JP2003177568A - Dry toner, method for manufacturing the same, developing method and transfer method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner having high transferability and giving high image quality, a durable toner less liable to stick to a carrier and machine parts, having small particle diameter, free from ultrafine particles and having a narrow particle size distribution, a toner having such a shape that a residual toner after transfer can be cleaned with a simple device or a toner which retains the required particle diameter and particle size distribution by cubical shrinkage at 10-90% shrinkage rate in an aqueous medium with a solid fine particle dispersant and ensures both proper glossiness and releasability as a full color toner and to provide a method for manufacturing the same and a transfer method. <P>SOLUTION: (1) The dry toner has an average degree of circularity of 0.93-0.99 and ≤20 number % content of fine powder having ≤2 μm. (2) In the method for manufacturing the dry toner, a toner composition is dispersed in an aqueous medium with a solid fine particle dispersant, and after dispersion in the aqueous medium containing an organic solvent soluble in water, the toner composition is converted to particles through a cubical shrinkage step. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic recording,
Toner used as a developer for developing an electrostatic charge image in electrostatic printing, etc., and its manufacturing method. For details, refer to a copying machine using a direct or indirect electrophotographic developing system, a laser printer, a plain paper fax, etc. The present invention relates to a toner for electrophotography used in and a manufacturing method thereof. Further, a full-color copying machine using a direct or indirect electrophotographic multicolor image developing system, a full-color laser printer, an electrophotographic toner used for a full-color plain paper fax, etc., and a manufacturing method thereof,
It also relates to a toner developing method and a toner transferring method.

[0002]

2. Description of the Related Art Developers used in electrophotography, electrostatic recording, electrostatic printing, etc., are once attached to an image carrier such as a photoconductor on which an electrostatic image is formed in the developing process. Then, after being transferred from the photoconductor to a transfer medium such as transfer paper in the transfer step, it is fixed on the paper surface in the fixing step. At that time, as a developer for developing the electrostatic charge image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer not requiring a carrier (magnetic toner, Non-magnetic toner) is known. Conventionally, as dry toners used in electrophotography, electrostatic recording, electrostatic printing, etc., toner binders such as styrene resin and polyester which are melt-kneaded together with a colorant and finely pulverized are used.

In order to obtain a high-quality and high-quality image, an improvement has been attempted by reducing the particle size of the toner, but the particle shape is indefinite by the usual kneading and pulverizing method. However, even after the classification step, the ultrafine particles had a drawback that the particles had a strong adhesive force and remained attached to the toner having a target particle size and could not be classified.In the machine, stirring with a carrier in the developing section, When used as a component type developer, such ultrafine particles adhere to and adhere to carriers and machine parts due to contact stress caused by a developing roller, a toner supply roller, a layer thickness regulating blade, a friction charging blade, etc. There is a phenomenon that the image quality is deteriorated due to being embedded in the toner surface. Further, due to its shape, the fluidity as a powder is poor, a large amount of fluidization is required, and the filling rate into the toner bottle is low, which is an obstacle to compactness. Therefore, it is the present situation that the merit of reducing the particle size is not utilized. Further, the pulverization method has a limit of particle diameter, and cannot cope with further reduction in particle diameter.

Further, in order to form a full-color image, the process of transferring an image formed of multicolor toner from a photoconductor to a transfer medium or paper has become complicated, which is caused by an irregular shape such as pulverized toner. Due to such poor transferability, there are problems such as missing of a transferred image and a large amount of toner consumption for compensating for it. However, spherical toner
A device for removing toner remaining on the photoconductor or transfer medium (for example, cleaning blade or cleaning brush)
In that case, it cannot be removed and cleaning failure occurs. In addition, since it is spherical, the surface of the toner is exposed to the outside in all directions, so it is easy to be exposed to contact with a charging member such as a carrier or a charging blade, and an external additive on the toner surface or charge control existing on the outermost surface is controlled. There is a problem in durability such that the agent is easily embedded in the toner surface and the fluidity of the toner is directly reduced.

Therefore, there is an increasing demand to reduce the toner consumption by further improving the transfer efficiency to obtain a high-quality image with no missing image and to reduce the running cost. If the transfer efficiency is very good, there is no need for a cleaning unit to remove untransferred toner from the photoconductor or transfer medium, the size and cost of the device can be reduced, and waste toner can be eliminated. Because. Various spherical toner manufacturing methods have been devised in order to compensate for the drawbacks of the irregular shape effect. In the toner production method by suspension polymerization, only spherical toner can be produced, and since it is irregularly sheared during suspension and dispersion in water, ultrafine powder is easily generated, which makes it easy to clean, adhere to carriers and mechanical parts. The problem of has not been solved. On the other hand, in the toner production method by emulsion polymerization, it is possible to produce spherical particles from amorphous toner, but it is necessary to adjust the shape by heating in the post-treatment, and aggregation in water, ultrafine powder that does not aggregate during association remains. The problem of carrier contamination and sticking to mechanical parts due to such fine particles has not been solved.

[0006] As a method for solving these problems, Japanese Patent Application Laid-Open No. 2004-242242 discusses a method involving volume shrinkage called a polymer dissolution suspension method. In this method, the toner material is dispersed and dissolved in a volatile solvent such as an organic solvent having a low boiling point, and this is emulsified and made into droplets in an aqueous medium containing a dispersant, and then the volatile solvent is removed. At that time, when a solid fine particle dispersant which does not dissolve in the aqueous medium is selected as the dispersant, although volume contraction of the liquid droplets occurs, only irregular particles are obtained. Further, when the solid content in the solvent was increased in order to increase the productivity, the viscosity of the dispersed phase increased, and the resulting particles had a large particle size and their distribution was broad. On the contrary, when the molecular weight of the resin used was reduced to lower the viscosity of the dispersed phase, the fixability (particularly hot offset resistance) had to be sacrificed.

On the other hand, in Patent Document 2, the resin used in the polymer dissolution suspension method is made to have a low molecular weight to reduce the viscosity of the dispersed phase, facilitate emulsification, and improve the fixing property by causing a polymerization reaction in the particles. is doing. However, the shape of the particles was not adjusted to improve transferability and cleaning performance. In addition, since it is irregularly sheared during suspension and dispersion in water, ultrafine powder is likely to be generated, and the problem of sticking to carriers and mechanical parts has not yet been solved. Further, these dry toners are developed and transferred to paper and the like, and then fixed by being heated and melted by using a heat roll. At that time, if the temperature of the heat roll is too high, the toner will be excessively melted and fused to the heat roll (hot offset). Becomes a problem.

On the other hand, from the viewpoint of energy saving and downsizing of the apparatus, the hot offset generation temperature is higher (hot offset resistance) and the fixing temperature is lower (low temperature fixing property).
Toner is sought. Further, it is necessary that the toner has heat-resistant storability so that it does not block during storage and at ambient temperature in the apparatus. In particular, in full-color copying machines and full-color printers, the glossiness and color-mixing property of the image are required, so the toner must have a lower melt viscosity, and a sharp melt polyester type toner binder is used. However, since such a toner is apt to cause hot offset, it has been conventionally practiced to apply silicone oil or the like to a heat roll in a device for full color. However,
The method of applying the silicone oil to the heat roll requires an oil tank and an oil applying device, which makes the device complicated and large. It also causes deterioration of the heat roll, requiring maintenance at regular intervals. Further, the adhesion of oil to copy paper, OHP (overhead projector) film, and the like is unavoidable, and particularly in OHP, there is a problem of deterioration in color tone due to the adhered oil. Further, until now, there has been no attempt to control the shape by paying attention to the volumetric shrinkage rate when a solid fine particle dispersant that has an important influence on the shape is used.

[0009]

[Patent Document 1] JP-A-7-152202

[Patent Document 2] JP-A-11-149179

[0010]

The problems to be solved by the present invention are as follows (1) to (6). (1) Providing a highly transferable toner that provides high image quality (2) Providing a durable toner that has a small particle size that does not adhere to carriers and mechanical parts and that does not contain ultrafine particles and has a narrow particle size distribution (3) To provide a toner having a shape capable of cleaning the residual toner after transfer with a simple device (4) 10% in an aqueous medium using a solid fine particle dispersant
To obtain a toner that maintains a desired particle size and particle size distribution by volumetric shrinkage with a shrinkage ratio of 90% and has both appropriate glossiness and releasability as a full-color toner (5) (1) to (4) Providing a method for producing a toner (6) Providing a full-color developing method and a transferring method for the toner according to (1) to (4) above.

[0011]

[Means for Solving the Problems] The above problems are solved in the following 1) to
It is solved by the invention of 18). 1) A dry toner having an average circularity of 0.93 to 0.99 and a fine powder content of 2 μm or less of 20 number% or less. 2) The dry toner according to 1), which has an average circularity of 0.95 to 0.98. 3) The dry toner according to 1), which has a fine powder content of 10% by number or less. 4) 10% in an aqueous medium using a solid fine particle dispersant
A volume average particle diameter of 3 to 10 μm and a ratio of the volume average particle diameter to the number average particle diameter of 1.10 to 1.25, which is obtained by volumetric shrinkage with a shrinkage rate of ˜90% 1) ~
The dry toner according to any one of 3). 5) The volume average particle diameter is 4 to 7 μm and the ratio of the volume average particle diameter to the number average particle diameter is 1.15 to 1.20, which is obtained by the volume contraction with the contraction rate of 30% to 70%. 4. The dry toner according to 4) above. 6) The toner binder in the dry toner contains a modified polyester and an unmodified polyester, and the weight ratio of the modified polyester and the unmodified polyester is 1/99 to 80 /
20 is a dry toner according to any one of 1) to 5). 7) The dry toner according to 6), wherein the modified polyester is modified with a substituent bonded via a urea or urethane bond. 8) The peak molecular weight of the toner binder in the dry toner is 1000 to 30000, and 1) to
The dry toner according to any one of 7). 9) The acid value of the toner binder in the dry toner is 1 to 3
The dry toner according to any one of 1) to 8), which is 0 mgKOH. 10) The glass transition point (Tg) of the toner binder in the dry toner is 50 to 70 ° C. 1)
To 9). 11) A toner composition is dispersed in an aqueous medium using a solid fine particle dispersant, dispersed in an aqueous medium containing an organic solvent capable of dissolving water, and then subjected to a volume shrinking step to form particles. Dry toner manufacturing method. 12) The method for producing a dry toner according to 11), which comprises a step of removing the solid fine particle dispersant after the volume contraction. 13) The method for producing a dry toner according to 11) or 12), wherein the toner composition contains a modified polyester. 14) Dissolving or dispersing a toner composition containing a modified polyester in an organic solvent, and forming a polyester having a urethane or urea bond during the step of dispersing in a water-based medium containing an organic solvent capable of dissolving water. 13. The method for producing a dry toner according to 13). 15) By a plurality of developing devices equipped with a developing roll and a developing blade for uniformly regulating the layer thickness of the developer supplied onto the developing roll, electrostatic divided into each color formed on a single photoconductor. A method for developing a latent image with a developer corresponding to each color, wherein the developer using the dry toner according to any one of 1) to 10) is used. 16) A plurality of developing devices equipped with a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll, and electrostatically divided into each color formed on a single photoconductor. In the method of developing a latent image with a developer corresponding to each color and transferring the latent image to an intermediate transfer member by an electric field, the developer using the dry toner according to any one of 1) to 10) is used. And the transfer method. 17) Divided into each color formed on a plurality of photoconductors corresponding to the developing device by a plurality of developing devices provided with a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll. In the method of developing the formed electrostatic latent image with a developer corresponding to each color, 1) to
10. A developing method using a developer using the dry toner according to any one of 10). 18) Dividing into each color formed on a plurality of photoconductors corresponding to the developing device by a plurality of developing devices provided with a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll. In the method of developing the formed electrostatic latent image with a developer corresponding to each color and transferring to the intermediate transfer member by an electric field, the developer using the dry toner according to any one of 1) to 10) is used. A transfer method comprising:

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Generally, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but on the contrary, it is disadvantageous in terms of transferability and cleaning property. is there. The inventors of the present invention have found that the use of a toner having a specific circularity and a small content of ultrafine powder of 2 μm or less gives a high image quality with good transferability and good cleaning property. When the dry toner of the present invention is used as a two-component developer, the toner is not fused to the surface of the carrier during long-term stirring in the developing device, and the charging ability of the carrier is not deteriorated. It has been found that when used as a developer, high durability can be realized without filming of the toner to the developing roller or fusion of the toner to a member such as a blade for thinning the toner layer. The present invention has been completed.

Further, the volume average particle diameter is 3 to 10 μm and the volume average particle diameter and the number average particle are obtained by volume shrinking with a shrinkage ratio of 10% to 90% in an aqueous medium using a solid fine particle dispersant. The diameter ratio is 1.10 to 1.25 and the circularity is 0.
With a dry toner of 93 to 0.99, heat-resistant storage stability,
It excels in both low-temperature fixability and hot offset resistance, especially when used in full-color copiers and the like, and has excellent image glossiness. Further, in the case of a two-component developer, even if the toner balance is long-term, In addition, fluctuations in the particle size of the toner in the developer are reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Further, when it is used as a one-component developer, even if the toner balance is achieved, the fluctuation of the toner particle size is reduced, and the filming of the toner on the developing roller and the thinning of the toner are performed. The toner was not fused to the member such as the blade, and good and stable developability and images were obtained even when the developing device was used for a long time (stirring).

On the contrary, when the particle size 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 the balance of the toner in the developer is achieved. In many cases, the variation of the toner particle size becomes large.
Further, it was revealed that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25. Further, when the volume average particle diameter / number average particle diameter is smaller than 1.10, there is a preferable aspect from the viewpoint of stabilizing the behavior of the toner and making the charge amount uniform, but the toner cannot be sufficiently charged. It was revealed that the cleaning property may be deteriorated. Further, when the volume average particle diameter / number average particle diameter is smaller than 1.10, it is preferable from the viewpoint of stabilizing the behavior of the toner and making the charge amount uniform, but the toner cannot be charged sufficiently or cleaning is performed. It became clear that it may worsen the sex. Furthermore, the preferable volume average particle diameter / number average particle diameter is 1.15 to 1.20.

Particularly in the present invention, in order to give an appropriate shape, it is important to use a solid fine particle dispersant in a production method having a volume contraction step of 10 to 90% in volume contraction in an aqueous medium. is there. Here, the volumetric shrinkage is Vo when the volume of the oil phase (dispersion phase) in which the toner composition is dispersed before emulsifying and dispersing in the aqueous medium is Vo, and the volume of the dispersion phase after emulsifying and dispersing to remove volatile components is Vt. Volume shrinkage ratio = (1−Vt / Vo) × 100, and the change in properties before emulsification and after being emulsified and dispersed into particles is measured. Specifically, it can be determined by the method exemplified below. (1) A method of measuring the weight and true specific gravity of the oil phase before emulsification and the obtained toner (2) Measuring the average particle size of the droplets after emulsification and dispersion in an aqueous medium and the particles from which volatile components have been removed A method of converting the volume If the volume contraction rate is out of the range of 10 to 90%, the particle shape becomes irregular, which is not preferable. Moreover, a more preferable range is 30 to 70%.

<Method of adjusting shape and content of ultrafine particles> Usually, solid fine particles adhere to the surface of emulsified oil droplets to stabilize the droplets in a spherical shape. As the volatile components are removed, the volume of the liquid droplets decreases, but the solid fine particles remain attached as they are. Since the drop of the surface area of the droplet is slow, it cannot keep up with the decrease of the volume, and the sphere cannot be maintained and becomes amorphous. However, if the adsorption force at the interface of the solid particles is weakened when removing the volatile components, desorption from the liquid droplets occurs, the slow decrease in the surface area of the liquid droplets is mitigated, and the surface area of the liquid droplets decreases as the volume decreases. Particles are formed while maintaining the irregular spheres. For example, add a surfactant or protective polymer colloid to exchange and adsorb,
The adsorption force at the interface of the solid particles can be weakened by adjusting the pH in the aqueous medium to change the charge of the droplet surface and the solid particles.

Further, the shape can be adjusted by partially dissolving and removing the solid fine particles adhering to the surface when removing the volatile component. Further, in order to reduce the content of ultrafine particles of 2 μm or less, when the viscosity of the oil droplets during emulsification and dispersion is relatively high, it is difficult for the fine portions to break when subjected to shearing force, and coalescence becomes easier. It is advantageous. However, if the viscosity of the oil phase is increased from the beginning, on the contrary, there is a problem that even small-sized droplets cannot be dispersed. In the present invention, a solid fine particle dispersant is used to dissolve or disperse a toner composition in an organic solvent, and the organic solvent used in the oil phase is obtained by dispersing the toner composition in an aqueous medium containing an organic solvent soluble in water. Diffuses into the aqueous medium, has an appropriate viscosity that is difficult to tear and easily coalesces, and the ultrafine particle content can be reduced. Specifically, it depends on the manufacturing method described later.

<Particle size distribution measuring method> For the average particle size and particle size distribution of toner, Coulter Multisizer III (manufactured by Coulter Co.) is used, and a personal computer (manufactured by IBM Co.) is connected, and dedicated analysis software (manufactured by Coulter Co.). Was used to analyze the data. The Kd value was set by using standard particles of 10 μm, and the aperture current was set by automatic setting. As the electrolytic solution, a 1% NaCl aqueous solution was prepared using first-grade sodium chloride. In addition, ISOTO
N-II (manufactured by Coulter Scientific Japan) can be used. As the measuring method, the electrolytic aqueous solution 1
A surfactant, preferably 0.1 to 5 ml of alkylbenzene sulfonate as a dispersant was added to 0 to 150 ml, and 2 to 20 mg of a measurement sample was further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and 2 μm using an 100 μm aperture tube.
The volume and number of the above toners were measured 50,000 counts to calculate the volume distribution and number distribution. Then, the volume-based volume average particle diameter obtained from the volume distribution and the number-based number average particle diameter obtained from the number distribution according to the present invention were obtained.

<Circularity Measurement Method> It is important that the toner according to the present invention has a specific shape and distribution, and an average circularity of less than 0.95 and an irregular shape too far from a sphere are satisfactory. High quality images without transferability and dust cannot be obtained. The practical upper limit of the average circularity is 0.9.
It is 9. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through a detection band on the flat plate to optically detect and analyze a particle image with a CCD camera. . A toner having an average circularity of 0.95 or more, which is a value obtained by dividing the perimeter of the equivalent circle having the same projected area obtained by this method by the perimeter of the existing particles, has a reproducible and high-definition with appropriate density. It has been found to be effective in forming images. The average circularity is preferably 0.95
It is 0.98. The fine powder content of 2 μm or less is 20
The number is less than or equal to%, preferably less than or equal to 10%. This value can be measured as an average circularity by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, a surfactant, preferably an alkylbenzene sulfonate, as a dispersant is added in an amount of 0.1 to 0.
Add 5 ml, and further add about 0.1 to 0.5 g of the measurement sample. The suspension in which the sample is dispersed is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the dispersion liquid concentration is 3000 to 10,000 /
The shape and distribution of the toner is measured by the above apparatus as μl.

<Molecular Weight Measuring Method> The molecular weight distribution of the toner binder component of the present invention is measured by the following method. About 1 g of toner is weighed in an Erlenmeyer flask and then THF
(Tetrahydrofuran) 10 to 20 g is added to obtain a THF solution having a binder concentration of 5 to 10%. The column is stabilized in a heat chamber at 40 ° C., THF as a solvent is caused to flow through the column at this temperature at a flow rate of 1 ml / min, and 20 μl of the THF sample solution is injected. The molecular weight of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared from the monodisperse polystyrene standard sample and the retention time. The calibration curve is prepared using a polystyrene standard sample. As the monodisperse polystyrene standard sample, for example, a product having a molecular weight of 2.7 × 10 ^{2 to} 6.2 × 10 ⁶ manufactured by Tosoh Corporation is used. A refractive index (RI) detector is used as the detector. As the column, for example, TS manufactured by Tosoh Corporation
Kgel, G1000H, G2000H, G2500
H, G3000H, G4000H, G5000H, G6
000H, G7000H, GMH are used in combination. Main peak molecular weight is usually 1000-3000
It is 0, preferably 1500 to 10000, and more preferably 2000 to 8000. If it is less than 1,000, the heat resistant storage stability is deteriorated, and if it exceeds 30,000, the low temperature fixability is deteriorated. The content of components having a molecular weight of 30,000 or more is 1 to 10
%, Preferably 3 to 6%. When it is less than 1%, sufficient hot offset resistance cannot be obtained, and when it is 10% or more, gloss and transparency are deteriorated. The value of Mw / Mn is preferably 5 or less. When it is 5 or more, the sharp melt property is lost and the glossiness is impaired.

<Glass Transition Point (Tg) Measuring Method> In the DSC measurement of the present invention, the heat exchange of the toner is measured and its behavior is observed. Therefore, from the principle of measurement, a highly accurate internal heat input compensation type It must be measured with a differential scanning calorimeter. For example, DSC-200 manufactured by Seiko Instruments Inc. can be used. The measuring method is performed according to ASTM D3418-82. The DSC curve used in the present invention has a temperature of 10 ° C./min and a temperature of 0 after the temperature is raised once and the previous history is taken.
D measured when the temperature is lowered or raised in the range of up to 200 ° C
SC curve is used. Specifically, it measures by the following procedures. (1) The sample is crushed, a sample having a weight of 10 ± 1 mg is weighed into an aluminum sample container, and the aluminum lid is crimped on the sample container. (2) Glass transition point (T
g) is measured. Here, the temperature of the sample is from room temperature to 1
After heating to 200 ° C at 0 ° C / min, 10 at 150 ° C
The sample is allowed to stand for 10 minutes, then the sample is cooled to 0 ° C. at a temperature lowering rate of 50 ° C./min and then left for 10 minutes, and finally the nitrogen atmosphere (2
0 cc / min) at a temperature rising rate of 10 ° C./min and again 2
DSC measurement is performed by heating to 00 ° C. At this time, Tg is the temperature at which the curve is clearly deviated from the baseline at the time of temperature rise, that is, the differential value of the peak curve is positive and the increase of the differential value starts to increase, or the differential value is from negative to positive. Is the temperature at which

<Modified polyester> The modified polyester means that the polyester resin has a bonding group other than an ester bond with the functional group contained in the acid and / or alcohol monomer unit, or is composed of the polyester resin. It refers to different resin components bound by covalent bonds, ionic bonds, or the like. Examples thereof include those obtained by reacting a polyester terminal with a compound that forms a bond other than an ester bond, and specifically, a functional group such as an isocyanate group that reacts with an acid group and / or a hydroxyl group is introduced into the terminal to generate active hydrogen. Those which are further reacted with the contained compound to modify the ends or to undergo extension reaction are also included. Further, if the compound has a plurality of active hydrogen groups, those in which polyester terminals are bonded to each other are also included (urea modified polyester, urethane modified polyester, etc.). In addition, a reactive group such as a double bond may be introduced into the polyester main chain, and radical polymerization may be introduced from there to introduce a carbon-carbon bond graft component into the side chain or a double bond may be bridged. Included (styrene-modified, acrylic-modified polyester, etc.). Further, those obtained by copolymerizing resin components having different constitutions in the main chain of polyester or reacting with carboxyl groups or hydroxyl groups at the terminals, for example, silicone resins modified at the terminals with carboxyl groups, hydroxyl groups, epoxy groups, and mercapto groups. Copolymers (such as silicone-modified polyester) are also included.

The urea-modified polyester will be specifically described below as an example. <Urea-modified polyester (polyester modified via urea bond)> Examples of the urea-modified polyester (i) 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 polycondensation product of a polyol (a) and a polycarboxylic acid (b), which is obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (c). Can be 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, a mercapto group and the like, among which the alcoholic hydroxyl group is preferable. Examples of the polyol (a) include a diol (a-1) and a polyol (a-2) having a valence of 3 or more. Mixtures are preferred.

As the diol (a-1), alkylene glycols (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, etc.) , Bisphenol S); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the alicyclic diols; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the bisphenols, and the like. To be Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycol having 2 to 12 carbon atoms. It is a combination of. As the trihydric or higher polyol (A-2), 3 to 8 is used.
Or higher polyhydric aliphatic alcohols (glycerin,
Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc .; trivalent or higher valent phenols (trisphenol PA, phenol novolac, cresol novolac, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols, etc. .

As the polycarboxylic acid (b), dicarboxylic acid (b-1) and polycarboxylic acid having a valence of 3 or more (b)
2), and (b-1) alone and a mixture of (b-1) and a small amount of (b-2) are preferable. As the dicarboxylic acid (b-1), alkylenedicarboxylic acid (succinic acid,
Adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, etc.) and the like. 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 (b-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). As the polycarboxylic acid (II), an acid anhydride or a lower alkyl ester (such as methyl ester, ethyl ester, isopropyl ester) of the above may be used to react with the polyol (II). The ratio of the polyol (a) and the polycarboxylic acid (b) is the equivalent ratio of the hydroxyl group [OH] and the carboxyl group [COOH] = [OH] / [COOH]
And usually 2/1 to 1/1, preferably 1.5 / 1 to 1 /
1, and more preferably 1.3 / 1 to 1.02 / 1.

As the polyisocyanate (c), aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) ); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); Aroaliphatic diisocyanates (α, α, α ', α'-tetramethylxylylene diisocyanate, etc.); Isocyanurates; , Those blocked with caprolactam; and combinations of two or more of these. The ratio of polyisocyanate (C) is
Equivalent ratio of isocyanate group [NCO] and hydroxyl group [OH] of polyester having hydroxyl group = [NCO] / [O]
H], usually 5/1 to 1/1, preferably 4/1 to 1.
It is 2/1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, the low temperature fixability deteriorates, and when [NCO] / [OH] is less than 1, the urea content in the modified polyester becomes low and the hot offset resistance deteriorates.

The content of the polyisocyanate (C) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30%.
%, More preferably 2 to 20% by weight. 0.5
If it is less than 10% by weight, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
On the other hand, if it exceeds 40% by weight, the low temperature fixability is deteriorated. The number of isocyanate groups contained per molecule of the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, and more preferably 1.
8 to 2.5. If the number is less than 1 per molecule, the molecular weight of the urea-modified polyester becomes low, and the hot offset resistance deteriorates.

As amines (B), diamine (B
1) Trivalent or higher polyamines (B2), amino alcohols (B3), amino mercaptans (B4), amino acids (B5), and those in which the amino groups of B1 to B5 are blocked (B6). Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,
3'-dimethyldicyclohexylmethane, cyclohexanediamine, isophoronediamine, etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine,
Hexamethylenediamine) and the like. 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. The amino groups of B1 to B5 blocked (B6) include amines and ketones of B1 to B5 (acetone, methyl ethyl ketone,
Examples thereof include a ketimine compound and an oxazoline compound obtained from methyl isobutyl ketone). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

Further, if necessary, an elongation terminator may be used to adjust the molecular weight of the urea-modified polyester.
Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.),
And those obtained by blocking them (ketimine compounds) and the like. The ratio of the amines (B) is such that the isocyanate group [NCO] in the prepolymer (A) having an isocyanate group and the amino group [NHx] in the amines (B).
Equivalent ratio = [NCO] / [NHx], usually 1/2 to 2
/ 1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. [NCO] / [N
When Hx] exceeds 2 or is less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates.

In the present invention, the urea-modified polyester (i) may contain a urethane bond as well as a urea bond. The molar ratio of the urea bond content and the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60.
/ 40 to 30/70. The molar ratio of urea bond is 10
If it is less than%, the hot offset resistance is deteriorated. The urea-modified polyester (i) of the present invention has a one-shot method,
It is produced by the prepolymer method. The weight average molecular weight of (i) is usually 10,000 or more, preferably 21 to 10,000,000, and more preferably 31 to 1,000,000. If it is less than 10,000, the hot offset resistance is deteriorated. The number average molecular weight of (i) is
When the unmodified polyester (ii) described below is used, the number average molecular weight is not particularly limited and may be a number average molecular weight convenient for obtaining the above weight average molecular weight. (I) When alone,
The number average molecular weight is usually 20,000 or less, preferably 10
00-10,000, more preferably 2000-8000
Is. If it exceeds 20,000, the low-temperature fixability and the glossiness when used in a full-color device deteriorate.

<Unmodified Polyester> In the present invention, not only the urea-modified polyester (i) may be used alone, but the unmodified polyester (ii) may be contained as a toner binder component together with this (i).
The combined use of (ii) improves the low-temperature fixability and the glossiness when used in a full-color device, and is therefore preferable to single use. Examples of (ii) include a polycondensation product of the same polyol (a) as the polyester component (i) and a polycarboxylic acid (b), and the preferred ones are also the same as (i). Further, instead of (ii), it is possible to use a polyester modified through a chemical bond other than a urea bond, for example, a polyester modified through a urethane bond. It is preferable that at least a part of (i) and (ii) are compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, it is preferable that the polyester component excluding the modified portion of (i) and (ii) have a similar composition.

(I) and (ii) when containing (ii)
The weight ratio of is required to be within the range of 1/99 to 80/20, usually 5/95 to 80/20, preferably 5/9.
5-30 / 70, more preferably 5 / 95-25 / 7
5, particularly preferably 7/93 to 20/80.
When the weight ratio of (i) is less than 1%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. Similarly, the upper limit of (i) is 80%. The range of the composition ratio applies not only to the case of the urea-modified polyester (i) but also to the case of the other modified polyester used in the present invention. The peak molecular weight of (ii) is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 80.
00. If it is less than 1000, the heat-resistant storage stability is deteriorated and 1
When it exceeds 0000, the low temperature fixability is deteriorated. The hydroxyl value of (ii) is preferably 5 mgKOH or more, more preferably 10 to 120 mgKOH, and particularly preferably 2
It is 0 to 80 mg KOH. If it is less than 5 mgKOH, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is usually 1 to 30 mgKOH, preferably 5 to 20 m.
It is gKOH. By having an acid value, it tends to be negatively charged.

In the present invention, the glass transition point (Tg) of the toner binder is usually 50 to 70 ° C., preferably 55.
~ 65 ° C. If it is lower than 50 ° C, the heat-resistant storage stability of the toner is deteriorated, and if it is higher than 70 ° C, the low temperature fixing property becomes insufficient.
Due to the coexistence of the urea-modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storability even if it has a low glass transition point, as compared with a known polyester-based toner. The storage elastic modulus of the toner binder is 10,000 dyne / cm ^{2 at} a measurement frequency of 20 Hz.
The temperature (TG ') is usually 100 ° C or higher, preferably 110 to 200 ° C. If it is less than 100 ° C, the hot offset resistance is deteriorated. As the viscosity of the toner binder, a toner having a temperature (Tη) of 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 90 to 160 ° C. is used. If the temperature exceeds 180 ° C., the low temperature fixability deteriorates. 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 (T
G'-Tη) is preferably higher than 0 ° C, more preferably 10 ° C or higher, and particularly preferably 20 ° C or higher. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is 0
It is preferably in the range of 100 ° C, more preferably 10-9.
It is 0 ° C., and particularly preferably 20 to 80 ° C.

<Coloring Agent> As the coloring agent of the present invention, all known dyes and pigments can be used, 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), Balkan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Red iron oxide, red lead,
Lead Vermilion, Cadmium Red, Cadmium Mercury Red, Antimon Vermilion, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carn Min B
S, Permanent Red (F2R, F4R, FRL, F
RLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G,
Resor 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, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil. Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkali Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine, Navy Blue, Anthraquinone Blue, Fast Ioretto B, methyl violet lake, cobalt violet, manganese violet, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, viridian, emerald green, Pigment Green B, Naphthol Green B, green gold, acid green lake,
Malachite green lake, phthalocyanine green,
Anthraquinone green, titanium oxide, zinc oxide, lithobon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 1 based on the toner.
It is 0% by weight.

The colorant used in the present invention can also be used as a masterbatch compounded with a resin. As the binder resin to be manufactured or kneaded with the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, polymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene and substitution products thereof are used. Styrene-p-chlorostyrene copolymer,
Styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer,
Styrene-methyl acrylate copolymer, 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- Styrene-based copolymers such as isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, Polyvinyl acetate Ethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, Examples include chlorinated paraffin and paraffin wax, which may be used alone or as a mixture.

The above masterbatch can be obtained by mixing and kneading a resin for a masterbatch and a colorant with a high shearing force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Further, a method of mixing and kneading an aqueous paste containing water of a colorant called a flushing method with a resin and an organic solvent, transferring the colorant to the resin side, and removing water and an organic solvent component is also a wet method of the colorant. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three roll mill is preferably used.

<Release Agent> The toner of the present invention may contain a wax together with a toner binder and a colorant. As the wax, known waxes can be used, and examples thereof include polyolefin wax (polyethylene wax, polypropylene wax, etc.); long-chain hydrocarbon (paraffin wax, sazole wax, etc.); carbonyl group-containing wax, etc. Of these, preferred is a carbonyl group-containing wax. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18 -Octadecanediol distearate, etc.); polyalkanol ester (tristearyl trimellitate, distearyl maleate, etc.); polyalkanoic acid amide (ethylenediamine dibehenylamide, etc.); polyalkylamide (trimellitic acid tristearylamide, etc.) And dialkyl ketone (such as distearyl ketone). Among these, polyalkanoic acid esters are preferable.

The melting point of the wax used in the present invention is usually 4
The temperature is 0 to 160 ° C, preferably 50 to 120 ° C, and more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. adversely affects the heat resistant storage stability, and a wax having a melting point of more than 160 ° C. easily causes cold offset at the time of fixing at a low temperature. The melt viscosity of the wax is 5 to 1000 cps as a measured value at a temperature 20 ° C. higher than the melting point.
Is preferable, and more preferably 10 to 100 cps. A wax exceeding 1000 cps has a poor effect of improving hot offset resistance and low-temperature fixability. The content of wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

<Charge Control Agent> The toner of the present invention may contain a charge control agent, if necessary. All known charge control agents can be used, for example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdic acid chelate pigment, rhodamine dye,
Alkoxy amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), alkylamide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, and salicylic acid derivative metal salt Etc. Specifically, the Nigrosine dye Bontron 03 and the quaternary ammonium salt Bontron P-
51, Bontron S-34 as a metal-containing azo dye, E-82 as an oxynaphthoic acid-based metal complex, E-84 as a salicylic acid-based metal complex, and E-89 as a phenol-based condensate (all manufactured by Orient Chemical Industry Co., 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 of salt NEG VP2036, copy charge NX
VP434 (above, manufactured by Hoechst), LRA-901,
LR-147 which is a boron complex (manufactured by Nippon Kalit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymeric compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. Is mentioned.

The amount of the charge control agent used in the present invention is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. Although not included, it is used in the range of 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the binder resin. If it exceeds 10 parts by weight, the chargeability of the toner is too large, the effect of the main charge control agent is diminished, the electrostatic attraction force with the developing roller is increased, and the fluidity of the developer is lowered,
This causes a decrease in image density. These charge control agents and release agents can be melt-kneaded together with the masterbatch and the resin, or can be added when they are dissolved or dispersed in an organic solvent.

<Method of Producing Toner in Aqueous Medium> As the aqueous medium used in the present invention, water may be used alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (methanol, isopropanol,
Ethylene glycol etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve etc.), lower ketones (acetone, methyl ethyl ketone etc.) and the like. The toner binder can be manufactured by the method exemplified below. Polyol (a)
And polycarboxylic acid (II) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxy titanate and dibutyltin oxide, and water generated is distilled off while reducing the pressure as necessary. , To obtain a polyester having a hydroxyl group. Then add 4 to this polyester
The polyisocyanate (C) is reacted at 0 to 140 ° C to obtain a prepolymer (A) having an isocyanate group. Furthermore, at 0 to 140 ° C., amines (B) are added to (A).
To obtain a polyester modified with a urea bond. When reacting (C) and reacting (A) and (B), a solvent can be used if necessary.
As usable solvents, aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.); ethers Examples thereof include those that are inactive with respect to polyisocyanate (C), such as classes (tetrahydrofuran etc.)

When the unmodified polyester (ii) is used in combination, it is treated in the same manner as the polyester having a hydroxyl group (ii)
Is prepared, and this is dissolved and mixed in the solution after the reaction of the above (i) is completed. A volatile solvent in which the modified polyesters (i) and (A) are soluble is used in order to reduce the volume of the toner composition and reduce the viscosity of the oil phase. The solvent is preferably a volatile solvent having a boiling point of less than 100 ° C. from the viewpoint of easy removal, and examples thereof include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,
1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene,
Methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferable. It is also possible to adjust the volume shrinkage by using a solvent that is soluble in an aqueous medium such as alcohol and water together. The amount of the solvent used is usually 10 to 900 parts by weight with respect to 100 parts by weight of the toner composition.

Toner particles are prepared, for example, by dispersing a dispersion of a prepolymer (A) having an isocyanate group and another toner composition in a volatile organic solvent in an aqueous medium (B).
It may be formed by reacting with, or the modified polyester (i) produced in advance may be used. As a method for stably forming a dispersion composed of the modified polyester (i) or prepolymer (A) and the toner composition in an aqueous medium, the urea-modified polyester (i) or the prepolymer (A) is added to the aqueous medium. A method of adding the composition of the toner raw material and dispersing with a shearing force can be used. The prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials) such as colorant, colorant masterbatch, release agent, charge control agent, and unmodified polyester resin are dispersed in an aqueous medium. Although they may be mixed at the time of forming, it is more preferable that the toner raw materials are mixed in advance and then the mixture is added to and dispersed in an aqueous medium. For the dispersion, a mixer with ordinary stirring, more preferably, a homogenizer having a high-speed rotating body and a stator, a high-pressure homogenizer, a disperser using a dispersion medium such as a ball mill, a bead mill, and a sand mill is used.

Further, in the present invention, other toner raw materials such as a colorant, a release agent and a charge control agent do not necessarily have to be mixed when the particles are formed in the aqueous medium, and the particles are formed. It may be added later. For example,
After forming particles not containing a colorant, the colorant can be added by a known dyeing method. The method of dispersion is not particularly limited, but low-speed shearing method, high-speed shearing method,
Known equipment such as a friction type, a high pressure jet type, and an ultrasonic wave can be applied. A high-speed shearing method is preferable for adjusting the particle size of the dispersion to 2 to 20 μm. The emulsifying machine having a rotary blade is not particularly limited, and any commercially available emulsifying machine or dispersing machine can be used. For example, Ultra Turrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homo Mixer (manufactured by Tokushu Kika Kogyo), Ebara Milder (manufactured by Ebara Corporation),
TK pipeline homomixer, TK homomic line flow (made by Tokushu Kika Kogyo Co., Ltd.), colloid mill (made by Shinko Pantec Co., Ltd.), slasher, trigonal wet type fine pulverizer (made by Mitsui Miike Kakoki Co., Ltd.), Cavitron (Eurotech). Continuous flow emulsifier such as Fine Flow Mill (manufactured by Taiheiyo Kiko Co., Ltd.), CLEARMIX (manufactured by M Technique Co., Ltd.),
Examples include batch or continuous dual-use emulsifiers such as FILMIX (manufactured by Tokushu Kika Kogyo Co., Ltd.).

When a high-speed shearing disperser is used, the number of revolutions is not particularly limited, but it is usually 1,000 to 30,000 rp.
m, preferably 5000-20000 rpm. The dispersion time is not particularly limited, but in the case of the batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 15
It is 0 ° C (under pressure), preferably 10 to 98 ° C. Higher temperatures are preferred because the dispersion of the urea-modified polyester (i) and the prepolymer (A) has a low viscosity and is easy to disperse. The amount of the aqueous medium used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts by weight of the toner composition containing the urea-modified polyester (i) and the prepolymer (A). When the amount is less than 50 parts by weight, the toner composition is poorly dispersed, and toner particles having a predetermined particle diameter cannot be obtained. When the amount exceeds 2000 parts by weight, it is not economical. Although the solid fine particle dispersant is dispersed in the aqueous medium, other dispersants can be used together in order to adjust the adsorptivity of the solid fine particle dispersant to the liquid droplets as described above. The other dispersant can be added before emulsifying the toner composition or when removing volatile components after emulsification.

<Solid Fine Particle Dispersant> The solid fine particle dispersant is a solid which is hardly soluble in water in an aqueous medium and is preferably inorganic fine particles having an average particle diameter of 0.01 to 1 μm. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatom. Examples thereof include soil, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide and silicon nitride. More preferably, tricalcium phosphate, calcium carbonate, colloidal titanium oxide, colloidal silica, hydroxyapatite and the like can be used. Particularly preferred is hydroxyapatite synthesized by reacting sodium phosphate and calcium chloride in water under basic conditions.

Examples of the solid fine particle dispersant of organic substances include fine crystals of low molecular weight organic compounds and polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization. Polymer particles made of a polymer, a polycondensation resin such as a silicone resin, a benzoguanamine resin, or nylon, or a thermosetting resin can be used. When a solid fine particle dispersant that is soluble in an alkali, such as calcium phosphate salt or polymer fine particles copolymerized with (meth) acrylic acid having a carboxyl group, is used, an acid such as hydrochloric acid or sodium hydroxide is used. After the solid fine particle dispersant is dissolved with a base or a base, the solid fine particle dispersant is removed from the toner particles whose shape is adjusted by a method such as washing with water. In addition, it can be removed by an operation such as decomposition with an enzyme.

<Others, Dispersant Used in Combination during Emulsification or Added Later> Alkylbenzene sulfonate, α-olefin sulfonate, anionic surfactant such as phosphoric acid ester, alkylamine salt, aminoalcohol fatty acid derivative, polyamine Amino acid type cations such as fatty acid derivatives and imidazolines, and quaternary ammonium salt type cations such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride. Nonionic surfactants such as surfactants, fatty acid amide derivatives and polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N
-Ampholytic surfactants such as dimethyl ammonium betaine.

By using a surfactant having a fluoroalkyl group, the effect can be obtained with a very small amount. The preferred anionic surfactant having a fluoroalkyl group has 2 to 1 carbon atoms.
Fluoroalkylcarboxylic acid of 0 and its metal salt, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (C6-C11)
Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoralkanoyl (C6-
C8) -N-Ethylamino] -1-propanesulfonic acid sodium salt, fluoroalkyl (C11 to C20) carboxylic acid and metal salt, perfluoroalkylcarboxylic acid (C7 to C13) and metal salt thereof, perfluoroalkyl (C4-C12) Sulfonic acid and metal salt thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkyl (C6-
C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate and the like can be mentioned.

The trade name is Surflon S-111,
S-112, S-113 (Asahi Glass Co., Ltd.), Florard F
C-93, FC-95, FC-98, FC-129 (Sumitomo 3M), Unidyne DS-101, DS-102
(Manufactured by Daikin Industries, Ltd.), Megafac F-ll0, F-
120, F-113, F-191, F-812, F-8
33 (manufactured by Dainippon Ink and Chemicals), Ektop EF-102,
103, 104, 105, 112, 123A, 123
B, 306A, 501, 201, 204 (manufactured by Tochem Products), Futgent F-100, F-150.
(Manufactured by Neos) and the like. As the cationic surfactant, aliphatic primary, secondary or tertiary amines having a fluoroalkyl group, perfluoroalkyl (C6
To C10) sulfonamidopropyltrimethylammonium salt and other aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts and the like. Made), Florard FC-13
5 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries, Ltd.), Megafac F-150, F-824
(Manufactured by Dainippon Ink and Chemicals, Inc.), Ektop EF-132 (manufactured by Tochem Products), Futergent F-300 (manufactured by Neos) and the like.

Stabilization of dispersed droplets may be controlled by a polymeric protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid,
Acids such as itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride; containing hydroxyl groups (meth)
Acrylic monomers such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid- γ-hydroxypropyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylic acid ester, diethylene glycol monomethacrylic acid ester, glycerin monoacrylic acid ester, glycerin monomethacrylic acid Acid ester,
N-methylol acrylamide, N-methylol methacrylamide, etc .; vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc .; esters of vinyl alcohol and compounds containing a carboxyl group, for example Vinyl acetate, vinyl propionate, vinyl butyrate, etc .; acid amides such as acrylamide, methacrylamide, diacetone acrylamide; acid chlorides such as acrylic acid chloride, methacrylic acid chloride; vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, etc. Homopolymers or copolymers having a nitrogen atom of, or a heterocycle thereof; polyoxyethylene, polyoxypropylene, polyoxyethylene alkyl , Polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester, etc. Polyoxyethylene-based; celluloses such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like can be used.

When a dispersant is used, the dispersant may be left on the surface of the toner particles, but it is preferable to remove the dispersant by washing after the elongation and / or cross-linking reaction from the viewpoint of charging the toner. The extension and / or crosslinking reaction time is selected depending on the reactivity based on the combination of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. It's time. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Further, a known catalyst can be used if necessary. Specific examples thereof include dibutyltin laurate and dioctyltin laurate. In order to remove the organic solvent from the obtained emulsified dispersion, a method of gradually elevating the temperature of the entire system to completely evaporate and remove the organic solvent in the droplets can be adopted. Alternatively, it is also possible to spray the emulsified dispersion in a dry atmosphere to completely remove the non-water-soluble organic solvent in the droplets to form fine toner particles, and also to evaporate and remove the aqueous dispersant. As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, a combustion gas, or the like, in particular, various air streams heated to a temperature higher than the boiling point of the highest boiling point solvent used are generally used. A short time processing such as spray dryer, belt dryer, rotary kiln, etc. can obtain the desired quality.

When the emulsion is dispersed, the particle size distribution is wide, and when the particle size distribution is maintained and the washing and drying processes are carried out, the particle size distribution can be adjusted by classifying it into a desired particle size distribution. As a classification operation, a fine particle portion can be removed by a cyclone, a decanter, a centrifugal separator or the like in the liquid. Of course, the classification operation may be performed after the powder is obtained by drying, but it is preferable to perform the classification operation in a liquid in terms of efficiency.
The obtained unnecessary fine particles or coarse particles can be returned to the kneading step again and used for forming particles. At that time, the fine particles or the coarse particles may be in a wet state. It is preferable to remove the used dispersant from the obtained dispersion as much as possible, and it is preferable to perform it at the same time as the classification operation described above.
The obtained toner powder after drying is mixed with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or a mechanical impact force is applied to the mixed powder. As a result, it is possible to prevent the heterogeneous particles from being detached from the surface of the composite particles obtained by immobilizing and fusing on the surface. Specific means include a method of applying an impact force to the mixture by a blade rotating at a high speed, a method of introducing the mixture into a high-speed air stream, accelerating the particles, and colliding the particles or composite particles with a suitable collision plate. is there. As the equipment, an Ong mill (manufactured by Hosokawa Micron Co., Ltd.), a type I mill (manufactured by Nippon Pneumatic Co., Ltd.) was modified to reduce the grinding air pressure, a hybridization system (manufactured by Nara Machinery Co., Ltd.), and a kryptron system. (Made by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

<Dry Toner Manufacturing Method> The dry toner can be manufactured by the following method, but is not limited to these. In addition, when preparing a developer, in order to improve the fluidity, storability, developability and transferability of the developer,
Inorganic fine particles such as the hydrophobic silica fine powder described above may be added to and mixed with the developer produced as described above. A general mixer for powder is used for mixing the external additives, but it is preferable to equip a jacket or the like to adjust the internal temperature. To change the history of the load applied to external additives,
The external additive may be added midway or gradually. Of course, the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. A strong load may be applied first, and then a relatively weak load may be applied, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Loedige mixer, a Nauta mixer, and a Henschel mixer. To further adjust the shape of the obtained toner, a method in which a toner material consisting of a toner binder and a colorant is melt-kneaded and then finely pulverized is mechanically adjusted using a hybridizer, mechanofusion or the like. Alternatively, the toner material is dissolved and dispersed in a solvent in which the toner binder is soluble, and then the solvent is removed using a spray dry device to obtain a spherical toner, which is a so-called spray dry method. However, the method is not limited to these.

<External Additive> Inorganic fine particles can be preferably used as an external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention. The primary particle size of the inorganic fine particles is preferably 5 to 2 μm, and particularly preferably 5 to 500 μm. Moreover, the specific surface area by the BET method is 20 to 500 m ² / g.
Is preferred. The usage rate of these inorganic fine particles is
It is preferably 0.01 to 5% by weight, and particularly preferably 0.01 to 2.0% by weight, based on the whole toner. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatom. Examples thereof include soil, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide and silicon nitride.

In addition, high-molecular fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation system of methacrylic acid ester or acrylic acid ester copolymer, silicone, benzoguanamine, nylon, etc., Polymer particles made of a thermosetting resin may be mentioned. Such a fluidizing agent can prevent deterioration of fluidity characteristics and charging characteristics under high humidity by performing surface treatment to increase hydrophobicity. For example, as a preferred surface treatment agent, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group,
Examples include organic titanate-based coupling agents, aluminum-based coupling agents, silicone oils and modified silicone oils. Examples of the cleaning property improver for removing the developer remaining on the photoreceptor or primary transfer medium after transfer include, for example, zinc stearate, fatty acid metal salts such as calcium stearate, polymethylmethacrylate fine particles, and soap-free polystyrene fine particles. Examples thereof include polymer fine particles produced by emulsion polymerization and the like. As the polymer fine particles, those having a relatively narrow particle size distribution and a volume average particle diameter of 0.01 to 1 μm are preferable.

<Carrier for Two-Component Developer> When the toner of the present invention is used as a two-component developer, it may be mixed with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is: Toner 1 to 100 parts by weight of carrier
10 parts by weight is preferred. As a magnetic carrier, particle size 2
Conventionally known materials such as iron powder, ferrite powder, magnetite powder, and magnetic resin carrier having a particle size of 0 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide and epoxy resin. Further, polyvinyl resins and polyvinylidene resins, for example, acrylic resins, polymethylmethacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polystyrene resins such as polystyrene and styrene acrylic copolymer resins, halogens such as polyvinyl chloride. Olefin resin, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, vinylidene fluoride and acrylic single amount Fluoroterpolypolymers such as copolymers with polymers, copolymers of vinylidene fluoride and vinyl fluoride, terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, etc. Chromatography, and silicone resins. If necessary, conductive powder or the like may be contained in the coating resin. As conductive powder,
Metal powder, carbon black, titanium oxide, tin oxide, zinc oxide and the like can be used. These conductive powders have an average particle size of 1μ
It is preferably m or less. When the average particle size is larger than 1 μm, it becomes difficult to control the electric resistance. The toner of the present invention can also be used as a magnetic toner or a non-magnetic toner for a one-component developer that does not use a carrier.

[0058]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, "part" in Examples and Comparative Examples
Is "parts by weight".

Examples and Comparative Examples Test 1 [Preparation and Evaluation of Toner Having Different Amount of Organic Solvent Added in Aqueous Medium and Average Circularity and Fine Particle Content by Treatment Before Desolvation] << Synthesis of Toner Binder >> 724 parts of bisphenol A ethylene oxide 2 mol adduct, 276 parts of terephthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, and the mixture was heated under normal pressure to 230
The polycondensation reaction was performed at 8 ° C. for 8 hours, and the reaction was further performed under a reduced pressure of 10 to 15 mmHg for 5 hours to obtain an unmodified polyester (a) having a peak molecular weight of 5300. 100 parts of this unmodified polyester (a) is dissolved and mixed in 100 parts of ethyl acetate,
An ethyl acetate solution of the toner binder was obtained. A portion of the toner was taken and dried under reduced pressure to isolate the toner binder. Tg is 62
The acid value was 10 ° C. << Preparation of Toner >> 200 parts of an ethyl acetate solution of the above-mentioned toner binder, 5 parts of carnauba wax, 4 parts of copper phthalocyanine blue pigment, 1 part of zinc tertiary butyl salicylate are put in a closed pot and 5 mmφ zirconia beads are used. And ball-milled for 24 hours to obtain a toner composition. Separately, ion-exchanged water 6 in the beaker
00 parts, methyl ethyl ketone X parts, tricalcium phosphate 60 parts, sodium dodecylbenzene sulfonate 0.3
Parts were added and uniformly dissolved and dispersed. Then, the temperature inside the beaker was maintained at 20 ° C., and the above toner composition was charged while stirring at 12000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) and stirred for 3 minutes to emulsify. Then, this mixed solution was transferred to a flask equipped with a stir bar and a thermometer, 0.3 part of sodium lauryl sulfate and 35 parts of 35% concentrated hydrochloric acid Y part were added,
The mixture was stirred for 30 minutes at room temperature and dissolved. Then, 30 ℃, 5
The solvent was removed under reduced pressure of 0 mmHg. When the dispersion was analyzed by gas chromatography, the residual ethyl acetate was 50 ppm based on the toner particles. Subsequently, 120 parts of 35% concentrated hydrochloric acid was added to dissolve tricalcium phosphate, followed by filtration. The cake obtained was redispersed in distilled water and filtered, and the operation was repeated 3 times, and then 40
Toner particles were obtained by drying under reduced pressure at 24 ° C. for 24 hours. Finally,
To 100 parts of toner particles, 0.5 parts of hydrophobic silica and 0.5 part of hydrophobized titanium oxide were added and mixed with a Henschel mixer to obtain a toner of the present invention. The conditions for producing these toners and the characteristic values of the toners are as shown in Table 1 below.

[0060]

[Table 1]

Table 2 shows the evaluation results of fine line reproducibility and cleaning property of each toner obtained as described above. << Image Evaluation Method >> 5 parts by weight of each color toner obtained,
95 parts by weight of the following carrier was mixed with a blender for 10 minutes to prepare a developer. At that time, in order to obtain sufficient developability of the toner and to prevent the background stain due to the oppositely charged toner, the charge amount is 15 to 25 (μC / g) in absolute value.
The stirring time and speed were adjusted so as to be about the same. [Carrier] -Core material: spherical ferrite particles having an average particle size of 50 μm-Coating material constituent material: Silicone resin in which aminosilane coupling agent is dispersed (aminosilane coupling agent and silicone resin are dispersed in toluene to prepare a dispersion liquid) After that, the core material was spray-coated in a heated state, then baked and cooled to an average coating resin film thickness of 0.2 μm.)

For fine line reproducibility, the developer prepared as described above was put in a commercially available color copying machine (PRETER550: made by Ricoh), and the image occupancy rate was 7%.
000 paper was used for running, and the fine line parts of the initial 10th image and the 30,000th image at that time were compared with the original, and they were magnified 100 times with an optical microscope and observed to check for missing lines. The condition was evaluated on a four-point scale, comparing with a graded sample. As for the cleaning property, after running 30,000 sheets under the same conditions as in the case of fine line reproducibility, 10 full-color solid images are continuously output and stopped during the development of the 10th sheet, and toner after the cleaning blade on the photoconductor is used. Was transferred to a tape, and the degree of smearing of the tape was evaluated by comparing with a 4-step sample. Both fine line reproducibility and cleaning performance are excellent.
The image quality is high in the order of>○>Δ> ×. Especially, the evaluation of x is a level that cannot be adopted as a product.

[0063]

[Table 2] As can be seen from the results in Table 2, the toner of the present invention is excellent in the fine line reproducibility in the initial stage, the fine line reproducibility after the run, and the cleaning property. If it is too small, the reproducibility of the initial fine lines will be poor. On the other hand, if the content of the fine powder of 2 μm or less is more than the range of the present invention, the fine line reproducibility after the run is deteriorated, and the toner has poor durability.

Test 2 [Experiment for Confirming Effect of Shrinkage, Particle Size, Particle Size Distribution, and Shape on Image Quality] The toner of the present invention H in Table 1 is referred to as Example 1, and as in Examples 2 to 12 below. The effects of shrinkage, particle size distribution, and shape on image quality were investigated by changing various manufacturing conditions.

Example 2 Toner composition 2 after ball mill dispersion obtained in Example 1
10 parts was diluted with 576 parts of ethyl acetate, and 210 parts of this diluted dispersion was treated in the same manner as in Example 1 and emulsified to form particles. Thereafter, the same operation as in Example 1 was carried out to obtain the toner of the present invention.

Example 3 Toner composition 3 after ball mill dispersion obtained in Example 1
Fifty parts were concentrated to 210 parts by an evaporator, and 210 parts of this concentrated dispersion was treated in the same manner as in Example 1 and emulsified into particles. Thereafter, the same operation as in Example 1 was carried out to obtain the toner of the present invention.

Example 4 Toner Composition 2 after Ball Mill Dispersion Obtained in Example 1
10 parts was diluted with 1165 parts of ethyl acetate, and 210 parts of the diluted dispersion was treated in the same manner as in Example 1 to emulsify into particles. Thereafter, the same operation as in Example 1 was carried out to obtain the toner of the present invention.

Example 5 Toner Composition 3 after Ball Mill Dispersion Obtained in Example 1
68 parts was concentrated to 210 parts by an evaporator, and 210 parts of this concentrated dispersion was treated in the same manner as in Example 1 to emulsify and then form particles. Thereafter, the same operation as in Example 1 was carried out to obtain the toner of the present invention.

Example 6 The toner obtained in Example 1 was further finely classified by an air classifier to obtain a toner of the present invention having a very narrow particle size distribution.

Example 7 TK Fillmix FM30-50 (manufactured by Tokushu Kika Co., Ltd.) was used in place of the emulsifying apparatus (TK type homomixer) used in Example 1, except that the emulsification was performed at 15000 rpm.
The same operation as in Example 1 was carried out to obtain a toner of the present invention.

Example 8 The toner of the present invention was prepared in the same manner as in Example 1 except that the amount of sodium dodecylbenzenesulfonate used for preparing the aqueous medium in Example 1 was changed to 0.2 part. Obtained.

Example 9 The toner of the present invention was prepared in the same manner as in Example 1 except that the amount of sodium dodecylbenzenesulfonate used for preparing the aqueous medium in Example 1 was changed to 0.1 part. Obtained.

Example 10 A comparative toner was obtained in the same manner as in Example 1 except that the operation of adding sodium lauryl sulfate after emulsification was omitted.

Example 11 A toner of the present invention was obtained in the same manner as in Example 1, except that the amount of sodium lauryl sulfate added after emulsification was changed to 0.1 part.

Example 12 A toner of the present invention was obtained in the same manner as in Example 1 except that the amount of sodium lauryl sulfate added after emulsification was changed to 0.5 part.

Table 3 shows the physical properties of the toner thus obtained and the results of image evaluation. The "shrinkage rate" in the table is obtained from the amount of ethyl acetate contained in the oil phase. "D
“V” is the volume average particle diameter (μm), and “Dv / Dn” represents the ratio of the volume average particle diameter to the number average particle diameter.

[0077]

[Table 3]

Test 3 [Confirmation of effect when modified polyester is used as toner binder] << Synthesis of modified polyester 1 >> 2 mol of bisphenol A ethylene oxide was placed in a reaction tank equipped with a cooling tube, a stirrer and a nitrogen introducing tube. 724 parts of adduct, 276 of isophthalic acid
And 2 parts of dibutyltin oxide are added under normal pressure, 2
After reacting at 30 ° C. for 8 hours and further under reduced pressure of 10 to 15 mmHg for 5 hours, the mixture was cooled to 160 ° C., and subsequently 32 parts of phthalic anhydride was added and reacted for 2 hours. Then, it was cooled to 80 ° C., and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate-containing prepolymer (1). Then, 267 parts of prepolymer (1) and 14 parts of isophoronediamine were added to 5 parts.
The reaction was carried out at 0 ° C. for 2 hours, and ethyl acetate was distilled off to obtain a urea-modified polyester (1) having a weight average molecular weight of 64,000.

<< Synthesis of Modified Polyester 2 >> In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 724 parts of bisphenol A ethylene oxide 2 mol adduct, 200 parts of isophthalic acid and 70 parts of fumaric acid, dibutyltin oxide. Add 2 parts, react under normal pressure at 230 ° C. for 8 hours, and further under reduced pressure of 10-15 mmHg for 5 hours, then cool to 160 ° C., then add 32 parts phthalic anhydride and react for 2 hours. Let Then, the mixture was cooled to 80 ° C., 200 parts of styrene, 1 part of benzoyl peroxide and 0.5 part of dimethylaniline were added in ethyl acetate and reacted for 2 hours. The ethyl acetate was distilled off to obtain a weight average molecular weight of 92.
000 polystyrene graft modified polyester (2)
Got

<< Preparation of Toner Binder 3 >> 30 parts of urea-modified polyester (1) and unmodified polyester (a)
970 parts (see Example 1) were mixed with ethyl acetate / MEK (methyl ethyl ketone) (volume ratio 1/1) mixed solvent 2000
Parts and dissolved to obtain an ethyl acetate / MEK solution of the toner binder (3). Part of the toner was taken and dried under reduced pressure to isolate the toner binder (3).

<< Preparation of Toner Binder 4 >> 500 parts of urea-modified polyester (1) and 500 parts of unmodified polyester (a) were mixed with ethyl acetate / MEK (volume ratio 1 /
1) Dissolved in 2000 parts of mixed solvent and mixed to obtain an ethyl acetate / MEK solution of toner binder (4). Part of the toner was taken and dried under reduced pressure to isolate the toner binder (4).

<< Preparation of Toner Binder 5 >> 750 parts of urea-modified polyester (1) and 250 parts of unmodified polyester (a) were mixed with ethyl acetate / MEK (volume ratio 1 /
1) Dissolved in 2000 parts of mixed solvent and mixed to obtain an ethyl acetate / MEK solution of toner binder (5). A part of the toner was taken and dried under reduced pressure to isolate the toner binder (5).

<< Preparation of Toner Binder 6 >> 850 parts of urea-modified polyester (1) and 150 parts of unmodified polyester (a) were mixed with ethyl acetate / MEK (volume ratio 1 /
1) Dissolved in 2000 parts of mixed solvent and mixed to obtain an ethyl acetate / MEK solution of toner binder (6). A part was taken and dried under reduced pressure to isolate the toner binder (6).

<< Synthesis of Toner Binder 7 >> 924 parts of 2 mol adduct of bisphenol A ethylene oxide and 276 parts of terephthalic acid were polycondensed at 230 ° C. under normal pressure for 8 hours, and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours. Then, an unmodified polyester (b) having a peak molecular weight of 5000 was obtained. 100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (b) were mixed with ethyl acetate /
2000 parts of MEK (volume ratio 1/1) mixed solvent was dissolved and mixed to obtain an ethyl acetate / MEK solution of the toner binder (7). A part of the toner was taken and dried under reduced pressure to isolate the toner binder (7). The acid value was 0.5.

<< Synthesis of Toner Binder 8 >> 824 parts of 2 mol adduct of bisphenol A ethylene oxide and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted under reduced pressure of 10-15 mmHg for 5 hours. Then, an unmodified polyester (c) having a peak molecular weight of 5000 was obtained. 100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (c) were mixed with ethyl acetate /
MEK (volume ratio 1/1) mixed solvent was dissolved and mixed in 2000 parts to obtain an ethyl acetate / MEK solution of toner binder (8). A part was taken and dried under reduced pressure to isolate the toner binder (8). The acid value was 2.

<< Synthesis of Toner Binder 9 >> 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours. Then, the mixture was cooled to 160 ° C., 32 parts of trimellitic anhydride was added thereto, and the mixture was reacted for 2 hours to give a peak molecular weight of 5
000 unmodified polyester (d) was obtained. 100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (d) were mixed with ethyl acetate / MEK (volume ratio 1 /
1) Dissolved in 2000 parts of a mixed solvent and mixed to obtain an ethyl acetate / MEK solution of toner binder (9). A part of the toner was taken and dried under reduced pressure to isolate the toner binder (9).
The acid value was 25.

<< Synthesis of Toner Binder 10 >> 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted for 5 hours under reduced pressure of 10 to 15 mmHg. After that, the mixture was cooled to 160 ° C., 48 parts of trimellitic anhydride was added thereto, and the mixture was reacted for 2 hours to obtain an unmodified polyester (e) having a peak molecular weight of 5000. 100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (e) were mixed with ethyl acetate / MEK (volume ratio 1 /
1) Dissolved in 2000 parts of a mixed solvent and mixed to obtain an ethyl acetate / MEK solution of the toner binder (10). A part of the toner was taken and dried under reduced pressure to isolate the toner binder (10). The acid value was 35.

<< Synthesis of Toner Binder 11 >> 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 2 hours under normal pressure, and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours. Then, an unmodified polyester (f) having a peak molecular weight of 1000 was obtained. 100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (f) were mixed with ethyl acetate /
MEK (volume ratio 1/1) dissolved in 2000 parts of mixed solvent and mixed, and ethyl acetate / MEK of toner binder (11)
A solution was obtained. A part was taken and dried under reduced pressure to isolate the toner binder (11). Tg was 45 ° C.

<< Synthesis of Toner Binder 12 >> 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 4 hours under normal pressure, and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours. Then, an unmodified polyester (g) having a peak molecular weight of 2000 was obtained. 100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (g) were mixed with ethyl acetate /
MEK (volume ratio 1/1) dissolved in 2000 parts of mixed solvent and mixed, and ethyl acetate / MEK of toner binder (12)
A solution was obtained. A part of the toner was taken and dried under reduced pressure to isolate the toner binder (12). Tg was 52 ° C.

<< Synthesis of Toner Binder 13 >> 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 10 hours under normal pressure, and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours. Then, an unmodified polyester (h) having a peak molecular weight of 30,000 was obtained. Urea modified polyester (1) 10
0 part and 900 parts of the unmodified polyester (h) were dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1) to prepare a toner binder (13) containing ethyl acetate /
A MEK solution was obtained. A part was taken and dried under reduced pressure to isolate the toner binder (13). Tg was 69 ° C.

<< Synthesis of Toner Binder 14 >> 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 12 hours under normal pressure, and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours. Then, an unmodified polyester (j) having a peak molecular weight of 30,000 was obtained. Urea modified polyester (1) 10
0 part and 900 parts of the unmodified polyester (j) were dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1), and mixed with ethyl acetate / toner binder (14).
A MEK solution was obtained. A part was taken and dried under reduced pressure to isolate the toner binder (14). Tg was 73 ° C.

Examples 13 to 26 << Preparation of Toner >> A toner was prepared by the same method as the toner G of the present invention in Test 1. That is, the toner binder 100 having the composition shown in Table 2 was placed in a closed pot.
Solution of 100 parts and 100 parts of ethyl acetate, 5 parts of carnauba wax, 4 parts of copper phthalocyanine blue pigment,
Put 1 part of zinc tert-butyl salicylate, 5m
Ball mill dispersion was carried out for 24 hours using mφ zirconia beads to obtain a toner composition. Separately, 600 parts of ion-exchanged water, 30 parts of methyl ethyl ketone, 60 parts of tricalcium phosphate and 0.3 part of sodium dodecylbenzenesulfonate were placed in a beaker and uniformly dissolved and dispersed. Next, while maintaining the beaker internal temperature at 20 ° C., the above toner composition was charged while stirring at 12000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo), and the mixture was stirred for 3 minutes to emulsify. Then, this mixed solution was transferred to a flask equipped with a stir bar and a thermometer, and 0.3 part of sodium lauryl sulfate, 35% was added.
30 parts of hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes to dissolve it. Then, the solvent was removed under reduced pressure of 30 ° C. and 50 mmHg. Analysis of the dispersion by gas chromatography showed that residual ethyl acetate was 50 p
It was pm. Then, add 120 parts of 35% concentrated hydrochloric acid,
After the tricalcium phosphate was dissolved, it was filtered off, and the cake obtained was redispersed in distilled water and filtered, and the operation was repeated three times. After that, the cake was dried under reduced pressure at 40 ° C. for 24 hours to obtain toner particles. Finally, 0.5 part of hydrophobic silica and 0.5 part of hydrophobized titanium oxide were mixed with 100 parts of toner particles by a Henschel mixer to obtain a toner of the present invention.

Table 4 shows the composition and physical properties of each toner obtained as described above.

[Table 4] In the table, Mp is the molecular weight distribution peak, Mw / Mn is the ratio of the weight average to the number average molecular weight, and Tg is the glass transition point (° C).

[0094]

[Table 5] From the results of Table 4 and Table 5, as compared with the toner G of the present invention which does not use the modified polyester in Test 1, the toner of the present invention of Test 3 using the modified polyester in an appropriate amount has an acid value, a molecular weight peak and a glass transition. It can be seen that when the temperature is within the range defined by the present invention, the low temperature fixing property and the high temperature offset resistance are excellent, and the GLOSS (gloss development temperature) at a lower temperature is high.

Each of the above toners was evaluated as follows. << Powder Flowability >> Bulk density was measured using a Hosokawa Micron powder tester. A toner having a better fluidity has a larger bulk density, and was evaluated in the following four stages. ×: less than 0.25 Δ: 0.25 or more and less than 0.30 ○: 0.30 or more and less than 0.35 ◎: 0.35 or more << Heat-resistant storage stability >> It was sieved through a mesh sieve for 2 minutes, and the residual rate on the wire mesh was taken as heat resistant storage stability. A toner having a better heat-resistant storage property has a smaller residual rate, and was evaluated according to the following four stages. ×: 30% or more △: 20 or more and less than 30% ○: 10 or more and less than 20% ◎: less than 10%

<< Fixing lower limit temperature >> Ricoh type 6200 paper was added to a copying machine MF-200 manufactured by Ricoh Co., Ltd. using a Teflon (registered trademark) roller as a fixing roller. It was set and a copy test was conducted. The fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad was 70% or more was defined as the lower limit fixing temperature. << Hot Offset Occurrence Temperature (HOT) >> A copy test was performed in the same manner as the above fixing lower limit temperature, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature. << Gloss development temperature (GLOSS) >> Commercial color copier (P
Fixing was evaluated using a fixing device (RETER550; manufactured by Ricoh). The fixing roll temperature at which the 60 ° gloss of the fixed image was 10% or more was defined as the gloss development temperature.

[0097]

EFFECTS OF THE INVENTION According to the present invention, (1) it is possible to provide a dry toner having a small particle size which gives a high image quality, a narrow particle size distribution, and an appropriate shape satisfying transferability and cleaning property. (2) It is possible to provide the dry toner according to (1) above, which is durable for use in an actual machine. (3) 10% in an aqueous medium using a solid fine particle dispersant
It is possible to provide a dry toner in which desired particle diameter and particle size distribution are maintained by volumetric shrinkage of 90% to 90%, and which has both appropriate glossiness and releasability as a full-color toner. (4) It is possible to provide a simple method for producing the dry toner according to the above (1) to (3). (5) It is possible to provide a method for developing and transferring a high-definition image in full color with the dry toner of (1) to (3) above.

Front page continuation (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) G03G 9/08 381 (72) Inventor Tsuneshin Sugiyama 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd. (72 ) Inventor Hiroshi Yamada 1-3-6 Nakamagome, Ota-ku, Tokyo, Ricoh Co., Ltd. (72) Inventor Kazuto Watanabe 1-3-3 Nakamagome, Ota-ku, Tokyo In-house, Ricoh (72) Shigeru Emoto 1-3-6 Nakamagome, Ota-ku, Tokyo (72) Inventor Masami Tomita 1-3-6 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Co., Ltd. (reference) 2H005 AA01 AA15 AB03 CA08 CA15 EA03 EA05 EA06 EA07 EA10 2H300 EJ45 EJ46 EJ50 EJ51 GG17 GG34 JJ02 KK03 KK06 KK08 KK13 KK14 MM11 MM12

Claims (18)

[Claims] 1. An average circularity of 0.93 to 0.99 and 2 μ
A dry toner characterized in that a fine powder content of m or less is 20% by number or less. 2. The dry toner according to claim 1, which has an average circularity of 0.95 to 0.98. 3. The dry toner according to claim 1, wherein the content of fine powder of 2 μm or less is 10% by number or less. 4. A volume average particle diameter of 3 to 10 μm and a volume average particle diameter and a number average particle diameter, which are obtained by volumetric shrinkage with a shrinkage ratio of 10% to 90% in an aqueous medium using a solid fine particle dispersant. 4. The dry toner according to claim 1, wherein the ratio is 1.10 to 1.25. 5. A volume average particle diameter of 4 to 7 μm and a ratio of the volume average particle diameter to the number average particle diameter of 1.15 to 1. The dry toner according to claim 4, wherein the dry toner is 20. 6. The toner binder in the dry toner contains a modified polyester and an unmodified polyester, and the weight ratio of the modified polyester and the unmodified polyester is 1/99.
The dry toner according to claim 1, wherein the dry toner is 80/20. 7. The dry toner according to claim 6, wherein the modified polyester is modified with a substituent bonded via a urea or urethane bond. 8. The dry toner according to claim 1, wherein the peak molecular weight of the toner binder in the dry toner is 1,000 to 30,000. 9. The acid value of the toner binder in the dry toner is 1 to 30 mgKOH.
9. The dry toner according to any one of 8 to 8. 10. The dry toner according to claim 1, wherein the glass transition point (Tg) of the toner binder in the dry toner is 50 to 70 ° C. 11. A solid fine particle dispersant is used to disperse a toner composition in an aqueous medium, and the dispersion is performed in an aqueous medium containing an organic solvent soluble in water, and then the particles are subjected to a volume shrinking step to form particles. And a method for producing a dry toner. 12. The method for producing a dry toner according to claim 11, further comprising the step of removing the solid fine particle dispersant after the volume contraction. 13. The method for producing a dry toner according to claim 11, wherein the toner composition contains a modified polyester. 14. A polyester having a urethane or urea bond is produced during a step of dissolving or dispersing a toner composition containing a modified polyester in an organic solvent and dispersing the toner composition in an aqueous medium containing an organic solvent soluble in water. 14. The method for producing a dry toner according to claim 13, wherein the dry toner is produced. 15. A plurality of developing devices equipped with a developing roll and a developing blade for uniformly controlling the layer thickness of the developer supplied onto the developing roll are divided into respective colors formed on a single photoconductor. A method for developing an electrostatic latent image with a developer corresponding to each color, wherein the developer using the dry toner according to claim 1 is used. 16. A plurality of developing devices equipped with a developing roll and a developing blade for uniformly regulating the layer thickness of the developer supplied onto the developing roll are divided into respective colors formed on a single photoconductor. In the method of developing the electrostatic latent image with a developer corresponding to each color and transferring to the intermediate transfer member by an electric field, the developer using the dry toner according to claim 1 is used. A transfer method characterized by the above. 17. A plurality of developing devices provided with a developing roll and a developing blade for uniformly regulating the layer thickness of the developer supplied onto the developing roll, and formed on a plurality of photoconductors corresponding to the developing device. A method of developing an electrostatic latent image divided into each color with a developer corresponding to each color, wherein the developer using the dry toner according to claim 1 is used. Development method. 18. A plurality of developing devices provided with a developing roll and a developing blade for uniformly regulating the layer thickness of the developer supplied onto the developing roll, are formed on a plurality of photoreceptors corresponding to the developing device. 11. A method using the dry toner according to claim 1, wherein the electrostatic latent image divided into each color is developed with a developer corresponding to each color and transferred to an intermediate transfer member by an electric field. A transfer method comprising using an agent.