JP2008026567A - Toner, manufacturing method of the toner, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a toner, capable of efficiently and easily manufacturing the toner of a uniform composition having a stable volume average grain size and a sharp grain size distribution, a toner which is produced by the manufacturing method of the toner, is improved in electrostatic charging properties, and can eventually prevent the occurrence of scumming, is improved in fine-line reproducibility, and can form a full-color image of high image quality, and to provide an image forming method that uses the toner. <P>SOLUTION: There is provided the manufacturing method of the toner which includes at least an emulsification step of emulsifying and dispersing a dissolved and dispersed material, formed by dissolving and dispersing a toner material, at least containing at least two kinds of resins, a colorant, and a release agent in an organic solvent into an aqueous medium containing resin particles, and in which the viscosity characteristic tanθ at 25°C of the dissolved and dispersed material is 0.70 to 0.95, and the apparent viscosity by a high shear viscometer of the dissolved and dispersed material is in the range of 100 to 400 mPa s. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

In general, an electrophotographic method is an electrostatic latent image forming step in which an electrostatic latent image is formed on a photoreceptor layer using a photoconductive material by using various means, and a toner image is developed using toner. A developing process for forming, a transferring process for transferring the toner image to a recording material such as paper, a fixing process for fixing the toner image transferred to the recording material to the recording material by heating, pressure, thermal pressure, solvent vapor, or the like; This includes a cleaning process for removing toner remaining on the body layer.
As a developer for developing such an electrostatic latent image, there are a two-component developer composed of a carrier and a toner, and a one-component developer (magnetic toner or non-magnetic toner) that does not require a carrier.

Conventionally, a melt-kneading pulverization method is known as a toner production method. In the pulverization method, the particle shape is indeterminate, and the developing roller, toner supply roller, layer thickness regulating blade, friction charging blade, etc. The toner may be pulverized by contact stress due to the generation of ultra fine particles or the fluidizing agent may be embedded in the toner surface, so that the image quality may deteriorate. In the pulverization method, the fluidity as a powder is poor due to the shape of the toner, a large amount of fluidizing agent is required, the filling rate into the toner bottle is low, and this is an obstacle to downsizing.
Recently, in order to obtain high-quality and high-quality images, improvements have been made by reducing the particle size of the toner. There is a problem that it can not cope with the conversion.

  For this reason, various toner production methods other than the above pulverization method have been studied. For example, there is a polymer suspension method including a step of emulsifying an oil phase obtained by dissolving or dispersing a toner material containing a resin, a colorant, wax, and the like in an organic solvent into a droplet having a toner size by mechanical emulsification in an aqueous phase. Proposed. In this proposal, when a solid organic fine particle dispersant is used as a stabilizer for emulsified droplets in the aqueous phase, fine droplets having a relatively narrow particle size distribution (Dv / Dn) can be produced.

  Further, Patent Document 1 prescribes the relationship between the viscosity range and the viscosity of the toner composition liquid and the dispersion liquid in the step of obtaining an O / W emulsion by emulsifying using a collisional shear force by beads. According to Patent Document 1, it is disclosed that a toner having a sharp particle size distribution can be efficiently produced. However, in this proposal, both the toner composition liquid and the dispersion liquid focus only on the viscosity, and in the emulsification process, an emulsion is formed by shearing.

Patent Document 2 defines a range of the dynamic adhesive behavior of the dispersion, which has excellent low-temperature fixability and offset resistance in a wide temperature range, and can be used for high-definition images. A particle size distribution is obtained.
In Patent Document 2, the viscous behavior of the dispersion is taken into account in order to emulsify by a high shearing action. However, in this proposal, since the dispersion is introduced into the aqueous medium and emulsification is performed, no attention is paid to the specific gravity of each liquid that greatly contributes to the smooth dispersion of the dispersion and the stability of the emulsion.

  Patent Document 3 discloses a method for producing a toner by dispersing and emulsifying a dispersion in which a binder resin, a colorant, and a release agent are dissolved in an organic solvent. The viscosity of the dispersion is measured with a rotational viscometer to define the viscosity range and the viscosity ratio. By taking such means, it becomes possible to control the target particle size and particle size distribution in which the colorant is dispersed. In this Patent Document 3, the viscosity of the dispersion and the viscosity ratio are defined, but viscoelasticity is not taken into consideration. In the case of a method of forming droplets by applying shear, viscoelasticity is included. It is important to define the characteristic values of the dissolved or dispersed material.

  Furthermore, compared to black toner, color toner reproduces various colors by superimposing different colors of toner, so that control of charging conditions becomes a problem and it is necessary to provide excellent charging characteristics. For this reason, for example, Patent Document 4 proposes that a dissolved or dispersed material is emulsified and dispersed in an aqueous medium containing a surfactant, and a surfactant having a polarity opposite to that of the surfactant is added after the emulsified dispersion. Yes.

  However, a toner production method capable of easily and efficiently producing a uniform toner having a composition having a stable volume average particle diameter and a sharp particle size distribution, and the toner production method improves the chargeability. As a result, it is possible to prevent the occurrence of background stains, improve the fine line reproducibility, and have not yet obtained a toner capable of forming a high-quality full-color image, and further improvement and development are desired at present. .

Japanese Patent Laid-Open No. 11-249336 JP 2003-162095 A JP 2005-173017 A Japanese Patent Laid-Open No. 2004-54139

  An object of the present invention is to solve the conventional problems in response to the above-mentioned demands and achieve the following object. That is, the present invention relates to a toner production method capable of efficiently and easily producing a uniform toner having a stable volume average particle diameter and a sharp particle size distribution, and the toner production method. As a result, the object of the present invention is to provide a toner capable of preventing the occurrence of scumming, improving the fine line reproducibility, and forming a high-quality full-color image, and an image forming method using the toner.

  As a result of intensive investigations by the present inventors in order to solve the above-mentioned problems, a solution or dispersion (oil phase) in which the toner material before being subjected to shearing by the emulsifier (after pre-stirring) is dissolved or dispersed in an organic solvent. It has been found that a toner having a uniform volume average particle size and a sharp particle size distribution can be efficiently produced by setting the supply conditions of the water phase and the premix conditions.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A solution or dispersion in which a toner material containing at least two kinds of resins, a colorant, and a release agent is dissolved or dispersed in an organic solvent is emulsified or dispersed in an aqueous medium containing resin fine particles. A method for producing a toner comprising at least an emulsifying step.
A toner having a viscosity characteristic tan θ at 25 ° C. of the dissolved or dispersed material of 0.70 to 0.95 and an apparent viscosity of 100 to 400 mPa · s of a high shear viscometer of the dissolved or dispersed material. It is a manufacturing method.
<2> The method for producing a toner according to <1>, wherein the viscosity ratio represented by the following formula 1 using a high shear viscometer of the dissolved or dispersed material is 1.5 to 2.5.
<Formula 1>
Viscosity ratio = (apparent viscosity at 100 rpm) ÷ (apparent viscosity at 1,000 rpm)
<3> The method for producing a toner according to any one of <1> to <2>, wherein the recovery rate of the structural viscosity of the dissolved or dispersed material is 90% or more.
<4> The method for producing a toner according to any one of <1> to <3>, wherein the Casson yield value of the dissolved or dispersed material by a high shear viscometer is 5.0 to 10.0.
<5> The method for producing a toner according to any one of <1> to <4>, wherein the acid value of the dissolved or dispersed material is 5.0 to 15.0 mg KOH / g.
<6> The method for producing a toner according to any one of <1> to <5>, wherein the amine value of the dissolved or dispersed material is 1.0 to 10.0 mgKOH / g.
<7> The method for producing a toner according to any one of <1> to <6>, wherein the concentration in terms of solid content of the dissolved or dispersed material is 40 to 60% by mass.
<8> The toner according to any one of <1> to <7>, wherein a mixed mass ratio of the dissolved or dispersed material to the aqueous medium (dissolved or dispersed: aqueous medium) is 50:50 to 30:70. It is a manufacturing method.
<9> If the specific gravity of the dissolved or dispersed material is ρ1 and the specific gravity of the aqueous medium is ρ2, the ratio (ρ1 / ρ2) is 0.95 to 1.05, and any one of <1> to <8> It is a manufacturing method of the described toner.
<10> The method for producing a toner according to any one of <1> to <9>, wherein at least two kinds of resins are polyester resins having different weight average molecular weights.
<11> A toner produced by the method for producing a toner according to any one of <1> to <10>.
<12> The volume average particle diameter is 3 to 10 μm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.05 to 1.25 <11>.
<13> A developer comprising the toner according to any one of <11> to <12>.
<14> A toner-containing container filled with the toner according to any one of <11> to <12>.
<15> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <11> to <12> to be a visible image And a developing means for forming the process cartridge.
<16> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <11> to <12> The image forming apparatus includes at least a developing step for developing to form a visible image, 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. An image forming method.
<17> 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 according to <11> to <12> Developing means for developing a visible image by developing using any of the toners, Transfer means for transferring the visible image to a recording medium, and Fixing means for fixing the transferred image transferred to the recording medium And an image forming apparatus characterized by comprising:

The method for producing a toner of the present invention includes an aqueous system containing resin fine particles obtained by dissolving or dispersing a toner material containing at least two kinds of resins, a colorant, and a release agent in an organic solvent. Including at least an emulsification step of emulsifying or dispersing in a medium,
The viscosity or tan θ at 25 ° C. of the dissolved or dispersed material is 0.70 to 0.95, and the apparent viscosity of the dissolved or dispersed material with a high shear viscometer is 100 to 400 mPa · s at 25 ° C. In the toner production method of the present invention, a uniform toner having a stable volume average particle size and a sharp particle size distribution can be produced easily and efficiently.

  Since the toner of the present invention is produced by the toner production method of the present invention, it has a stable volume average particle diameter and a sharp particle size distribution, and can faithfully develop an electrostatic latent image. The occurrence of dirt can be prevented, and a high-quality full-color 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 developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. 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. In the image forming method of the present invention, since the toner of the present invention is used, the electrostatic latent image can be developed faithfully, the occurrence of background stains can be prevented, and a high-quality full-color image can be formed.

  According to the present invention, it is possible to solve the conventional problems, and a toner production method capable of efficiently and easily producing a uniform toner having a composition having a stable volume average particle size and a sharp particle size distribution, and As a result of improving the chargeability as a result of the toner manufacturing method, a toner capable of preventing the occurrence of background stains, improving fine line reproducibility and forming a high-quality full-color image, and an image forming method using the toner Can be provided.

(Toner and toner production method)
The method for producing a toner of the present invention includes an aqueous system containing resin fine particles obtained by dissolving or dispersing a toner material containing at least two kinds of resins, a colorant, and a release agent in an organic solvent. It includes at least an emulsification step for emulsification or dispersion in a medium, 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.

  Here, FIG. 1 is a diagram showing an example of a continuous emulsification step in the toner production method of the present invention. A toner material containing at least two kinds of resins, a colorant, and a release agent is dissolved or dispersed in an organic solvent, and a ketimine compound as an extender is mixed in a solution or dispersion (hereinafter referred to as “A oil”). Phase ”203), an aqueous medium containing resin fine particles as a dispersant (hereinafter also referred to as“ aqueous phase ”204), and a prepolymer having an isocyanate bond dissolved in an organic solvent. Or a dispersed solution or dispersion (hereinafter also referred to as “B oil phase” 202) is continuously fed in a certain amount, and the A oil phase 203 and the B oil phase 202 are Before mixing with the aqueous phase 204, pre-stirring is performed with a static mixer 205 (the liquid after this pre-stirring is referred to as “oil phase”; that is, dissolution or dispersion of toner material). Next, the oil phase mixed with the static mixer and the aqueous phase 204 are mixed, and the pipeline homomixer 201 in the retention volume of the emulsifying mechanism part is subjected to shearing to continuously emulsify.

  In this case, in order to obtain an emulsified liquid droplet having a stable volume average particle diameter and a sharp particle size distribution, the oil phase component, which is a mixture of the A oil phase and the B oil phase, has a shear rate (shear force). It is important to exhibit certain characteristics, and it is important that the “apparent viscosity” and “viscosity ratio” associated therewith be within a certain range. In addition, the ratio of specific gravity of each component is important in order to smoothly disperse the oil phase component in the aqueous medium and maintain the dispersed state.

The viscosity characteristic tan θ at 25 ° C. of the dissolved or dispersed toner material (the oil phase) is 0.70 to 0.95, preferably 0.70 to 0.80. When the viscosity characteristic tan θ is less than 0.70, the thixotropic property of the dissolved or dispersed material is strong, and a large sensitivity is generated in the shape and particle size distribution of the droplets depending on the state of shearing, so that a stable particle size cannot be obtained. If it exceeds 0.95, the thixotropic property is weak, the sensitivity of the shape and particle size distribution of the droplets due to the state of shearing is lost, and granulation adjustment and the like may be difficult.
The apparent viscosity of the dissolved or dispersed material with a high shear viscometer is 100 to 400 mPa · s, preferably 200 to 400 mPa · s, and more preferably 300 to 400 mPa · s. When the apparent viscosity is less than 100 mPa · s, the energy from the shear blade of the emulsifier may not be efficiently transferred to the dissolved or dispersed material. , The stability of emulsion formation may be lacking.

The viscosity ratio represented by the following mathematical formula 1 by the high shear viscometer of the dissolved or dispersed material is preferably 1.5 to 2.5, and more preferably 2.0 to 2.5. When the viscosity ratio is less than 1.5, the energy from the shear blade of the emulsifier may not be efficiently transferred to the dispersion or dispersion. When the viscosity ratio exceeds 2.5, the energy efficiency from the shear blade of the emulsifier However, as a result of great sensitivity in the shape and particle size distribution of the droplets, a stable particle size may not be obtained.
<Formula 1>
Viscosity ratio = (apparent viscosity at 100 rpm) ÷ (apparent viscosity at 1,000 rpm)

In addition, since the droplet is subjected to shear many times within the retention volume of the emulsification mechanism, it is necessary to evaluate the viscoelasticity of the oil droplet after being subjected to the shear. The recovery rate of the structural viscosity of the dissolved or dispersed material is preferably 90% or more, and more preferably 95% or more. When the recovery rate is 90% or more, the particle size does not collapse even in continuous shearing, and a sharp particle size distribution is obtained.
The Casson yield value of the dissolved or dispersed material by a high shear viscometer is preferably 5.0 to 10.0, and more preferably 8.0 to 10.0. If the Casson yield value is less than 5.0, it may be difficult to obtain the target shape, and if it exceeds 10.0, the shape controllability of the droplet may be difficult.

An emulsion is formed by dissolving or dispersing the dispersion (oil phase) by an emulsifier, and the shape and particle size distribution of the droplets are greatly affected by the state of shear. Also, since the shear peripheral speed is different between the center and the tip of the shear blade of the emulsifier, and the oil droplets are subjected to shear several times within the part retention volume of the emulsifier, the viscoelasticity of the dissolved or dispersed material is an important factor. It becomes.
Therefore, it is necessary to define the characteristics in consideration of the viscoelasticity of the oil phase. By defining the characteristics in this way, it is possible to deal with a relatively wide shear peripheral speed region. This viscoelasticity can be controlled by changing the level of dissolution or dispersion (specifically, the peripheral speed or dispersion time of the disperser). In addition, since an apparent viscosity and a viscosity ratio of a certain level or more exist, energy due to shear is efficiently transmitted to the dissolved or dispersed material, and a sharp particle size distribution can be stably formed. As a result, it is very effective in preventing the occurrence of scumming, and a high-quality full-color image that can faithfully develop the electrostatic latent image can be reproduced.

-Measurement method of oil phase viscosity characteristics-
The viscosity characteristics tan θ and Casson yield value can be measured using a high shear viscometer under the following conditions.
〔Measurement condition〕
・ Device: AR2000 (TA Instruments)
・ Shear stress: 120 Pa / 5 min ・ Geometry: 40 mm steel plate ・ Geometry gap: 1 mm
・ Analysis software: TA DATA ANALYSIS (TA Instruments)

The Casson yield value (stress yield value Pa) is an extrapolation point of s ⁻¹ = 0 of the shear rates s ⁻¹ = 1 and s ⁻¹ = 2 from the Casson flow equation. The range of shear rate on measurement is ^{0 s −1 to} 300 s ⁻¹ .
The viscosity characteristic tan θ measures the flow curve of the oil phase. Conditions and 0.5mm gap (GAP) in 25 ° C., measurement range, shear rate and ^{0s -1 → 1800s -1 → 0s -1} . The viscosity characteristic tan θ can be obtained from the shear rate s ⁻¹ and the Log-Log graph of shear stress. The range of shear rate is at ^{0s -1 ~2000s} -1.
The apparent viscosity indicates “P / 100” when the shear stress value at a shear rate of 100 s ⁻¹ is P.
The viscosity ratio indicates a ratio between the apparent viscosity at a shear rate of 100 s ^{−1 and} the apparent viscosity at a shear rate of 1000 s ⁻¹ .
Further, the recovery rate of the structural viscosity is defined as a shear stress value of ^{0 s −1} → 1800 s ^{−1 in} the oil phase flow curve, and a shear stress value of 1800 s ⁻¹ → ⁰ s ⁻¹ in the shear rate. Assuming P2, “P2 / P1” is indicated.

The acid value of the dissolved or dispersed (oil phase) of the toner material is preferably 5.0 to 15.0 mgKOH / g, more preferably 10.0 to 15.0 mgKOH / g.
The amine value of the toner material dissolved or dispersed (oil phase) is preferably 1.0 to 10.0 mgKOH / g, more preferably 5.0 to 10.0 mgKOH / g.
In the range of the acid value and the amine value, toner properties such as particle size control, low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and charging stability can be improved. When the acid value exceeds 15.0 mgKOH / g, the extension or crosslinking reaction of the modified polyester is insufficient, and the high temperature offset resistance may be affected. On the other hand, if it is less than 5.0 mgKOH / g, the dispersion stabilizing effect by the base compound cannot be obtained, and the extension or crosslinking reaction of the modified polyester tends to proceed, which may cause a problem in production stability.
Considering the acid value of the dissolved or dispersed material, it is effective to keep the amine value within the above range in order to form a sharp particle size distribution.

  The acid value of the dissolved or dispersed material can be adjusted by changing the number of trimellitic anhydride added used in the synthesis of the low molecular weight polyester. The amine value of the dissolved or dispersed material can be adjusted by changing the number of added parts of the ketimine compound as an extender.

Here, the acid value can be measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner was added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Furthermore, 30 ml of ethanol was added to prepare a sample solution.
The measurement can be calculated by the above-described apparatus, and specifically, can be calculated as follows.
Titration is carried out in advance with standardized N / 10 caustic potassium to alcohol solution, and the acid value is obtained from the consumption amount of the alcohol potassium solution by the following formula.
Acid value = KOH (ml number) × N × 56.1 / sample mass where N is a factor of (N / 10) KOH.

The amine value can be titrated with a previously evaluated N / 10 hydrochloric acid-alcohol solution, and the amine value can be determined from the consumption of hydrochloric acid-alcohol solution by the following formula.
Amine number = HCl (ml number) × N × 56.1 / sample mass where N is a factor of (N / 10) HCl.

40-60 mass% is preferable and, as for the solid content conversion density | concentration of the said melt | dissolution thru | or dispersion | distribution, 40-50 mass% is more preferable. When the solid content converted value of the dispersion is in the above range, coalescence due to aggregation after the emulsion formation is prevented, and a stable emulsion state can be maintained.
The solid content converted value of the dissolved or dispersed material can be adjusted by changing the number of added ethyl acetate.

  The mixing mass ratio of the dissolution or dispersion and the aqueous medium (dissolution or dispersion: aqueous medium) is preferably 50:50 to 30:70, and more preferably 40:60 to 45:55. From the viewpoint of the collision probability of particles, it is effective to form a sharp particle size distribution by keeping the mixing mass ratio of the dissolved or dispersed material and the aerated aqueous medium within the above range.

When the specific gravity of the dissolved or dispersed material is ρ1 and the specific gravity of the aqueous medium is ρ2, the ratio (ρ1 / ρ2) is preferably 0.95 to 1.05, and more preferably 1.00 to 1.05. In this range, the oil phase component is smoothly dispersed in the aqueous medium. In order to maintain the dispersion state, the ratio of the specific gravity of the dissolved or dispersed material to the aqueous medium is important.
The specific gravity can be measured by, for example, an “oval Coriolis flow meter” installed as a flow meter.

The toner has a volume average particle diameter (Dv) of preferably 3 to 10 μm, and more preferably 5 to 8 μm.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In the case of the agent, toner filming on the developing roller and toner fusion to the member such as a blade are likely to occur because the toner layer is thinned. When the balance of the toner in the developer is performed, the toner particle size may vary greatly.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is preferably 1.05 to 1.25, and more preferably 1.05 to 1.15.
In general, it is said that the smaller the toner particle size, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, leading to a decrease in the charging ability of the carrier, When used as a developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention. On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.
On the other hand, when the volume average particle size / number average particle size is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount, but the toner is not sufficiently charged. It has become clear that there is a case where the cleaning property is deteriorated.

  The volume average particle diameter (Dv) and the ratio (Dv / Dn) of the volume average particle diameter to the number average particle diameter (Dv / Dn) are, for example, a particle size measuring device (“Coulter Counter TAII”, manufactured by Coulter Electronics). It can be measured by measuring with an aperture diameter of 100 μm and analyzing with analysis software (Beckman Coulter Multisizer 3 Version 3.51).

The at least two kinds of resins used in the toner of the present invention are not particularly limited and can be appropriately selected according to the purpose. For example, a low molecular weight polyester resin and a high molecular weight polyester resin) are also included. Moreover, the combination (for example, polyester resin and polyester resin precursor) of resin and this resin precursor is also contained. Further, a combination of a non-modified resin and a modified resin (for example, a non-modified polyester resin and a modified polyester resin) is also included.
Examples of such binder resins include polystyrene resins, poly-α-still styrene resins, styrene-acrylonitrile copolymers, styrene-chlorostyrene copolymers, styrene-propylene copolymers, and styrene-butadiene copolymers. Styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloroacrylic acid Styrenic resins (monopolymers or copolymers containing styrene or styrene-substituted products) such as methyl copolymers, styrene-acrylonitrile-acrylic acid ester copolymers, polyester resins, epoxy resins, vinyl chloride resins, rosin modified malees Acid resin, phenol resin, polyethylene resin, Repropylene resin, petroleum resin, polyurethane resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyrate resin, and the like. Among these, from the viewpoint of fixability and reproducibility of full-color images, A combination of a modified polyester resin and an unmodified polyester resin is particularly preferred.

-Modified polyester resin-
The modified polyester resin is a polyester resin in which a functional group contained in an acid / alcohol monomer unit and a bonding group other than an ester bond are present, or a resin component having a different structure is covalently bonded or ionic bonded in the polyester resin. It means the state that is connected by.

As such a modified polyester resin, for example, a polyester terminal is reacted with something other than an ester bond, specifically, a functional group such as an acid group or an isocyanate group that reacts with a hydroxyl group is introduced into the terminal to activate the polyester resin. Also included are those obtained by further reacting with a hydrogen compound to denature the ends or by extending the reaction.
In addition, compounds having a plurality of active hydrogen groups include those in which polyester ends are bonded to each other (urea-modified polyester, urethane-modified polyester, etc.).
In addition, a reactive group such as a double bond is introduced into the polyester main chain, and radical polymerization is caused therefrom to introduce a graft component of a carbon-carbon bond to the side chain, or a double bond is bridged. (For example, styrene-modified polyester, acrylic-modified polyester, etc.)
Silicone modified by copolymerization of resin components having different constitution in the main chain of polyester, reaction with a carboxyl group or hydroxyl group at the terminal (for example, terminal carboxyl group, hydroxyl group, epoxy group), or mercapto group Those copolymerized with a resin (such as silicone-modified polyester) are also included.
Among these, polyesters modified with urea bonds (urea-modified polyester resins) are particularly preferable.

Examples of the polyester (i) modified with a urea bond include a reaction product of a polyester prepolymer (A) having an isocyanate group and an amine (B).
Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group, which is further reacted with a polyisocyanate (3). Is mentioned. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, and a mercapto group. Among these, alcoholic hydroxyl groups are particularly preferable.

Examples of the polyol (1) include a diol (1-1) or a trivalent or higher polyol (1-2). The diol (1-1) alone or the diol (1-1) and a small amount of trivalent or higher. A mixture of (1-2) is preferred.
Examples of the diol (1-1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (Diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Bisphenols (bisphenol A) Bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol Alkylene oxide of the bisphenols (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferred, and particularly preferred are alkylene oxide adducts of bisphenols and combinations thereof with alkylene glycols having 2 to 12 carbon atoms. is there.
Examples of the trivalent or higher polyol (1-2) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); (Trisphenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polycarboxylic acid (2) include a dicarboxylic acid (2-1) and a trivalent or higher polycarboxylic acid (2-2). The dicarboxylic acid (2-1) alone and the dicarboxylic acid (2-1) ) And a small amount of a trivalent or higher polycarboxylic acid (2-2).
Examples of the dicarboxylic acid (2-1) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, Terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

The ratio of the polyol (1) and the polycarboxylic acid (2) is preferably 2/1 to 1/1 as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1 is more preferable, and 1.3 / 1 to 1.02 / 1 is still more preferable.
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; phenols, oximes, polyisocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.

The ratio of the polyisocyanate (3) is preferably 5/1 to 1/1 as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. / 1 to 1.2 / 1 is more preferable, and 2.5 / 1 to 1.5 / 1 is still more preferable. When the [NCO] / [OH] exceeds 5, the low-temperature fixability may be deteriorated. On the other hand, when the molar ratio of [NCO] is less than 1, the urea content in the modified polyester is lowered, and the hot offset resistance may be deteriorated.
The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass, and 2 to 20% by mass. Is more preferable. When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, which may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. Fixability may deteriorate.
The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is preferably 1 or more, more preferably 1.5 to 3 on average, and more preferably 1.8 to 2.5 on average. preferable. When the number is less than 1 per molecule, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance may be deteriorated.

  The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino group of (B1) to (B5) (B6). These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), or those obtained by blocking them (ketimine compounds).

  The ratio of the amines (B) is the equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine (B). 1/2 to 2/1 is preferable, 1.5 / 1 to 1 / 1.5 is more preferable, and 1.2 / 1 to 1 / 1.2 is still more preferable. When [NCO] / [NHx] is more than 2 or less than ½, the molecular weight of the urea-modified polyester (i) is lowered, and the hot offset resistance may be deteriorated.

  In the present invention, the polyester (i) modified with a urea bond may contain a urethane bond together with a urea bond. The molar ratio between the urea bond content and the urethane bond content is preferably 100/0 to 10/90, more preferably 80/20 to 20/80, and still more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10 mol%, the hot offset resistance may be deteriorated.

The urea-modified polyester (i) is produced by a one-shot method or a prepolymer method. The urea-modified polyester (i) has a mass average molecular weight of preferably 10,000 or more, more preferably 20,000 to 10,000,000, and still more preferably 30,000 to 1,000,000. When the mass average molecular weight is less than 10,000, the hot offset resistance may be deteriorated.
The number average molecular weight of the urea-modified polyester is not particularly limited in the case of using an unmodified polyester (ii) described later, and can be appropriately selected according to the purpose. It may be a number average molecular weight that can be easily obtained. (I) When used alone, the number average molecular weight is preferably 20,000 or less, more preferably 1,000 to 10,000, and still more preferably 2,000 to 8,000. When the number average molecular weight exceeds 20,000, low temperature fixability and gloss when used in a full color apparatus may be deteriorated.

-Unmodified polyester resin-
In the present invention, not only the polyester (i) modified with the urea bond but also the polyester (ii) not modified can be contained as a toner binder component together with the (i). By using the unmodified polyester resin (ii) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to the single use. Examples of the unmodified polyester resin (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (i). The unmodified polyester resin (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance.
When the unmodified polyester resin (ii) is contained, the mass ratio of (i) and (ii) is preferably 5/95 to 80/20, more preferably 5/95 to 30/70, and 5/95 to 25/75 is more preferable, and 7/93 to 20/80 is particularly preferable. If the mass ratio of (i) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

The peak molecular weight of the unmodified polyester resin (ii) is preferably 1,000 to 30,000, more preferably 1,500 to 10,000, and still more preferably 2,000 to 8,000. If it is less than 1,000, the heat-resistant storage stability may be deteriorated, and if it exceeds 10,000, the low-temperature fixability may be deteriorated.
The hydroxyl value of the unmodified polyester resin (ii) is preferably 5 mgKOH / g or more, more preferably 10 to 120 mgKOH / g, still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin (ii) is preferably 1 to 30 mgKOH / g, and more preferably 5 to 20 mgKOH / g.

In the present invention, the glass transition temperature (Tg) of the toner binder is preferably 50 to 70 ° C, and more preferably 55 to 65 ° C. When the glass transition temperature is less than 50 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient. Due to the coexistence of the urea-modified polyester resin, the toner of the present invention tends to have good heat-resistant storage stability even when the glass transition temperature is low, as compared with known polyester-based toners. As the storage elastic modulus of the toner binder, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10,000 dyne / cm ² is preferably 100 ° C. or more, and more preferably 110 to 200 ° C. When the temperature (TG ′) is less than 100 ° C., the hot offset resistance may be deteriorated. As the viscosity of the toner binder, the temperature (Tη) at which a poise of 1,000 is obtained at a measurement frequency of 20 Hz is preferably 180 ° C. or less, and more preferably 90 to 160 ° C. When the temperature (Tη) exceeds 180 ° C., the low-temperature fixability may be deteriorated. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low-temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and still more preferably 20 ° C. or higher. The upper limit of the difference (TG′−Tη) is not particularly limited and can be appropriately selected depending on the purpose. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg (Tη−Tg) is preferably 0 to 100 ° C., more preferably 10 to 90 ° C., and still more preferably 20 to 80 ° C.

-Resin fine particles-
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate. Resin, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, vinyl resin, polyurethane resin, epoxy resin, and polyester resin are particularly preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.

The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer. For example, styrene- (meth) acrylate resin, styrene-butadiene copolymer, (meth) acrylic acid-acrylate polymer, styrene -An acrylonitrile copolymer, a styrene-maleic anhydride copolymer, a styrene- (meth) acrylic acid copolymer, etc. are mentioned.
Further, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). ", Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate, and the like.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

  The glass transition temperature of the resin fine particles is preferably 65 to 85 ° C. When the glass transition temperature is less than 65 ° C., the heat-resistant storage stability under a high temperature environment is lowered, and there is a problem in that toner blocking occurs, which may affect toner transferability. On the other hand, when the glass transition temperature exceeds 85 ° C., there is a problem that the low temperature fixability is hindered and offset occurs.

-Colorant-
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, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin 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 is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content exceeds 15% by mass, the pigment may be poorly dispersed in the toner. The electrical characteristics may be degraded.

  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, alicyclic Examples thereof include hydrocarbons, aromatic petroleum resins, chlorinated paraffins, and paraffins. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable. When the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable. When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenol-based condensate E-89 (both manufactured by Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.) ), Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst), LRA-901, Boron complex LR-147 (Nippon Carlit), quinacridone, azo pigment; Acid group, a carboxyl group, polymer compounds having a quaternary ammonium salt, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1-10 mass parts is preferable, and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

-External additive-
As the external additive for assisting the fluidity, developability and chargeability of the toner, inorganic fine particles are suitable. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g. The addition amount of the inorganic fine particles is preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the toner.
The inorganic fine particles are not particularly limited and may be appropriately selected depending on the intended purpose.For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, Tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

Examples of other external additives include polymer-based fine particles. Examples of the polymer fine particles include polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as methacrylic acid ester and acrylic acid ester copolymer, silicone, benzoguanamine, and nylon, and thermosetting. Examples thereof include polymer particles made of a resin.
Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles have a relatively narrow particle size distribution, and the volume average particle size is preferably 0.01 to 1 μm.

  The method for producing a toner of the present invention comprises a resin fine particle obtained by dissolving or dispersing (oil phase) a toner material containing at least two kinds of resins, a colorant, and a release agent in an organic solvent. The organic solvent is removed after emulsification or dispersion in a water-based medium containing the reaction.

-Organic solvent-
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, and methyl isobutyl ketone. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.

-Dispersion-
The dispersion is prepared by dispersing the toner solution in an aqueous medium.
When a solution or dispersion obtained by dissolving or dispersing the toner material in an organic solvent is dispersed in the aqueous medium, a dispersion (oil droplets) made of the solution or dispersion is formed in the aqueous medium.

--- Aqueous medium--
The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.

The toner solution is preferably dispersed in the aqueous medium with stirring.
The dispersion method is not particularly limited and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction disperser. High pressure jet disperser, ultrasonic disperser, and the like. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 3,000 to 30,000 rpm is preferable, 5,000 to 20,000 rpm is more preferable, and the dispersion time is preferably 0.1 to 5 minutes in the case of a batch method, and the dispersion temperature is under pressure. 0-150 degreeC is preferable and 40-98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

  An example of the method for producing the toner will be described below. Preparation of an aqueous medium phase, preparation of the toner solution, preparation of the dispersion, addition of the aqueous medium, and other steps are performed.

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The toner solution is prepared by mixing the amines (B), the isocyanate group-containing polyester prepolymer (A), the colorant, the release agent, the charge control agent, the unmodified polyester resin in the organic solvent. The toner material can be dissolved or dispersed.
In the toner material, components other than the isocyanate group-containing polyester prepolymer (A) are added and mixed in the aqueous medium when the resin fine particles are dispersed in the aqueous medium in the preparation of the aqueous medium phase. Alternatively, when the toner solution is added to the aqueous medium phase, it may be added to the aqueous medium phase together with the toner solution.

The dispersion liquid can be prepared by emulsifying or dispersing the previously prepared toner solution in the previously prepared aqueous medium phase. In the emulsification or dispersion, when the isocyanate group-containing polyester prepolymer (A) and the amines (B) are subjected to an extension reaction or a crosslinking reaction, the urea-modified polyester resin is generated.
For example, the urea-modified polyester resin can be obtained by emulsifying or dispersing the toner solution containing the isocyanate group-containing polyester prepolymer (A) together with the amines (B) in the aqueous medium phase. And (2) emulsifying the toner solution in the aqueous medium to which the active hydrogen group-containing compound has been added in advance. Or may be dispersed to form a dispersion, and may be produced by subjecting both to an extension reaction or a crosslinking reaction in the aqueous medium phase, or (3) the toner solution is added and mixed in the aqueous medium. Later, the active hydrogen group-containing compound is added, a dispersion is formed, and both are formed by subjecting both to an extension reaction or a crosslinking reaction from the particle interface in the aqueous medium phase. Good. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the urea-modified polyester resin by the emulsification or dispersion are not particularly limited and may be appropriately selected. The reaction time is preferably 10 minutes to 40 hours, preferably 2 hours to 24 hours is more preferable, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

  Examples of a method for stably forming the dispersion containing the isocyanate group-containing polyester prepolymer (A) in the aqueous medium phase include, for example, the isocyanate group-containing polyester prepolymer (A) in the aqueous medium phase. A method of adding the toner solution prepared by dissolving or dispersing the toner material such as the colorant, the release agent, the charge control agent, and the unmodified polyester resin in the organic solvent, and dispersing it by shearing force , Etc. The details of the dispersion method are as described above.

In preparing the dispersion, if necessary, a dispersant is used from the viewpoint of stabilizing the dispersion (oil droplets composed of the toner solution) and sharpening the particle size distribution while obtaining a desired shape. Is preferred.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a sparingly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, and S-113 (all manufactured by Asahi Glass Co., Ltd.); Florad FC-93, FC-95, FC- 98, FC-129 (both manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-101, DS-102 (both manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F -191, F-812, F-833 (all manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 ( All of them are manufactured by Tochem Products Co., Ltd.); Footent F-100, F150 (both manufactured by Neos) and the like.

Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.
Examples of commercially available cationic surfactants include Surflon S-121 (Asahi Glass Co., Ltd.); Florad FC-135 (Sumitomo 3M Co., Ltd.); Unidyne DS-202 (Daikin Industries Co., Ltd.), MegaFuck F-150, F-824 (both manufactured by Dainippon Ink and Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products); and Futterent F-300 (manufactured by Neos).

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, amides Examples thereof include homopolymers or copolymers of compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In preparing the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  The organic solvent is removed from the obtained dispersion (emulsified slurry). The organic solvent is removed by (1) a method of gradually raising the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets, and (2) spraying the emulsified dispersion in a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As a method of applying the mechanical impact force, for example, a method of applying an impact force to the mixture with a blade rotating at high speed, an appropriate collision between particles or composite particles by introducing the mixture into a high-speed air stream and accelerating the mixture is accelerated. The method of making it collide with a board, etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.), and a pulverization air pressure are lowered, a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

<Developer>
The developer used in the present invention contains at least the toner of the present invention, and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 to 200 μm, and more preferably 40 to 100 μm. When the average particle size (volume average particle size (D ₅₀ )) is less than 10 μm, in the distribution of carrier particles, the number of fine powder systems increases, and the magnetization per particle may be lowered to cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may be reduced and toner scattering may occur. In the case of a full color having many solid portions, the reproduction of the solid portions may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluorine And a copolymer of vinylidene fluoride and vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene-acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.
The mixing ratio of the toner and the carrier of the two-component developer is generally 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

Since the developer contains the toner of the present invention, an excellent, clear and high-quality image can be stably formed.
The developer used in the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component developing method, a non-magnetic one-component developing method, and a two-component developing method. It can be particularly suitably used for a process cartridge, an image forming apparatus, and an image forming method.

<Toner container>
The toner-containing container used in the present invention contains the toner or developer of the present invention 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 may be appropriately selected depending on the intended purpose. However, a material having good dimensional accuracy is preferable, for example, a resin is preferable. Among these, for example, polyester Preferred examples include resins, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, polyacryl resins, polycarbonate resins, ABS resins, polyacetal resins, and the like.
The container containing toner is easy to store and transport, has excellent handleability, and can be suitably used for replenishing toner by being detachably attached to a process cartridge, an image forming apparatus, etc. of the present invention described later. .

<Process cartridge>
The process cartridge used in the present invention can develop 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. A developing unit that forms a visual image, and further includes other units such as a charging unit, a transfer unit, a cleaning unit, and a discharging unit, 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 carried on the surface of the developer carrying member.
The process cartridge can be detachably provided in various electrophotographic image forming apparatuses, facsimile machines, and printers, and is preferably provided detachably in an image forming apparatus described later.

  Here, for example, as shown in FIG. 2, the process cartridge includes an electrostatic latent image carrier (photosensitive drum) 101, a charging device 102, a developing unit 104, and a cleaning unit 107. Furthermore, it has other means as needed. Reference numeral 103 denotes exposure by an exposure apparatus, 105 denotes a recording medium, and 108 denotes a transfer unit.

  Next, an image forming process using the process cartridge shown in FIG. 2 will be described. The photosensitive drum 101 as an electrostatic latent image carrier is rotated in the direction of the arrow while being charged by the charging device 102 and exposed to light 103 by an exposure device (not shown). Is formed. The electrostatic latent image is developed by the developing unit 104, and the obtained visible image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photosensitive drum after the transfer is cleaned by the cleaning means 107, further neutralized by the neutralizing means (not shown), and the above operation is repeated again.

  As an image forming apparatus used in the present invention, the electrostatic latent image carrier and components such as a developing device and a cleaning device are integrally combined as a process cartridge, and this unit is attached to and detached from the apparatus main body. You may comprise. Further, at least one selected from a charging device, a developing device, a transfer device, a separation device, and a cleaning device is integrally supported together with an electrostatic latent image carrier to form a process cartridge, and is detachably attached to the apparatus main body. One unit may be configured to be detachable using guide means such as a rail of the apparatus main body.

(Image forming apparatus and image forming method)
The image forming apparatus used in 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. It has other selected 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 other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. , Including recycling process, control process, etc.

  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 and the like of the electrostatic latent image carrier are not particularly limited and can be appropriately selected depending on the purpose. Examples of the shape include a drum shape and a sheet. And endless belts. The structure may be a single-layer structure or a laminated structure, and the size may be appropriately selected according to the size and specifications of the image forming apparatus. Examples of the material include inorganic photoreceptors such as amorphous silicon, selenium, CdS, and ZnO; organic photoreceptors (OPC) such as polysilane and phthalopolymethine, and the like.

  For example, the amorphous silicon photosensitive member is heated to 50 to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method, or the like is applied on the support. A photosensitive layer made of a-Si is formed by a film forming method. Among these, the plasma CVD method is particularly preferable, and specifically, a method in which the source gas is decomposed by direct current, high frequency, or microwave glow discharge to form a photosensitive layer made of a-Si on the support is preferable. .

The organic photoreceptor (OPC) has (1) optical characteristics such as a wide light absorption wavelength range and a large amount of light absorption, (2) electrical characteristics such as high sensitivity and stable charging characteristics, (3) In general, it is widely applied because of the wide selection range of materials, (4) ease of production, (5) low cost, and (6) non-toxicity. The layer structure of such an organic photoreceptor is roughly divided into a single layer structure and a laminated structure.
The single-layered photoreceptor has a support and a single-layer type photosensitive layer provided on the support, and further includes a protective layer, an intermediate layer, and other layers as necessary.
The laminated structure of the photoreceptor comprises a support, and a laminate type photosensitive layer having at least a charge generation layer and a charge transport layer in this order on the support, and further includes a protective layer and an intermediate layer as necessary. And other layers.

The electrostatic latent image can be formed by, for example, uniformly charging the surface of the electrostatic latent image carrier and then exposing it like an image, and using the electrostatic latent image forming means. Can do.
The electrostatic latent image forming means includes at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure unit that exposes the surface of the electrostatic latent image carrier imagewise. .

  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 roller, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to a roller, and can be selected according to the specifications and form of the image forming apparatus. In the case of using a magnetic brush, the magnetic brush is composed of, for example, various ferrite particles such as Zn-Cu ferrite as a charging member, a nonmagnetic conductive sleeve for supporting it, and a magnet roll included therein. The When using a magnetic brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound around a metal or other conductive cored bar. Or by attaching it to the charger.
The charger is not limited to the contact charger as described above. However, since an image forming apparatus in which ozone generated from the charger is reduced is obtained, a contact charger is used. preferable.

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).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-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.

There is no restriction | limiting in particular as said intermediate transfer body, According to the objective, it can select suitably from well-known transfer bodies, For example, a transfer belt, a transfer roller, etc. are mentioned suitably.
The static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably several Ωcm or more and 10 ³ Ωcm or less. Thus, by setting the volume resistance of the intermediate transfer member to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means hardly remains on the intermediate transfer member. Therefore, transfer unevenness during secondary transfer can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

There is no restriction | limiting in particular as a material of the said intermediate transfer body, Although it can select suitably according to the objective from well-known materials, the following are suitable.
(1) A material having a high Young's modulus (tensile modulus) is used as a single layer belt. For example, PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) and PAT (Polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) and PC blend material, ETFE and PAT blend material, PC and PAT blend material, thermosetting of carbon black dispersion Examples thereof include polyimide. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and rib displacement is unlikely to occur particularly during color image formation.
(2) A belt having a two- to three-layer structure in which a belt having a high Young's modulus of (1) is used as a base layer and a surface layer or an intermediate layer is formed on the outer periphery thereof. It has a performance capable of preventing the line image from being lost due to the hardness of the single layer belt.
(3) It is an elastic belt having a relatively low Young's modulus using resin, rubber or elastomer, and such an elastic belt has an advantage that almost no void in the line image occurs due to its softness. In addition, the elastic belt is wider than the drive roll and stretch roll, and the elasticity of the belt ears protruding from the roll can be used to prevent meandering, thus reducing costs without requiring ribs or meandering prevention devices. it can.
Among these, the elastic belt (3) is particularly preferable.
The elastic belt is deformed corresponding to the toner layer and the recording medium having poor smoothness in the transfer portion. In other words, since the elastic belt deforms following the local unevenness, good adhesion can be obtained without excessively increasing the transfer pressure with respect to the toner layer, there is no void in characters, and flatness is poor. A transfer image with excellent uniformity can be obtained even on a recording medium.

  There is no restriction | limiting in particular as resin used for the said elastic belt, Although it can select suitably according to the objective, For example, polycarbonate resin, fluororesin (ETFE, PVDF), polystyrene resin, chloropolystyrene resin, poly-alpha -Methylstyrene resin, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-acrylic) Acid methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer Polymer (eg, styrene-methyl methacrylate copolymer) Styrene resins such as styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylate copolymer, etc. Or a styrene-substituted monopolymer or copolymer), methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (for example, silicone-modified acrylic resin, vinyl chloride resin-modified) Acrylic resin, acrylic-urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyethylene resin, polypropylene Resin, polybutadiene Emissions, polyvinylidene chloride resins, ionomer resins, polyurethane resins, silicone resins, ketone resins, ethylene - ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, polyamide resin and modified polyphenylene oxide resins. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as rubber | gum used for the said elastic belt, According to the objective, it can select suitably, For example, natural rubber, butyl rubber, fluorine-type rubber, acrylic rubber, EPDM rubber, NBR rubber, acrylonitrile-butadiene-styrene rubber , Isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydride Examples thereof include phosphorus rubber, silicone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, and hydrogenated nitrile rubber. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as an elastomer used for the said elastic belt, According to the objective, it can select suitably, For example, a polystyrene-type thermoplastic elastomer, a polyolefin-type thermoplastic elastomer, a polyvinyl chloride-type thermoplastic elastomer, a polyurethane-type thermoplasticity Examples thereof include elastomers, polyamide-based thermoplastic elastomers, polyurea thermoplastic elastomers, polyester-based thermoplastic elastomers, and fluorine-based thermoplastic elastomers. These may be used individually by 1 type and may use 2 or more types together.

  The conductive agent for adjusting the resistance value used in the elastic belt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, metal powder such as carbon black, graphite, aluminum, nickel; tin oxide, titanium oxide And conductive metal oxides such as antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), and indium oxide-tin oxide composite oxide (ITO). The conductive metal oxide may be coated with insulating fine particles such as barium sulfate, magnesium silicate, and calcium carbonate.

  In addition, the surface layer of the elastic belt prevents contamination of the electrostatic latent image carrier by the elastic material, reduces the frictional resistance of the belt surface, reduces the adhesion of the toner, and improves the cleaning property and the secondary transfer property. What can do is preferable. The surface layer is made of, for example, a binder resin such as a polyurethane resin, a polyester resin, or an epoxy resin, and a material capable of increasing the lubricity by reducing the surface energy, such as a fluororesin, a fluorine compound, a fluorocarbon, titanium dioxide, a silicon car It is preferable to contain powder or particles such as bites. Further, it is possible to use a material having a reduced surface energy by forming a fluorine-rich surface layer by heat treatment, such as a fluorine-based rubber material.

  There is no restriction | limiting in particular as a manufacturing method of the said elastic belt, Although it can select suitably according to the objective, For example, (1) Centrifugal molding method which pours material into a rotating cylindrical type | mold and forms a belt, ( 2) Spray coating method to form a film by spraying a liquid paint, (3) Dipping method in which a cylindrical mold is dipped in a solution of the material, and (4) Casting to be injected into an inner mold or an outer mold And (5) a method in which a compound is wound around a cylindrical mold and vulcanized and polished.

The method for preventing the elastic belt from stretching is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) a method of adding a material for preventing elongation to the core layer, 2) A method of forming a rubber layer on a core layer with little elongation, and the like.
There is no restriction | limiting in particular as a material which prevents the said elongation, Although it can select suitably according to the objective, For example, natural fibers, such as cotton and silk; Polyester fiber, nylon fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol Synthetic fibers such as fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers and phenol fibers; inorganic fibers such as carbon fibers, glass fibers and boron fibers; iron fibers, copper fibers, etc. A metal fiber etc. are mentioned, What made these materials into the shape of a woven fabric or a thread form is used suitably.

The method for forming the core layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) a woven fabric woven in a cylindrical shape is covered with a mold or the like and coated thereon (2) A method of providing a covering layer on one or both sides of a core layer by immersing a woven fabric woven in a cylindrical shape in liquid rubber or the like, and (3) a thread on a mold or the like at an arbitrary pitch. For example, a method of winding in a spiral shape and providing a coating layer thereon may be used.
The thickness of the coating layer depends on the hardness of the coating layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur in the surface layer. Further, since the amount of expansion / contraction increases and the expansion and contraction of the image increase, it is not preferable that the thickness is too thick (about 1 mm or more).

The transfer means (the primary transfer means, 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 an unfixed image after development can be transferred, and can be appropriately selected according to the purpose. A PET base for OHP Etc. 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 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and 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 unit is not particularly limited, and may be selected from known cleaners as long as it can remove the toner remaining on the electrostatic latent image carrier. For example, a magnetic brush cleaner Suitable examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the toner removed by 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 means is a process for controlling the steps, and can be suitably performed by the control means.
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.

  Next, 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. 3 includes a photosensitive drum 10 as the electrostatic latent image carrier, a charging roller 20 as the charging unit, an exposure device 30 as the exposure unit, and a developing unit. A developing device 40, an intermediate transfer member 50, a cleaning device 60 as the cleaning unit having a cleaning blade, and a static elimination lamp 70 as the static elimination unit.

  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 the transfer means capable of applying a transfer bias for transferring (secondary transfer) a transfer image to the recording medium 95. The transfer roller 80 is arranged so as to be opposed. 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 connected to the electrostatic latent image carrier 10 and the intermediate transfer member in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion with the body 50 and the contact portion between the intermediate transfer member 50 and the recording medium 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. Further, 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 electrostatic latent image carrier 10.

  In the image forming apparatus 100 shown in FIG. 3, for example, the charging roller 20 uniformly charges the photosensitive drum 10. 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 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 recording medium 95. As a result, a transfer image is formed on the recording medium 95. The residual toner on the electrostatic latent image carrier 10 is removed by the cleaning device 60, and the charge on the electrostatic latent image carrier 10 is once removed by the static elimination 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. 4 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 3, and a black developing unit 45K, a yellow developing unit 45Y, and a magenta are disposed around the electrostatic latent image carrier 10. Except that the developing unit 45M and the cyan developing unit 45C are directly opposed to each other, they have the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 4, the same components as those in FIG. 3 are denoted by the same reference numerals.

Next, a tandem type image forming apparatus that performs the image forming method of the present invention using the image forming apparatus of the present invention will be described.
The tandem type image forming apparatus has a plurality of image forming elements including at least an electrostatic latent image carrier, a charging unit, a developing unit, and a transfer unit. In this tandem type image forming apparatus, four image forming elements for yellow, magenta, cyan, and black are mounted, and each visible image is created in parallel by the four image forming elements, and is recorded on a recording medium or an intermediate transfer member. Therefore, a full color image can be formed at a higher speed.

  As the tandem type image forming apparatus, (1) as shown in FIG. 5, the surface moves so as to pass through a transfer position that is a region facing each electrostatic latent image carrier 1 of a plurality of image forming elements. A direct transfer system in which the visible image formed on each electrostatic latent image carrier 1 is sequentially transferred to the recording medium S by the transfer means 2, and (2) a plurality of images as shown in FIG. The visible image on each electrostatic latent image carrier 1 of the forming element is once transferred sequentially to the intermediate transfer body 4 by the transfer means (primary transfer means) 2, and then the image on the intermediate transfer body 4 is transferred to the secondary transfer means 5. There is an indirect transfer method in which the image is transferred to the recording medium S at once. In FIG. 6, a transfer conveyance belt is used as the secondary transfer unit, but a roller shape may be used.

Comparing the direct transfer method (1) and the indirect transfer method (2), the direct transfer method (1) is a tandem type image forming unit T in which the electrostatic latent image carriers 1 are arranged. The sheet feeding device 6 must be disposed on the upstream side, and the fixing device 7 serving as a fixing unit must be disposed on the downstream side, which increases the size of the recording medium in the conveying direction. On the other hand, in the indirect transfer method (2), the secondary transfer position can be set relatively freely, and the paper feeding device 6 and the fixing device 7 are arranged so as to overlap the tandem type image forming unit T. There is an advantage that downsizing is possible.
In the direct transfer method (1), the fixing device 7 is disposed close to the tandem image forming unit T in order not to increase the size in the recording medium conveyance direction. Therefore, the fixing device 7 cannot be disposed with a sufficient margin that the recording medium S can bend, and an impact when the leading end of the recording medium S enters the fixing device 7 (particularly with a thick recording medium). In addition, the fixing device 7 tends to affect upstream image formation due to the speed difference between the recording medium conveyance speed when passing through the fixing device 7 and the recording medium conveyance speed by the transfer conveyance belt. On the other hand, in the indirect transfer method (2), the fixing device 7 can be arranged with a sufficient margin that the recording medium S can be bent, and therefore the fixing device 7 hardly affects the image formation.
For these reasons, indirect transfer systems have recently attracted attention. In this type of color image forming apparatus, as shown in FIG. 6, the transfer residual toner remaining on the electrostatic latent image carrier 1 after the primary transfer is removed by a cleaning device 8 serving as a cleaning unit, and the electrostatic latent image is thus removed. The surface of the carrier 1 is cleaned to prepare for the image formation again. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

The tandem image forming apparatus shown in FIG. 7 is a tandem 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. 7. 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 body 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming means 18 of yellow, cyan, magenta, and black are arranged in parallel and facing 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 recording medium conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22.
In the vicinity of the secondary transfer device 22 and the fixing device 25, a sheet reversing device 28 for reversing the recording medium for image formation on both sides of the recording medium is disposed.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 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.

  The black, yellow, magenta, and cyan image information is obtained from each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image forming unit) in the tandem developing device 120. Each image forming unit forms black, yellow, magenta, and cyan toner images. 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 developing device 120 is respectively shown in FIG. Electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image carrier is uniformly charged, and the electrostatic latent image carrier is exposed (L in FIG. 8) for each color image corresponding to each color image information. An exposure device (not shown) for forming an electrostatic latent image corresponding to each color image on the photoconductor, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) on the electrostatic latent image. Develop with A developing device 61 for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a charge eliminating device 64 are provided. Each single color image (black image, yellow image, magenta image, and cyan image) can be formed based on the color image information. The black image, the yellow image, the magenta image, and the cyan image formed in this manner are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15 and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on the body 10C is sequentially transferred (primary transfer). 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 the recording medium from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper 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 to stop. Alternatively, the sheet feeding roller 142 is rotated to feed out the recording medium on the manual feed tray 54, separated one by one by the separation roller 145, 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 time with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and the recording medium is sent between the intermediate transfer member 50 and the secondary transfer device 22. Then, by transferring (secondary transfer) the composite color image (color transfer image) onto the recording medium by the secondary transfer device 22, a color image is transferred and formed on the recording medium. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The recording medium 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 transfer image) is generated by heat and pressure. ) Is fixed on the recording medium. Thereafter, the recording medium is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the paper discharge tray 57. Alternatively, the recording medium is switched by the switching claw 55 and reversed by the sheet reversing device 28 to return to the transfer position. After guiding and recording an image on the back side, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming method and the image forming apparatus of the present invention, the present invention has a stable volume average particle diameter and a sharp particle size distribution, can faithfully develop an electrostatic latent image, and can prevent the occurrence of background stains. Therefore, a high-quality full-color image can be formed.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples and comparative examples, the oil phase viscosity characteristics, specific gravity, toner volume average particle diameter (Dv) and particle size distribution (Dv / Dn), mass average molecular weight of polyester resin, acid value, amine value The measurement of was performed as follows.

<Method of measuring oil phase viscosity characteristics of dissolved or dispersed>
The viscosity characteristics tanθ and Casson yield value of the dissolved or dispersed material were measured under the following conditions using a high shear viscometer.
〔Measurement condition〕
・ Device: AR2000 (TA Instruments)
・ Shear stress: 120 Pa / 5 min ・ Geometry: 40 mm steel plate ・ Geometry gap: 1 mm
・ Analysis software: TA DATA ANALYSIS (TA Instruments)

The Casson yield value (stress yield value Pa) is an extrapolation point of s ⁻¹ = 0 of the shear rates s ⁻¹ = 1 and s ⁻¹ = 2 from the Casson flow equation. The range of shear rate on measurement is ^{0 s −1 to} 300 s ⁻¹ .
The viscosity characteristic tan θ measures the flow curve of the oil phase. Conditions GAP is a 0.5mm at 25 ° C., measurement range, shear rate and ^{0s -1 → 1800s -1 → 0s -1} .
The viscosity characteristic tan θ can be obtained from the shear rate s ⁻¹ and the Log-Log graph of the shear stress. The range of shear rate is at ^{0s -1 ~2000s} -1.
The apparent viscosity indicates “P / 100” when the shear stress value at a shear rate of 100 s ⁻¹ is P.
The viscosity ratio indicates a ratio between the apparent viscosity at a shear rate of 100 s ^{−1 and} the apparent viscosity at a shear rate of 1000 s ⁻¹ .
Further, the recovery rate of the structural viscosity is defined as a shear stress value of ^{0 s −1} → 1800 s ^{−1 in} the oil phase flow curve, and a shear stress value of 1800 s ⁻¹ → ⁰ s ⁻¹ in the shear rate. Assuming P2, “P2 / P1” is indicated.

<Method for Measuring Acid Value and Amine Value of Dissolved or Dispersed>
Specifically, the acid value and amine value of the dissolved or dispersed material were determined by the following procedure. However, when the sample did not dissolve, a solvent such as dioxane or THF was used as the solvent.
・ Measuring device: potentiometric automatic titrator DL-53 Titrator (Metler Toledo)
-Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
・ Analysis software: LabX Light Version1.00.000
-Calibration of apparatus: A mixed solvent of 120 ml of toluene and 30 ml of ethanol was used.
・ Measurement temperature: 23 ℃
Specific measurement conditions are as follows.
Stir
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
Measure 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
Steepest 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
Potential 2 No
Stop for reevaluation No

-Method of measuring acid value-
The acid value was measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner was added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Furthermore, 30 ml of ethanol was added to prepare a sample solution.
The acid value can be calculated using the above conditions and apparatus. Specifically, the acid value was calculated as follows.
Titration was performed using N / 10 caustic potassium-alcohol solution standardized in advance, and the acid value was determined from the consumption amount of the alcohol potassium solution by the following formula.
Acid value = KOH (ml number) × N × 56.1 / sample mass where N is a factor of (N / 10) KOH.

-Method for measuring amine value-
The measurement of the amine value can be calculated using the above conditions and apparatus. Specifically, the amine value was calculated as follows.
Titration was carried out with a previously evaluated N / 10 hydrochloric acid-alcohol solution, and the amine value was determined from the consumption of hydrochloric acid-alcohol solution by the following formula.
Amine number = HCl (ml number) × N × 56.1 / sample mass where N is a factor of (N / 10) HCl.

<Measurement of specific gravity of dissolved or dispersed material>
The specific gravity of the dissolved or dispersed material was measured with an “Oval Coriolis flow meter” installed as a flow meter.

<Measurement of Volume Average Particle Size (Dv) and Particle Size Distribution (Dv / Dn) of Toner>
The volume average particle size and particle size distribution of the toner were analyzed using a Coulter Multisizer III (manufactured by Coulter), connected to a personal computer (manufactured by IBM) and using dedicated analysis software (manufactured by Coulter). A standard particle having a particle diameter of 10 μm was set, and the aperture current was set at an automatic setting. As the electrolytic solution, a 1% by mass NaCl aqueous solution is prepared using first grade sodium chloride. In addition, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant (alkyl benzene sulfonate) was added as a dispersant to 100 to 150 ml of an electrolytic aqueous solution, and 2 to 20 mg of a measurement sample was further added. The electrolyte in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and a volume distribution (Dv) is measured by measuring 50,000 counts of the volume and number of toners of 2 μm or more using a 100 μm aperture tube. ) And number distribution (Dn). Then, the volume-based volume average particle size obtained from the volume distribution and the number-based number average particle size obtained from the number distribution were obtained.

<Measurement of mass average molecular weight of polyester resin>
The mass average molecular weight of the polyester resin was measured by GPC (gel permeation chromatography) under the following conditions.
・ Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Sample: 0.1 mL of a sample having a concentration of 0.05 to 0.6% was injected.
From the molecular weight distribution of the polyester resin measured under the above conditions, the weight average molecular weight of the polyester resin was calculated using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. In the case of an isocyanate terminal-modified polyester resin, a sample in which n-dibutylamine in an amount 3 times the amount of isocyanate groups present in the polyester resin was added and the isocyanate terminal was sealed was used.

(Example 1)
<Preparation of Toner 1>
-Synthesis of low molecular weight polyester 1-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propylene oxide 3-mole adduct, 208 parts by mass of terephthalic acid, adipic acid 46 parts by mass and 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after 5 hours of reaction under reduced pressure of 10 to 15 mmHg, 44 parts by weight of trimellitic anhydride was placed in the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to synthesize “low molecular weight polyester 1”. did. The obtained [Low molecular weight polyester 1] had a number average molecular weight of 2,500, a weight average molecular weight of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25 mgKOH / g.

-Production of master batch (MB) 1-
1,200 parts by weight of water, 540 parts of carbon black (Printex 35, manufactured by Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1,200 parts by weight of polyester resin were added, and Henschel mixer (Mitsui Mining Co., Ltd.) (Made by company). The obtained mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer to prepare “masterbatch 1”.

-Synthesis of ketimine compound (extender) 1-
170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone (MEK) were charged in a reaction vessel in which a stir bar and a thermometer were set, and reacted at 50 ° C. for 5 hours to synthesize “ketimine compound 1”. The amine value of the obtained “ketimine compound 1” was 418 mgKOH / g.

-Production of oil phase 1-
In a container in which a stir bar and a thermometer are set, 378 parts by mass of “low molecular polyester 1”, 110 parts by mass of carnauba wax, charge control agent (CCA, salicylic acid metal complex E-84, manufactured by Orient Chemical Industry Co., Ltd.) 22 A mass part and 947 parts by mass of ethyl acetate were charged, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts by mass of “Masterbatch 1” and 500 parts by mass of ethyl acetate were charged in the container and mixed for 1 hour to obtain “raw material solution 1”.
1,324 parts by mass of the obtained “raw material solution 1” was transferred into a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, Filled with 80% by volume of 5 mm zirconia beads, carbon black and carnauba wax were dispersed under conditions of 3 passes. Subsequently, 1,324 parts by mass of a 65% by mass ethyl acetate solution of “low molecular polyester 1” was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment and Wax Dispersion 1]. The resulting “pigment and wax dispersion 1” had a solid content concentration (130 ° C., 30 minutes) of 50 mass%.
Next, 749 parts by mass of “Pigment and Wax Dispersion 1” and 2.9 parts by mass of “Ketimine Compound 1” are placed in a container and 5,000 rpm using a homodisper (manufactured by Koki Kogyo Co., Ltd.). For 15 minutes. Thus, “A oil phase 1” was produced.

-Preparation of oil phase 1-
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, anhydrous Put 22 parts by weight trimellitic acid and 2 parts by weight dibutyltin oxide, react under normal pressure at 230 ° C. for 8 hours, and then react under reduced pressure of 10-15 mmHg for 5 hours to synthesize “intermediate polyester 1” did. The obtained “intermediate polyester 1” had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g. .
Next, 410 parts by mass of “Intermediate Polyester 1”, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. By reacting for a time, "Prepolymer 1" was synthesized. The obtained “Prepolymer 1” had a free isocyanate mass% of 1.53%. Thus, “B oil phase 1” was produced.

-Preparation of aqueous phase 1-
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 83 parts by mass of styrene Part, 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to vinyl resin (a copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) An aqueous dispersion (“fine particle dispersion 1”) was obtained.
The obtained “fine particle dispersion 1” was measured with a particle size distribution analyzer (LA-920, manufactured by HORIBA, Ltd.), and the volume average particle size was 105 nm. Further, a part of [Fine Particle Dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 59 ° C., and the mass average molecular weight was 150,000.
Next, 83 parts by weight of “Fine Particle Dispersion 1”, 990 parts by weight of water, 37 parts by weight of 48.5% by weight aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.), and ethyl acetate 90 parts by mass were mixed and stirred to obtain a milky white liquid. This is designated as “aqueous phase 1”.

-Emulsification process-
Using 60.4 parts by mass of “A oil phase 1”, 7.4 parts by mass of “B oil phase 1”, and 101.6 parts by mass of “aqueous phase 1”, the shear peripheral speed of the emulsifier is 17. An emulsion was formed at 0 m. When the physical properties of the dissolved or dispersed (oil phase) composed of “A oil phase 1” and “B oil phase 1” before being sheared by the emulsifier (after pre-stirring) were measured, the following results were obtained. It was.
Viscosity characteristics tan θ (25 ° C.): 0.92
・ Apparent viscosity by high shear viscometer: 250 mPa · s
・ Viscosity ratio: 1.7
・ Recovery rate of structural viscosity: 95%
Casson yield value: 6.0
-Acid value of the dispersion: 11.0 mg KOH / g
-Amine value of the dispersion: 4.5 mg KOH / g
-Solid content conversion value of dispersion: 40% by mass
-Dispersion / aqueous medium Mass ratio: 40/60
Specific gravity of dispersion ρ1 / Specific gravity of aqueous medium ρ2: 0.97

-Preparation of toner-
The obtained emulsified dispersion was heated to 45 ° C., and the solvent was removed at a stirring blade outer peripheral end peripheral speed of 10.5 m / s under atmospheric pressure (101.3 kPa). The solvent removal time required 20 hours. Then, it was filtered, washed and dried to produce “toner base particle 1”.
100 parts by mass of the obtained “toner base particle 1” and 0.25 part by mass of a charge control agent (Orient Chemical Co., Ltd., Bontron E-84) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and a turbine type The peripheral speed of the blades was set to 50 m / sec, the operation was performed for 2 minutes, and the suspension for 1 minute was performed for 5 cycles for a total of 10 minutes.
Next, 0.5 part by mass of hydrophobic silica (H2000, manufactured by Clariant Japan Co., Ltd.) was added, the peripheral speed was 15 m / sec, mixing was performed for 30 seconds, and 1 minute rest was performed for 5 cycles. Further, 0.5 part by mass of hydrophobic silica and 0.5 part by mass of hydrophobic titanium oxide were mixed with a Henschel mixer, and coarse particles were removed with a screen having a mesh opening of 37 μm to produce the black toner of Example 1. did.

(Example 2)
<Preparation of Toner 2>
In Example 1, “A oil phase 2” was prepared in the same manner as in Example 1, except that “Preparation of A oil phase 1” was changed to “Preparation of A oil phase 2” described below.

-Preparation of oil phase 2-
In a container in which a stir bar and a thermometer are set, 378 parts by mass of “low molecular polyester 1”, 110 parts by mass of carnauba wax, charge control agent (CCA, salicylic acid metal complex E-84, manufactured by Orient Chemical Industry Co., Ltd.) 22 A mass part and 947 parts by mass of ethyl acetate were charged, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts by mass of “Masterbatch 1” and 500 parts by mass of ethyl acetate were charged in the container and mixed for 1 hour to obtain “raw material solution 1”.
1,324 parts by mass of the obtained “raw material solution 1” was transferred into a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, Filled with 80% by volume of 5 mm zirconia beads, carbon black and wax were dispersed under conditions of 3 passes. Next, 1,324 parts by mass of a 65% by weight ethyl acetate solution of “low molecular weight polyester 1” was added, and one pass was performed with a bead mill under the above conditions to obtain “pigment and wax dispersion 1” (“pigment and wax dispersion 1”). The solid content concentration (130 ° C., 30 minutes) was 50% by mass).
749 parts by mass of the obtained “pigment and wax dispersion 1” and 3.5 parts by mass of “ketimine compound 1” are placed in a container and mixed at 3,000 rpm for 15 minutes using an Ebara Milder (manufactured by Ebara Seisakusho). did. Thus, “A oil phase 2” was produced.

-Emulsification process-
Using 68.0 parts by mass of “A oil phase 2”, 8.3 parts by mass of “B oil phase 1”, and 93.1 parts by mass of “aqueous phase 1”, the shear peripheral speed of the emulsifier is 17. An emulsion was formed at 0 m. When the physical properties of the dissolved or dispersed (oil phase) composed of “A oil phase 2” and “B oil phase 1” before being sheared by the emulsifier (after pre-stirring) were measured, the following results were obtained. It was.
Viscosity characteristics tan θ (25 ° C.): 0.90
-Apparent viscosity with high shear viscometer: 300 mPa · s
・ Viscosity ratio: 1.5
・ Recovery rate of structural viscosity: 95%
Casson yield value: 6.0
-Acid value of the dispersion: 11.0 mg KOH / g
-Amine number of the dispersion: 5.4 mg KOH / g
-Solid content conversion value of dispersion: 40% by mass
-Dispersion / aqueous medium Mass ratio: 45/55
Specific gravity of dispersion ρ1 / Specific gravity of aqueous medium ρ2: 0.98

-Preparation of toner-
Thereafter, a black toner of Example 2 was produced in the same manner as Example 1.

(Example 3)
<Preparation of Toner 3>
In Example 1, “A oil phase 3” was prepared in the same manner as in Example 1, except that “Preparation of oil phase A 1” was changed to “Preparation of oil phase A 3” described below.

-Preparation of oil phase 3-
In a container in which a stir bar and a thermometer are set, 378 parts by mass of “low molecular polyester 1”, 110 parts by mass of carnauba wax, charge control agent (CCA, salicylic acid metal complex E-84, manufactured by Orient Chemical Industry Co., Ltd.) 22 A mass part and 947 parts by mass of ethyl acetate were charged, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts by mass of “Masterbatch 1” and 500 parts by mass of ethyl acetate were charged into the container and mixed for 1 hour to obtain “raw material solution 1”.
1,324 parts by mass of the obtained “raw material solution 1” was transferred into a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, Filled with 80% by volume of 5 mm zirconia beads, carbon black and wax were dispersed under conditions of 3 passes. Next, 1,324 parts by mass of a 65% by mass ethyl acetate solution of “low molecular polyester 1” was added, and the mixture was passed once with a bead mill under the above conditions to obtain “pigment and wax dispersion 1”. The resulting “pigment and wax dispersion 1” had a solid content concentration (130 ° C., 30 minutes) of 50 mass%.
749 parts by mass of the obtained “pigment and wax dispersion 1” and 3.5 parts by mass of “ketimine compound 1” were placed in a container, and 15% at 3,000 rpm using a homomixer (made by Tokushu Kika Kogyo Co., Ltd.). Mixed for minutes. Thus, “A oil phase 3” was produced.

-Emulsification process-
Using 52.9 parts by mass of “A oil phase 3”, 6.5 parts by mass of “B oil phase 1”, and 110.1 parts by mass of “aqueous phase 1”, the shear peripheral speed of the emulsifier is 17. The emulsion was formed at 0 m. When the physical properties of the dissolved or dispersed (oil phase) composed of “A oil phase 3” and “B oil phase 1” before being sheared by the emulsifier (after pre-stirring) were measured, the following results were obtained. It was.
Viscosity characteristics tan θ (25 ° C.): 0.91
-Apparent viscosity with high shear viscometer: 350 mPa · s
・ Viscosity ratio: 2.0
・ Recovery rate of structural viscosity: 93%
Casson yield value: 7.0
-Acid value of the dispersion: 11.0 mg KOH / g
-Amine number of the dispersion: 5.4 mg KOH / g
-Solid content conversion value of dispersion: 40% by mass
-Dispersion / aqueous medium Mass ratio: 35/65
Specific gravity of dispersion ρ1 / Specific gravity of aqueous medium ρ2: 0.98

-Preparation of toner-
Thereafter, a black toner of Example 3 was produced in the same manner as Example 1.

Example 4
<Preparation of Toner 4>
-Production of master batch (MB) 2-
1,200 parts by weight of water, C.I. I. Pigment Yellow 4G (PY 4G) (manufactured by Clariant, trade name: Novoperm Yellow 4G) 540 parts by mass and 1,200 parts by mass of polyester resin were added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to produce “masterbatch 2”.

-Production of oil phase 4-
In a container in which a stir bar and a thermometer are set, 378 parts by mass of “low molecular polyester 1”, 110 parts by mass of carnauba wax, charge control agent (CCA, salicylic acid metal complex E-84, manufactured by Orient Chemical Industry Co., Ltd.) 22 A mass part and 947 parts by mass of ethyl acetate were charged, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts by mass of “Masterbatch 2” and 500 parts by mass of ethyl acetate were charged into the container and mixed for 1 hour to obtain “raw material solution 1”.
1,324 parts by mass of the obtained “raw material solution 1” was transferred into a container, and a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.) was used. Filled with 80% by volume of 5 mm zirconia beads, under conditions of 3 passes, C.I. I. Pigment Yellow 4G and wax were dispersed. Next, 1,324 parts by mass of a 65% by mass ethyl acetate solution of “low molecular polyester 1” was added, and the mixture was passed once with a bead mill under the above conditions to obtain “pigment and wax dispersion 1”. The resulting “pigment and wax dispersion 1” had a solid content concentration (130 ° C., 30 minutes) of 50 mass%.
749 parts by mass of the obtained “pigment and wax dispersion 1” and 3.5 parts by mass of “ketimine compound 1” were placed in a container, and 3,000 rpm using a homomixer (manufactured by Koki Kogyo Co., Ltd.). For 15 minutes. Thus, “A oil phase 4” was produced.

-Emulsification process-
Using 52.9 parts by mass of “A oil phase 4”, 6.5 parts by mass of “B oil phase 1”, and 110.1 parts by mass of “aqueous phase 1”, the shear peripheral speed of the emulsifier is 17. An emulsion was formed at 0 m. When the physical properties of the dissolved or dispersed (oil phase) composed of “A oil phase 4” and “B oil phase 1” before being sheared by the emulsifier (after pre-stirring) were measured, the following results were obtained. It was.
Viscosity characteristics tan θ (25 ° C.): 0.88
・ Apparent viscosity by high shear viscometer: 380 mPa · s
-Viscosity ratio: 1.6
・ Recovery rate of structural viscosity: 92%
Casson yield value: 8.5
-Acid value of the dispersion: 11.0 mg KOH / g
-Amine number of the dispersion: 5.4 mg KOH / g
-Solid content conversion value of dispersion: 40% by mass
-Dispersion / aqueous medium Mass ratio: 35/65
Specific gravity of dispersion ρ1 / Specific gravity of aqueous medium ρ2: 0.96

-Preparation of toner-
Thereafter, the yellow toner of Example 4 was produced in the same manner as in Example 1.

(Example 5)
-Production of Toner 5-
In Example 4, 60.4 parts by mass of “A oil phase 4”, 7.4 parts by mass of “B oil phase 1”, and 101.6 parts by mass of “aqueous phase 1” were emulsified in the emulsification step. The shear peripheral speed of the machine was 17.0 m and an emulsion was formed. When the physical properties of the dissolved or dispersed (oil phase) composed of “A oil phase 4” and “B oil phase 1” before being sheared by the emulsifier (after pre-stirring) were measured, the following results were obtained. It was.
Viscosity characteristics tan θ (25 ° C.): 0.88
・ Apparent viscosity by high shear viscometer: 380 mPa · s
・ Viscosity ratio: 1.7
・ Recovery rate of structural viscosity: 92%
Casson yield value: 8.5
-Acid value of the dispersion: 11.0 mg KOH / g
-Amine number of the dispersion: 5.4 mg KOH / g
-Solid content conversion value of dispersion: 40% by mass
-Dispersion / aqueous medium Mass ratio: 40/60
Specific gravity of dispersion ρ1 / Specific gravity of aqueous medium ρ2: 0.96

-Preparation of toner-
Thereafter, a yellow toner of Example 5 was produced in the same manner as in Example 1.

(Example 6)
<Preparation of Toner 6>
-Production of master batch (MB) 3-
1,200 parts by weight of water, C.I. I. Pigment Red 1022 (PR 1022) (Dainippon Ink Chemical Co., Ltd., trade name: TOSHIKI RED 1022) 540 parts by mass and polyester resin 1,200 parts by mass are added and mixed with a Henschel mixer (Mitsui Mining Co., Ltd.). Then, the obtained mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then cooled by rolling and pulverized with a pulverizer to prepare “masterbatch 3”.

-Preparation of oil phase 6-
In a container in which a stir bar and a thermometer are set, 378 parts by mass of “low molecular polyester 1”, 110 parts by mass of carnauba wax, charge control agent (CCA, salicylic acid metal complex E-84, manufactured by Orient Chemical Industry Co., Ltd.) 22 A mass part and 947 parts by mass of ethyl acetate were charged, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts by mass of “Masterbatch 3” and 500 parts by mass of ethyl acetate were charged into the container and mixed for 1 hour to obtain “Raw material solution 1”.
1,324 parts by mass of the obtained “raw material solution 1” was transferred into a container, and a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.) was used. Filled with 80% by volume of 5 mm zirconia beads, under conditions of 3 passes, C.I. I. Pigment Red 1022 and wax dispersion. Next, 1,324 parts by mass of a 65% by mass ethyl acetate solution of “low molecular polyester 1” was added, and the mixture was passed once with a bead mill under the above conditions to obtain “pigment and wax dispersion 1”. The obtained “pigment and wax dispersion 1” had a solid content concentration (130 ° C., 30 minutes) of 50 mass%.
749 parts by mass of the obtained “pigment and wax dispersion 1” and 3.5 parts by mass of “ketimine compound 1” are put in a container, and 3,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Mix for 15 minutes. Thus, “A oil phase 6” was produced.

-Emulsification process-
Using 52.9 parts by mass of “A oil phase 6”, 6.5 parts by mass of “B oil phase 1”, and 110.1 parts by mass of “aqueous phase 1”, the shear peripheral speed of the emulsifier is 17. An emulsion was formed at 0 m. When the physical properties of the dissolved or dispersed (oil phase) composed of “A oil phase 6” and “B oil phase 1” before being sheared by the emulsifier (after pre-stirring) were measured, the following results were obtained. It was.
Viscosity characteristics tan θ (25 ° C.): 0.89
-Apparent viscosity with high shear viscometer: 350 mPa · s
・ Viscosity ratio: 1.8
・ Recovery rate of structural viscosity: 91%
Casson yield value: 8.5
-Acid value of the dispersion: 11.0 mg KOH / g
-Amine number of the dispersion: 5.4 mg KOH / g
-Solid content conversion value of dispersion: 40% by mass
-Dispersion / aqueous medium Mass ratio: 35/65
Specific gravity of dispersion ρ1 / Specific gravity of aqueous medium ρ2: 0.96

-Preparation of toner-
Thereafter, the magenta toner of Example 6 was produced in the same manner as in Example 1.

(Example 7)
<Preparation of Toner 7>
In Example 6, “mixing for 15 minutes at 3,000 rpm using a homomixer (made by Tokushu Kika Kogyo Co., Ltd.)” to “mixing for 15 minutes at 3,000 rpm using an Ebara Milder (made by Ebara Seisakusho)” Except having changed, it carried out similarly to Example 6, and produced "A oil phase 7".

-Emulsification process-
Using 52.9 parts by mass of “A oil phase 7”, 6.5 parts by mass of “B oil phase 1”, and 110.1 parts by mass of “aqueous phase 1”, the shear peripheral speed of the emulsifier is 17. An emulsion was formed at 0 m. When the physical properties of the dissolved or dispersed (oil phase) composed of “A oil phase 7” and “B oil phase 1” before being sheared by the emulsifier (after pre-stirring) were measured, the following results were obtained. It was.
Viscosity characteristics tan θ (25 ° C.): 0.78
-Apparent viscosity with high shear viscometer: 180 mPa · s
Viscosity ratio: 1.85
・ Recovery rate of structural viscosity: 88%
-Casson yield value: 4.5
-Acid value of the dispersion: 11.0 mg KOH / g
-Amine number of the dispersion: 5.4 mg KOH / g
-Solid content conversion value of dispersion: 40% by mass
-Dispersion / aqueous medium Mass ratio: 35/65
Specific gravity of dispersion ρ1 / Specific gravity of aqueous medium ρ2: 0.96

-Preparation of toner-
Thereafter, in the same manner as in Example 1, the magenta toner of Example 7 was produced.

(Comparative Example 1)
<Preparation of Comparative Toner 1>
-Synthesis of low molecular weight polyester 2-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propylene oxide 3-mole adduct, 208 parts by mass of terephthalic acid, adipic acid 46 parts by mass and 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after 5 hours of reaction under reduced pressure of 10 to 15 mmHg, 64 parts by weight of trimellitic anhydride was placed in the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to synthesize “low molecular weight polyester 2”. did. The obtained “low molecular polyester 2” had a number average molecular weight of 2,600, a mass average molecular weight of 6,800, a glass transition temperature (Tg) of 43.2 ° C., and an acid value of 32.0 mgKOH / g.

  Next, in preparation of A oil phase 4 of Example 4, “3.5 parts by mass of“ ketimine compound 1 ”was put in a container, and at 3,000 rpm using a homomixer (made by Tokushu Kika Kogyo Co., Ltd.). Except that “mixing for 15 minutes” is changed to “mixing for 10 minutes at 2,000 rpm using a homomixer (made by Koki Kogyo Co., Ltd.)” by putting 1.5 parts by mass of “ketimine compound 1” in a container. In the same manner as in Example 4, “A oil phase 8” was produced.

-Emulsification process-
Using 45.3 parts by mass of “A oil phase 8”, 4.9 parts by mass of “B oil phase 1”, and 128.5 parts by mass of “aqueous phase 1”, the shear peripheral speed of the emulsifier is 17. An emulsion was formed at 0 m. When various properties of the dissolved or dispersed (oil phase) composed of “A oil phase 8” and “B oil phase 1” before being sheared by the emulsifier (after pre-stirring) were measured, the following results were obtained. It was.
Viscosity characteristics tan θ (25 ° C.): 0.96
-Apparent viscosity with high shear viscometer: 450 mPa · s
・ Viscosity ratio: 1.4
・ Recovery rate of structural viscosity: 85%
-Casson yield value: 4.5
-Acid value of the dispersion: 16.0 mg KOH / g
-Amine value of the dispersion: 2.3 mg KOH / g
-Solid content conversion value of dispersion: 35% by mass
-Dispersion / aqueous medium Mass ratio: 30/70
Specific gravity of dispersion ρ1 / Specific gravity of aqueous medium ρ2: 0.94

-Preparation of toner-
Thereafter, a yellow toner of Comparative Example 1 was produced in the same manner as in Example 1.

(Comparative Example 2)
<Preparation of Comparative Toner 2>
-Synthesis of low molecular weight polyester 3-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propylene oxide 3-mole adduct, 208 parts by mass of terephthalic acid, adipic acid 46 parts by mass and 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after 5 hours of reaction under reduced pressure of 10 to 15 mmHg, 16 parts by weight of trimellitic anhydride was put in the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to synthesize “low molecular weight polyester 3”. did. The obtained “low molecular weight polyester 3” had a number average molecular weight of 2,350, a weight average molecular weight of 6,500, a glass transition temperature (Tg) of 42.5 ° C., and an acid value of 32.0 mgKOH / g.

  Next, in preparation of A oil phase 4 of Example 4, “3.5 parts by mass of“ ketimine compound 1 ”was put in a container, and at 3,000 rpm using a homomixer (made by Tokushu Kika Kogyo Co., Ltd.). “Mixing for 15 minutes” was changed to “Mixing for 10 minutes at 2,000 rpm using Homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.)” by putting 1.5 parts by weight of “Ketimine Compound 1” in a container In the same manner as in Example 4, “A oil phase 9” was produced.

-Emulsification process-
Using 45.3 parts by mass of “A oil phase 9”, 4.9 parts by mass of “B oil phase 1”, and 128.5 parts by mass of “aqueous phase 1”, the shear peripheral speed of the emulsifier is 17. An emulsion was formed at 0 m. When the physical properties of the dissolved or dispersed (oil phase) composed of “A oil phase 9” and “B oil phase 1” before being sheared by the emulsifier (after pre-stirring) were measured, the following results were obtained. It was.
Viscosity characteristics tan θ (25 ° C.): 0.96
-Apparent viscosity with high shear viscometer: 90 mPa · s
・ Viscosity ratio: 1.4
・ Recovery rate of structural viscosity: 88%
-Casson yield value: 4.5
-Acid value of the dispersion: 16.0 mg KOH / g
-Amine value of the dispersion: 6.0 mg KOH / g
-Solid content conversion value of dispersion: 35% by mass
-Dispersion / aqueous medium Mass ratio: 30/70
Specific gravity of dispersion ρ1 / Specific gravity of aqueous medium ρ2: 0.94

-Preparation of toner-
Thereafter, a yellow toner of Comparative Example 2 was produced in the same manner as in Example 1.

  Next, for each of the obtained toners, image evaluation (thin line reproducibility) and charge amount were evaluated as follows. The results are shown in Tables 1 and 2.

<Image evaluation (fine line reproducibility)>
Each toner is put into a remodeling machine from which the fixing oil portion of an intermediate transfer type color copying machine (IMAGIO COLOR 5000, manufactured by Ricoh Co., Ltd.) has been removed, and 6000 paper manufactured by Ricoh Co., Ltd. is printed with a printing ratio of 7%. Running was performed using. Compare the original 10th image and the 30,000th image of the thin line with the original, and zoom in at 100x using an optical microscope. It was evaluated with. A rating of 1 to 5 is the best. In addition, 3.5 or more is set as a pass.

<Measurement of charge amount>
A developer was prepared by mixing 60 g of ferrite carrier and 3 g of toner, and 6 g of the developer was weighed, charged into a metal cylinder that could be sealed, and blown to determine the charge amount. The toner concentration was adjusted to 4.5 to 5.5% by mass. The optimum range of the charge amount is −35 ± 4 μC / g.

From the results of Tables 1 and 2, it can be seen that Examples 1-7 have a proper toner charge amount and good image evaluation (thin line reproducibility) as compared with Comparative Examples 1-2.
The image evaluation in Examples 4 and 5 is “4”, which is slightly inferior to the other examples because Dv / Dn is slightly poor at 1.21 and 1.22.

  The toner of the present invention manufactured by the toner manufacturing method of the present invention improves the chargeability, thereby preventing the occurrence of background stains, improving fine line reproducibility, and forming a high-quality full-color image. And widely applied to electrophotographic developers, toner-containing containers, process cartridges, image forming apparatuses, and the like.

FIG. 1 is a diagram showing an example of a continuous emulsification process in the toner production method of the present invention. FIG. 2 is a schematic configuration diagram showing an example of a process cartridge used in the present invention. FIG. 3 is a schematic configuration diagram showing an example of an image forming apparatus used in the image forming method of the present invention. FIG. 4 is a schematic configuration diagram showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 5 is a schematic configuration diagram showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 6 is a schematic configuration diagram showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 7 is a schematic configuration diagram showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 8 is a schematic enlarged view of the image forming element portion of FIG.

Explanation of symbols

1 Electrostatic latent image carrier (photosensitive drum)
DESCRIPTION OF SYMBOLS 2 Transfer apparatus 3 Sheet conveyance belt 4 Intermediate transfer body 5 Secondary transfer apparatus 6 Paper feed apparatus 7 Fixing apparatus 8 Cleaning apparatus 9 Intermediate transfer body cleaning apparatus 10 Electrostatic latent image carrier (photosensitive drum)
10K Electrostatic latent image carrier for black 10Y Electrostatic latent image carrier for yellow 10M Electrostatic latent image carrier for magenta 10C Electrostatic latent image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device DESCRIPTION OF SYMBOLS 18 Image forming means 20 Charging roller 21 Exposure apparatus 22 Secondary transfer apparatus 23 Roller 24 Secondary transfer belt 25 Fixing apparatus 26 Fixing belt 27 Pressure roller 28 Sheet reversing apparatus 30 Exposure apparatus 32 Contact glass 33 1st traveling body 34 2nd Traveling body 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 Development roller La 44Y Development roller 44M Development roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation 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 cleaning device 64 discharge device 70 discharge lamp 80 transfer roller 90 cleaning device 95 recording medium 100 image forming device 101 electrostatic latent image Carrier 102 Charging device 103 Exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem developer 130 Document table 142 Feed roller 143 Paper bank 1 44 Paper Feed Cassette 145 Separation Roller 146 Paper Feed Path 147 Transport Roller 148 Paper Feed Path 150 Copier Main Body 160 Charging Device 200 Paper Feed Table 210 Image Fixing Device 220 Heating Roller 230 Pressure Roller 300 Scanner 400 Automatic Document Feeder (ADF)

Claims (13)

An emulsification step of emulsifying or dispersing a solution or dispersion obtained by dissolving or dispersing a toner material containing at least two kinds of resins, a colorant, and a release agent in an organic solvent in an aqueous medium containing resin fine particles. A method for producing a toner containing at least
A toner characterized in that a viscosity characteristic tan θ at 25 ° C. of the dissolved or dispersed material is 0.70 to 0.95, and an apparent viscosity measured by a high shear viscometer of the dissolved or dispersed material is 100 to 400 mPa · s. Manufacturing method. The method for producing a toner according to claim 1, wherein the viscosity ratio of the dissolved or dispersed material represented by the following formula 1 using a high shear viscometer is 1.5 to 2.5.
<Formula 1>
Viscosity ratio = (apparent viscosity at 100 rpm) ÷ (apparent viscosity at 1,000 rpm)   The method for producing a toner according to claim 1, wherein the structural viscosity recovery rate of the dissolved or dispersed material is 90% or more.   The toner production method according to any one of claims 1 to 3, wherein a Casson yield value of the dissolved or dispersed material by a high shear viscometer is 5.0 to 10.0.   The method for producing a toner according to claim 1, wherein the acid value of the dissolved or dispersed material is 5.0 to 15.0 mg KOH / g.   The toner production method according to claim 1, wherein the amine value of the dissolved or dispersed material is 1.0 to 10.0 mg KOH / g.   The method for producing a toner according to any one of claims 1 to 6, wherein the concentration in terms of solid content of the dissolved or dispersed material is 40 to 60% by mass.   The method for producing a toner according to claim 1, wherein a mixing mass ratio of the dissolved or dispersed material and the aqueous medium (dissolved or dispersed: aqueous medium) is 50:50 to 30:70.   9. The method for producing a toner according to claim 1, wherein the ratio (ρ1 / ρ2) is 0.95 to 1.05, where ρ1 is a specific gravity of the dissolved or dispersed material and ρ2 is a specific gravity of the aqueous medium. .   The method for producing a toner according to claim 1, wherein the at least two resins are polyester resins having different weight average molecular weights.   A toner manufactured by the method for manufacturing a toner according to claim 1.   The volume average particle diameter is 3 to 10 µm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.05 to 1.25. Toner. 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 claim 11 to form a visible image An image forming method comprising: a developing step for forming the 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.