.01 to 0.03 μm and a specific surface area of 60 to 140 m ² / g was used.

( Reference Example 1)
-Production of Toner A-
-Polyester resin a ... 100 mass parts-C.I. I. Pigment Blue 15,3 ... 5 parts by mass Charge control agent (PBE-304, manufactured by Orient Scientific Industry Co., Ltd.) ... 3 parts by mass

The toner material was mixed using a Henschel mixer, 10 parts by weight of finely collected toner collected in advance was added, and kneading was carried out for 30 minutes with two rolls whose roll surface was set at 100 ° C. Thereafter, after rolling and cooling and coarse pulverization, a jet mill type pulverizer (I-2 type mill: manufactured by Nippon Pneumatic Industry Co., Ltd.) and a wind classifier using a swirling flow (DS classifier: manufactured by Nippon Pneumatic Industry Co., Ltd.) Blue colored particles having a weight average particle diameter of 7.0 μm and a number% of particle diameters of 4 μm or less and 9.8% by number were obtained.
Furthermore, 1.8 parts by mass of hydrophobic silica (H2000, manufactured by Clariant Japan, BET specific surface area 120 m ² / g) as additive 1 and 0.4 parts by mass of surface-treated titanium oxide (T1) as additive 2 Toner A was prepared by adding a part thereof and mixing with a Henschel mixer.

( Example 2, Example 5, Reference Examples 3-4 and Comparative Examples 1-5)
-Production of Toner B to Toner J-
In Reference Example 1, toner B to toner J were prepared in the same manner as in Reference Example 1 except that the binder resin, charge control agent, additive 1, additive 2, and fine powder toner shown in Table 2 were used. Was made.
In addition, the following was used for the hydrophobic silica as the additive 1.
Hydrophobic silica (RX-50, manufactured by Nippon Aerosil Co., Ltd., BET specific surface area 50 m ² / g)
Hydrophobic silica (H3004: Clariant Japan, BET specific surface area 200 m ² / g)

* Charge control agent E-304 represents PBE-304, manufactured by Orient Scientific Industry Co., Ltd.
* The amounts in Table 2 are parts by mass.

With respect to the obtained toners of Reference Example 1, Example 2, Example 5, Reference Examples 3 to 4, and Comparative Examples 1 to 5, the degree of toner aggregation, charging of the actual machine, and image quality were evaluated as follows. The results are shown in Table 3.

<Measurement of toner aggregation degree>
For the degree of toner aggregation, a powder tester (manufactured by Hosokawa Micron Corporation, PT-N type) is used, and the sieves are 75 μm, 45 μm, and 22 μm, and the sieves are stacked three times with the coarser side up. The toner was passed through a sieve under measurement conditions, and the ratio of the toner remaining on the sieve to the whole was measured.
-Measurement conditions-
Toner amount: 2.0 g
Amplitude: 1.0 mm
Vibration time: 10 seconds

<Measurement of actual machine charge>
For the actual machine charge amount, the charge amount on the developer carrying member was measured. For the measurement, a suction type small charge amount measuring device (q / m Meter) Model 210HS manufactured by TREK was used.

<Image quality evaluation>
For the non-magnetic one-component developing toners obtained in Examples and Comparative Examples, a copy test was performed using an image forming apparatus (manufactured by Ricoh Co., Ltd., IMAGEIO NEO C320), and the following items were evaluated. In the copy test, toner replenishment was repeated 6 times, and a 100,000-color full color mode was performed. Immediately after starting the copy test, after copying 50,000 sheets, and after copying 100,000 sheets, the toner charge amount on the developer carrier in the developing unit and the degree of aggregation of the toner in the developing unit were measured and obtained. The image quality was evaluated. The image quality was visually evaluated for the presence or absence of background stains, white streak images, and the like.

In each item, an image chart having a 3% image area was continuously run up to 100,000 sheets, and the following evaluation was performed.
(1) Background stain The blank image is stopped during development, the developer on the photoconductor after development is transferred to tape, and the difference from the image density of the untransferred tape is determined by 938 Spectrodensitometer (manufactured by X-Rite) ).

(2) White streak and thin layer formation Immediately after the start of the copy test, after 50,000 copies have been made, and after 100,000 copies have been made, the toner carrier thin layer formation and the presence of white streak images are based on the following criteria: evaluated.
〔Evaluation criteria〕
○: Uniform and good state.
Δ: Some white streaks with a width of less than 0.3 mm are observed, but streaks are not clearly seen in the image.
X: A white streak having a width of 0.3 mm or more is generated, and the image is clearly missing as a white streak in the image.

(3) Filming The presence or absence of toner filming on the developing sleeve or the photoreceptor was observed and evaluated according to the following criteria.
〔Evaluation criteria〕
○: No filming.
Δ: Filming on streaks is observed.
X: There is filming as a whole.

From the results in Table 3, the toners of Reference Example 1, Example 2, Example 5, and Reference Examples 3 to 4 have good performance in the evaluation of image quality, background stain, and thin layer formation using an image forming apparatus. It is recognized that there is almost no problem from the viewpoint of maintainability.
On the other hand, the toner of Comparative Example 1 was poor in toner aggregation at the initial stage, and after 50,000 sheets, formation of a uniform thin layer was inhibited by the toner aggregate, and white streaks were generated on the image.
The toner of Comparative Example 2 had no particular problem in the initial stage, but after 100,000 sheets, the toner chargeability with time was different from that in the initial stage, and background staining occurred on the image.
In the toner of Comparative Example 3, the content of the charge control agent was too small, and after 50,000 sheets, formation of a uniform thin layer was inhibited by the toner aggregates, and white streaks were generated on the image.
Since the toner of Comparative Example 4 contains too much fine powder toner, after 100,000 sheets, the chargeability of the toner over time was different from that in the initial stage, and background staining occurred on the image.
In the toner of Comparative Example 5, after 100,000 sheets, in addition to background stains and white streaks on the image, filming occurred overall.

The toner manufactured by the toner manufacturing method of the present invention has stable chargeability even when a specific binder resin and a large amount of charge control agent are used, and generation of background stains, white stripes, filming, etc. Therefore, it has sufficient durability, high image quality is obtained, and is suitably used for high-quality image formation.
The developer, toner-containing container, process cartridge, image forming apparatus and image forming method of the present invention using the toner of the present invention are suitably used for high-quality image formation.

FIG. 1 is a schematic explanatory view showing an example of the process cartridge of the present invention. FIG. 2 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 4 is a schematic explanatory view showing an example of carrying out the image forming method of the present invention by the image forming apparatus (tandem color image forming apparatus) of the present invention. FIG. 5 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 photoconductor cleaning device 64 static eliminator 70 static elimination lamp 71 cleaning blade 72 support member 80 transfer roller 90 cleaning device 95 transfer paper 100 image forming apparatus 101 photoconductor DESCRIPTION OF SYMBOLS 102 Charging means 103 Exposure 104 Developing means 105 Transfer body 107 Cleaning means 108 Transfer means 120 Tandem type developer 130 Document table 142 Feed roller 143 Paper bank 14 Paper feed cassette 145 separating roller 146 feed path 147 transport rollers 148 feed path 150 copier main body 200 feeder table 300 Scanner 400 automatic document feeder (ADF)

Claims (12)

A kneading step for kneading a toner material containing at least a binder resin, a colorant, and a charge control agent, a pulverizing step for pulverizing the obtained kneaded product, and particles having a predetermined particle size by classifying the obtained pulverized product A toner manufacturing method including a classification step of adjusting to
The binder resin includes a polyester resin having an acid value of 20 KOHmg / g or less, the content of the charge control agent in the toner material is 2% by mass or more, and at least one of the pulverization step and the classification step in advance In the kneading step, 1 to 20% by mass of the finely powdered toner that is the collected non-specified particles is added to the toner material,
The toner contains at least two additives, the at least two additives, aluminum and Al ₂ O ₃ have any of the coating, the titanium oxide fine particles surface-treated with further organic treatment agent And a silica fine particle hydrophobized with at least one selected from silicone oil and hexamethyldisilazane .   The polyester resin does not contain a tetrahydrofuran (THF) insoluble component, and in the molecular weight distribution in gel permeation chromatography (GPC), the content of the component having a molecular weight of 500 or less is 4% by mass or less, and the molecular weight is 3,000 to The toner production method according to claim 1, wherein the toner has one peak in an area of 9,000.   The method for producing a toner according to claim 1, wherein the charge control agent is a metal salt of salicylic acid. Additive is Al ₂ O ₃ The method for producing a toner according to claim 1, further comprising titanium oxide fine particles having a surface treatment with hexyltrimethoxysilane. The method for producing a toner according to claim 1, wherein the additive is added in an amount of 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the toner base. A toner manufactured by the method for manufacturing a toner according to claim 1. A developer comprising the toner according to claim 6. The developer according to claim 7, wherein the developer is a non-magnetic one-component developer. A toner-filled container filled with the toner according to claim 6. An electrostatic latent image carrier and at least developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to claim 6 to form a visible image. Feature process cartridge. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image using the toner according to claim 6. An image forming apparatus, comprising: a developing unit that forms a visible image; a transfer unit that transfers the visible image to a recording medium; and a fixing unit that fixes the transferred image transferred to the recording medium. . An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and a developing step of developing the electrostatic latent image using the toner according to claim 6 to form a visible image. And an image forming method comprising: a transfer step of transferring the visible image onto a recording medium; and a fixing step of fixing the transfer image transferred onto the recording medium.