JP4031488B2 - Dry toner production method, development method, and transfer method - Google Patents

Description

  The present invention relates to a method for producing a toner used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc., and more specifically, using a direct or indirect electrophotographic development system. The present invention relates to a manufacturing method of toner for electrophotography used for copying machines, laser printers, plain paper fax machines, and the like. Further, the present invention relates to a method for producing an electrophotographic toner used in a full-color copying machine, a full-color laser printer, a full-color plain paper fax machine or the like using a direct or indirect electrophotographic multicolor image developing method, and a toner developing method and a transferring method.

In the developing process, a developer used in electrophotography, electrostatic recording, electrostatic printing, and the like is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then transferred to a transfer process. After being transferred from the photoconductor to a transfer medium such as transfer paper, the toner is fixed on the paper surface in a fixing step. At that time, as a developer for developing an 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 toners are known.
Conventionally, as dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like, toner binders such as styrene resins and polyesters are melt-kneaded and finely pulverized together with colorants and the like.

In order to obtain high-quality and high-quality images, improvements have been made by reducing the particle diameter of the toner. However, the particle shape is indefinite in the production method by the usual kneading and pulverization methods, and classification is performed. Even after going through the process, the ultrafine particles have the disadvantage that they have strong adhesion and remain attached to the toner of the target particle size and cannot be classified. Inside the machine, stirring with the carrier in the developing section, or one-component development When used as an agent, such ultrafine particles adhere to and adhere to the carrier and mechanical parts due to contact stress caused by the developing roller, toner supply roller, layer thickness regulating blade, friction charging blade, etc., and the fluidizing agent is applied to the toner surface. A phenomenon that image quality is deteriorated due to embedding has occurred. Further, because of 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 downsizing. Therefore, the current situation is that the merit of reducing the particle size is not utilized. In addition, the pulverization method has a limit on the particle size and cannot cope with further reduction in particle size.

Furthermore, in order to create full-color images, the process of transferring images formed from multicolor toners from the photoreceptor to transfer media and paper has become complicated, and transferability due to irregular shapes such as pulverized toner Due to the poorness of the image, problems such as omission of the transferred image and a large amount of toner consumption have occurred.
However, the spherical toner cannot be removed by a device (for example, a cleaning blade or a cleaning brush) for removing the toner remaining on the photosensitive member or the transfer medium, resulting in poor cleaning. In addition, the toner surface is exposed to the outside in all directions due to its spherical shape, and is easily exposed to contact with a charging member such as a carrier or a charging blade. 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 for further improving transfer efficiency to reduce toner consumption to obtain a high-quality image with no missing images, or to reduce running costs. If the transfer efficiency is very good, there is no need for a cleaning unit for removing untransferred toner from the photoconductor or transfer medium, and there is an advantage that equipment can be reduced in size and cost, and waste toner is eliminated. Because. Various spherical toner manufacturing methods have been devised to compensate for the disadvantages of such irregular shape effects.
In the toner production method by suspension polymerization, only spherical toner can be produced, and since it is sheared irregularly when suspended in water, ultrafine powder is easily generated, and it is easy to clean and adheres to carriers and machine parts. The problem is not solved.
On the other hand, in the toner manufacturing method by emulsion polymerization, it is possible to manufacture from an irregular shaped toner to a spherical shape, but it is necessary to adjust the shape by heating in the post-treatment, and there remains ultrafine powder that does not aggregate during water aggregation or aggregation. The problem of carrier contamination and adhesion to mechanical parts due to such fine particles has not been solved.

As a method for solving these problems, Patent Document 1 discusses a method called volumetric shrinkage called a polymer dissolution suspension method.
In this method, a toner material is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified and formed into droplets in an aqueous medium containing a dispersant, and then the volatile solvent is removed. At that time, although the volumetric shrinkage of the droplets occurs, when a solid fine particle dispersant that does not dissolve in an aqueous medium is selected as the dispersant, only amorphous particles can be obtained. Further, when the solid content in the solvent was increased in order to increase productivity, the viscosity of the dispersed phase increased, and the resulting particles had a large particle size and a broad distribution. On the other hand, when the molecular weight of the resin used is reduced to lower the viscosity of the dispersed phase, the fixability (especially hot offset resistance) must be sacrificed.

On the other hand, in Patent Document 2, the resin used in the polymer dissolution suspension method has a low molecular weight to lower the viscosity of the dispersed phase, to facilitate emulsification, and to improve the fixing property by carrying out a polymerization reaction in the particles. . However, the transferability and cleaning properties were not improved by adjusting the shape of the particles.
In addition, since it is sheared irregularly when suspended in water, ultrafine powder is easily generated, and the problem of sticking to carriers and machine parts has not been solved.
Also, these dry toners are developed and transferred onto paper or the like, and then fixed by heating and melting using a hot roll. At that time, if the hot roll temperature is too high, there will be a problem that the toner will be melted excessively and fused to the hot roll (hot offset). If the hot roll temperature is too low, the toner will not melt sufficiently and fixing will be insufficient Problem arises.

On the other hand, from the viewpoint of energy saving and downsizing of the apparatus, a toner having a higher hot offset generation temperature (hot offset resistance) and a lower fixing temperature (low temperature fixing property) is required. In addition, heat storage stability is required so that the toner does not block during storage and at ambient temperature in the apparatus. In particular, full-color copiers and full-color printers require glossiness and color mixing of their images, so the toner must have a lower melt viscosity, and a sharp-melt polyester toner binder is used. However, since such toner tends to cause hot offset, conventionally, in a full-color device, silicone oil or the like is applied to a heat roll.
However, the method of applying silicone oil to the hot roll requires an oil tank and an oil application device, and the device becomes complicated and large. Moreover, it causes deterioration of the heat roll and requires maintenance every certain period. Furthermore, the adhesion of oil to copy paper, OHP (overhead projector) film, etc. is unavoidable. In particular, OHP has a problem of deterioration of color tone due to the adhered oil.
Moreover, there has been no attempt to control the shape by paying attention to the volumetric shrinkage when using a solid fine particle dispersant that has an important influence on the shape.

JP-A-7-152202 JP-A-11-149179

  The present invention includes (1) a toner having high transferability that gives high image quality, (2) a durable toner having a small particle size with little adhesion to the carrier and machine parts and a narrow particle size distribution not containing ultrafine particles, (3) Toner having a shape that allows the transfer residual toner to be cleaned with a simple device, (4) Desired particle size by volume shrinkage of 10% to 90% shrinkage in an aqueous medium using a solid fine particle dispersant. , Providing a production method for obtaining a toner that maintains a particle size distribution and has both proper glossiness and releasability as a full-color toner, and full-color development using the toner produced by the production method The object is to provide a method and a transfer method.

The above-described problems are solved by the following inventions 1) to 7 ).
1) preparative toner composition is dissolved or dispersed in an organic solvent, the step of emulsification and dispersion in an aqueous medium using a solid particulate dispersion agent, the step of the part of the particle dispersant from emulsified dispersed droplets desorbed , through a process of removing volume shrinkage step, a particle dispersant that was not desorbed said portion in the step of desorbing the average circularity is equal to or to obtain particles of from 0.933 to 0.986 dry Toner manufacturing method.
2) The method for producing a dry toner according to 1 ), wherein the toner composition contains a modified polyester.
3) a toner composition comprising a modified polyester is dissolved or dispersed in an organic solvent, in the step of dispersing in water-based medium, 2, characterized in that to produce a polyester having a urethane or urea bond) dry toner according Manufacturing method.
4) The electrostatic discharge divided into each color formed on a single photosensitive member by a plurality of developing devices including a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll. A method for developing a latent image with a developer corresponding to each color, wherein a developer using a dry toner produced by any one of methods 1) to 3) is used.
5) The electrostatic discharge divided into each color formed on a single photoconductor 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 a method of developing a latent image with a developer corresponding to each color and transferring it to an intermediate transfer member by an electric field, a developer using dry toner produced by any one of methods 1) to 3) is used. A transfer method characterized by the above.
6) Divided into each color formed on a plurality of photoconductors corresponding to the developing device by a plurality of developing devices including a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll. a method of developing with a developer corresponding to the electrostatic latent image to each color, 1), characterized by using a developer using dry toner produced by any of the methods 1-3) Development method.
7) Divided into each color formed on a plurality of photoconductors corresponding to the developing device by a plurality of developing devices having a developing roll and a developing blade for uniformly regulating the layer thickness of the developer supplied onto the developing roll. In the method in which the developed electrostatic latent image is developed with a developer corresponding to each color and transferred to an intermediate transfer member by an electric field, development using dry toner produced by any one of methods 1) to 3) A transfer method using an agent.

Hereinafter, the present invention will be described in detail.
In general, 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 it is disadvantageous for transferability and cleaning properties. is there. The present inventors have found that a high image quality with good transferability and good cleaning properties can be obtained by using a toner having a specific circularity and an ultrafine powder having a content of 2 μm or less, and has led to the present invention.
In addition, when the dry toner produced by the method of the present invention is used as a two-component developer, the toner does not fuse to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier decreases. When used in a one-component developer, toner filming to the developing roller and toner fusion to a member such as a blade for thinning the toner do not occur. Has been found to be possible to achieve the present invention.

  Moreover, the ratio of the volume average particle diameter to the number average particle diameter when the volume average particle diameter is 3 to 10 μm and is obtained by volume shrinkage with a shrinkage of 10% to 90% in an aqueous medium using a solid fine particle dispersant. Is 1.10 to 1.25 and circular toner has a circularity of 0.93 to 0.99, and has excellent heat resistance, low temperature fixability, and hot offset resistance, especially for full-color copying machines. In the case of two-component developers, even if the toner balance for a long time is performed, fluctuations in the particle size of the toner in the developer are reduced, and long-term agitation in the developing device is achieved. In this case, good and stable developability can be obtained. In addition, when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner filming on the developing roller and the toner layer are made thin. The toner was not fused to a member such as a blade, and good and stable developability and images were obtained even when the developing device was used (stirred) for a long time.

Conversely, when the toner particle diameter is larger than the above-mentioned range, it becomes difficult to obtain a high-resolution and high-quality image, and the toner particles when the toner balance in the developer is performed. In many cases, the variation in diameter becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.
Further, when the volume average particle size / number average particle size is smaller than 1.10, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and uniformizing the charge amount, but the toner cannot be sufficiently charged. It became clear 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 equalizing the charge amount, but the toner cannot be sufficiently charged or the cleaning is performed. It became clear that it might worsen sex.
Furthermore, a preferable volume average particle diameter / number average particle diameter is 1.15 to 1.20.

In particular, 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 shrinkage step with a volume shrinkage of 10 to 90% in an aqueous medium. Here, the volume shrinkage ratio is Vo, which is the volume of the oil phase (dispersed phase) in which the toner composition before being emulsified and dispersed in the aqueous medium is dispersed, and Vt is the volume of the dispersed phase after emulsified and dispersed to remove volatile components. As
Volume shrinkage = (1−Vt / Vo) × 100
The change in characteristics is measured before emulsification and after being emulsified and dispersed.
Specifically, it can be determined by the following method.
(1) A method for measuring the weight and true specific gravity of the oil phase before emulsification and the obtained toner (2) The average particle size of the particles after the emulsion and dispersion in the aqueous medium and the particles from which volatile components have been removed is measured. , Method of Volume Conversion If the volume shrinkage is out of the range of 10 to 90%, the particle shape becomes indefinite, which is not preferable. Moreover, a more preferable range is 30 to 70%.

<Method of adjusting shape and ultrafine particle content>
Usually, the solid fine particles adhere to the surface of the emulsified oil droplets and stabilize the droplets in a spherical shape. As the volatile components are removed, the volume of the droplets decreases, but the solid fine particles remain attached. The drop in the surface area of the droplet is slow, so it cannot catch up with the decrease in volume, and the sphere cannot be maintained and becomes amorphous.
However, if the adsorption force at the interface of the solid microparticles is weakened when removing the volatile components, desorption from the droplet occurs, and the slowing of the decrease in the surface area of the droplet is mitigated, and the surface decreases as the volume decreases. Particles are maintained while maintaining a quasi-spherical shape with irregularities.
For example, adsorption at the interface of solid particles by adding a surfactant or polymer protective colloid to exchange and adsorbing, or adjusting the pH of the aqueous medium to change the charge of the droplet surface and solid particles Can weaken power.

The shape can also be adjusted by partially dissolving and removing solid fine particles adhering to the surface when removing volatile components.
In addition, in order to reduce the content of ultrafine particles of 2 μm or less, if the droplet viscosity of the oil droplet at the time of emulsification dispersion is relatively high, it is difficult to break up into fine parts when subjected to shearing force, and it becomes easy to unite. It is advantageous. However, if the viscosity of the oil phase is increased from the beginning, there is a problem that it is impossible to disperse even small droplets.
In the present invention, the organic solvent used in the oil phase is obtained by dissolving or dispersing the toner composition in an organic solvent using a solid fine particle dispersant and dispersing the toner composition in an aqueous medium containing water and a soluble organic solvent. Diffuses into the aqueous medium and has an appropriate viscosity that is difficult to tear and easy to coalesce, and the content of ultrafine particles can be reduced.
Specifically, it depends on the manufacturing method described later.

<Particle size distribution measurement method>
The average particle size and particle size distribution of the toner were analyzed using a Coulter Multisizer III (manufactured by Coulter), a personal computer (manufactured by IBM), and data analysis using dedicated analysis software (manufactured by Coulter). The Kd value was set using standard particles of 10 μm, and the aperture current was set at an automatic setting.
As the electrolytic solution, a 1% NaCl aqueous solution was prepared using first grade sodium chloride.
In addition, ISOTON-II (manufactured by Coulter Scientific Japan) can be used.
As a measurement method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, was added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample was further added.
The electrolytic solution in which the sample is suspended is dispersed for about 1 to 3 minutes using an ultrasonic wave disperser, and the volume and number distribution of the toner is measured by 50,000 counts of toners of 2 μm or more using a 100 μm aperture tube. And calculated. Then, the volume-based volume average particle size obtained from the volume distribution and the number-based number average particle size obtained from the number distribution were obtained.

<Circularity measurement method>
It is important that the toner produced by the method of the present invention has a specific shape and distribution. When the average circularity is less than 0.93 and the amorphous shape is too far away from the sphere, satisfactory transferability and High-quality images without dust cannot be obtained. The practical upper limit of the average circularity is 0.99.
As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. .
A toner having an average circularity of 0.93 or more, which is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle, is a highly precise and reproducible toner with an appropriate density. It has been found to be effective in forming images. The average circularity is preferably 0.95 to 0.98. The fine powder content of 2 μm or less is 20% by number or less, preferably 10% by number or less. 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 measurement method, a surfactant, preferably an alkylbenzene sulfonate, is added in an amount of 0.1 to 0.5 ml as a dispersant in 100 to 150 ml of water from which impure solids have been removed in advance. Add about 1-0.5g. The suspension in which the sample is dispersed is subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic wave disperser, and the shape and distribution of the toner are measured by the above apparatus with the dispersion concentration being 3000 to 10,000 / μl.

<Molecular weight measurement method>
The molecular weight distribution of the toner binder component of the toner according to the present invention is measured by the following method.
About 1 g of toner is weighed in an Erlenmeyer flask, and 10 to 20 g of THF (tetrahydrofuran) 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., and THF as a solvent is allowed 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 retention value and the logarithmic value of a calibration curve prepared from a monodisperse polystyrene standard sample. A calibration curve is created using a polystyrene standard sample. As a monodisperse polystyrene standard sample, the thing of the range of molecular weight 2.7 * 10 < ² > -6.2 * 10 < ⁶ > by the Tosoh company, for example is used.
A refractive index (RI) detector is used as the detector.
As the column, for example, TSKgel, G1000H, G2000H, G2500H, G3000H, G4000H, G5000H, G6000H, G7000H, GMH manufactured by Tosoh Corporation are used in combination.
The main peak molecular weight is usually 1000 to 30000, preferably 1500 to 10000, more preferably 2000 to 8000. If it is less than 1000, the heat resistant storage stability is deteriorated, and if it exceeds 30000, the low-temperature fixability is deteriorated.
The content of components having a molecular weight of 30000 or more is 1 to 10%, preferably 3 to 6%. If it is less than 1%, sufficient hot offset resistance cannot be obtained, and if it is 10% or more, glossiness and transparency are deteriorated.
The value of Mw / Mn is preferably 5 or less. If it is 5 or more, the sharp melt property is lacking and the glossiness is impaired.

<Method for measuring glass transition point (Tg)>
In the DSC measurement of the toner manufactured by the method of the present invention, since the heat exchange of the toner is measured and the behavior is observed, the high-accuracy internal heat input compensation type differential scanning calorimeter is measured from the measurement principle. There is a need to. For example, DSC-200 manufactured by Seiko Electronics Co., Ltd. can be used.
The measurement method is performed according to ASTM D3418-82. In the present invention, a DSC curve is used that is measured when the temperature is lowered once and the temperature is raised in the range of a temperature rate of 10 ° C./min and a temperature of 0 to 200 ° C. after raising the temperature once and taking a previous history.
Specifically, the measurement is performed according to the following procedure.
(1) A sample is pulverized, a sample having a weight of 10 ± 1 mg is weighed into an aluminum sample container, and an aluminum lid is crimped thereon.
(2) The glass transition point (Tg) is measured by DSC method in a nitrogen atmosphere.
Here, the sample was heated from room temperature to 200 ° C. at a temperature rising rate of 10 ° C./min and then left at 150 ° C. for 10 minutes, then cooled to 0 ° C. at a temperature lowering rate of 50 ° C./min and then left for 10 minutes. Finally, in a nitrogen atmosphere (20 cc / min), the DSC measurement is performed by heating again to 200 ° C. at a heating rate of 10 ° C./min. At this time, Tg is the temperature at which the curve is clearly separated from the baseline during temperature rise, that is, the temperature at which the differential value of the peak curve is positive and the differential value starts to increase, or the differential value is from negative to positive. The temperature that becomes.

<Modified polyester>
The modified polyester is a polyester resin in which a bonding group other than an ester bond with a functional group contained in an acid and / or alcohol monomer unit is present, or a resin component having a different structure is covalently bonded in the polyester resin. Refers to those bonded by ionic bonds.
For example, the polyester terminal can be reacted with a compound that generates a bond other than an ester bond. 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 and activated hydrogen. Those obtained by further reacting with the containing compound to modify the end or extend the reaction are also included.
Further, compounds having a plurality of active hydrogen groups include those in which polyester ends are bonded to each other (such as urea-modified polyester and urethane-modified polyester).
In addition, a reactive group such as a double bond is introduced into the polyester main chain, radical polymerization is caused therefrom, and a carbon-carbon bond graft component is introduced into the side chain or the double bonds are bridged. Included (styrene modified, acrylic modified polyester, etc.).
In addition, a resin component having a different structure is copolymerized in the main chain of the polyester or reacted with a carboxyl group or a hydroxyl group at the end, for example, a silicone resin having a terminal modified with a carboxyl group, a hydroxyl group, an epoxy group, or a mercapto group Copolymerized ones (such as silicone-modified polyester) are also included.

Hereinafter, the urea-modified polyester will be specifically described as an example.
<Urea-modified polyester (polyester modified through urea bonds)>
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 polycondensate of a polyol (ii) and a polycarboxylic acid (b) and a polyester having an active hydrogen group, which is further reacted 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 these, an alcoholic hydroxyl group is preferable.
Examples of the polyol (I) include a diol (I-1) and a tri- or higher valent polyol (I-2). Mixtures are preferred.

Diol (I-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. 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 glycols having 2 to 12 carbon atoms. It is a combined use.
The trivalent or higher polyol (I-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polycarboxylic acid (b) include dicarboxylic acid (b-1) and trivalent or higher polycarboxylic acid (b-2), (b-1) alone, and (b-1) and a small amount of ( The mixture of b-2) is preferred.
Dicarboxylic acids (ro-1) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). 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 (ro-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as polycarboxylic acid (b), you may make it react with polyol (i) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.
The ratio of the polyol (I) and the polycarboxylic acid (B) is an equivalent ratio of the hydroxyl group [OH] and the carboxyl group [COOH] = [OH] / [COOH], usually 2/1 to 1/1, preferably 1 0.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

Examples of polyisocyanates (c) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates as phenol derivatives, oximes, caprolactam And a combination of two or more of these.
The ratio of polyisocyanate (C) is an equivalent ratio of isocyanate group [NCO] and hydroxyl group [OH] of the polyester having a hydroxyl group = [NCO] / [OH], usually 5/1 to 1/1, preferably 4 / 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, the low-temperature fixability deteriorates. When [NCO] / [OH] is less than 1, the urea content in the modified polyester decreases, 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% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates 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 deteriorates.
Prepolymer (A) having an isocyanate group The number of isocyanate groups contained per molecule is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. . If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

As amines (B), diamine (B1), triamine or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned.
Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, cyclohexane) Diamine, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).
Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).
The ratio of amines (B) is equivalent ratio of isocyanate group [NCO] in prepolymer (A) having isocyanate groups to amino group [NHx] in amines (B) = [NCO] / [NHx]. In general, it is 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1.2 / 1 to 1 / 1.2.
When [NCO] / [NHx] exceeds 2 or 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 together with a urea bond. The molar ratio of the urea bond content to 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. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.
The urea-modified polyester (i) in the present invention is produced by a one-shot method or a prepolymer method.
The weight average molecular weight of (i) is usually 10,000 or more, preferably 2 to 10 million, and more preferably 3 to 1 million. If it is less than 10,000, the hot offset resistance deteriorates.
The number average molecular weight of (i) is not particularly limited when the below-mentioned unmodified polyester (ii) is used, and may be a number average molecular weight convenient for the weight average molecular weight.
(I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. If it exceeds 20000, the low-temperature fixability and the gloss when used in a full-color device are deteriorated.

<Unmodified polyester>
In the present invention, not only the urea-modified polyester (i) is used alone, but also the unmodified polyester (ii) can be contained as a toner binder component together with the (i). The combined use of (ii) improves the low-temperature fixability and gloss when used in a full-color device, and is therefore preferable to single use.
Examples of (ii) include the same polycondensates of polyol (I) and polycarboxylic acid (B) as in the polyester component (i), and preferred ones are also the same as (i).
In place of (ii), it is also 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 (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, it is preferable that the polyester component excluding the modified portion of (i) and (ii) have a similar composition.

When (ii) is contained, the weight ratio of (i) and (ii) needs to be in the range of 1/99 to 80/20, and is usually 5/95 to 80/20, preferably 5/95. To 30/70, more preferably 5/95 to 25/75, and 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%.
This range of composition ratios applies not only to the urea-modified polyester (i) but also to other modified polyesters used in the present invention.
The peak molecular weight of (ii) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, the heat-resistant storage stability is deteriorated, and if it exceeds 10,000, 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 20 to 80 mgKOH. 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 mgKOH. By giving the 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 to 65 ° C. If it is less than 50 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the urea-modified polyester resin, the dry toner produced by the method of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners.
As the storage elastic modulus of the toner binder, a toner binder having a temperature (TG ′) of 10000 dyne / cm ^{2 at} a measurement frequency of 20 Hz is usually 100 ° C. or more, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates.
As the viscosity of the toner binder, one having a temperature (Tη) of 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or less, preferably 90 to 160 ° C. If it 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 (TG′−Tη) is preferably greater than 0 ° C., more preferably 10 ° C. or more, and particularly preferably 20 ° C. or more. 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 preferably in the range of 0 to 100 ° C., more preferably 10 to 90 ° C., and particularly preferably 20 to 80 ° C. .

<Colorant>
As the colorant used in 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), Vulcan Fast Yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Physe Red Parachloro Tonitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing 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, pyrazolo Red, Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bituminous Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Ki, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As a binder resin to be kneaded with the production of the master batch or the master batch, in addition to the modified and unmodified polyester resins listed above, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and polymers of substituted products thereof. Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, 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, Len-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like can be mentioned, and these are used alone or in combination.

The masterbatch can be obtained by mixing and kneading the masterbatch resin and the colorant under high shearing force. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin.
In addition, a so-called flushing method in which an aqueous paste containing water of a colorant is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed is also a wet 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 shearing dispersion device such as a three-roll mill is preferably used.

<Release agent>
The toner produced by the method of the present invention may contain a wax together with a toner binder and a colorant.
Known waxes can be used, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sazol wax, etc.); carbonyl group-containing wax, and the like. Of these, carbonyl group-containing waxes are preferred.
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 esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearylamide, etc.) And dialkyl ketones (such as distearyl ketone).
Of these, polyalkanoic acid esters are preferred.

The melting point of the wax used in the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat-resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature.
Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point.
Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability.
The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

<Charge control agent>
The toner produced by the method of the present invention may contain a charge control agent as necessary.
Any known charge control agent can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified) Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.
Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenolic condensate E-89 (above, Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary Copy charge PSY VP2038 of ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR- which is a boron complex 147 (manufactured by Nippon Carlit), copper phthalocyanine, perylene, quinaclide , Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin, and preferably in the range of 0.2 to 5 parts by weight. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline.
These charge control agents and release agents can be melt-kneaded together with the masterbatch and the resin, and of course, they may be added when dissolved and dispersed in an organic solvent.

<Toner production method in aqueous medium>
As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (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 produced by the method exemplified below.
The polyol (i) and the polycarboxylic acid (b) 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 while reducing the pressure as necessary. Distill off to obtain a polyester having a hydroxyl group.
Next, this polyester is reacted with polyisocyanate (C) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group.
Further, the amine (B) is reacted with (A) at 0 to 140 ° C. to obtain a polyester modified with a urea bond.
When reacting (c) and reacting (A) and (B), a solvent may be used as necessary.
Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.); ethers Inactive to polyisocyanate (c), such as a class (such as tetrahydrofuran).

When the unmodified polyester (ii) is used in combination, (ii) is produced by the same method as that for the polyester having a hydroxyl group, and this is dissolved and mixed in the solution after the completion of the reaction (i).
In order to shrink the volume of the toner composition and lower the viscosity of the oil phase, a volatile solvent in which the modified polyester (i) or (A) is soluble is used.
The solvent is preferably a volatile solvent having a boiling point of less than 100 ° C. from the viewpoint of easy removal. For example, 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.
In addition, volume shrinkage can be adjusted by using a solvent that can be dissolved in an aqueous medium such as alcohol or water.
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.

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

In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. It may be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.
The dispersion method is not particularly limited, and known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an acoustic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing method is preferable.
The emulsifier having a rotary blade is not particularly limited, and any emulsifier and disperser that are generally commercially available can be used. For example, Ultra Thalax (manufactured by IKA), Polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Special Machine Industries), Ebara Milder (manufactured by Ebara Corporation), TK pipeline homomixer, TK homomic line Flow (manufactured by Koki Kogyo Kogyo Co., Ltd.), colloid mill (manufactured by Shinko Pantech Co., Ltd.), thrasher, trigonal wet pulverizer (manufactured by Mitsui Miike Chemical Co., Ltd.), Cavitron (manufactured by Eurotech Co., Ltd.), fine flow mill (Pacific Kiko) A continuous emulsifier such as a continuous emulsifier such as CLEAMIX (manufactured by M Technique Co., Ltd.), a fill mix (manufactured by Tokushu Kika Kogyo Co., Ltd.) or the like.

When a high-speed shearing disperser is used, the rotation speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm.
The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 10 to 98 ° C. Higher temperatures are preferred in that the dispersion made of urea-modified polyester (i) or prepolymer (A) has a low viscosity and is easily dispersed.
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). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, toner particles having a predetermined particle diameter cannot be obtained, and if it exceeds 2000 parts by weight, it is not economical.
The solid fine particle dispersant is dispersed in the aqueous medium, but as described above, other dispersants can be used in combination in order to adjust the adsorptivity of the solid fine particle dispersant to the droplets. The other dispersant can be added before emulsification of the toner composition or when the volatile component is removed after emulsification.

<Solid particulate dispersant>
The solid fine particle dispersant is present in a solid state 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, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, 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 also be used. In particular, hydroxyapatite synthesized by reacting sodium phosphate and calcium chloride in water under basic conditions is preferable.

Examples of organic solid fine particle dispersants include microcrystals of low molecular weight organic compounds and polymer fine particles, such as polystyrene, methacrylate esters, acrylate ester copolymers obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization. , Polymer particles of polycondensation resin such as silicone resin, benzoguanamine resin, nylon, and thermosetting resin.
In the case of using a solid fine particle dispersant that is soluble in alkali such as calcium phosphate salt, polymer fine particles copolymerized with (meth) acrylic acid having a carboxyl group, an acid such as hydrochloric acid or sodium hydroxide is used. The solid fine particle dispersant is removed from the toner particles whose shape has been adjusted by a method of dissolving the solid fine particle dispersant with water or a base and then washing with water. In addition, it can be removed by an operation such as enzymatic degradation.

<Other dispersants used at the time of emulsification or added later>
Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, alkyltrimethylammonium salts, Nonionic interfaces such as dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, quaternary ammonium salt type cationic surfactants such as benzethonium chloride, fatty acid amide derivatives, polyhydric alcohol derivatives, etc. Activators include amphoteric surfactants such as alanine, dodecyl di (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

In addition, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount.
Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6 ~ C11) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11 -C20) carboxylic acid and metal salt, perfluoroalkylcarboxylic acid (C7-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) Examples thereof include ethyl phosphate ester.

Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), MegaFuck F-l10, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F-150 (manufactured by Neos).
In addition, as cationic surfactants, aliphatic primary, secondary or tertiary amines having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, Benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like are listed, and trade names include Surflon S-121 (manufactured by Asahi Glass Co., Ltd.), Florard FC-135 (manufactured by Sumitomo 3M Co., Ltd.), Unidyne DS-202. (Daikin Kogyo Co., Ltd.), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.) It is done.

The stabilization of the dispersed droplets may be adjusted with a polymer protective colloid.
For example, acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride; (meth) acrylic monomers containing hydroxyl groups For example, 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 monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Ter, 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; esters of compounds containing vinyl alcohol and carboxyl groups For example, vinyl acetate, vinyl propionate, vinyl butyrate; 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 Homopolymers or copolymers such as those having a nitrogen atom such as imine or a heterocyclic ring thereof; polyoxyethylene, polyoxypropylene, polyoxyethylene alcohol Lumine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester, etc. Polyoxyethylene type; celluloses such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and the like can be used.

When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.
The elongation 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. It's time.
The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C.
Moreover, a well-known catalyst can be used as needed. 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 raising the temperature of the entire system and completely removing the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation.
As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
As the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder by drying, but it is preferable in the liquid to perform the classification operation.
The obtained unnecessary fine particles or coarse particles can be returned to the kneading step and used for forming particles. At that time, fine particles or coarse particles may be in a wet state.
The dispersant used is preferably removed from the obtained dispersion as much as possible, and is preferably performed simultaneously with the classification operation described above.
The resulting dried toner powder is mixed with different particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, and mechanical impact force is applied to the mixed powder. In this way, it is possible to prevent detachment of foreign particles from the surface of the composite particles obtained by immobilizing and fusing them on the surface.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture into a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there.
As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system (Made by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

<Dry toner manufacturing method>
The dry toner can be produced by the following method, but is not limited thereto. In addition, when preparing the developer, in order to improve the fluidity, storage stability, developability, and transferability of the developer, the hydrophobic silica fine particles listed above are further listed in the developer produced as described above. Inorganic fine particles such as powder may be added and mixed.
For mixing external additives, a general powder mixer is used, but it is preferable to adjust the internal temperature by providing a jacket or the like. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa.
Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.
In order to further adjust the shape of the obtained toner, a toner material comprising a toner binder and a colorant is melt-kneaded and then finely pulverized and then mechanically adjusted using a hybridizer, mechano-fusion, etc. In addition, after dissolving and dispersing the toner material in a solvent in which the toner binder is soluble, a so-called spray-drying method in which a spherical toner is obtained by removing the solvent using a spray-drying device, or spherical by heating in an aqueous medium. However, it is not limited to these.

<External additive>
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used.
The primary particle size of the inorganic fine particles is preferably 5 mμ to 2 μm, particularly preferably 5 to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.
The use ratio of the inorganic fine particles 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, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylate esters, acrylate copolymers, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting Examples thereof include polymer particles made of a resin.
Such a fluidizing agent can prevent deterioration of flow characteristics and charging characteristics under high humidity by performing surface treatment to increase hydrophobicity.
For example, preferable surface treatment agents include silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like. It is done.
Examples of cleaning improvers for removing the developer remaining on the photosensitive member and the primary transfer medium after transfer include soap-free fatty acid metal salts such as zinc stearate and calcium stearate, polymethyl methacrylate fine particles, polystyrene fine particles, and the like. Examples thereof include fine polymer particles produced by emulsion polymerization.
The fine polymer particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

<Carrier for two-component developer>
When the toner produced by the method of the present invention is used for a two-component developer, it may be mixed with a magnetic carrier, and the carrier to toner content ratio in the developer is 100 parts by weight of the carrier. 1 to 10 parts by weight of toner is preferred.
As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 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. Also, polyvinyl resins and polyvinylidene resins such as acrylic resins, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polystyrene resins such as polystyrene and styrene acrylic copolymer resins, and halogens such as polyvinyl chloride. Polyolefin resin, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, vinylidene fluoride and acrylic monomer Fluoropolyesters such as copolymers with vinylidene, copolymers of vinylidene fluoride and vinyl fluoride, terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers Chromatography, and silicone resins.
Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle size of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control the electric resistance.
The toner produced by the method 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.

  According to the present invention, (1) a highly transferable toner that gives high image quality, (2) a small particle size that has little adhesion to carriers and mechanical parts, a narrow particle size distribution that does not contain ultrafine particles, and is durable Toner, (3) Toner having a shape that can be cleaned with a simple device, (4) Desired volume shrinkage of 10% to 90% in aqueous medium using solid particulate dispersant It is possible to provide a production method capable of obtaining a toner that maintains the particle size and particle size distribution and has both proper gloss and releasability as a full color toner. Further, it is possible to provide a full-color development method and transfer method using the toner produced by the production method.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples.
In the examples and comparative examples, “parts” is “parts by weight”.

Examples and Comparative Examples ★ Test 1
[Preparation and evaluation of toner with varying amount of organic solvent added to aqueous medium, average circularity and fine particle content by treatment before solvent removal]
≪Synthesis of toner binder≫
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of terephthalic acid and 2 parts of dibutyltin oxide are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and subjected to a polycondensation reaction at 230 ° C. for 8 hours under normal pressure. The mixture was further reacted for 5 hours under reduced pressure of 10 to 15 mmHg to obtain an unmodified polyester (a) having a peak molecular weight of 5300.
100 parts of this unmodified polyester (a) was dissolved and mixed in 100 parts of ethyl acetate to obtain an ethyl acetate solution of a toner binder. A portion was taken and dried under reduced pressure to isolate the toner binder. The Tg was 62 ° C. and the acid value was 10.
≪Toner creation≫
Place 200 parts of ethyl acetate solution of the above toner binder, 5 parts of carnauba wax, 4 parts of copper phthalocyanine blue pigment, 1 part of zinc ditertiary butylsalicylate in a sealed pot, and ball mill dispersion for 24 hours using 5 mmφ zirconia beads. And a toner composition was obtained.
Separately, 600 parts of ion exchange water, X part 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, the internal temperature of the beaker was maintained at 20 ° C., and the toner composition was added while stirring at 12000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
Next, this mixed solution was transferred to a flask equipped with a stir bar and a thermometer, 0.3 parts of sodium lauryl sulfate and Y part of 35% concentrated hydrochloric acid were added, and the mixture was stirred and dissolved at room temperature for 30 minutes.
Subsequently, the solvent was removed under reduced pressure at 30 ° C. and 50 mmHg.
When the dispersion was analyzed by gas chromatography, the residual ethyl acetate was 50 ppm with respect to the toner particles.
Subsequently, 120 parts of 35% concentrated hydrochloric acid was added to dissolve the tricalcium phosphate, followed by filtration, and the operation of redispersing and filtering the obtained cake in distilled water was repeated three times. And dried under reduced pressure for 24 hours to obtain toner particles.
Finally, 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were added to 100 parts of toner particles and mixed with a Henschel mixer to obtain a toner according to the present invention.
These toner preparation conditions and toner characteristic values are as shown in Table 1 below.

Table 2 shows the evaluation results of the 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 and 95 parts by weight of the following carrier were mixed for 10 minutes with a blender to prepare a developer.
At that time, in order to obtain sufficient developability of the toner and to prevent background contamination due to the reversely charged toner, the stirring time and speed are adjusted so that the charge amount is about 15 to 25 (μC / g) in absolute value. Adjusted.
[Carrier]
・ Core material: Spherical ferrite particles with an average particle size of 50 μm ・ Coating material constituent material: Silicone resin in which aminosilane coupling agent is dispersed (After dispersing the aminosilane coupling agent and silicone resin in toluene and adjusting the dispersion, (The core material was spray-coated in a heated state, then fired and cooled to an average coated resin film thickness of 0.2 μm.)

For fine line reproducibility, the developer prepared as described above is placed in a commercially available color copying machine (PRETER550: manufactured by Ricoh), and running is performed using 6000 paper manufactured by Ricoh with a printing ratio of 7% image occupancy. Compare the original 10th image and the 30,000th image thin line with the original, observe it at 100x magnification with an optical microscope, and compare the line omission state with the step sample. It was evaluated with.
For cleaning performance, after running 30,000 sheets under the same conditions as in the case of fine line reproducibility, 10 full-color images are output continuously, stopped during development of the 10th sheet, and toner after the cleaning blade on the photoconductor The tape was transferred, and the degree of soiling of the tape was evaluated by comparison with a four-stage sample.
In both fine line reproducibility and cleaning properties, the image quality is higher in the order of ＞>○>Δ> ×. In particular, the evaluation of x is a level that cannot be adopted as a product.

表２の結果から分るように、本発明に係るトナーは、初期の細線再現性、ラン後の細線再現性、クリーニング性に優れるが、特に平均円形度が前述した範囲よりも大きいとクリーニング性に劣るようになり、また、小さ過ぎると初期の細線再現性が悪くなる。一方、２μｍ以下の微粉の含有量が前述した範囲よりも多いとラン後の細線再現性が悪くなり、耐久性に劣るトナーとなる。

As can be seen from the results in Table 2, the toner according to the present invention is excellent in initial fine line reproducibility, fine line reproducibility after run, and cleaning properties. In addition, if it is too small, the initial fine line reproducibility is deteriorated. On the other hand, if the content of fine powder of 2 μm or less is larger than the above-described range, the fine line reproducibility after the run is deteriorated and the toner is inferior in durability.

★ Test 2
[Experiment to confirm the effect of shrinkage, particle size, particle size distribution, and shape on image quality]
The toner H of the present invention shown in Table 1 (toner H obtained by the production method of the present invention) is referred to as Example 1, and various production conditions are changed as in Examples 2 to 12 below. The effect of distribution and shape on image quality was investigated.

Example 2
210 parts of the toner composition after ball mill dispersion obtained in Example 1 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 to form particles after emulsification. Thereafter, the same operation as in Example 1 was performed to obtain a toner according to the present invention.

Example 3
350 parts of the toner composition after the ball mill dispersion obtained in Example 1 was concentrated to 210 parts by an evaporator, and 210 parts of this concentrated dispersion was processed in the same manner as in Example 1 to form particles after emulsification. Thereafter, the same operation as in Example 1 was performed to obtain a toner according to the present invention.

Example 4
210 parts of the toner composition after ball mill dispersion obtained in Example 1 was diluted with 1165 parts of ethyl acetate, and 210 parts of this diluted dispersion was treated in the same manner as in Example 1 to form particles after emulsification. Thereafter, the same operation as in Example 1 was performed to obtain a toner according to the present invention.

Example 5
368 parts of the toner composition after ball mill dispersion obtained in Example 1 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 form particles after emulsification. Thereafter, the same operation as in Example 1 was performed to obtain a toner according to the present invention.

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

Example 7
It replaced with the emulsification apparatus (TK type | mold homomixer) used in Example 1, and it operated similarly to Example 1 except the point emulsified at 15000 rpm using TK Philmix FM30-50 (made by special equipment company). Thus, a toner according to the present invention was obtained.

Example 8
A toner according to the present invention was obtained in the same manner as in Example 1 except that the amount of sodium dodecylbenzenesulfonate used in preparation of the aqueous medium in Example 1 was changed to 0.2 parts.

Example 9
A toner according to the present invention was obtained in the same manner as in Example 1 except that the amount of sodium dodecylbenzenesulfonate used in preparation of the aqueous medium in Example 1 was changed to 0.1 part.

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 among the operations in Example 1.

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

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

  Table 3 shows the physical properties and image evaluation results of the toner obtained as described above. “Shrinkage” in the table is determined from the amount of ethyl acetate contained in the oil phase. “Dv” is the volume average particle size (μm), and “Dv / Dn” represents the ratio of the volume average particle size to the number average particle size.

★ Test 3
[Confirmation of effect when modified polyester is used for toner binder]
≪Synthesis of modified polyester 1≫
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 230 ° C. for 8 hours under normal pressure. The reaction was further carried out under reduced pressure of 10 to 15 mmHg for 5 hours, followed by cooling to 160 ° C., followed by addition of 32 parts of phthalic anhydride and reaction for 2 hours.
Subsequently, it cooled to 80 degreeC and made it react with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the isocyanate containing prepolymer (1) was obtained.
Next, 267 parts of prepolymer (1) and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours, and ethyl acetate was distilled off to obtain urea-modified polyester (1) having a weight average molecular weight of 64,000.

≪Synthesis of modified polyester 2≫
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 724 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid and 70 parts of fumaric acid, and 2 parts of dibutyltin oxide were placed at 230 ° C. under normal pressure. The mixture was further reacted for 8 hours under a reduced pressure of 10 to 15 mmHg, then cooled to 160 ° C., and subsequently 32 parts of phthalic anhydride was added and reacted for 2 hours.
Next, the mixture is cooled to 80 ° C., 200 parts of styrene, 1 part of benzoyl peroxide and 0.5 part of dimethylaniline are added in ethyl acetate and reacted for 2 hours. The ethyl acetate is distilled off and polystyrene having a weight average molecular weight of 92,000 is obtained. Graft-modified polyester (2) was obtained.

<< Creation of toner binder 3 >>
30 parts of urea-modified polyester (1) and 970 parts of unmodified polyester (a) (see Example 1) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (methyl ethyl ketone) (volume ratio 1/1), and the toner is mixed. An ethyl acetate / MEK solution of binder (3) was obtained.
A part was taken and dried under reduced pressure to isolate toner binder (3).

<< Creation of toner binder 4 >>
500 parts of urea-modified polyester (1) and 500 parts of unmodified polyester (a) are dissolved and mixed in 2000 parts of an ethyl acetate / MEK (volume ratio 1/1) mixed solvent, and the toner binder (4) ethyl acetate / MEK is mixed. A solution was obtained.
A part was taken and dried under reduced pressure to isolate the toner binder (4).

<< Creation of toner binder 5 >>
750 parts of urea-modified polyester (1) and 250 parts of unmodified polyester (a) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1), and ethyl acetate / MEK of toner binder (5). A solution was obtained.
A part was taken and dried under reduced pressure to isolate the toner binder (5).

<< Creation of toner binder 6 >>
850 parts of urea-modified polyester (1) and 150 parts of unmodified polyester (a) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1), and ethyl acetate / MEK of toner binder (6). A solution was obtained.
A part was taken and dried under reduced pressure to isolate the toner binder (6).

<< Synthesis of Toner Binder 7 >>
924 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted for 5 hours under reduced pressure of 10 to 15 mmHg to give an unmodified polyester having a peak molecular weight of 5000. (B) was obtained.
100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (b) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1), and ethyl acetate / MEK of toner binder (7). A solution was obtained.
A part 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 bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted for 5 hours under reduced pressure of 10 to 15 mmHg to give an unmodified polyester having a peak molecular weight of 5000. (C) was obtained.
100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (c) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1), and ethyl acetate / MEK of toner binder (8) is mixed. A solution was obtained.
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, then reacted for 5 hours under reduced pressure of 10 to 15 mmHg, then cooled to 160 ° C., 32 parts of trimellitic anhydride was added thereto and reacted for 2 hours to obtain an unmodified polyester (d) having a peak molecular weight of 5000.
100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (d) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1), and the ethyl acetate / MEK of toner binder (9) is mixed. A solution was obtained.
A part 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, then reacted for 5 hours under reduced pressure of 10 to 15 mmHg, then cooled to 160 ° C., 48 parts of trimellitic anhydride was added thereto and 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) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1), and ethyl acetate / MEK of toner binder (10). A solution was obtained.
A part 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-mole adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 2 hours under normal pressure, and then reacted for 5 hours under reduced pressure of 10 to 15 mmHg to give an unmodified polyester having a peak molecular weight of 1000 (F) was obtained.
100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (f) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1), 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-mole adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 4 hours under normal pressure, and then reacted for 5 hours under reduced pressure of 10 to 15 mmHg to give an unmodified polyester having a peak molecular weight of 2000. (G) was obtained.
100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (g) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1), and ethyl acetate / MEK of toner binder (12) is mixed. A solution was obtained.
A part 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-mole adduct and 276 parts of terephthalic acid are polycondensed at 230 ° C. for 10 hours under normal pressure, and then reacted for 5 hours under reduced pressure of 10 to 15 mmHg to give an unmodified polyester having a peak molecular weight of 30000 (H) was obtained.
100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (h) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1), and ethyl acetate / MEK of toner binder (13). A 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-mole adduct and 276 parts of terephthalic acid are subjected to polycondensation under normal pressure at 230 ° C. for 12 hours and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours to give an unmodified polyester having a peak molecular weight of 30000 (J) was obtained.
100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (j) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (volume ratio 1/1), and ethyl acetate / MEK of toner binder (14). A solution was obtained.
A part was taken and dried under reduced pressure to isolate the toner binder (14). Tg was 73 ° C.

Examples 13-26
≪Toner creation≫
A toner was prepared by the same method as the toner G of the present invention in Test 1.
That is, in a sealed pot, 200 parts of a solution composed of 100 parts of a toner binder having the composition shown in Table 2 and 100 parts of ethyl acetate, 5 parts of carnauba wax, 4 parts of copper phthalocyanine blue pigment, 1 part of zinc dibutyl butylsalicylate And a ball mill dispersion was performed for 24 hours using 5 mmφ zirconia beads to obtain a toner composition.
Separately, 600 parts of ion exchange 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, the internal temperature of the beaker was maintained at 20 ° C., and the toner composition was added while stirring at 12000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) and stirred for 3 minutes to emulsify.
Next, this mixed solution was transferred to a flask equipped with a stir bar and a thermometer, 0.3 parts of sodium lauryl sulfate and 30 parts of 35% hydrochloric acid were added, and the mixture was stirred and dissolved at room temperature for 30 minutes.
Subsequently, the solvent was removed under reduced pressure at 30 ° C. and 50 mmHg.
When the dispersion was analyzed by gas chromatography, the residual ethyl acetate was 50 ppm with respect to the toner particles.
Subsequently, 120 parts of 35% concentrated hydrochloric acid was added to dissolve the tricalcium phosphate, followed by filtration, and the operation of redispersing and filtering the obtained cake in distilled water was repeated three times, followed by washing at 40 ° C. And dried under reduced pressure for 24 hours to obtain toner particles.
Finally, 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were mixed with 100 parts of toner particles using a Henschel mixer to obtain a toner according to the present invention.

表中、Ｍｐは分子量分布ピーク、Ｍｗ／Ｍｎは重量平均と個数平均分子量の比、Ｔｇはガラス転移点（℃）である。 Table 4 summarizes the composition and physical properties of each toner obtained as described above.

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.).

表４、表５の結果から、テスト１における変性ポリエステルを用いていない本発明トナーＧと比較すると、変性ポリエステルを適量用いたテスト３の本発明に係るトナーは、酸価、分子量ピーク、ガラス転移温度が前述した数値範囲内のものの場合、低温定着性と高温耐オフセット性に優れ、また、より低温でのＧＬＯＳＳ（光沢発現温度）が高いことが分る。

From the results of Tables 4 and 5, when compared with the toner G of the present invention that does not use the modified polyester in Test 1, the toner according to the present invention of Test 3 using an appropriate amount of the modified polyester has an acid value, molecular weight peak, glass transition When the temperature is within the above-mentioned numerical range, it can be seen that the low temperature fixing property and the high temperature offset resistance are excellent, and the GLOSS (gloss expression temperature) at a lower temperature is high.

The above toners were evaluated as follows.
≪Powder flowability≫
The bulk density was measured using a powder tester made by Hosokawa Micron. The toner with better fluidity has a higher bulk density and was evaluated in the following four stages.
X: Less than 0.25
Δ: 0.25 to less than 0.30
○: 0.30 or more and less than 0.35
A: 0.35 or more <Heat resistant storage stability>
After storing the toner at 50 ° C. for 8 hours, the toner was sieved with a 42 mesh sieve for 2 minutes, and the residual rate on the wire mesh was regarded as heat resistant storage stability. The toner with better heat-resistant storage stability has a lower residual rate, and was evaluated in the following four stages.
×: 30% or more
Δ: 20 to less than 30%
○: 10 to less than 20%
A: Less than 10%

≪Fixing temperature limit≫
Using a device in which the fixing unit of the Ricoh Copier MF-200, which uses a Teflon (registered trademark) roller as a fixing roller, was modified, Ricoh type 6200 paper was set on this and a copying test was performed. The fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad becomes 70% or more was determined as the minimum fixing temperature.
≪Hot offset generation temperature (HOT) ≫
A copy test was conducted in the same manner as the above-mentioned minimum fixing 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.
≪Glossy expression temperature (GLOSS) ≫
The fixing was evaluated using a fixing device of a commercially available color copying machine (PRETER 550; 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.

Claims (7)

The door toner composition is dissolved or dispersed in an organic solvent, the step of emulsification and dispersion in an aqueous medium using a solid particulate dispersion agent, the step of the part of the particle dispersant from emulsified dispersed droplets desorbed volume A dry toner characterized by obtaining particles having an average circularity of 0.933 to 0.986 through a shrinking step and a step of removing the fine particle dispersant that has not been removed in the step of removing the part. Production method. Method for producing a dry toner according to claim 1, wherein the toner composition is characterized in that it comprises a modified polyester. The toner composition comprising a modified polyester is dissolved or dispersed in an organic solvent, in the step of dispersing in water based medium, the dry toner according to claim 2, characterized in that to produce a polyester having a urethane or urea bond Production method. The electrostatic latent image divided into each color formed on a single photosensitive member 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. A developing method using a developer using dry toner produced by any one of claims 1 to 3 in a method of developing a toner with a developer corresponding to each color. The electrostatic latent image divided into each color formed on a single photoconductor by a plurality of developing devices having a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll. was developed by a developing agent corresponding to each color, a method of transferring to an intermediate transfer body by the electric field, the use of developer using dry toner produced by the method of any of claims 1-3 A characteristic transfer method. Each color formed on a plurality of photoconductors corresponding to the developing device was divided by a plurality of developing devices including a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll. A method for developing an electrostatic latent image with a developer corresponding to each color, wherein the developer using a dry toner produced by any one of the methods of claims 1 to 3 is used. . Each color formed on a plurality of photoconductors corresponding to the developing device was divided by a plurality of developing devices including a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll. was developed by a developing agent corresponding electrostatic latent image to each color, a method of transferring to an intermediate transfer body by the electric field, the developer using the dry toner produced by the method of any of claims 1-3 A transfer method characterized by using.