JP5495685B2 - toner - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method or a toner jet method.

  In the electrophotographic industry, the image resolution of printers and the like has been increased to 1200, 2400 dpi. Accordingly, the development method of the printer apparatus is also required to have higher definition. Also, copying machines are becoming more sophisticated, digitized, and full-color, and high resolution and high definition have been demanded as with printers.

  Further, in recent years, as copiers and printers using electrophotography have been widely used, including in homes, etc., there is an increasing demand for making copy machines or printers inexpensive and small. In response to the above requirements, it has been demanded to enable a design with simpler components.

  In that respect, the non-magnetic one-component development system is more preferable because the two-component development system uses a carrier and requires a mechanism for controlling the mixing ratio of the carrier and the toner.

  There are two types of such non-magnetic one-component development methods: contact development in which the toner carrier and the latent image carrier are in contact and non-contact development in which the toner carrier and the latent image carrier are not in contact. The contact development method is advantageous in that the edge effect is suppressed and the effect is good, and the density unevenness of the image is less likely to occur even if toner frictional charging is somewhat nonuniform. However, since the latent image carrier and the toner carrier are in contact with each other, the toner is liable to deteriorate due to the stress caused by the friction, the toner fluidity and the frictional charging uniformity are lowered, the fog is increased, and the transfer efficiency is increased. A decrease occurs and is not preferable. Further, it is not preferable because the toner is easily fused or filmed to the frictional charging member, the developing roller, the photosensitive member, etc., and the image quality is lowered. Furthermore, even if the toner carrying member rubs the surface of the photoconductor, the toner is insufficiently tribocharged. If the toner is triboelectrically charged to some extent, the toner will easily adhere to the surface of the photoconductor. May be reduced, which is not preferable. On the other hand, the non-contact development method is superior to the contact system in adjusting the density of a halftone image or the like. However, if the triboelectric charge of the developer on the developer carrier is insufficient, the developer cannot fly to the latent image carrier, resulting in a low density. Further, if the developer is not uniformly charged, image unevenness or the like in which the density is locally reduced on the image occurs. Furthermore, there is a problem that the frictional charging is insufficient and the developer that has not been able to fly to the latent image carrier is scattered and the interior of the apparatus is soiled. Also, the image quality related to the edge portion of the image such as Hakiyo is inferior to the contact system. Under such circumstances, there are the following methods for designing toner with a focus on miniaturization of copying machines and printers. In a toner having a core-shell structure, a hybrid resin is used as the main component of the shell, so that a toner excellent in offset resistance, low-temperature fixability and blocking resistance, and excellent in frictional charging stability under high temperature and high humidity can be obtained. There is a way. However, when further lower temperature fixability is required, compatibility with blocking resistance is insufficient, and particularly in use in a non-magnetic one-component development system, a latent image carrier, a developer carrier, and a layer thickness regulating member. It is easy to generate a problem such as fusing (see Patent Document 1).

  Further, as another method, there is a method in which a toner excellent in storage stability, fixing property, offset resistance, and charging property can be obtained by containing alkenyl succinic acid at the terminal of the polyester resin. However, when used for a long period of time, the triboelectric chargeability becomes insufficient, causing a problem that a sufficient image density cannot be obtained (see Patent Document 2).

JP 2006-330408 A JP 2007-248582 A

  An object of the present invention is to provide a toner that solves the above problems. That is, the object of the present invention is to have excellent low-temperature fixability, offset resistance, and anti-blocking property, and to prevent fogging and thinning of the toner on the latent image carrier and developer carrier surface even during long-term use. It is an object of the present invention to provide a toner capable of obtaining an excellent image without causing problems such as member contamination such as adhesion and fusion to a layer thickness regulating member.

The present invention, toner particles obtained by a hybrid resin mixture containing a heavy polymerizable monomer and the hybrid resin was suspended polymerized in an aqueous medium,
Inorganic fine powder ,
A toner having
The polymerizable monomer includes a styrene derivative and an acrylic polymerizable monomer,
The hybrid resin,
A vinyl polymer unit;
A polyester unit ;
There is a resin having a chemically bonded molecular structure,
The hybrid resin is a vinyl-modified polyester resin produced by polymerizing a vinyl monomer to polyester,
The vinyl monomer includes a styrene derivative,
The hybrid resin relates to a toner having peaks at 4.6 ppm to 4.9 ppm and 5.0 ppm to 5.2 ppm in ¹ H-NMR measurement using a deuterated chloroform solvent.

According to the present invention, a hybrid resin having a peak at 4.6 to 4.9 ppm and 5.0 to 5.2 ppm and polymerizability in ¹ H-NMR measurement using at least deuterated chloroform solvent in an aqueous medium. By producing and using toner particles by polymerizing a hybrid resin mixture containing monomers in an aqueous medium, it has excellent low-temperature fixability, offset resistance, and blocking resistance, but also has a concentration even for long-term use. It is possible to obtain an excellent image free from problems such as thinness, fogging, toner and external additives on the latent image carrier and developer carrier surface, and fusion to a layer thickness regulating member. it can.

It is explanatory drawing of a flow tester outflow curve.

As a result of intensive studies by the present inventors, a toner having toner particles and inorganic fine powder obtained by polymerizing a hybrid resin mixture containing at least a polymerizable monomer and a hybrid resin in an aqueous medium,
The hybrid resin contains at least a resin having a molecular structure in which a vinyl polymer unit and a polyester unit are chemically bonded,
In the measurement of ¹ H-NMR of the hybrid resin using a deuterated chloroform solvent, it has been found that it is important to satisfy having peaks at 4.6 ppm to 4.9 ppm and 5.0 ppm to 5.2 ppm. The present invention has been completed.

Details will be described below. ^In the measurement of ¹ H-NMR, the hybrid resin having peaks of 4.6 ppm to 4.9 ppm and 5.0 ppm to 5.2 ppm has a carbon-carbon unsaturated double bond at the end of the vinyl polymer unit. It shows having (derived from a styrene unit).

  Therefore, when the hybrid resin mixture containing the hybrid resin and the polymerizable monomer is polymerized in an aqueous medium, the following phenomenon occurs. First, a carbon-carbon unsaturated double bond present at the terminal of the vinyl polymer unit of the hybrid resin is polymerized with a polymerizable monomer present in the hybrid resin mixture to construct a crosslinked structure. In particular, when the hybrid resin is controlled to be distributed on the toner surface, the toner surface has a moderately crosslinked structure. As a result, the toner becomes moderately strong and has good fixability, while maintaining good anti-blocking properties and good image quality over a long period of time. Furthermore, the inorganic fine powder present on the surface of the toner particles is difficult to be embedded due to this appropriate cross-linking structure, and when attached by means such as a Henschel mixer, it has an appropriate adhesion strength and is not easily released from the surface of the toner particles. This is particularly desirable because the image quality can be maintained over a long period of use.

  In addition, when the main binder of the toner is a polymer derived from the polymerizable monomer by polymerizing with the polymerizable monomer, the main binder and the hybrid resin are chemically bonded to each other. It is hard to break even if added.

  Furthermore, polyester resins generally have a lower melt viscosity than styrene-acrylic resins. Therefore, since the polyester unit is present in the hybrid resin, the hybrid resin has a lower melt viscosity than the styrene-acrylic resin alone. Therefore, it is effective for the low-temperature fixability of the toner. In addition, the following effects can also be obtained when the hybrid resin is controlled so as to be distributed on the toner surface or when the hybrid resin is distributed so as to cover the wax in the toner particles. For example, the polyester unit shields and prevents substances that are not compatible with the polyester contained in the toner particles, such as wax, from being exposed to the toner particle surface even when the toner is exposed to a high temperature environment. become. In addition, unlike the case of using a polyester resin alone, it is a hybrid resin, so that it is difficult to inhibit the dispersion of the colorant, etc., so that the dispersion state of the colorant is maintained well, and a toner having good coloring power and chargeability is obtained. The advantage of the hybrid resin is that it can be used.

  In addition, since it has an unsaturated double bond only at the terminal of the vinyl polymer unit of the hybrid resin, the reaction efficiency of the crosslinking reaction is good, and a crosslinked structure can be efficiently constructed with a small amount of unsaturated bonds. Therefore, it is disadvantageous in terms of low-temperature fixability due to excessive crosslinking, and the wax contained in the toner particles is difficult to ooze out at the time of fixing, making it difficult to exhibit releasability and disadvantageous in terms of offset resistance. You can avoid the situation.

  If there are many unsaturated double bonds in the portion other than the terminal of the vinyl polymer unit, the frequency of occurrence of a crosslinking reaction between the vinyl polymer units in the hybrid resin increases, and the effect of the present invention is improved. Weaken. Further, if an unsaturated bond is present on the polyester unit side and no unsaturated double bond is present in the vinyl polymer unit, only a hybridization reaction occurs, and the effect of the present invention cannot be obtained. For the reasons described above, the toner becomes reasonably strong, does not impair fixing properties, and does not impair image quality even in blocking resistance and long-term use. At that time, the inorganic fine powder existing on the toner surface is difficult to be embedded by the appropriate cross-linking structure, and when attached by means such as a Henschel mixer, it has an appropriate adhesion strength and is not easily released from the toner surface. Desirable for long-term use. The polyester unit content in the hybrid resin is preferably 55% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, and particularly preferably 70% by mass to 90% by mass. .

  When the polyester unit content is 55% by mass or more, excellent low-temperature fixability due to the low melt viscosity of the polyester, and at the time of fixing, a rapid release layer is formed by wax. desirable. Furthermore, it is preferable because the shielding effect is great in that it prevents the wax from seeping out on the toner surface at a stage other than the fixing stage.

Further, when the hybrid resin has peaks in the range of 4.6 ppm to 4.9 ppm and 5.0 ppm to 5.2 ppm in ¹ H-NMR measurement, the polyester unit content is 55 mass% to 95 mass%. This is particularly effective. Specifically, in addition to the shielding effect derived from the polyester unit, a further effect can be obtained by the improvement of the stress resistance and the shielding effect by the formation of the crosslinked structure. In particular, the use in an image forming method and apparatus for collecting a transfer residual toner by bringing a rubber blade into contact with a latent image carrier is remarkable. That is, it is preferable in that the occurrence of poor cleaning due to the fusion of the toner to the cleaning blade or the like by heat generated by the friction between the latent image carrier and the cleaning blade can be suppressed. Further, at that time, when the acid value of the hybrid resin is adjusted to control the hybrid resin to be distributed on the surface layer portion of the toner, it is preferable from the viewpoint of chargeability of the toner. In particular, it is possible to suppress excessive charging of toner having a small particle diameter, which is one of the causes of defective cleaning.

  If the polyester unit content in the hybrid resin exceeds 95% by mass, the effect of hybridization is reduced, which is not preferable.

  The ratio of the hybrid resin in the hybrid resin mixture is preferably 1.0% by mass or more and 25.0% by mass or less, and more preferably 1.0% by mass or more and 15.0% by mass or less. This is because the timing of precipitation of the hybrid resin accompanying the decrease of the polymerizable monomer in the polymerization reaction in the aqueous medium is optimized from the hybrid resin mixture. When the ratio of the hybrid resin in the hybrid resin mixture is 25.0% by mass or less, the timing of precipitation is not too early, which is preferable in terms of controlling the distribution of the hybrid resin in the toner particles. In addition, when the polymerization reaction is performed in a state where the hybrid resin mixture contains other substances such as a colorant and wax, the dispersion state of the colorant and wax is deteriorated if the hybrid resin is precipitated too early. , Because it is unevenly distributed. As a result, the image quality is likely to be deteriorated in various points such as image density, toner charging property, and fixing property. In controlling the dispersion state of other substances, the ratio of the hybrid resin in the hybrid resin mixture is preferably 25.0% by mass or less, particularly preferably 15.0% by mass or less. In particular, in the case of controlling the hybrid resin to be distributed on the surface layer in the resin particles produced by polymerizing the hybrid resin mixture, it is necessary to increase the acid value of the hybrid resin to some extent. However, if so, the solubility of the hybrid resin in the polymerizable monomer is lowered, so that the ratio of the hybrid resin in the hybrid resin mixture is limited. Therefore, when controlling the hybrid resin to be distributed on the surface layer, the hybrid resin is distributed almost uniformly on the surface of the resin particles when the ratio of the hybrid resin in the hybrid resin mixture is 25.0% by mass or less. Therefore, it is desirable that the distribution of triboelectric charge of the toner becomes sharp. In addition, the cross-linked structure produced by using the hybrid resin is also preferable in terms of stress resistance because it is uniformly distributed. As a result, the adhesion state of the inorganic fine powder existing on the toner surface is not uneven. Therefore, the toner has excellent fluidity, chargeability, and stress resistance. In particular, inorganic fine powders that are free from the toner or easily released from the surface of the toner are less likely to be generated. This is preferable because it is suppressed.

  If the ratio of the hybrid resin in the hybrid resin mixture is less than 1.0% by mass, the content of the hybrid resin mixture is not preferable because the effect of the present invention is diminished. In particular, in the resin particles produced by polymerizing the hybrid resin mixture, the hybrid resin is controlled to be distributed on the surface layer. This is not preferable because the film thickness of the surface layer becomes thin and the shielding effect is lowered.

  The acid value of the hybrid resin is preferably 3.0 mgKOH / g or more and 25.0 mgKOH / g or less. In the polymerization reaction in an aqueous medium, the hybrid resin precipitates from the hybrid resin mixture as the polymerizable monomer decreases. At this time, when the acid value of the hybrid resin is 3.0 or more, the hybrid resin is distributed in the surface layer portion of the resin particles to be generated. This is preferable because the shielding effect by the polyester unit and the crosslinked structure functions effectively. In particular, since a cross-linked structure is effectively constructed in the vicinity of the surface of the resin particles to be generated, it is preferable because it is possible to effectively suppress the exudation of the substance in the core portion of the resin particles to be generated. Furthermore, the composition of the core part is preferable in that the emphasis can be placed on the fixability. Furthermore, since the acid value of the hybrid resin is 3.0 mgKOH / g or more, it is preferable in terms of the triboelectric chargeability of the toner from the polarization of the molecule, and since it is 25.0 mgKOH / g or less, the triboelectric charging due to the influence of humidity. Since the degree of leakage is in an appropriate range, it is preferable because it has sufficient triboelectric chargeability even in a high humidity environment. In addition, since an appropriate cross-linked structure exists on the surface of the resin particles, the inorganic fine powder existing on the toner surface exists in an appropriate attached state. At that time, the inorganic fine powder and the hybrid resin present on the surface layer have an appropriate adhesive force in terms of triboelectric charging, which is preferable because better image quality can be maintained even when used for a long period of time. Particularly in terms of contamination of the frictional charging member, the frictional charging property of the toner and the electrostatic adhesion between the inorganic fine powder and the toner particles present on the surface of the toner particles are good, so the frictional charging member can be used even for long-term use. This is preferable because contamination can be suppressed.

  It is preferable that the content of the double bond in the hybrid resin is 0.30 unit% or more and 3.50 unit% or less when one monomer constituting the hybrid resin is converted into one unit.

  When the hybrid resin mixture is polymerized in an aqueous medium such that the content of the double bond in the hybrid resin is 0.30 unit% or more and 3.50 unit% or less, crosslinking between vinyl polymer units is performed. It is preferable because an appropriate cross-linked structure can be constructed without causing a reaction preferentially. At this time, since the elasticity of the toner is appropriate, the transfer efficiency is improved due to a synergistic effect with the good triboelectric charging property of the toner, which is preferable. Further, the content of the double bond in the hybrid resin mixture is preferably 0.30 unit% or more and 100.00 unit% or less, and more preferably 1.00 unit% or more and 70.00 unit% or less. , 8.00 unit% or more and 70.00 unit% or less, and more preferably 8.00 unit% or more and 50.00 unit% or less. This is preferable from the viewpoint of optimizing the fixing property, blocking resistance, and the adhesion state of the inorganic fine powder on the toner surface because the strength of the toner becomes appropriate. As a method for controlling the content of the unsaturated double bond in the hybrid resin, the content of the polyester unit in the hybrid resin, the composition ratio of the vinyl monomer to be bonded to the polyester unit, and the polymerization under a pressurized environment The reaction temperature can be controlled. Basically, the higher the reaction temperature during the polymerization reaction in a pressurized environment, the more easily the unsaturated double bond is generated. As a method for controlling the content of the double bond in the hybrid resin mixture, in addition to the method for controlling the content of the unsaturated double bond in the hybrid resin, the content of the hybrid resin in the hybrid resin mixture It can be controlled by changing the ratio.

The abundance ratio of double bonds in the resin is as follows: a hydrogen signal (corresponding to ¹ H each) of a methine group in the vicinity of 4.6 ppm to 4.9 ppm and a methine in the vicinity of 5.0 ppm to 5.2 ppm in the ¹ H-NMR spectrum. This was done by confirming the group hydrogen (each equivalent to ¹ H) signal.

(Measurement of ¹ H-NMR (nuclear magnetic resonance) spectrum)
Measurement apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.), measurement frequency: 400 MHz, pulse condition: 5.0 μs, frequency range: 10500 Hz, integration frequency: 1024 times, measurement temperature: 60 ° C., sample: measurement sample 50 mg Is put in a sample tube having an inner diameter of 5 mm, CDCl3 is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C.

When the viscosity of the toner particles at 100 ° C. is η100 (Pa · s) and the viscosity at 110 ° C. is η110 (Pa · s), the following formula:
AηT = { log (η110) −log (η100) } / (110-100)
It is preferable that the average viscosity change amount AηT represented by the following formula satisfies 0.000 ≧ AηT ≧ −0.064, and η100 is 10000 Pa · s or more and 50000 Pa · s or less.

  If the toner of the present invention is 0.000 ≧ AηT ≧ −0.064, the viscosity at 100 ° C. is preferably 10000 Pa · s or more and 50000 Pa · s or less, more preferably 20000 Pa · s or more and 35000 Pa · s or less. It is. By adjusting the viscosity at 100 ° C. to this range, a toner having excellent low-temperature fixability, image glossiness, and durability can be obtained. Further, since the inorganic fine powder added as an external additive can be satisfactorily suppressed from being embedded in the surface of the toner particles, the occurrence of fog can be suppressed. Furthermore, contamination to peripheral members can be suppressed.

In the toner of the present invention, AηT = { log (η110) −log (η100) } / (110-100) indicating −1.064 to −0.064 indicating an average viscosity change amount per 1 ° C. from 100 ° C. to 110 ° C. 0.000, more preferably −0.060 to 0.000. By satisfying such requirements, the toner of the present invention is excellent in low-temperature fixability, and has an image having high and stable glossiness, and has excellent high-temperature offset resistance and durability while maintaining its performance. Indicates.

  The viscosity of 100 ° C. to 110 ° C. correlates with toner fixing properties, particularly gloss. By reducing the viscosity change (absolute value) due to the temperature change, it is possible to reduce the gloss unevenness due to the temperature change of the fixing device and the use environment such as temperature and humidity. The method of controlling AηT can be controlled by the degree of formation of a crosslinked structure formed by the reaction of an unsaturated double bond present at the vinyl polymer terminal of the hybrid resin used in the present invention.

  As a method for controlling the viscosity of the toner at 100 ° C., in addition to the formation of a crosslinked structure due to the unsaturated double bond of the hybrid resin, the type and amount of the wax contained in the production of the toner particles, the type of the crosslinkable polymerizable monomer And the amount, the type and amount of the polymerization initiator, and the reaction temperature during the polymerization reaction. The toner preferably contains a resin having a sulfonic acid, a sulfonic acid base, or a sulfonic acid ester. This is preferable because the charging property of the toner is improved by containing a resin having a sulfonic acid or a sulfonic acid base or a sulfonic acid ester.

  In addition, the toner preferably contains a resin having a sulfonic acid, a sulfonic acid base, or a sulfonic acid ester (hereinafter also referred to as a resin having a sulfonic acid functional group) from the viewpoint of improving the chargeability.

  Moreover, when the resin having the sulfonic acid functional group is contained in the hybrid resin mixture and polymerized, the following additional effects can be obtained. That is, the reaction between the unsaturated double bond of the hybrid resin and the polymerizable monomer is also added to the reaction with the resin having the sulfonic acid functional group, and a portion where the resin is chemically bonded is also generated. Therefore, the toner carrier and the latent image carrier are less likely to be contaminated even during long-term use. Moreover, the resin having the sulfonic acid functional group is entangled with the crosslinked structure constructed by the unsaturated double bond of the hybrid resin. This is also preferable because the resin having a sulfonic acid functional group is not easily released from the toner, so that the toner carrier and the latent image carrier are hardly contaminated even in long-term use.

  The molecular weight distribution of the THF soluble content of the hybrid resin, the resin having a sulfonic acid functional group, and the toner is measured by gel permeation chromatography (GPC) as follows.

First, the toner is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: tetrahydrofuran (THF), flow rate: 1.0 ml / min, oven temperature: 40.0 ° C., sample injection amount: 0.10 ml.

  In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

  The glass transition point of the hybrid resin, the resin having a sulfonic acid functional group, the wax, and the toner can be determined by DSC measurement.

  Further, the peak temperature of the maximum endothermic peak of the hybrid resin, the resin having a sulfonic acid functional group, the wax, and the toner is determined according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). taking measurement. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 10 mg of toner is precisely weighed, put in an aluminum pan, an empty aluminum pan is used as a reference, and a temperature rising rate is 10 ° C./min between a measuring range of 30 to 200 ° C. Measure with. In this temperature rising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. At this time, the intersection of the intermediate point line of the base line before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature Tg of the binder resin.

  The number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of the sample is called the acid value, and the test is conducted as follows. The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the binder resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.

7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of the pulverized binder resin sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. . Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Measuring Method of Toner Viscosity at 1/2 Method Temperature, 100 ° C. and 110 ° C.>
The viscosity of the toner at 1/2 method temperature, 100 ° C. and 110 ° C. was measured by using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation). Follow the manual. In this device, while applying a constant load from the top of the measurement sample by the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is extruded from the die at the bottom of the cylinder, and the temperature at this time And the relationship between the amount of descent of the piston is measured (see FIG. 1). In the present invention, measurement is performed from 50 ° C. to 200 ° C., and the apparent viscosity calculated at 100 ° C. is defined as the viscosity (Pa · s) of the toner or hybrid resin at 100 ° C.

The apparent viscosity η (Pa · s) at 100 ° C. is calculated as follows. First, the flow rate Q (cm ³ / s) is calculated from the following equation (1). In the formula, the cross-sectional area of the piston is A (cm ² ), and the time required for the piston to descend between 0.10 mm above and below the position of the piston at 100 ° C. (interval 0.20 mm) is Δt (Seconds).
Q = (0.20 × A) / (10 × Δt) (1)

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

As a measurement sample, about 1.0 g of toner is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used. The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising method, start temperature: 50 ° C., ultimate temperature: 200 ° C., measurement interval: 1.0 ° C.
Temperature increase rate: 4.0 ° C./min, piston cross-sectional area: 1.000 cm ² , test load (piston load): 10.0 kgf (0.9807 MPa), preheating time: 300 seconds, die hole diameter: 1. 0 mm, die length: 1.0 mm.

  The toner particles used in the present invention preferably have a circularity of 0.970 or more and 0.995 or less, and more preferably 0.970 or more and 0.990 or less. This is because the toner is excellent in triboelectric chargeability, fluidity and cleaning properties. Of the toner particles having a particle diameter of 2 μm or more, the ratio of circularity ≦ 0.90 is preferably 10.0 number% or less, and more preferably 5.0 number% or less. This is because the toner is preferable in the uniformity of triboelectric charging.

<Measuring method of average circularity>
The average circularity of the toner particles is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  For the measurement, the above-mentioned flow type particle image analyzer equipped with “UPlanApro” (magnification 10 times, numerical aperture 0.40) as an objective lens is used, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. It was used. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

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

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

  When the particle image is circular, the degree of circularity is 1, and the degree of unevenness on the outer periphery of the particle image increases, and the degree of circularity decreases. After calculating the circularity of each particle, the range of the circularity of 0.200 to 1.000 is divided into 800, the arithmetic average value of the obtained circularity is calculated, and the value is defined as the average circularity. This value represents how spherical the toner is, with 1.000 being a true sphere, and a value smaller than that representing gradually becoming irregular irregularities.

  The toner preferably has a weight average particle diameter of 3.0 μm or more and 9.0 μm or less, and more preferably 3.0 μm or more and 6.50 μm or less.

<Measurement of Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

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

  Prior to measurement and analysis, the dedicated software was set as follows. On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water is placed in a water tank of an ultrasonic disperser, and about 2 ml of the contamination N is added thereto.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. When the graph / volume% is set in the dedicated software, the “average diameter” on the “Analysis / volume statistics (arithmetic average)” screen is the weight average particle diameter (D4), and the graph / number% is set. The “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

  The toner of the present invention preferably has a glass transition temperature of 50 ° C. or higher and 70 ° C. or lower, and more preferably 55 ° C. or higher and 70 ° C. or lower.

  The peak temperature of the maximum endothermic peak of the wax and toner is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 10 mg of toner is precisely weighed, put in an aluminum pan, an empty aluminum pan is used as a reference, and a temperature rising rate is 10 ° C./min between a measuring range of 30 to 200 ° C. Measure with. In this temperature rising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. At this time, the intersection of the intermediate point line of the base line before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature Tg of the binder resin.

  The hybrid resin preferably has a peak molecular weight (Mp) of 3500 or more and 75000 or less, more preferably 5000 or more and 55000 or less, still more preferably 6000 or more and 55000 or less, and particularly preferably 7000 or more and 15000 or less.

  When the peak molecular weight is less than 3,500, the stability of the polymerization field is lowered in the polymerization reaction in the aqueous medium. Therefore, it is difficult to obtain a toner with a uniform particle size distribution, and even if it has a cross-linked structure, the external additive on the toner surface is likely to be buried due to durability in continuous image output, which tends to cause a decrease in transferability and filming. On the other hand, when the peak molecular weight exceeds 75,000, it takes much time to dissolve the condensation resin in the polymerizable monomer. Further, the viscosity of the polymerizable monomer composition increases, and it becomes difficult to obtain a toner having a small particle size and a uniform particle size distribution.

  The hybrid resin preferably has a weight average molecular weight (Mw) of 5,000 or more and 100,000 or less, more preferably 6500 or more and 85000 or less, and further preferably 6500 or more and 25000 or less. If it is outside the above range, the same tendency as in the case of the weight average molecular weight is exhibited. The hybrid resin preferably has a number average molecular weight (Mn) of 2000 or more and 80000 or less, more preferably 3000 or more and 60000 or less, and further preferably 3500 or more and 12000 or less.

  The hybrid resin has a glass transition point (Tg) of 50 ° C to 100 ° C, preferably 60 ° C to 80 ° C, more preferably 65 ° C to 80 ° C, and particularly preferably 65 ° C to 75 ° C. When the glass transition point is lower than 50 ° C., the blocking resistance of the toner is lowered. When the glass transition point exceeds 100 ° C., the low-temperature fixability and low-temperature offset resistance of the toner deteriorate. Tg represents a value obtained by the midpoint method.

The molecular weight distribution of the THF soluble part of the toner is measured by gel permeation chromatography (GPC) as follows. First, the toner is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: tetrahydrofuran (THF), flow rate: 1.0 ml / min, oven temperature: 40.0 ° C., sample injection amount: 0.10 ml.

  In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

  In the present invention, the acid value (AV1) of the hybrid resin and the acid value (AV2) of the resin having the sulfonic acid or sulfonate group or sulfonic acid ester are AV1 <AV2 <3.5 × AV1. Preferably, the relationship AV1 <AV2 <2.5 × AV1 is satisfied, and it is further preferable that the relationship AV1 <AV2 <2.0 × AV1 is satisfied. In this case, in the granulation step at the time of producing toner particles by a wet method, the resin having the sulfonic acid, sulfonate group, or sulfonate ester coexists with the hybrid resin in the aqueous medium. Since the ratio of uneven distribution on the outermost surface is increased, the triboelectric charging ability of the toner is preferable because the triboelectric charging performance of the resin having the sulfonic acid or sulfonic acid base or sulfonic acid ester can be effectively exhibited.

  As a method for producing a polyester unit used as the hybrid resin, for example, a method using a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound, or a transesterification reaction is used. The catalyst may be a general acidic or alkaline catalyst used in the esterification reaction, such as zinc acetate or a titanium compound. Thereafter, it may be highly purified by a recrystallization method, a distillation method or the like. A particularly preferred production method is a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound because of the diversity of raw materials and the ease of reaction.

  The composition of the polyester when polyester is used as the condensation resin will be described below. As alcohol components, ethyl glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2 -Ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol A ethylene oxide 2-10 mol adduct, bisphenol A propylene oxide 2-10 mol adduct, 1,4-benzenediol ethylene oxide, 1,4- Examples thereof include diols such as benzenediol propylene oxide and 1,4-benzenediol methylpropylene oxide.

  Divalent carboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, or anhydrides thereof; succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, cyclohexanedicarboxylic acid, tri Alkyl dicarboxylic acids such as ethylene dicarboxylic acid and malonic acid or anhydrides thereof, and succinic acid or anhydrides substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms; fumaric acid, maleic acid, citraconic acid, itacone An unsaturated dicarboxylic acid such as an acid or an anhydride thereof may be mentioned.

  A particularly preferred alcohol component is a bisphenol A derivative, and an acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-dodecenyl succinic acid, or its anhydride, fumaric acid, maleic acid, anhydrous Dicarboxylic acids such as maleic acid. In the polyester unit, a trivalent or higher polycarboxylic acid or polyol may be used in a small amount within a range not adversely affecting the present invention.

  Trivalent or higher polycarboxylic acids include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid Acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,3-dicarboxyl-2-methyl-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2 , 7,8-octanetetracarboxylic acid and their anhydrides.

  Examples of the trivalent or higher polyol include sulfitol, 1,2,3,6-hexanetetol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-methanetriol. Glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

  Examples of the method for producing the hybrid resin include a method in which a polymerization reaction is allowed to proceed under a pressurized environment when a vinyl polymer unit is produced. Specifically, the transesterification reaction between the hydroxyl group contained in the polyester and the (meth) acrylic acid ester contained in the vinyl polymer, the hydroxyl group contained in the polyester and the carboxyl group contained in the vinyl polymer Esterification reaction, esterification reaction between carboxyl group contained in polyester and hydroxyl group contained in vinyl polymer, radical generation in polyester by hydrogen abstraction reaction, adding vinyl monomer, pressurization Examples of the method include polymerization in an environment. At that time, the degree of pressurization is preferably 0.20 MPa or more and 0.45 MPa or less. In a pressurized environment of less than 0.20 MPa, an unsaturated double bond is unlikely to be generated at the end of the vinyl polymer, and when it exceeds 0.45 MPa, production is difficult, which is not preferable.

  As the vinyl polymerizable monomer used when the hybrid resin is produced, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Examples of the monofunctional polymerizable monomer include styrene; styrene derivatives such as α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso- Acrylic materials such as propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate Polymerizable monomer; Methacrylic polymerizable monomer in which the acrylic polymerizable monomer is changed to methacrylate.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Acrylic polyfunctional polymerizable monomers such as diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate; Methacrylic polyfunctional polymerizable monomer obtained by replacing the acrylic polyfunctional polymerizable monomer with methacrylate; divinylbenzene, divinylnaphthalene, divinyl ester Tel and the like.

  As the vinyl monomer, those having a carboxyl group and a hydroxyl group and those containing (meth) acrylic acid esters are preferable. This is because when a functional group having a strong polarity such as a carboxyl group is present in the vinyl polymer unit of the hybrid resin, the vinyl polymer unit has an appropriate polarity. This is preferable because the toner particles are stabilized during the production of the particles.

  In addition, it is preferable that the vinyl polymer unit of the hybrid resin is a copolymer with acrylic acid because the toner surface becomes strong and excellent in durability due to hydrogen bonding by the carboxyl group of acrylic acid. However, when the content of acrylic acid in the hybrid resin exceeds 3.0% by mass, the hygroscopicity is increased in a high temperature and high humidity environment, and the triboelectric charging property of the toner is lowered, which is not preferable.

  As a polymerization initiator used for polymerizing the polymerizable monomer described above in producing the hybrid resin, oil-soluble compounds other than those used in the present invention can be used as long as the effects of the present invention are not impaired. An initiator and / or a water-soluble initiator can be used as appropriate. For example, oil-soluble initiators include azo compounds such as 2,2′-azobisisobutyronitrile; t-butylperoxyneodecanoate, t-hexylperoxypivalate, lauroyl peroxide, t- Examples thereof include peroxides such as butyl peroxy 2-ethylhexanoate, t-butyl peroxyisobutyrate, di-t-butyl peroxyisophthalate, and di-t-butyl peroxide.

  Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloric acid Salt, azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2 -Hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}, hydrochloride ferrous sulfate or hydrogen peroxide.

  Particularly, it is preferably a peroxide, and when the polyester resin is vinyl-modified by a hydrogen abstraction reaction, the 10-hour half-life temperature is preferably 70 ° C. or higher and 170 ° C. or lower, and 75 ° C. or higher and 130 ° C. or lower is used. It is more preferable because it has moderate reactivity.

As a manufacturing method of this hybrid resin of this invention, the manufacturing method shown to the following (1) thru | or (4) can be mentioned, for example.
(1) A method of forming a hybrid polymer while polymerizing a polyester in the presence of a vinyl polymer formed in a pressurized environment. An organic solvent can be appropriately used.
(2) A method for producing the hybrid resin by forming a polyester and then polymerizing a vinyl monomer in a pressurized environment in the presence of the polyester.
(3) After the vinyl polymer and polyester are formed, the hybrid resin is produced by adding a vinyl monomer in the presence of these polymers and polymerizing in a pressurized environment. Also in this case, an organic solvent can be appropriately used.
(4) After each of the vinyl polymer and polyester formed in a pressurized environment is formed, the hybrid resin is produced by bonding both by an ester bond, an amide bond or the like. Moreover, an organic solvent can be used suitably.

  Among the production methods (1) to (4) above, the production method (2) in particular may generate a molecular weight control of the vinyl polymer unit and an unsaturated double bond at the end of the vinyl polymer unit. Easy and preferred.

  In this case, the polymerization initiator used is t-butylperoxyneodecanoate, t-hexylperoxypivalate, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate. Peroxides such as dirate, di-t-butylperoxyisophthalate and di-t-butylperoxide are preferred in terms of hydrogen abstraction reaction from the polyester resin and hybridization efficiency. It is also preferable in terms of the efficiency of generating a double bond.

  Furthermore, among the production methods of (2) above, a graft type hybrid resin obtained by subjecting polyester to a hydrogen abstraction reaction using a polymerization initiator or the like and graft polymerization of a vinyl monomer is preferable from the viewpoint of stress resistance. . This is because the vinyl polymer is grafted from a plurality of points of the polyester unit portion of the hybrid resin obtained by this production method, so that the vinyl polymer unit is multipoint with respect to the other resins of the toner particles. Therefore, the toner surface can be strongly protected because it functions as an anchor. In addition, since a crosslinked structure formed by a polymerization reaction with an unsaturated double bond is also randomly formed at many points, the toner has no uneven stress resistance, which is preferable.

  Furthermore, it is because the resin having the sulfonic acid functional group is easily entangled and can be distributed on the surface layer without inhibiting each function. The resin having a sulfonic acid functional group preferably has a certain acid value, and generally the acid of the resin and the base of the colorant are combined in a combination with a colorant that is often basic. Thus, since the charge leakage sites of the pigment are covered with the resin, the toner preferably has excellent triboelectric charging properties.

  Monomers used for producing the resin having a sulfonic acid functional group include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamido-2-methylpropane sulfonic acid vinyl sulfone. Acid, methacrylsulfonic acid, or maleic acid monoamide-2-methylpropanesulfonic acid, maleimido-2-methylpropanesulfonic acid, one of the hydrogens of the methyl group of o-, (p-) methylstyrene is methylpropanesulfonic acid The thing substituted by the amino group is mentioned, The thing which made the sulfonic acid group which these have, and the esterified thing is mentioned. Preferred is (meth) acrylamide containing a sulfonic acid group.

  The resin having a sulfonic acid functional group may be a homopolymer of the above monomer, but is preferably a copolymer of the above monomer and another monomer. As the monomer that forms a copolymer with the above monomer, a polymerizable monomer such as the above-mentioned vinyl aromatic hydrocarbon and the above-mentioned (meth) acrylic acid ester is preferably used.

  Examples of the polyfunctional polymerizable monomer include the aforementioned polyfunctional polymerizable monomers.

  The resin having a sulfonic acid functional group preferably contains 0.01% by mass or more and 20% by mass or less of a unit derived from the monomer having a sulfonic acid functional group, more preferably 0.05% by mass or more. The content is preferably 10% by mass or less, more preferably 0.1% by mass or more and 7% by mass or less. When the amount is less than 0.01% by mass, the effect of adding the resin having the sulfonic acid functional group cannot be sufficiently obtained. Compatibility is likely to decrease. Further, it is not preferable because impurities are likely to remain because moisture and counter ions are easily retained due to an increase in hygroscopicity during production.

  The resin having a sulfonic acid functional group is 0.01% by mass or more and 10% by mass of a monomer unit having an aromatic group having no ionic group, nonionic electron donating group and electron withdrawing group as a substituent in the side chain. % Or less, and more preferably 0.10% by mass or more and 5.0% by mass or less is preferable because the dispersion state in the toner becomes better. In particular, in the case of an acrylic ester or methacrylic ester monomer unit, the effect is great.

The resin having a sulfonic acid functional group is
X (SO ₃ ⁻ ) n · mY ^{k +}
(X represents a polymer site derived from the polymerizable monomer, Y ⁺ represents a counter ion, k is a valence of the counter ion, m and n are integers, and n = k × m is there.)
It has the following structure. As counter ions, ions, Na ions, K ions, Ca ions, and ammonium ions are preferable, and hydrogen ions are more preferable.

  The acid value (mgKOH / g) of the resin having a sulfonic acid functional group is preferably 3 or more and 80 or less, more preferably 5 or more and 40 or less, and still more preferably 10 or more and 30 or less. If the acid value is within the above range, good charge control action can be obtained, and environmental stability can be further improved.

  The resin having a sulfonic acid functional group is preferably contained in an amount of 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight per 100 parts by weight of the binder resin. is there. When the content of the monomer having a sulfonic acid functional group is less than 0.01 parts by mass, it is difficult to obtain a sufficient charge control action. When the content exceeds 15 parts by mass, granulation is performed in an aqueous medium. In carrying out, the granulation property is lowered, and developability and transferability are lowered.

  Furthermore, in the present invention, it is preferable that 0.001 part by mass or more and 3 parts by mass or less of the unit derived from the monomer having a sulfonic acid functional group is contained per 100 parts by mass of the binder resin, and further 0 0.005 parts by mass or more and 2 parts by mass or less, particularly 0.01 parts by mass or more and 1.5 parts by mass or less are preferable.

  The content of the resin having a sulfonic acid functional group in the toner is measured by an arbitrary method such as X-ray photoelectron spectroscopy. Moreover, it can also measure using capillary electrophoresis etc.

  As for the molecular weight of the resin having a sulfonic acid functional group, the weight average molecular weight (Mw) is preferably 500 or more and 100,000 or less, more preferably 1000 or more and 70,000 or less, and further preferably 5000 or more and 50000 or less. When the weight average molecular weight (Mw) is within the above range, a sufficient charging improvement effect can be obtained while suppressing member contamination.

  In addition, when obtaining the physical properties as described above, if extraction of the resin having a sulfonic acid functional group from the toner is required, the extraction method is not particularly limited, and any method can be handled.

  Further, the glass transition temperature of the resin having a sulfonic acid functional group is preferably 50 ° C. or higher and 100 ° C. or lower, more preferably 50 ° C. or higher and 80 ° C. or lower, from the viewpoints of fixability and storage stability.

  The wax preferably has a weight average molecular weight (Mw) of 350 or more and 4000 or less, and a number average molecular weight (Mn) of 200 or more and 4000 or less, more preferably Mw of 400 or more and 3500 or less, and Mn of 250 or more and 3500 or less. is there.

  The molecular weight distribution of the wax is measured by gel permeation chromatography (GPC) as follows.

To o-dichlorobenzene for gel chromatography, special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added so that the concentration becomes 0.10 wt / vol%, and dissolved at room temperature. In a sample bottle, o-dichlorobenzene added with wax and the above-described BHT is added and heated on a hot plate set at 150 ° C. to dissolve the wax. Once the wax has melted, place it in a preheated filter unit and place it on the body. The sample that has passed through the filter unit is used as a GPC sample. The sample solution is adjusted so that the concentration is about 0.15% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Column: TSKgel GMHHR-H HT 2 series (manufactured by Tosoh Corporation)
Temperature: 135.0 ° C
Solvent: o-dichlorobenzene for gel chromatography (BHT added at 0.10 wt / vol%)
Flow rate: 1.0 ml / min
Injection volume: 0.4ml

  In calculating the molecular weight of the wax, a standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

  At least one of the waxes used in the present invention has a melting point (temperature corresponding to the maximum endothermic peak of the DSC endothermic curve) of 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., more preferably 50 ° C. to 80 ° C. The following are good.

  Examples of the wax include polymethylene wax such as paraffin wax, polyolefin wax, microcrystalline wax, and Fischer-Tropsch wax, amide wax, higher fatty acid, long chain alcohol, ester wax, ketone wax, and derivatives such as graft compounds and block compounds. These include those having a sharp maximum endothermic peak in the DSC endothermic curve from which low molecular weight components have been removed.

  As the wax preferably used, at least one is a linear alkyl alcohol having 15 to 100 carbon atoms, a linear fatty acid, a linear acid amide, a linear ester, a montan derivative, or a Fischer-Tropsch wax. Can be mentioned. Those from which impurities such as liquid fatty acids have been previously removed from these waxes are also preferred.

  Further, the wax preferably used is preferably a solid ester wax in order to improve the translucency of the fixed image. An ester wax having 1 to 6 ester groups is preferable, and an ester wax having 1 to 4 ester groups is more preferable. When the toner is produced by a polymerization method, the wax is blended in an amount of 1 part by weight to 40 parts by weight (more preferably 10 parts by weight to 30 parts by weight) with respect to 100 parts by weight of the polymerizable monomer. The toner is preferably contained in an amount of 1 to 40 parts by weight (more preferably 10 to 30 parts by weight) of wax per 100 parts by weight of the binder resin.

The toner of the present invention may use a charge control agent.
Examples of the charge control agent for controlling the toner to be negatively charged include the following substances. Examples thereof include organometallic compounds, monoazo metal compounds, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, calixarene, silicon compounds, nonmetal carboxylic acid compounds, and derivatives thereof. In addition, as the charge control agent for controlling the toner to be positively charged, there are the following substances. For example, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate and the like, onium salts such as phosphonium salts and their lake pigments, Phenylmethane dyes and their lake pigments, metal salts of higher fatty acids; these can be used alone or in combination of two or more. Among these, a charge control agent such as a quaternary ammonium salt is particularly preferably used. The charge control agent may be contained in an amount of 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin in the toner.

  The toner of the present invention contains a colorant. As the black colorant, carbon black, which is toned to black using the yellow / magenta / cyan colorant shown below, is used. As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used as pigments. As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The coloring agent is used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

Next, a method for producing the toner of the present invention will be described.
As a method for producing the toner of the present invention, toner production by a suspension polymerization method, an association polymerization method or an emulsion dispersion method is preferred.

  Among them, the suspension polymerization method that can easily obtain a toner having a small particle diameter is preferable. In the case of production by suspension polymerization, toner particles are produced by polymerizing raw materials such as a colorant and wax contained in the toner particles in the hybrid resin mixture. In this case, it is preferable because a colorant or wax is easily included by the cross-linked structure formed in the toner of the present invention. In addition, a seed polymerization method in which a monomer is further adsorbed to the obtained polymer particles and then polymerized using a polymerization initiator can also be suitably used in the present invention. At this time, it is also possible to use a compound having polarity dispersed or dissolved in the monomer to be adsorbed.

  During suspension polymerization, the pH in the aqueous medium during granulation is not particularly limited, but is preferably pH 4.5 to 13.0, more preferably 4.5 to 12.0, and particularly preferably 4. 5 to 11.0, most preferably 4.5 to 7.5. When the pH is less than 4.5, a part of the dispersion stabilizer dissolves, making it difficult to stabilize the dispersion, and granulation may not be possible. On the other hand, when the pH exceeds 13.0, components added to the toner may be decomposed, and sufficient charging ability may not be exhibited. When granulation is performed in the acidic region, it is possible to suppress an excessive content of the metal derived from the dispersion stabilizer in the toner, and it is easy to obtain a toner that satisfies the provisions of the present invention. Become.

  The toner particles are preferably washed with an acid having a pH of 3 or less, more preferably 1.5 or less. By washing the toner particles with an acid, the dispersion stabilizer present on the surface of the toner particles can be reduced.

  Examples of the dispersion stabilizer used in the present invention include magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, and calcium metasilicate. , Calcium sulfate, barium sulfate, hydroxyapatide and the like.

  An organic compound such as polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, and starch may be used in combination with the dispersion stabilizer.

  These dispersion stabilizers are preferably used in an amount of 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Furthermore, you may use together 0.001 mass% or more and 0.1 mass% or less surfactant for refinement | miniaturization of these dispersion stabilizers.

  As the polymerizable monomer used when the toner of the present invention is produced by the polymerization method, a vinyl polymerizable monomer capable of radical polymerization is used.

  As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Examples of monofunctional polymerizable monomers include styrene; styrene derivatives such as α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene; methyl acrylate, ethyl acrylate, n -Propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl Acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxy An acrylic polymerizable monomer such as ethyl acrylate; and a methacrylic polymerizable monomer obtained by changing the acrylate of the acrylic polymerizable monomer to methacrylate.

  Examples of the polyfunctional polymerizable monomer include the aforementioned polyfunctional polymerizable monomers.

  In the present invention, the above monofunctional polymerizable monomers are used alone or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. To do. The polyfunctional polymerizable monomer can also be used as a crosslinking agent. Furthermore, it is also possible to use these in combination with a macromonomer.

  The polymerization initiator used in the polymerization of the polymerizable monomer described above is an oil-soluble initiator and / or a water-soluble initiator other than those used in the present invention as long as the effects of the present invention are not impaired. An agent can be used as appropriate. For example, oil-soluble initiators include azo compounds such as 2,2′-azobisisobutyronitrile, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, lauroyl peroxide, t-butyl. Examples thereof include peroxides such as peroxy 2-ethylhexanoate, t-butyl peroxyisobutyrate, di-t-butyl peroxyisophthalate, and di-t-butyl peroxide.

  Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloric acid Salt, azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2 -Hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}, hydrochloride ferrous sulfate or hydrogen peroxide.

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

  Moreover, in this invention, it can also be set as resin which has bridge | crosslinking using a crosslinking agent, The compound which has a 2 or more polymerizable double bond can be used as a crosslinking agent. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline; And divinyl compounds such as divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

  In the toner of the present invention, various known inorganic and organic additives can be used for the purpose of imparting various properties (fluidity, abrasiveness, slipperiness, charge controllability, etc.). The additive to be used preferably has a particle size of 1/10 or less of the weight average diameter of the toner particles from the viewpoint of durability when added to the toner. The particle size of the additive means the average particle size obtained by observing the surface of the toner particles with a scanning electron microscope.

  These additives may be used in an amount of 0.01 to 5 parts by mass (preferably 0.02 to 3 parts by mass) with respect to 100 parts by mass of toner particles. These additives may be used alone or in combination.

  Of these additives, the inorganic fine particles are preferably hydrophobized.

  The range of the degree of hydrophobicity is preferably 20% or more and 99% or less, more preferably 40% or more and 99% or less, and particularly in the case of silica, 80% or more is preferable.

  A silane coupling agent, a titanium coupling agent, a silicone oil, etc. can be utilized as a hydrophobic treating agent for hydrophobizing inorganic fine particles.

  Next, the toner of the present invention can be applied to, for example, a known image forming apparatus or a process cartridge, but application to an apparatus employing a non-magnetic one-component developing system is particularly suitable.

For the measurement of fog, an evaluation machine, which will be described later, is used as an image forming apparatus, in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), in a high temperature and high humidity environment (H / H: temperature 32). .5 ° C, humidity 80% RH) and low temperature and low humidity environment (L / L: temperature 10 ° C, humidity 10% RH). After the printing of 13,000 durable sheets from the beginning, it was left for 6 days in each environment, and then the fog amount of the first image sample was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. Calculated from the formula. The smaller the value, the less fog. A fogging amount of 2% or less was regarded as no practical problem. As a transfer material used for the durability test, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
Fog amount (%) = (Whiteness before printout) − (Whiteness of non-image forming portion (white background portion) of recording material after printing)

The fluttering is described below in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH). Using an evaluation machine, a durability test was performed in a system that pauses for 1 minute every time two sheets were printed at a printing rate of 1%. After printing 13,000 sheets of durability from the beginning, it was left in each environment for 6 days, and then the first sheet The image samples were evaluated visually. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Not generated at all B: One on the image C: Two to three on the image, but no problem in practical use D: Remarkably generated

Image density reduction is described below in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH). A durability test was conducted by using a test machine with a printing rate of 1% and a pause of 1 minute every time two sheets were printed. From the beginning, the 5,000th and 8000th endurance image samples were REFECT manufactured by Tokyo Denshoku Co., Ltd. The concentration was measured using METER MODELTC-6DS, and the concentration difference was evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Density decrease is less than 0.01 B: Density decrease is 0.01 or more and 0.02 or less C: Density decrease is 0.03 or more and 0.05 or less D: Density decrease is 0.06 or more and 0.07 or less E: Density drop is 0.08 or more and 0.10 or less F: Density drop is 0.11 or more

The solid image uniformity was evaluated in a room temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH). Using a printing machine, endurance tests were performed with continuous printing at a printing rate of 1%. Immediately after printing the 10th and 4000th images and after leaving them in each environment for 7 days after printing 4000 sheets, a full solid chart respectively. Was printed, and image evaluation was performed according to the following criteria. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Toner is uniformly transferred and colored on the entire surface. B: A portion having a low density partially exists after 50 mm from the front end of the image. C: The toner is not transferred to the paper after 50 mm from the front end of the image. There is an exposed part of the skin

The initial image density is an evaluation machine described below in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH). , The durability test was performed with continuous printing at a printing rate of 1%, and before printing the durability test and immediately after printing the 10th and 100th images of the durability test, a single solid chart was printed on each image. The image density of was measured. The density of the image sample was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Concentration 1.30 or more B: Concentration 1.25 or more and 1.29 or less C: Concentration 1.20 or more and 1.24 or less D: Concentration 1.15 or more and 1.19 or less E: Concentration 1.14 or less

  Fixing property is in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), in a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH), and in a very low temperature and low humidity environment ( (SL / L: temperature 0 ° C., humidity 10% RH) Using an evaluation machine, which will be described later, the machine and the toner-filled cartridge are in an environment-friendly state (after being left in the environment for 24 hours) and then turned on. Immediately after the image was printed, a 200 μm wide horizontal line pattern (width 200 μm, interval 200 μm) was printed out, and the 50th printed image was used for evaluation of the fixing property. The fixing property was evaluated by rubbing the image with Sylbon paper at a load of 100 g for 5 reciprocations, and peeling of the image was evaluated by the average of the reduction rate (%) of the reflection density.

For the evaluation, bond paper having a surface smoothness of 10 [sec] or less was used. The evaluation criteria are shown below.
A: Density reduction rate less than 3% B: Density reduction rate 3% or more and less than 5% C: Density reduction rate 5% or more and less than 10% D: Density reduction rate 10% or more and less than 15% E: Density reduction rate 15% or more 20 %Less than

  Offset resistance is described below in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH). Using this evaluation machine, 100 sheets of solid images were printed out immediately after turning on the power and waiting for the machine and toner-filled cartridges to become familiar with the environment (after being left in the environment for 24 hours). Was evaluated.

  For the evaluation, an OHP film (CG3700, manufactured by Sumitomo 3M Limited) was used. The evaluation criteria are shown below.

Fixability A: No offset is generated at all B: Offset is generated slightly, but there is no practical problem (and the number of generated sheets is 1)
C: Offset occurred very slightly, but there was no practical problem (and 2 sheets were generated)
D: Offset occurred very slightly, but there was no practical problem (and 3 to 4 sheets generated)
E: Offset is noticeable or 5 or more

The toner is fused and fixed to the toner layer regulating member in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C.). , Humidity 80% RH), using an evaluation machine described later, and performing a durability test in a system that pauses for 1 minute every time two sheets are printed at a printing rate of 1%. The regulating member was visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Not generated at all B: Slightly generated on the toner layer regulating member but not on the image C: Slightly generated on the image but no problem in practical use (one small streak at the end) )
D: Minor occurrence on the image but no practical problem (2 to 3 minor streaks at the end)
E: Prominent on the image

Filming on the latent image carrier is performed in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH). Then, using an evaluation machine described later, a durability test was performed by continuous printing at a printing rate of 1%, and an image sample of 2000th durability from the beginning was visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Not generated at all B: Slightly generated but practically no problem C: Slightly generated but practically no problem D: Remarkably generated

Cleanability is under normal temperature and humidity (N / N: temperature 23.5 ° C, humidity 60% RH), low temperature and low humidity (L / L: temperature 15 ° C, humidity 10% RH), extremely low temperature and low humidity ( (SL / L: Temperature 0 ° C., Humidity 10% RH) Using an evaluation machine described later, 4000 sheets were continuously printed out at a printing rate of 2%, and the cleaning property and image quality were visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. (A with good cleaning, A with poor, that is, the elasticity of the blade is reduced and the toner slips through, causing slight black horizontal streaks in the image. What occurred was indicated by C.)

The transfer efficiency is described below in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH). Using an evaluator, a durability test was performed in such a manner that every time two sheets were printed at a printing rate of 1%, the durability test was performed for 1 minute. After printing 13,000 sheets from the beginning, the latent image carrier was left for 3 days in each environment. To the intermediate transfer member (primary transfer) and the transfer efficiency from the intermediate transfer member to the transfer material (secondary transfer). A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.

  The transfer efficiency is calculated as follows.

[Transfer efficiency]
A solid image of 10 cm ² was formed on the photoconductor, and the amount W1 of the toner on the photoconductor and the amount of toner W2 on the paper after transfer were calculated from the ratio between the two: W2 / W1 × 100 (%). .

After the endurance test, a solid image with a 5% image area ratio was formed, and the amount of toner in the toner image before transfer (per unit area) and the amount of toner after transfer (per unit area) were measured. The transfer efficiency was calculated from the value as follows. Note that image formation was performed one by one for primary transfer evaluation and for secondary transfer evaluation.
Primary transfer efficiency (%) = {(toner amount on intermediate transfer member) / (toner amount before transfer on photoconductor)} × 100
A: 92% or more B: 88% to less than 92% C: 84% to less than 88% D: less than 84%

The blocking resistance was determined by visual observation of the degree of aggregation when about 10 g of toner was placed in a 100 cc polycup and left at 50 ° C. for 3 days.
A: Toner agglomerates are not present B: Toner agglomerates are present in a very small amount, but when they are solved, the agglomerates are released C: Toner agglomerates are present and cannot be solved

Image unevenness is in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH), and in a low temperature and low humidity environment. Under the following conditions (L / L: temperature 15 ° C., humidity 10% RH), after printing 8000 sheets with continuous printing at a printing rate of 1%, left in each environment for 2 days, then The first halftone image was evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.

As the evaluation image, an image having a 50% density halftone image printed on the entire surface was used. The image samples were evaluated as follows.
A: There is no unevenness on the image. B: There is slight unevenness on the image, but there is no practical problem. C: There is significant unevenness on the image.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but this does not limit the present invention in any way. In addition, “parts” in the following examples and the like are “parts by mass”.

[Production of polyester resin 1]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, 0.025 part of the polyester monomer and tetrabutoxy titanate described in Table 1 were charged, and under nitrogen atmosphere and normal pressure Reaction was performed at 210 degreeC for 5 hours. Thereafter, 0.010 part of tetrabutoxy titanate was added, reacted at 220 ° C. for 3 hours, and further reacted under reduced pressure of 10 to 20 mmHg for 2 hours to obtain polyester resin 1. Table 2 shows the physical properties of the obtained polyester resin.

[Production of polyester resin 2]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, 0.025 part of the polyester monomer and tetrabutoxy titanate described in Table 1 were charged, and under nitrogen atmosphere and normal pressure Reaction was performed at 210 degreeC for 5 hours. Thereafter, 0.020 part of tetrabutoxy titanate was added, reacted at 220 ° C. for 3 hours, and further reacted under reduced pressure of 10 to 20 mmHg for 2 hours to obtain polyester resin 2. Table 2 shows the physical properties of the obtained polyester resin.

[Production of polyester resin 3]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, 0.200 parts of the polyester monomer and dibutyltin oxide listed in Table 1 were charged, and 210 under a nitrogen atmosphere and normal pressure. The reaction was carried out at 5 ° C. for 5 hours. Thereafter, the mixture was reacted at 220 ° C. for 3 hours, and further reacted under reduced pressure of 10 to 20 mmHg for 2 hours. Thereafter, an appropriate amount of trimellitic acid was added at the same temperature to adjust the acid value, and polyester resin 3 was obtained. Table 2 shows the physical properties of the obtained polyester resin.

[Production of polyester resin 4]
A polyester resin 4 was obtained in the same manner as the polyester resin 2 except that the composition of the raw material used was changed as shown in Table 1. Table 2 shows the physical properties of the obtained polyester resin.

[Production of polyester resin 5]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, 0.025 part of the polyester monomer and tetrabutoxy titanate described in Table 1 were charged, and under nitrogen atmosphere and normal pressure Reaction was performed at 210 ° C. for 5 hours, and then reaction was performed at 220 ° C. for 1.5 hours to obtain a polyester resin 5. Table 2 shows the physical properties of the obtained polyester resin.

[Production of polyester resin 6]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, 0.025 part of the polyester monomer and tetrabutoxy titanate described in Table 1 were charged, and under nitrogen atmosphere and normal pressure Reaction was performed at 210 degreeC for 5 hours. Thereafter, 0.020 part of tetrabutoxy titanate was added, reacted at 220 ° C. for 3 hours, and further reacted under reduced pressure of 10 to 20 mmHg for 2 hours to obtain polyester resin 6. Table 2 shows the physical properties of the obtained polyester resin.

[Production of styrene-acrylic resin 1]
35 parts of xylene was placed in a pressure resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer, and the temperature was raised to 205 ° C. The pressure at this time was 0.31 MPa. A mixture of 100 parts of styrene, 1.5 parts of acrylic acid and 2.0 parts of di-tert-butyl peroxide was charged into a dropping funnel and dropped into xylene at 205 ° C. under pressure (0.31 MPa) over 2 hours. did. After the dropwise addition, the reaction was further carried out at 205 ° C. for 2 hours to complete the solution polymerization, and xylene was removed. The obtained resin had a weight average molecular weight of 8900 and an acid value of 13.0 mgKOH / g. Moreover, in the measurement of ¹ H-NMR, it has peaks at 4.6 ppm to 4.9 ppm and 5.0 ppm to 5.2 ppm, and the content of terminal unsaturated double bonds is 0.9 unit%. there were. This is designated as styrene-acrylic resin 1.

[Production of styrene-acrylic resin 2]
Styrene-acrylic resin 2 was obtained in the same manner as in the production of styrene-acrylic resin 1 except that acrylic acid was changed to 0.5 part and di-tert-butyl peroxide was changed to 3.0 parts. The obtained resin had a weight average molecular weight of 5900 and an acid value of 6.0 mgKOH / g. Further, in the measurement of ¹ H-NMR, there are peaks at 4.6 ppm to 4.9 ppm and 5.0 ppm to 5.2 ppm, and the content of terminal unsaturated double bonds is 0.9 unit%. It was.

[Production of vinyl-modified polyester resin 1]
Under a nitrogen atmosphere, 50 parts of xylene and 70 parts of polyester resin 1 were placed in a pressure resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer, and the temperature was raised to 210 ° C. The pressure at this time was 0.32 MPa. A mixture of 30.0 parts of styrene, 1.50 parts of acrylic acid and 1.00 part of di-t-butyl peroxide (Perbutyl D, manufactured by NOF Corporation) as a polymerization initiator in 10 parts of xylene. What was charged in the dropping funnel was dropped under pressure (0.31 MPa) over 2 hours. After dropping, the reaction was further carried out at 210 ° C. for 3 hours to complete the solution polymerization, and the pressure was reduced while heating at 75 ° C. to remove xylene. Further, vinyl-modified polyester resin 1 was obtained by washing with cyclohexane. Table 4 shows the physical properties of the obtained vinyl-modified polyester resin.

[Production of vinyl-modified polyester resins 2 to 28]
Vinyl modified polyester resins 2 to 28 were obtained in the same manner as the vinyl modified polyester resin 1 except that the composition of the raw materials used was changed as shown in Table 3. Table 4 shows the physical properties of the obtained vinyl-modified polyester resin.

[Production of vinyl-modified polyester resin 29]
Under nitrogen atmosphere, 50 parts of xylene and 50 parts of polyester resin 3 are held at 140 ° C., and 3.00 parts of di-t-butyl peroxide (Perbutyl D, manufactured by NOF Corporation) as a polymerization initiator, What mixed 50.00 parts of styrene and 3.50 parts of acrylic acid was dripped over 2 hours, and it heated up at 150 degreeC after that, and was made to react for 6 hours. Further, the pressure was reduced while heating, and the residual monomer was removed to obtain a vinyl-modified polyester resin 29. Table 4 shows the physical properties of the obtained vinyl-modified polyester resin.

[Production of vinyl-modified polyester resins 30, 31]
Vinyl modified polyester resins 30 and 31 were obtained in the same manner as the vinyl modified polyester resin 29 except that the composition of the raw materials used was changed as shown in Table 3. Table 4 shows the physical properties of the obtained vinyl-modified polyester resin.

[Production of vinyl-modified polyester resin 32]
A mixture of 50 parts of xylene, 50 parts of polyester resin 3, 45 parts of styrene acrylic resin 2 and 0.050 part of tetrabutoxytitanate is reacted at 210 ° C. for 5 hours under a nitrogen atmosphere and at normal pressure. The mixture was reacted at 0 ° C. for 3 hours and further reacted under reduced pressure of 10 to 20 mmHg for 2 hours to obtain a vinyl-modified polyester resin 32. Table 4 shows the physical properties of the obtained vinyl-modified polyester resin.

[Production of resin 1 having sulfonic acid group]
In a 2 L flask equipped with a stirrer, condenser, thermometer, nitrogen introduction tube, 100 parts of toluene, 350 parts of methanol, 470 parts of styrene, 40 parts of 2-acrylamido-2-methylpropanesulfonic acid, 70 parts of 2-ethylhexyl acrylate , 20 parts of benzyl methacrylate and 10 parts of lauryl peroxide were added, and the solution was polymerized at 65 ° C. for 10 hours with stirring and nitrogen introduction. The contents were taken out from the flask, washed with isopropyl alcohol, and dried under reduced pressure at 40 ° C. for 96 hours. The mixture was roughly crushed with a hammer mill, and the crushed product was further dried under reduced pressure at 40 ° C. for 48 hours. Resin 1 having a sulfonic acid group was produced. The physical properties of the obtained resin were Mw = 24000, Tg = 67 ° C., residual monomer = 350 ppm, and acid value = 20 mgKOH / g.

[Production of resin 2 having sulfonic acid group]
In a 2 L flask equipped with a stirrer, condenser, thermometer, nitrogen introduction tube, 100 parts of toluene, 350 parts of methanol, 470 parts of styrene, 50 parts of 2-acrylamido-2-methylpropanesulfonic acid, 60 parts of 2-ethylhexyl acrylate , 20 parts of benzyl methacrylate and 10 parts of lauryl peroxide were added, and the solution was polymerized at 65 ° C. for 10 hours with stirring and nitrogen introduction. The contents were taken out from the flask, washed with isopropyl alcohol, and dried under reduced pressure at 40 ° C. for 96 hours. The mixture was roughly crushed with a hammer mill, and the crushed product was further dried under reduced pressure at 40 ° C. for 48 hours. Resin 2 having a sulfonic acid group was produced. The physical properties of the obtained resin were Mw = 20000, Tg = 66 ° C., residual monomer = 360 ppm, and acid value = 24 mgKOH / g.

[Production of hydrophobic silica 1]
Silica (AEROSIL 200CF, manufactured by Nippon Aerosil Co., Ltd.) was treated with 10 parts of hexamethyldisilazane to obtain hydrophobic silica 1. The primary particle size was 12 nm and the degree of hydrophobicity was 70.

[Production of hydrophobic silica 2]
Silica (AEROSIL 200CF, manufactured by Nippon Aerosil Co., Ltd.) was treated with 20 parts of chlorophenyl silicone oil to obtain hydrophobic silica 2. The primary particle size was 12 nm and the degree of hydrophobicity was 97.

[Production of hydrophobic silica 3]
Silica (AEROSIL 200CF, manufactured by Nippon Aerosil Co., Ltd.) was treated with 10 parts of hexamethyldisilazane and then further treated with 20 parts of chlorophenyl silicone oil to obtain hydrophobic silica 3. The primary particle size was 12 nm and the degree of hydrophobicity was 97.

[Production of hydrophobic titanium oxide 1]
Titanium oxide (P25, manufactured by Nippon Aerosil Co., Ltd.) was treated with 20 parts of γ-mercaptopropyltrimethoxysilane in toluene, filtered and dried to obtain hydrophobic titanium oxide 1. The primary particle size was 25 nm and the degree of hydrophobicity was 60.

(Toner Production Example 1)
Dispersion medium:
To 1000 parts of ion-exchanged water in the reaction vessel, 14 parts of sodium phosphate and 4.5 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12000 rpm, an aqueous calcium chloride solution containing 8 parts of calcium chloride dissolved in 10 parts of ion-exchanged water is added to the aqueous system. A medium was prepared.
Polymerizable monomer composition:
Styrene 55 parts Colorant (CI Pigment Red 122 / CI Pigment Red 57 = 1/1) Charge Control Agent (Orient Chemical Industries, Ltd .: Bontron E-89) 0.15 parts The above materials were put into an attritor dispersing machine (Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 1.7 mm to obtain a polymerizable monomer composition.

In the polymerizable monomer composition,
-Styrene 18.6 parts-n-butyl acrylate 18.4 parts-Vinyl-modified polyester resin 1 8 parts-Resin 1 having a sulfonic acid group 0.3 parts-Release agent No. 5 (melting point = 70 ° C.) 10 parts were added.

  The above material was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). In this, 3.0 parts of a polymerization initiator t-hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) is dissolved and polymerized. A functional monomer composition was prepared.

The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, stirred at 10,000 rpm for 5 minutes with a TK homomixer under N ₂ purge at 65 ° C., and granulated at pH 5.8. . Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours and further to 90 ° C., and reacted for 6 hours.

  After completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved while stirring for 2 hours in a state where pH is 2 by adding 10% hydrochloric acid. The emulsion is filtered under pressure and further washed with 2000 parts or more of ion exchange water. The obtained cake is returned to 1000 parts of ion exchange water again, and washed again with stirring for 2 hours in a state where pH is 1 or less by adding 10% hydrochloric acid. The emulsion was filtered under pressure in the same manner as described above, washed with 2000 parts or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain magenta colored particles.

  100 parts of the obtained magenta colored particles, 1.5 parts of hydrophobic silica 1 and 0.3 part of hydrophobic titanium oxide 1 are added and mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to have an external additive. Toner 1 was obtained. The physical properties and the like of the obtained toner 1 are shown in Table 6.

(Toner Production Examples 2 to 45, 48 to 55)
Except for the formulation shown in Table 5, toners 2 to 45 and 48 to 55 having external additives were obtained in the same manner as in Example 1. The properties of the obtained toners 2 to 45 and 48 to 55 are shown in Table 6.

(Toner particle production example 46)
--Preparation of resin particle dispersion 1--
・ Styrene 75 parts ・ N-butyl acrylate 25 parts ・ Acrylic acid 3 parts ・ Vinyl-modified polyester resin 25 10 parts The above mixture was mixed and dissolved into a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) 1.5 parts and 2.2 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) dissolved in 120 parts of ion-exchanged water are dispersed in a flask, emulsified, and 10 minutes. While slowly mixing, 10 parts of ion-exchanged water having 1.5 parts of ammonium persulfate dissolved therein was added, and after nitrogen substitution, 1-cyclohexyl-1-methylethylperoxyneodecanoate (Nippon Oils and Fats) was added. Product name “Percyclo ND-40E”, molecular weight: 313, 10 hour half-life temperature: 41.4 ° C., active oxygen content: 2.05%) 1.0 part slowly over 5 minutes It was further added with 拌. Thereafter, while stirring the inside of the flask, the contents are heated in an oil bath until the temperature reaches 70 ° C., and emulsion polymerization is continued for 4 hours to disperse resin particles having an average particle diameter of 0.29 μm. Dispersion 1 was prepared.

--Preparation of resin particle dispersion 2--
・ Styrene 40 parts ・ n-butyl acrylate 58 parts ・ divinylbenzene 0.03 part ・ acrylic acid 3 parts A mixture of the above and dissolved is a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Nonipol 400) 1 .5 parts and 2.2 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) dissolved in 120 parts of ion-exchanged water were dispersed in a flask, emulsified, and slowly stirred for 10 minutes. 10 parts of ion-exchanged water in which 0.9 part of ammonium persulfate was dissolved was added to the mixture, and the atmosphere was replaced with nitrogen. Emulsion polymerization was continued for 4 hours as it was heated to prepare a resin particle dispersion 2 in which resin particles having an average particle diameter of 0.31 μm were dispersed.

--Preparation of resin particle dispersion 3--
・ Styrene 73 parts ・ N-butyl acrylate 25 parts ・ Divinylbenzene 0.10 parts ・ Acrylic acid 3 parts A mixture of the above and dissolved is a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Nonipol 400) 1 .5 parts and 2.2 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) dissolved in 120 parts of ion-exchanged water were dispersed in a flask, emulsified, and slowly stirred for 10 minutes. 10 parts of ion-exchanged water in which 0.9 part of ammonium persulfate was dissolved was added to the mixture, and the atmosphere was replaced with nitrogen. Emulsion polymerization was continued for 4 hours as it was heated to prepare a resin particle dispersion 2 in which resin particles having an average particle diameter of 0.31 μm were dispersed.

-Preparation of colorant particle dispersion 1-
・ C. I. Pigment Red 122 20 parts, Anionic surfactant 3 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 parts or more were mixed and dispersed using a sand grinder mill. When the particle size distribution in the colorant particle dispersion 1 was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the contained colorant particles was 0.2 μm and 1 μm. No coarse particles exceeding were observed.

--- Preparation of release agent particle dispersion--
・ Release agent No. 5 (melting point = 70 ° C.) 50 parts / anionic surfactant 7 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
・ Ion-exchanged water 200 parts or more was heated to 95 ° C. and dispersed using a homogenizer (IKA: ULTRA TALLAX T50), then dispersed with a pressure discharge homogenizer, and the average particle size was 0.5 μm. A release agent particle dispersion was prepared by dispersing a release agent.

--Preparation of charge control particle dispersion--
-5 parts of a metal compound of di-alkyl-salicylic acid (charge control agent, Bontron E-84, manufactured by Orient Chemical Industries)
・ Anionic surfactant 3 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 parts or more were mixed and dispersed using a sand grinder mill. When the particle size distribution in the charge control particle dispersion 1 was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the charge control particles contained was 0.2 μm and 1 μm. No coarse particles exceeding were observed.

<Preparation of liquid mixture>
-Resin particle dispersion 2 280 parts-Resin particle dispersion 3 100 parts-Colorant dispersion 1 40 parts-Release agent dispersion 70 parts The above is a 1 liter Separa equipped with a stirrer, cooling tube and thermometer. It put into the bull flask and stirred. The mixture was adjusted to pH = 5.2 using 1N potassium hydroxide.

<Agglomerated particle formation>
To this mixed solution, 150 parts of an 8% aqueous sodium chloride solution was added dropwise as a flocculant, and the flask was heated to 55 ° C. with stirring in an oil bath for heating. At this temperature, 3 parts of resin particle dispersion 1 and 10 parts of charge control agent particle dispersion were added. After maintaining at 55 ° C. for 2 hours, observation with an optical microscope confirmed that aggregated particles having an average particle diameter of about 3.3 μm were formed.

<Fusion process>
Then, after adding 3 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) here, heating to 95 ° C. while continuing stirring using a magnetic seal in a stainless steel flask, Hold for 4.5 hours. After cooling, the reaction product is filtered, washed thoroughly with ion-exchanged water, then fluidized-bed dried at 45 ° C, and the shape is adjusted by dispersing in a gas phase of 200 to 300 ° C with a spray dryer. As a result, magenta colored particles were obtained.

  Toner having an external additive, 100 parts of the obtained magenta colored particles, 3.5 parts of hydrophobic silica 3 and 0.05 part of hydrophobic titanium oxide 1 are added and mixed with a Henschel mixer (manufactured by Mitsui Miike). 46 was obtained. The physical properties and the like of the obtained toner 46 are shown in Table 6.

(Toner Particle Production Example 47)
(Toner binder synthesis)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 660 parts of bisphenol A ethylene oxide 2-mole adduct, 100 parts of bisphenol A propylene oxide 2-mole adduct, 290 parts of terephthalic acid and 2.5 parts of dibutyltin oxide The reaction was carried out at 220 ° C. for 12 hours at normal pressure and further for 6.5 hours at a reduced pressure of 10 to 15 mmHg, then cooled to 190 ° C., and 32 parts of phthalic anhydride was added thereto for 2 hours. Reacted. Subsequently, it cooled to 80 degreeC and reacted with 180 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 to obtain urea-modified polyester (1) having a weight average molecular weight of 65,000. As above, 624 parts of bisphenol A ethylene oxide 2-mole adduct, 100 parts of bisphenol A propylene oxide 2-mole adduct, 138 parts of terephthalic acid, and 138 parts of isophthalic acid were subjected to polycondensation at 230 ° C. for 5 hours under normal pressure. The reaction was performed at a reduced pressure of 15 mmHg for 5.5 hours to obtain an unmodified polyester (a) having a peak molecular weight of 6300.

  Toner binder (1) 250 parts of urea-modified polyester (1), 130 parts of unmodified polyester (a), 600 parts of vinyl-modified polyester resin 25 and 20 parts of styrene are dissolved and mixed in 2000 parts of tetrahydrofuran solvent. A tetrahydrofuran solution was obtained.

(Production of toner)
In a beaker, 240 parts of a tetrahydrofuran solution of the toner binder (1), C.I. I. Pigment Red 122 pigment 4 parts, 1-cyclohexyl-1-methylethyl peroxyneodecanoate (manufactured by NOF Corporation, trade name “Percyclo ND”, molecular weight: 313, 10 hour half-life temperature: 41.4 ° C., activity (Oxygen content: 3.58%) 1.0 part was added and stirred at 12000 rpm with a TK homomixer at 55 ° C. to uniformly dissolve and disperse. In a beaker, 706 parts of ion-exchanged water, 294 parts of hydroxyapatite 10% suspension (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.17 parts of sodium dodecylbenzenesulfonate were uniformly dissolved. Next, the temperature was raised to 55 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 12000 rpm with a TK homomixer. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stirrer and a thermometer, heated to 98 ° C. to remove the solvent, filtered, washed and dried, and then classified by air to obtain magenta colored particles.

  100 parts of the obtained magenta colored particles, 2.5 parts of hydrophobic silica 3 and 0.5 parts of hydrophobic titanium oxide 1 are added and mixed with a Henschel mixer (Mitsui Miike Co., Ltd.). A toner 47 having an additive was obtained. The physical properties and the like of the obtained toner 47 are shown in Table 6.

[Evaluation machine]
Using a commercially available LBP-2710 (manufactured by Canon Inc.) modified to a process speed of 220 mm / s, the product toner is extracted from the commercially available magenta cartridge, the interior is cleaned by air blow, and the toner of the present invention In the case of other cyan, yellow and black cartridges, the product toner was removed and inserted into each station for evaluation.

[Examples 1 to 47]
The toners 1 to 47 were subjected to various image evaluations using an evaluation machine. The evaluation results are shown in Tables 7 to 10.

[Comparative Examples 1 to 8]
Each of the toners 48 to 55 was subjected to various image evaluations using an evaluation machine. The evaluation results are shown in Tables 7 to 10.

ＴＰＡ：テレフタル酸、ＩＰＡ：イソフタル酸、
ＤＭ−ＴＰＡ：ジメチルテレフタル酸、ＤＭ−ＩＰＡ：ジメチルイソフタル酸、ＤＳＡ：ドデセニルコハク酸、ＴＭＡ：トリメリット酸、
ＢＰ−Ａ（ＰＯ２）：ビスフェノールＡプロピレンオキサイド２モル付加物、
ＢＰ−Ａ（ＰＯ３）：ビスフェノールＡプロピレンオキサイド３モル付加物、
ＢＰ−Ａ（ＥＯ２）：ビスフェノールＡエチレンオキサイド２モル付加物

TPA: terephthalic acid, IPA: isophthalic acid,
DM-TPA: dimethyl terephthalic acid, DM-IPA: dimethyl isophthalic acid, DSA: dodecenyl succinic acid, TMA: trimellitic acid,
BP-A (PO2): Bisphenol A propylene oxide 2 mol adduct,
BP-A (PO3): Bisphenol A propylene oxide 3 mol adduct,
BP-A (EO2): Bisphenol A ethylene oxide 2-mole adduct

Claims (8)

Heavy polymerizable monomer and a hybrid resin mixture containing a hybrid resin and the toner particles obtained by suspension polymerization in an aqueous medium,
Inorganic fine powder ,
A toner having
The polymerizable monomer includes a styrene derivative and an acrylic polymerizable monomer,
The hybrid resin,
A vinyl polymer unit;
A polyester unit ;
There is a resin having a chemically bonded molecular structure,
The hybrid resin is a vinyl-modified polyester resin produced by polymerizing a vinyl monomer to polyester,
The vinyl monomer includes a styrene derivative,
The toner, wherein the hybrid resin has peaks at 4.6 ppm to 4.9 ppm and 5.0 ppm to 5.2 ppm in ¹ H-NMR measurement using a deuterated chloroform solvent. The styrene derivative contained in the polymerizable monomer is styrene, the acrylic polymerizable monomer contained in the polymerizable monomer is n-butyl acrylate, and the styrene derivative contained in the vinyl monomer is The toner according to claim 1, which is styrene. It said hybrid content of the polyester unit in the resin, the toner according to 請 Motomeko 1 or 2 Ru der 55 wt% to 95 wt% or less. The toner according to the proportion of the hybrid resin, any one der Ru請 Motomeko 1-3 1.0 wt% to 15.0 wt% or less in the hybrid resin mixture. It said hybrid acid value of the resin, the toner according to any one of 請 Motomeko 1-4 Ru Der below 3.0 mgKOH / g or more 25.0 mg KOH / g. The toner particles, a sulfonic acid group, the toner according to any one of 請 Motomeko 1-5 you containing a resin having a sulfonate group or a sulfonic acid ester group. It said hybrid when the resin has been converted as one unit monomer molecule constituting the content of the double bond in the hybrid resin, 請 Motomeko 1 Ru der 0.30 unit% or more 3.50 units% or less the toner according to any one of 6. When the viscosity of the toner particles at 100 ° C. is η100 (Pa · s) and the viscosity at 110 ° C. is η110 (Pa · s),
The η100 is 10000 Pa · s or more and 50000 Pa · s or less,
Following formula:
AηT = {log (η110) −log (η100)} / (110-100)
Average viscosity variation EiitaT The toner according to any one of 0.000 ≧ AηT ≧ -0.064 satisfying the <br/> claim 1-7 THAT represented.

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