JP2007041503A - Toner and toner production process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner excellent in low-temperature fixing property and offset resistance, having a wide fixing temperature range, giving a high-gloss fixed image in fixing, and capable of forming a high-quality toner image. <P>SOLUTION: In a chart of molecular weight distribution of the toner, (i) the toner has a main peak in the region of molecular weight of 16,000-60,000, and (ii) where the molecular weight at the main peak is represented by M1, and where the height at the molecular weight M1 is represented by H(M1), the height at a molecular weight of 4,000 by H(4000) and the height at a molecular weight of 15,000 by H(15000), the H(4000), the H(15000) and the H(M1) satisfy a specific proportion. The toner has a weight average molecular weight (Mw) of 15,000-80,000, and, in an endothermic chart, (i) the toner has an endothermic main peak in the range of 40-130°C, and (ii) the calorimetric integral value represented by the peak area of the endothermic main peak is 10-35 J per 1 g of the toner. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic charge image or a toner jet toner in an image forming method such as electrophotography and electrostatic printing, and a method for producing the toner.

  In order to visualize an electric or magnetic latent image on a recording medium, there is an image forming method in which the latent image is visualized using toner. A typical example is electrophotography. In this electrophotographic method, first, a latent image is electrically formed on a photosensitive member by various means, and then the latent image is developed with toner to form a toner image. Thereafter, the toner image is transferred to a transfer material such as paper as necessary, and then the toner image is fixed to the transfer material by using a fixing method such as heating, pressing, heating and pressing, or solvent vapor. And get an image.

  In the heat roller fixing method and the film fixing method, fixing is performed by allowing a toner image on a fixing sheet to pass through a heat roller or a fixing film. In this fixing method, the surface of the heat roller or the fixing film and the toner on the fixing sheet come into contact with each other, so that the thermal efficiency when the toner is fused on the fixing sheet is extremely good, and the fixing can be performed quickly. It is very good as an electrophotographic apparatus. However, in the above fixing method, the surface of the heat roller or the fixing film and the toner come into contact with each other in a molten state, so that a part of the toner adheres to the surface of the heat roller or the fixing film. For this reason, an offset phenomenon occurs in which the toner adhered to the surface of the heat roller or the fixing film is re-transferred to the next fixing sheet, and the fixing sheet may be soiled.

  Considering the recent demands for miniaturization, weight reduction, energy saving, and high reliability, it cannot be achieved without further improvement in toner performance such as fixing ability and offset resistance, and it can be realized without further improvement in toner. Difficult to do.

  Patent Document 1 discloses a toner containing a low molecular weight resin having a peak or shoulder in a specific molecular weight region and a high molecular weight resin having a peak or shoulder in a specific molecular weight region, and having a polyolefin-based wax. ing.

  Patent Document 2 discloses a toner that defines the molecular weight distribution by GPC of the THF-soluble component of the binder resin and the glass transition point of the binder resin and the toner.

Patent Document 3 discloses a toner that defines a specific molecular weight distribution and a weight average molecular weight. However, there is a demand for a toner that achieves further low-temperature fixability and higher gloss than the toners described in the above-mentioned patent documents.
Japanese Patent Laid-Open No. 2002-6553 Japanese Patent No. 2630972 JP-A-10-333359

  An object of the present invention is to provide a toner that solves the above problems.

  More specifically, an object of the present invention is to provide a toner that is excellent in low-temperature fixing property and offset resistance, has a wide fixing temperature range, and can obtain a high gloss fixed image at the time of fixing, and can form a high-quality toner image.

  As a result of intensive studies, the present inventors have been able to solve the above problems by adopting the following configuration. That is, it has been found that a toner capable of forming a high-quality toner image can be obtained by obtaining a high gloss fixed image at the time of fixing, excellent in low temperature fixing property and offset resistance, and having a wide fixing temperature range. I came to let you.

The present invention relates to a toner having toner particles containing at least a binder resin, a colorant and a wax, and a molecular weight distribution measured by gel permeation chromatography (GPC) of a tetrahydrofuran (THF) soluble content of the toner. In the chart of
i) having a main peak in the region of molecular weight 16000 or more and 60,000 or less,
ii) When the molecular weight of the main peak is M1, the height of the molecular weight M1 is H (M1), the height of the molecular weight 4000 is H (4000), and the height of the molecular weight 15000 is H (15000) H (4000), H (15000) and H (M1) are as follows: H (4000): H (15000): H (M1) = (0.10 or more and 0.95 or less) :( 0.20 More than 0.90): 1.00
In the endothermic chart measured by differential scanning calorimetry (DSC), the weight average molecular weight (Mw) of the THF soluble content of the toner determined by GPC is 15000 or more and 80000 or less.
i) the endothermic main peak is in the range of 40 ° C. or higher and 130 ° C. or lower;
ii) The toner has an integral value of heat expressed by a peak area of the endothermic main peak of 10 J or more and 35 J or less per 1 g of the toner.

The present invention also provides a dispersion of a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a wax, and a low molecular weight resin in an aqueous medium. A toner production method for producing toner particles by passing through at least a granulation step of polymerizing the polymerizable monomer in the droplets,
The resulting toner is a toner having toner particles containing at least a binder resin, a colorant and a wax,
In the chart of molecular weight distribution measured by gel permeation chromatography (GPC) of tetrahydrofuran (THF) soluble content of the toner,
i) having a main peak in the region of molecular weight 16000 or more and 60,000 or less,
ii) When the molecular weight of the main peak is M1, the height of the molecular weight M1 is H (M1), the height of the molecular weight 4000 is H (4000), and the height of the molecular weight 15000 is H (15000) H (4000), H (15000) and H (M1) are as follows: H (4000): H (15000): H (M1) = (0.10 or more and 0.95 or less) :( 0.20 More than 0.90): 1.00
Satisfied,
The weight-average molecular weight (Mw) of the THF soluble content of the toner determined by GPC is 15000 or more and 80000 or less,
In the endothermic chart measured by differential scanning calorimetry (DSC), the toner is
i) the endothermic main peak is in the range of 40 ° C. or higher and 130 ° C. or lower;
ii) The present invention relates to a method for producing a toner, wherein an integrated value of heat represented by a peak area of the endothermic main peak is 10 J or more and 35 J or less per 1 g of toner.

  According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability and offset resistance, has a wide fixing temperature range, can obtain a high gloss fixed image at the time of fixing, and can form a high-quality toner image.

  Hereinafter, the present invention will be described in detail.

As described above, the toner of the present invention is a toner having toner particles containing at least a binder resin, a colorant and a wax, and gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF) of the toner. In the molecular weight distribution chart measured by
i) having a main peak in the region of molecular weight 16000 or more and 60,000 or less,
ii) When the molecular weight of the main peak is M1, the height of the molecular weight M1 is H (M1), the height of the molecular weight 4000 is H (4000), and the height of the molecular weight 15000 is H (15000) H (4000), H (15000) and H (M1) are as follows: H (4000): H (15000): H (M1) = (0.10 or more and 0.95 or less) :( 0.20 More than 0.90): 1.00
In the endothermic chart measured by differential scanning calorimetry (DSC), the weight average molecular weight (Mw) of the THF soluble content of the toner determined by GPC is 15000 or more and 80000 or less.
i) Endothermic main peak is in the range of 40 ° C. or higher and 130 ° C. or lower,
ii) The heat quantity integrated value represented by the peak area of the endothermic main peak is 10 J or more and 35 J or less per 1 g of toner.

  The chart of the molecular weight distribution of the THF soluble content of the toner of the present invention can be measured under the following measurement conditions using a GPC measuring apparatus (HLC-8120 GPC manufactured by Tosoh Corporation).

<Measurement conditions>
Column (manufactured by Showa Denko KK): Shodex GPC KF-801, Shodex GPC KF-802, Shodex GPC KF-803, Shodex GPC KF-804, Shodex GPC KF-805, Shodex GPC KF-806, G 807 (diameter 8.0mm, length 30cm) 7 stations ・ Temperature: 40 ℃
・ Flow rate: 0.6ml / min
・ Detector: RI
Sample concentration: 10 μl of 0.1% by mass sample
Sample preparation is performed by placing a toner sample to be measured in tetrahydrofuran (THF), allowing it to stand for 6 hours, and then shaking it sufficiently (until the sample is no longer integrated), and then allowing it to stand for 1 day or longer. And let what passed the sample processing filter (pore size 0.45 micrometer) be a sample for GPC measurement. The calibration curve uses a molecular weight calibration curve created with a monodisperse polystyrene standard sample.

  An example of the molecular weight distribution chart of the THF soluble content of the preferred toner in the present invention is shown in FIGS.

  In the molecular weight distribution chart measured by GPC of the THF soluble part of the toner, the molecular weight distribution when the molecular weight at the main peak p (M1) is M1 and the height at that time is h (M1) [mV] is shown. It is shown in FIG. Here, h (M2) is the height at the sub-peak p (M2), h (4000) is the height at a molecular weight of 4000, and h (15000) is the height at a molecular weight of 15000.

  In the molecular weight distribution chart measured by GPC of the THF soluble part of the toner shown in FIG. 1, the molecular weight distribution chart when the height is converted to h (M1) [mV] = 1.00 is shown in FIG. Indicated.

  In FIG. 2, the height at the main peak P (M1) is H (M1) (the molecular weight at the main peak is M1), the height at the subpeak P (M2) is H (M2) (the molecular weight at the subpeak is M2). ). In FIG. 2, the height at a molecular weight of 4000 is indicated by H (4000), and the height at a molecular weight of 15000 is indicated by H (15000). As shown in FIG. 2, the toner of the present invention has the main peak in a region having a molecular weight of 16000 or more and 60,000 or less.

  FIG. 3 shows the same molecular weight distribution chart as that in FIG. 2. The integrated value in the region where the molecular weight is 500 or more and 2500 or less is S1, the integrated value in the region where the molecular weight is 2500 or more and 15000 or less is S2, and the molecular weight is 15000 or more and 1 million. The integral value in the following region is indicated by S3.

  FIG. 4 shows a chart of the molecular weight distribution measured by GPC of the THF-soluble component of the toner when having a maximum point p (M3) between the main peak p (M1) and the sub-peak p (M2). . Further, the minimum value between the main peak p (M1) and the maximum value p (M3) is p (L1), and the minimum value between the sub peak p (M2) and the maximum value p (M3) is p (L2). It was. Here, h (M3) is the height at the maximum value p (M3), h (L1) is the height at the minimum value p (L1), and h (L2) is the height at the minimum value p (L2). Indicates.

  FIG. 5 shows a molecular weight distribution chart when the height is converted to h (M1) [mV] = 1.00 in the molecular weight distribution chart measured by GPC of the soluble matter of THF shown in FIG. Indicated.

  In FIG. 5, the height at the main peak P (M1) is H (M1) (the molecular weight at the main peak is M1), the height at the subpeak P (M2) is H (M2) (the molecular weight at the subpeak is M2) ). In FIG. 5, the height at the maximum point P (M3) between the main peak P (M1) and the sub-peak P (M2) is H (M3) (the molecular weight at the maximum point P (M3) is M3 (M3). > M2)). In FIG. 5, the height at a molecular weight of 4000 is indicated by H (4000), and the height at a molecular weight of 15000 is indicated by H (15000). Further, the minimum value between the main peak P (M1) and the maximum value P (M3) is P (L1), and the minimum value between the sub peak P (M2) and the maximum value P (M3) is P (L2). It was. Here, H (L1) indicates the height at the minimum value P (L1), and H (L2) indicates the height at the minimum value P (L2). As shown in FIG. 5, the toner of the present invention has the main peak in a region having a molecular weight of 16000 or more and 60,000 or less.

  FIG. 6 shows the same molecular weight distribution chart as FIG. 5. The integrated value in the region where the molecular weight is 500 or more and 2500 or less is S1, the integrated value in the region where the molecular weight is 2500 or more and 15000 or less is S2, and the molecular weight is 15000 or more and 1 million. The integral value in the following region is indicated by S3.

  The toner satisfying the molecular weight distribution defined in the present invention as shown in FIGS. 1 to 6 has the effects described below.

  In the chart of molecular weight distribution measured by GPC of the THF soluble content of the toner, the toner containing a component in the molecular weight region of 4000 to 15000 is effective for low-temperature fixability, and has a low melt viscosity and a high gloss image. Is obtained.

  In addition, a toner containing a component having a molecular weight of 15000 or more and 60,000 or less has less change in viscosity due to temperature change than a wax, a low molecular weight polymer having a molecular weight of less than 15000, or a low molecular weight copolymer. A wide fixing temperature range can be obtained.

  In the present invention, a specific molecular weight is defined by having a main peak in a region having a molecular weight of 15000 or more and 60,000 or less and that the ratio of the height at each molecular weight is within the predetermined range of the present invention. The component which consists of can be mix | blended with sufficient balance. In particular, it contains components in a molecular weight range of 4000 to 15000 in a well-balanced manner, so that the viscosity decreases quickly and is excellent in the adhesive effect to paper. Demonstrates excellent fixing performance. It contains components in a molecular weight range of 15,000 or more and 60,000 or less in a well-balanced manner, so that it works to enhance the effect of softening and oozing of a wax, a low molecular weight polymer having a molecular weight of less than 15000, or a low molecular weight copolymer. . As a result, it exhibits excellent effects in low temperature fixability, durability, and expansion of the fixable temperature range.

  Here, when H (4000) is less than 0.10 with respect to H (M1), or H (15000) is less than 0.20 with respect to H (M1), the low-temperature fixability deteriorates. It is not preferable. In particular, when H (4000) is less than 0.10 relative to H (M1), it means that the amount of low molecular weight components effective for improving gloss is small, and gloss is lowered. Moreover, when H (4000) exceeds 0.95 with respect to H (M1) or H (15000) exceeds 0.90 with respect to H (M1), the offset resistance deteriorates. It is not preferable.

  In addition, the toner of the present invention preferably has a sub-peak in addition to the main peak in the region having a molecular weight of 16000 or more and 60,000 or less in a molecular weight distribution chart measured by GPC of THF-soluble matter in the toner. Furthermore, it is preferable to have this subpeak in the area | region of molecular weight 600 or more and 2000 or less. A toner containing a component having a molecular weight of 600 or more and 2000 or less can further improve the low-temperature fixability. By having a peak in the molecular weight M2, which is an extremely low molecular region, the melt viscosity of the toner at low temperatures can be lowered more effectively, the low temperature fixability can be improved, and a high gloss image can be obtained. Here, it is preferable that H (M2) / H (M1) ≧ 0.10. If H (M2) / H (M1) <0.10, the effect of low-temperature fixability may be reduced.

  In the present invention, in the molecular weight distribution chart measured by GPC of the THF-soluble matter in the toner, the integrated value (S1) of the region having a molecular weight of 500 to 2500 and the region having a molecular weight of 2500 to 15000 are shown. The ratio between the integral value (S2) and the integral value (S3) in the region having a molecular weight of 15000 or more and 1 million or less is S1: S2: S3 = (0.15 or more and 0.95 or less): 1.00: (1.50 or more) 8.00 or less). Since S1: S2: S3 = (0.15 or more and 0.95 or less): 1.00: (1.50 or more and 8.00 or less), the components contained in the toner are contained in a well-balanced manner. Further improvement in low-temperature fixability, offset resistance and high gloss of the fixed image can be achieved.

  When S2 is 1.00 and S1 is less than 0.15 or S3 exceeds 8.00, the low-temperature fixability may be deteriorated. Conversely, whether S1 exceeds 0.95, When S3 is less than 1.50, the offset resistance may be deteriorated.

An example of a more preferable molecular weight distribution in the present invention is shown in FIG. In the present invention, it is preferable that the molecular weight distribution chart measured by GPC of the THF soluble content of the toner has a maximum point P (M3) in a region having a molecular weight of 2500 or more and less than 15000. Further, in the molecular weight distribution chart measured by GPC of the THF soluble content of the toner, the height of the maximum point P (M3) is H (M3), and the maximum point P (M3) and the main peak H (M3), H (L1), and H (M1) are H (L1), where H (L1) is the height of the minimum point P (L1) when the minimum point P (L1) exists between them. The following conditions H (M3): H (L1): H (M1) = (0.10 or more and 0.95 or less): (0.20 or more and 0.99 or less): 1.00
By satisfying the above, the interaction between the resin component contained in a region having a molecular weight of 2500 or more and less than 15000 and the resin component contained in a region having a molecular weight of 15000 or more (particularly a molecular weight of 15000 or more and less than 200,000) is moderately moderated. Therefore, it is possible to effectively enhance the softening and oozing of wax, low molecular weight polymer having a molecular weight of less than 15000 or low molecular weight copolymer, and have excellent effects in low temperature fixability, durability, and expansion of the fixable temperature range. Demonstrate.

  When H (M3) is less than 0.10 or H (L1) exceeds 0.99 with respect to H (M1), the low-temperature fixability is deteriorated. Is more than 0.95, the offset resistance deteriorates, which is not preferable. On the other hand, when H (L1) is less than 0.20, the fixable temperature region becomes small, which is not preferable.

  The toner of the present invention has an endothermic main peak in a range of 40 ° C. or higher and 130 ° C. or lower in an endothermic chart measured by differential scanning calorimetry (DSC), and the amount of heat represented by the peak area of the endothermic main peak. The integral value Q is 10 J or more and 35 J or less per 1 g of toner.

  As described above, it has an endothermic main peak, has a main peak in a specific molecular weight region, and has a ratio of height (H (4000), H (15000), H (M1)) at a specific molecular weight. The toner is preferably configured so as to be in a predetermined range. Thereby, a desired high-performance toner can be obtained. This is because the endothermic main peak is in the range of 40 ° C. or higher and 130 ° C. or lower in the configuration defined in the present invention, and the heat quantity integral value Q expressed by the peak area of the endothermic main peak is 10 J or more and 35 J per 1 g of toner. By making the following, good releasability can be exhibited even at low temperature fixing. Further, the wax moderately relaxes the intermolecular force between the polymer chains of the binder resin, and the softening of the toner due to heat absorption during fixing and the curing of the resin due to heat dissipation of the toner can form an appropriate state. The calorie integral value Q represented by the peak area of the endothermic main peak can be adjusted by appropriately selecting the type of wax, its content, and the like. In addition, it is preferable that this endothermic main peak exists in the range of 50 to 110 degreeC, More preferably, it is 60 to 90 degreeC. Further, the heat quantity integral value Q of the endothermic main peak is more preferably 15 J or more and 35 J or less per 1 g of toner.

  When the heat absorption integral value Q of the endothermic main peak is less than 10 J per 1 g of toner, the fixability is deteriorated, the gloss of the fixed image is lowered, and it is not expected that the fixing member or the like is scraped or scratched. On the other hand, if the heat quantity integral value Q of the endothermic main peak exceeds 35 J per 1 g of toner, the plastic effect of the wax becomes too great and the offset resistance deteriorates.

  A production method for producing the toner of the present invention is a method for producing a toner directly in a medium (hereinafter also referred to as a polymerization method) such as a suspension polymerization method, an interfacial polymerization method or a dispersion polymerization method. preferable. The toner obtained by this polymerization method (hereinafter also referred to as “polymerized toner”) has high transferability because the shape of individual toner particles is almost spherical and the distribution of charge amount is relatively uniform. In particular, among the above polymerization methods, a suspension polymerization method is preferable as a production method for producing the toner of the present invention.

  Next, the suspension polymerization method will be described below.

  In the present invention, the suspension polymerization method comprises dispersing a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a wax, and a low molecular weight resin in an aqueous medium, and the polymerizable monomer composition. And a polymerization method for producing toner particles through at least a granulation step for producing the droplets and a polymerization step for polymerizing the polymerizable monomer in the droplets.

  Particularly in the present invention, the toner particles are preferably toner particles produced by the suspension polymerization method. Further, the weight average molecular weight (Mw) of the THF soluble content of the low molecular weight resin determined by GPC is preferably 2000 or more and 6000 or less from the viewpoint of low-temperature fixability and blocking resistance.

  In the production of the toner of the present invention, a resin can be added to the polymerizable monomer composition for the purpose of improving the shape of the toner particles, the dispersibility and fixing properties of the material, and the image characteristics. . For example, when a monomer component containing a hydrophilic functional group that cannot be used because it is soluble in an aqueous suspension and causes emulsion polymerization because the monomer is water-soluble, the following procedure is performed. That is, it can be used in the form of a copolymer such as a random copolymer, a block copolymer, and a graft copolymer of the above hydrophilic functional group-containing monomer component and a vinyl compound such as styrene or ethylene. It is. Further, it can be used in the form of the above-mentioned monomer component containing a hydrophilic functional group and a polycondensate such as polyester and polyamide, or an addition polymer such as polyether and polyimine. Examples of hydrophilic functional groups include amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups.

  In addition to the above, examples of the low molecular weight resin that can be added to the polymerizable monomer composition include the following. Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer , Styrene-butadi Copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene copolymer such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. In addition, the said low molecular weight resin can be used individually or in mixture.

  Among these low molecular weight resins, the glass transition point of the low molecular weight resin is preferably 40 ° C. or higher and 100 ° C. or lower. When the glass transition point is less than 40 ° C., the strength of the entire toner particles is lowered, and the transferability and development characteristics are liable to be lowered during a multi-endurance test. Further, the toner particles are aggregated in a high-temperature and high-humidity environment, resulting in a problem that storage stability is lowered. On the other hand, if the glass transition point exceeds 100 ° C., the problem of poor fixing tends to occur.

  The glass transition point of the low molecular weight resin is preferably 40 ° C. or higher and 70 ° C. or lower, more preferably 40 ° C. or higher and 65 ° C. or lower, from the viewpoint that low temperature fixability and a high gloss image can be obtained.

  The addition amount of the low molecular weight resin is preferably 0.1 to 75 parts by mass in 100 parts by mass of the binder resin in the toner particles. When the amount is less than 0.1 part by mass in 100 parts by mass of the binder resin in the toner particles, the effect of adding the low molecular weight resin is small.

  The toner of the present invention is preferably a toner having toner particles having at least a core part and a shell part. The toner particles have a shell portion so as to cover the core portion. By adopting such a structure, it is possible to prevent charging failure and blocking in each environment due to deposition of the core portion on the toner surface. Further, it is more preferable that a surface layer portion having a contrast different from that of the shell portion is present on the surface of the shell portion. The presence of this surface layer portion can improve environmental stability, durability, and blocking resistance.

  In the present invention, a specific method for measuring the cross-sectional shape of the toner includes the following method. First, after fully dispersing the toner in a room temperature curable epoxy resin, the toner is allowed to stand at a temperature of 40 ° C. for 2 days to be cured, and the obtained cured product is formed into a flaky sample using a microtome equipped with diamond teeth. cut. Next, ruthenium tetroxide and osmium tetroxide were used in combination, stained due to a slight difference in crystallinity, and further irradiated with an electron beam to show the difference in contrast due to electron density using a transmission electron microscope ( Take a picture using TEM).

  In the present invention, whether or not the toner particles have a core / shell structure can be determined based on the observation result with a transmission electron microscope according to the measurement method described above. Here, in the cross-sectional photograph in which the minor axis is D4 ± (D4 × 0.2) μm with respect to the weight average particle diameter D4 of the toner, the case where the core part is covered with the shell part is included. Judgment is made, and a cumulative ratio of 100 or more is observed and the ratio of inclusion is obtained as the inclusion ratio (number%).

  In the toner of the present invention, it was defined that a core / shell structure was formed when the encapsulation rate of the core part was in the range of 60 to 100% by number. When the encapsulation rate of the core part is less than 60% by number, environmental stability and durability stability may be deteriorated due to the influence of the core part exposure to the toner surface.

  In the toner of the present invention, whether or not a surface layer portion (hereinafter also referred to as a surface layer structure) exists on the surface of the shell portion is determined based on the result of the transmission electron microscope in accordance with the measurement method described above. be able to. In a cross-sectional photograph in which the minor axis is D4 ± (D4 × 0.2) μm with respect to the weight average particle diameter D4 of the toner, the ratio of the toner having a surface layer structure observed by accumulating a total of 100 toners is measured. %). In the present invention, when the toner surface layer structure ratio (number%) is in the range of 60 to 100 number%, it is determined that the surface layer structure is formed. When the toner surface layer structure ratio is less than 60% by number, the environmental stability and durability stability of the toner may be lowered.

  In the present invention, the ratio of the surface layer portion is preferably 0.5 to 80 area% based on the surface area of the toner particles.

  The material constituting the surface layer portion preferably has a molecular chain polar structure.

  In the present invention, the molecular chain polar structure refers to a molecular structure in which atoms in the molecule have many δ + or δ− electron density states.

  Resin molecules are composed of a plurality of types of atoms, and the constituent atoms have inherent electronegativity, and the values differ greatly depending on the atoms. Due to this difference in electronegativity, electrons are localized in the molecule. In this localization, the state changes depending on the type, number, and bonding mode of the atoms to be configured, and the polarity of the molecular chain changes.

  What is preferable as the molecular chain polar structure is, for example, a bond structure formed by condensation polymerization or addition polymerization. Specifically, ester bonds (—COO—), ether bonds (—O—), amide bonds (—CONH—), imine bonds (—NH—), urethane bonds (—NHCOO—), urea bonds ( -NHCONH-).

For example, in an ether chain (—CH ₂ —O—CH ₂ —) etc., the electrons on the carbon atom are slightly deficient (δ +), the electrons on the oxygen atom are slightly excessive (δ−), A bond angle with an oxygen atom as a vertex is in a state. Thus, if there are many polarized molecular chains, the polarity of the molecule, that is, the resin will increase, and if there are few polarized molecular chains, it will decrease. In general, molecules composed of hydrocarbons have low polarity.

  When the surface layer portion has a molecular chain polar structure, charging stability is improved. In addition, when toner particles are produced in a polar solvent such as an aqueous or hydrophilic medium, the surface layer portion having a molecular chain polar structure is more uniformly formed in the vicinity of the toner surface. Underlying charging stability and durability during high-speed printing are improved.

  Examples of the surface layer portion that is particularly preferably used in the present invention include a polyester resin or a derivative thereof.

  Preferred examples of the polymerizable monomer that can be used to produce the toner particles of the present invention include the following vinyl polymerizable monomers. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; 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 -Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, Diethyl phosphate ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as til methacrylate; methylene aliphatic monocarboxylic esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, Vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

The shell portion is composed of a vinyl polymer formed from these vinyl polymerizable monomers and an added resin. Among these vinyl polymerizable monomers, a styrene polymer, a styrene-acrylic copolymer, or a styrene-methacrylic copolymer is used from the viewpoint of efficiently covering the wax mainly forming the inside or the central portion. Is preferred.
The material constituting the core of the toner of the present invention is preferably wax.

  Examples of the wax component that can be used in the toner according to the present invention include the following. Petroleum wax such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof according to Fischer-Tropsch method, polyolefin wax and derivatives thereof such as polyethylene and polypropylene, carnauba wax, candelilla Natural waxes such as waxes and derivatives thereof, and derivatives include oxides, block copolymers with vinyl monomers, graft modified products, fatty acids such as higher aliphatic alcohols, stearic acid, palmitic acid, or compounds thereof, Acid amide wax, ester wax, ketone, hydrogenated castor oil and derivatives thereof, plant wax, animal wax, silicone resin.

  In particular, in the present invention, an ester wax having at least one long-chain ester moiety having 10 or more carbon atoms represented by the following formulas (1) to (6) is preferable without inhibiting the transparency of OHP.

（式中、ａ及びｂは０〜４の整数を示し、ａ＋ｂは４であり、Ｒ^１及びＲ^２は炭素数が１〜４０の有機基を示し、ｎ及びｍは０〜１５の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b represent an integer of 0 to 4, a + b represents 4, R ¹ and R ² represent an organic group having 1 to 40 carbon atoms, and n and m represent an integer of 0 to 15) N and m are not 0 at the same time.)

（式中、ａ及びｂは１〜３の整数を示し、ａ＋ｂは４であり、Ｒ^１は炭素数が１〜４０の有機基を示しｎ及びｍは０〜１５の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b represent an integer of 1 to 3, a + b is 4, R ¹ represents an organic group having 1 to 40 carbon atoms, and n and m represent an integer of 0 to 15; m is never 0 at the same time.)

（式中、ａ及びｂは０〜３の整数を示し、ａ＋ｂは２または３であり、Ｒ^１及びＲ^２は炭素数が１〜４０の有機基を示し、且つＲ^１とＲ^２との炭素数差が１０以上である基を示し、Ｒ^３は炭素数が１以上の有機基を示す。また、ｃは２または３であり、ａ＋ｂ＋ｃ＝１であり、ｎ及びｍは０〜１５の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b represent an integer of 0 to 3, a + b is 2 or 3, R ¹ and R ² represent an organic group having 1 to 40 carbon atoms, and R ¹ and R ² R ³ represents a group having a carbon number difference of 10 or more, R ³ represents an organic group having 1 or more carbon atoms, c is 2 or 3, a + b + c = 1, and n and m are 0-15. Indicates an integer, and n and m are not 0 at the same time.)

R ¹ —COO—R ² (4)
(Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, and R ¹ and R ² may be the same or different from each other.)

（式中、Ｒ^１及びＲ^２は炭素数が１〜４０の炭化水素基を示し、ｎは２〜２０の整数であり、且つＲ^１及びＲ^２は、お互いに同じでも異なる炭素数でもよい。）

(Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, n is an integer of 2 to 20, and R ¹ and R ² may be the same or different from each other) .)

（式中、Ｒ^１及びＲ^２は炭素数が１〜４０の炭化水素基を示し、ｎは２〜２０の整数であり、且つＲ^１及びＲ^２は、お互いに同じでも異なる炭素数でもよい。）

(Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, n is an integer of 2 to 20, and R ¹ and R ² may be the same or different from each other) .)

  As the molecular weight of the wax, those having a weight average molecular weight (Mw) of 300 or more and 1500 or less are preferable. If it is less than 300, the wax is likely to be exposed to the toner particle surface, and if it exceeds 1500, the low-temperature fixability is deteriorated. Particularly preferred is a range of 400 to 1250. Furthermore, when the ratio of the weight average molecular weight / number average molecular weight (Mw / Mn) is 1.5 or less, the peak of the DSC endothermic curve of the wax becomes sharper, and the mechanical strength of the toner particles at room temperature is improved. Particularly excellent toner characteristics exhibiting sharp melting characteristics upon fixing can be obtained.

  Specific examples of the ester wax include the following compounds.

  In recent years, the need for full-color double-sided images has increased, and when a double-sided image is formed, the toner image on the transfer material first formed on the front surface is also used when the next image is formed on the back surface. There is a possibility of passing again through the heating section. At that time, it is necessary to sufficiently consider the high temperature offset resistance of the fixed image of the toner. Specifically, it is preferable to add 2 to 30% by mass of wax in the toner particles. When the content is less than 2% by mass, the high temperature offset resistance is lowered, and further, the image on the back surface may show an offset phenomenon when fixing a double-sided image. When the amount is more than 30% by mass, toner particles are likely to be coalesced during granulation in the production by the polymerization method, and those having a wide particle size distribution are likely to be generated.

  The toner of the present invention preferably has an average circularity of 0.970 to 1.000 and a mode circularity of 0.98 to 1.00 for particles of 3 μm or more.

Here, “circularity” in the present invention is used as a simple method for quantitatively expressing the shape of the particles. In the present invention, flow type particle image analyzer FPIA-2100 manufactured by Toa Medical Electronics is used. The value obtained from the following equation is defined as circularity.
Circularity a = L ₀ / L
L ₀ : Perimeter of a circle having the same projected area as the particle image L: Perimeter of the particle image (L ₀ ; Perimeter of a circle having the same projected area as the particle image, L: Perimeter of the projected image of the particle)
The circularity in the present invention is an index of the degree of unevenness of the toner, and when the toner is a perfect sphere, the circularity is 1.00, and the circularity becomes smaller as the surface shape becomes more complicated.

  A toner having an average circularity of 0.970 or more and 1.000 or less is preferable from the viewpoint of extremely excellent transferability. This is presumably because the contact area between the toner and the photoconductor is small and the adhesion force of the toner to the photoconductor due to mirror image force, van der Waals force, etc. is reduced. Therefore, if such a toner is used, the transfer rate is high and the residual toner is greatly reduced. Therefore, the toner in the pressure contact portion between the charging member and the photosensitive member is very little, toner fusion is prevented, and image defects are prevented. It is considered to be significantly suppressed.

  These effects are more prominent in an image forming method including a contact transfer process in which transfer loss is likely to occur.

  Although the toner according to the present invention can be produced by a pulverization method, the toner obtained by this pulverization method is generally indefinite form. Therefore, in order to obtain an average circularity of 0.970 or more and 1.000 or less of the toner obtained by the pulverization method, it is often necessary to perform mechanical / thermal or some special treatment.

  In the toner circularity distribution, the mode circularity of 0.98 or more and 1.00 or more means that most of the toner particles have a shape close to a true sphere. In this case, the reduction in the adhesion force of the toner to the photosensitive member due to the mirror image force, van der Waals force, etc. becomes more remarkable, and the transfer efficiency becomes very high, which is preferable.

  Here, the mode circularity is as follows. First, the circularity from 0.40 to 1.00 is 0.40 or more and less than 0.41, 0.41 or more and less than 0.42, ..., 0.99 or more and less than 1.00, and 1.00. Thus, 61 is divided every 0.01. Then, the measured circularity of each particle is assigned to each divided range, and the circularity of the divided range where the frequency value is maximum in the circularity frequency distribution is referred to as mode circularity.

  In the present invention, it is preferable to add a charge control agent to the toner for the purpose of controlling the chargeability of the toner.

  Of these known charge control agents, those having little polymerization inhibition and aqueous phase transfer are preferred. Examples of the positive charge control agent include nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, guanidine derivatives, imidazole derivatives, amine compounds, and the like. Examples of negative charge control agents include metal-containing salicylic acid copolymers, metal-containing monoazo dye compounds, urea derivatives, styrene-acrylic acid copolymers, and styrene-methacrylic acid copolymers.

  The addition amount of these charge control agents is preferably 0.1 to 10% by mass of the binder resin or polymer monomer.

  The following are mentioned as a polymerization initiator used when manufacturing a toner particle by a polymerization method. 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4- Peroxide polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 20% by mass relative to the polymerizable monomer, and may be used alone or in combination.

  In order to control the molecular weight of the binder resin of the toner particles, a chain transfer agent may be added. A preferable addition amount is 0.001 to 15% by mass of the polymerizable monomer.

  In order to control the molecular weight of the binder resin of the toner particles, a crosslinking agent may be added. For example, as a crosslinkable monomer, the following are mentioned as a bifunctional crosslinking agent. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and the above acrylates were changed to methacrylate The.

  Moreover, the following are mentioned as a polyfunctional crosslinking | crosslinked monomer. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate and the like. A preferable addition amount of the crosslinking agent is 0.001 to 15% by mass of the polymerizable monomer.

  In the case of an aqueous dispersion medium, examples of the dispersion stabilizer for the particles of the polymerizable monomer composition include the following. Tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina Fine powder of inorganic compounds such as

In the present invention, various additives shown below can be included in addition to the above for the purpose of imparting various properties. The additive preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles in view of durability when added to the toner particles. The particle size of the additive means the average particle size obtained by observing the surface of the toner particles with an electron microscope. As additives for the purpose of imparting these characteristics, for example, the following are used.
1) Fluidity imparting agent: metal oxide (for example, silicon oxide, aluminum oxide, titanium oxide), carbon black, and carbon fluoride. Each of them is more preferably hydrophobized.
2) Abrasive: metal oxide (eg cerium oxide, aluminum oxide, magnesium oxide, chromium oxide), nitride (eg silicon nitride), carbide (eg silicon carbide), metal salt (eg strontium titanate, calcium sulfate, sulfuric acid) Barium, calcium carbonate).
3) Lubricant: Fluorine resin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
4) Charge controllable particles: metal oxides (for example, tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide), carbon black.

  These additives are used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of toner particles. These additives may be used alone or in combination.

  The toner of the present invention preferably has a weight average particle diameter D4 of 2.0 μm or more and 12.0 μm or less, more preferably 4.0 μm or more and 9.0 μm or less, and still more preferably Preferably has a weight average particle diameter of 5.0 μm or more and 8.0 μm or less.

  The glass transition point (Tg) of the toner of the present invention is 40 ° C. or higher and 100 ° C. or lower, preferably 40 ° C. or higher and 80 ° C. or lower. More preferably, it is 45 ° C. or more and 70 ° C. or less. When the glass transition point is lower than 40 ° C., the blocking resistance of the toner is lowered. When the glass transition point exceeds 100 ° C., the low temperature offset resistance of the toner and the transparency of the transmitted image of the overhead projector film are deteriorated.

  The THF insoluble content in the toner is preferably 0 to 90% by mass, more preferably 1 to 20% by mass, and most preferably 2 to 10% by mass.

  The THF-insoluble matter indicates the mass ratio of the ultra-high molecular weight polymer component (substantially crosslinked polymer) of the binder resin that has become insoluble in the THF solvent. The THF-insoluble content is defined as a value measured as follows.

About 1 g of toner is carefully evaluated (W ₁ g), put in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), and applied to a Soxhlet extractor. Then, 100 to 200 ml of THF is used as a THF solvent, and the soluble components extracted with the THF solvent are evaporated for 6 hours, followed by vacuum drying at 100 ° C. for several hours to accurately evaluate the amount of THF soluble matter (W ₂ g). The THF insoluble content of the toner is calculated from the following formula.

  In the present invention, the weight average molecular weight (Mw) in the gel permeation chromatography (GPC) of the soluble portion of tetrahydrofuran (THF) in the toner is from 15,000 to 80,000. Such toner exhibits good environmental stability and durability stability. Furthermore, it is preferable that the weight average molecular weight in the gel permeation chromatography (GPC) of the soluble part of tetrahydrofuran (THF) in the toner is 20000 or more and 50000 or less. If the weight-average molecular weight of GPC soluble in THF in the GPC is less than 15,000, the blocking resistance and durability are likely to deteriorate, and if it exceeds 80000, low-temperature fixability and high gloss images are difficult to obtain. .

  In the present invention, the ratio Mw / Mn of the weight average molecular weight and the number average molecular weight in gel permeation chromatography (GPC) of the soluble portion of tetrahydrofuran (THF) in the toner is preferably 10 or more and 100 or less. If Mw / Mn is less than 10, the fixable temperature range is narrow, and if it exceeds 100, the low-temperature fixability is deteriorated.

  In the present invention, examples of the dispersion stabilizer used when the toner is produced using the polymerization method include the following. Organic compounds such as polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, and starch. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  When an inorganic compound is used in the dispersion stabilizer, a commercially available one may be used as it is, but the inorganic compound may be produced in an aqueous dispersion medium in order to obtain fine particles. For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed with high stirring.

  For fine dispersion of the dispersion stabilizer, 0.001 to 0.1 parts by mass of a surfactant may be used with respect to 100 parts by mass of the polymer monomer. This is to promote the initial action of the dispersion stabilizer. Examples of the surfactant include the following. Sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium octylate, sodium stearate, and calcium oleate.

  As the colorant used in the present invention, a known colorant can be used.

  For example, the following are mentioned as a black pigment. Carbon black, aniline black, non-magnetic ferrite, magnetite.

  The following are mentioned as a yellow pigment. Yellow iron oxide, navel yellow, naphthol yellow S, hanzer yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, tartrazine lake.

  Examples of the orange pigment include the following. Permanent Orange GTR, Pyrazolone Orange, Vulcan Fast Orange, Benzidine Orange G, Indanthren Brilliant Orange RK, Indanthren Brilliant Orange GK.

  The following are mentioned as a red pigment. Bengala, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eosin Lake, Rhodamine Lake B, Alizarin Lake.

  The following are mentioned as a blue pigment. Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-free Phthalocyanine Blue, Phthalocyanine Blue Partial Chloride, Fast Sky Blue, Induslen Blue BG.

  Examples of purple pigments include fast violet B and methyl violet lake.

  Examples of the green pigment include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

  These colorants can be used alone or in combination, and further in a solid solution state.

  The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The added amount of the colorant is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin. When a magnetic material or a metal oxide is used as the black colorant, it is preferable to use 20 to 150 parts by mass with respect to 100 parts by mass of the binder resin, unlike other colorants.

  In the present invention, in order to produce toner particles using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and dispersion medium transferability of the colorant. If necessary, the surface may be modified by subjecting the colorant to a surface treatment with a substance that does not inhibit polymerization. In particular, since dyes and carbon black often have polymerization inhibiting properties, care must be taken when using them.

  A preferable method for treating the dye includes a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance. The obtained colored polymer is added to the polymerizable monomer composition. Moreover, about carbon black, you may process with the substance (for example, organosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

  The toner of the present invention can be used for both non-magnetic toner and magnetic toner. When the toner of the present invention is used as a magnetic toner, magnetic powder may be contained therein. As such magnetic powder, a substance that is magnetized in a magnetic field is used, for example, a powder of a ferromagnetic metal such as iron, cobalt or nickel, or a powder of a sulfurous iron oxide such as magnetite or ferrite. There is.

  When obtaining magnetic toner particles using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and dispersion medium transferability of the magnetic material. If necessary, surface modification (for example, surface treatment with a material that does not inhibit polymerization) ) Is preferable.

  During the toner particle production process, the temperature may be raised in the latter half of the polymerization reaction, and further in order to remove unreacted polymerizable monomers or by-products that cause odor during toner fixing, the latter half of the reaction or polymerization. A part of the dispersion medium may be distilled off from the reaction system after completion of the reaction. After completion of the reaction, the produced toner particles are washed, collected by filtration, and dried.

  In the suspension polymerization method, it is preferable to use 300 to 3,000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the polymerizable monomer composition.

  In the fixing of the toner of the present invention, the fixable temperature region is a temperature region between the low temperature offset end temperature and the high temperature offset start temperature.

  A method for measuring and evaluating physical properties relating to the toner of the present invention will be described below.

<DSC measurement>
In the present invention, a differential scanning calorimeter (DSC) (manufactured by M-DSC TA-Instruments) was used. The toner sample to be measured weighs 6 mg precisely. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 1.0 ° C./min and a normal temperature and normal humidity within a measurement temperature range of 20 ° C. to 200 ° C. Measurement is performed at a modulation amplitude of ± 0.5 ° C. and a frequency of 1 / min. The maximum glass transition point Tg (° C.) is calculated from the obtained reversing heat flow curve. Tg is obtained as Tg (° C.) as the center value of the intersection of the baseline before and after endotherm and the tangent of the curve due to endotherm. In the endothermic chart at the time of temperature rise measured by DSC, the integrated value of heat per gram of toner (J / g) represented by the peak area of the endothermic main peak was measured. Specifically, the analysis software Universal Analysis Ver. 2.5H (TA Instruments) is used. Using the function of Integral PeakLinear in the software, the calorific value integrated value is obtained from the reversing heat flow curve obtained from the above measurement. That is, the amount of heat per gram of toner represented by the peak area of the endothermic main peak in the present invention is calculated from the area surrounded by the straight line connecting the measurement points at 35 ° C. and 135 ° C. and the reversing heat flow curve. The integrated value (J / g) was used. An example of a reversing heat flow curve obtained by DSC measurement of the toner is shown in FIG. In FIG. 7 showing a reversing heat flow curve, the vertical axis represents Rev Heat Flow (W / g), and the horizontal axis represents Temperature (° C.).

<Measurement of weight average particle diameter of toner>
0.1 to 5 ml of a surfactant (alkylbenzene sulfonate) is added to 100 to 150 ml of the electrolyte solution, and 2 to 20 mg of a measurement sample is added thereto. The electrolyte solution in which the sample is suspended is dispersed for 1 to 3 minutes using an ultrasonic disperser, and a particle size distribution of 2 to 40 μm is measured with a 100 μm aperture using a Coulter counter multisizer, based on the volume, and the weight of the toner The average particle size shall be calculated.

<Fixing test>
A modified fixing device in which the fixing unit of the full color laser beam printer (LBP-2510, manufactured by Canon) was modified so that the fixing temperature could be adjusted was used. Using this printer, an unfixed toner image (0.5 mg / cm ² ) on an image receiving paper (75 g / m ² ) at a process speed of 120 mm / sec and a fixing temperature range of 110 to 240 ° C. at intervals of 5 ° C. Oil-less heat and pressure were applied to form a fixed image on the image receiving paper.

The fixability is determined by rubbing the fixed image 10 times with Kimwipe [S-200 ″ (Clesia Inc.) with a load of 75 g / cm ² , and the fixing temperature is the temperature at which the density reduction rate before and after rubbing is less than 5%. Used for evaluation of fixability.

<Image density measurement>
Using a Macbeth densitometer, the fixed image portion was measured using an SPI auxiliary filter.

<Durable image density measurement>
-Non-magnetic toner-
A modified machine (process speed: 120 mm / sec, fixing temperature 190 ° C.) of a full-color laser beam printer (LBP-2510, manufactured by Canon) is used. With this printer, 200 g of toner is set in the process cartridge in an environment of low temperature and low humidity (16 ° C./15% RH), normal temperature and normal humidity (24 ° C./60% RH), and high temperature and high humidity (30 ° C./76% RH). Then, it was printed out and evaluated. Specifically, up to 8000 sheets of recording paper (75 mg / cm ² ) were printed out with an image with a printing ratio of 2%, and the solid image density at the initial and 8000 sheet output was evaluated.
Rank A: 1.45 or higher Rank B: 1.44 to 1.40
Rank C: 1.39 to 1.35
Rank D: 1.34 to 1.30
Rank E: 1.29 to 1.25
Rank F: 1.24 or less

-For magnetic toner-
Similar to the case of the non-magnetic toner, except that a modified LBP-2160 (manufactured by Canon) (process speed: 120 mm / sec, fixing temperature 190 ° C.) was used instead of using LBP-2510 as a full-color laser beam printer. The measurement was performed under the following conditions.
Rank A: 1.45 or higher Rank B: 1.44 to 1.40
Rank C: 1.39 to 1.35
Rank D: 1.34 to 1.30
Rank E: 1.29 to 1.25
Rank F: 1.24 or less

<Blocking test>
About 10 g of toner was placed in a 100 ml glass bottle and allowed to stand at 45 ° C. and 50 ° C. for 10 days.
Rank A: No change Rank B: Agglomerates, but immediately unraveled rank C ... Unbreakable rank D ... No fluidity rank E ... Obvious caking

<Gross evaluation>
The gloss value of the image in the fixed image area was measured using a handy gloss meter gloss checker IG-310 (manufactured by Horiba Seisakusho).

  The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In addition, all the parts used in an Example show a mass part.

[Production of Styrenic Resin (1)]
A reactor equipped with a dropping funnel, a Liebig condenser and a stirrer was charged with 600.0 parts by mass of xylene and heated to 135 ° C. A mixture of 100.0 parts by mass of styrene monomer, 0.1 part by mass of n-butyl acrylate and 13.0 parts by mass of di-tert-butyl peroxide was charged into a dropping funnel, and dropped into xylene at 135 ° C. over 2 hours. did. Further, the solution polymerization was completed under reflux of xylene (137 ° C. to 145 ° C.), xylene was removed, and a styrene resin (1) was obtained. The resulting styrene resin (1) had a weight average molecular weight (Mw) of 3200, Mw / Mn of 1.19, and a glass transition point (Tg) of 55 ° C.

[Production of Styrenic Resins (2) to (4), (6), (9) and (10)]
Styrene resin (2) using the same production method as styrene resin (1) except that styrene monomer, n-butyl acrylate, di-tert-butyl peroxide, and xylene were used in the addition amounts shown in Table 2. To (4), (6), (9) and (10) were produced. Table 2 shows the weight average molecular weight (Mw), Mw / Mn, and glass transition point (Tg) of the obtained styrene resins (2) to (4), (6), (9) and (10). In addition, "-" of Table 2 means not adding.

[Production of Styrenic Resin (5)]
A mixture of 50.0 parts by mass of xylene, 80.0 parts by mass of styrene monomer, 20.0 parts by mass of n-butyl acrylate, and 2.0 parts by mass of di-tert-butyl peroxide was added to a reaction equipped with a Liebig condenser and a stirrer. Prepared for the machine. Then, polymerization was carried out at a polymerization temperature of 125 ° C. for 24 hours. Thereafter, xylene was removed to obtain a styrene resin (5). The weight average molecular weight (Mw) of the obtained styrene resin (5) was 290,000, Mw / Mn was 12.40, and the glass transition point (Tg) was 64 ° C.

[Production of Styrenic Resins (7) and (8)]
The same production method as the styrene resin (5) was used except that styrene monomer, n-butyl acrylate, di-tert-butyl peroxide, crosslinking agent (DVB) and xylene were used in the addition amounts shown in Table 2. Thus, styrene resins (7) and (8) were produced. Table 2 shows the weight average molecular weight (Mw), Mw / Mn, and glass transition point (Tg) of the obtained styrene resins (7) and (8). DVB means divinylbenzene.

<Example 1>
While adding 710 parts by weight of ion-exchanged water and 850 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution in a four-necked container, while stirring at 12,000 rpm using a high-speed stirring device TK-homomixer, Maintained at 60 ° C. To this, 68 parts by mass of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 124.0 parts by mass n-butyl acrylate 36.0 parts by mass Copper phthalocyanine pigment 13.0 parts by mass Styrenic resin (1) 40.0 parts by mass (Mw = 3200, Mw / Mn = 1.19)
Polyester resin (1) 10.0 parts by mass (terephthalic acid-propylene oxide modified bisphenol A (2 mol adduct) -ethylene oxide modified bisphenol A (2 mol adduct) (molar ratio 51:30:20); acid value 9; Glass transition point 60 ° C. Mw = 10000, Mw / Mn = 3.20)
Negative charge control agent (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.8 parts by mass Wax [Fischer-Tropsch wax (1), melting point 78.0 ° C.] 15.0 parts by mass

  The monomer mixture 1 was dispersed for 3 hours using an attritor. Polymeric monomer obtained by adding 20.0 parts by mass of 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate (toluene solution 50%) as a polymerization initiator to the monomer mixture 1 The monomer composition was put into an aqueous dispersion medium. And it granulated for 5 minutes, maintaining the rotation speed of a stirrer at 10,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 6 hours with slow stirring. Table 1 shows the raw materials and Table 2 shows the physical properties of the styrene resin (1).

  Next, the temperature in the container was raised to 80 ° C. and maintained for 4 hours, and then gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain slurry 1. Dilute hydrochloric acid was added to the container containing the slurry 1 to remove the dispersion stabilizer. Further, filtration, washing and drying were performed to obtain polymer particles (toner particles 1) having a weight average particle diameter of 6.2 μm.

With respect to the obtained toner particles 1 (100.0 parts by mass), 2.0 parts by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g and a specific surface area by the BET method of 100 m ² / g Toner (1-1) was obtained by externally adding 0.1 part by mass of titanium oxide. Other toner properties of toner (1-1) were measured and are shown in Table 1.

  Table 3 shows the measurement result of the molecular weight distribution chart measured by GPC of the THF soluble part of the toner (1-1).

  200 g of toner (1-1) is filled in a process cartridge of a modified laser beam printer (Canon: LBP-2510), and low temperature and low humidity (16 ° C./15% RH), normal temperature and normal humidity (24 ° C./60%) RH) and high temperature and high humidity (30 ° C./76% RH) were printed out and evaluated. Specifically, an image having a printing ratio of 2% was printed up to 8000 sheets, and the solid image density at the initial stage and when outputting 8000 sheets was evaluated. The results are shown in Table 4. Next, fixing evaluation was performed, and the results are also shown in Table 4.

<Example 2>
Toner particles 2 were obtained in the same manner as in Example 1 except for the raw materials shown in Table 1.

For toner particles 2 (100.0 parts by mass), 0.8 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by BET method and titanium oxide 0 having a specific surface area of 100 m ² / g by BET method Toner (2-1) was obtained by externally adding 1 part by mass. Table 1 shows the physical properties of Toner (2-1).

  Measurement of the molecular weight distribution of the obtained toner (2-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (2-1) was set in a process cartridge of a modified laser beam printer (Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Example 3>
Toner particles 3 were obtained in the same manner as in Example 1 except for the raw materials shown in Table 1.

For toner particles 3 (100.0 parts by mass), 0.8 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by the BET method and titanium oxide 0 having a specific surface area of 100 m ² / g by the BET method Toner (3-1) was obtained by externally adding 1 part by mass. Table 1 shows the physical properties of Toner (3-1).

  Measurement of the molecular weight distribution of the obtained toner (3-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (3-1) was set in a process cartridge of a modified laser beam printer (Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Example 4>
Toner particles 4 were obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used.

With respect to the obtained toner particles 4 (100.0 parts by mass), 2.0 parts by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g and a specific surface area by the BET method of 100 m ² / g Toner (4-1) was obtained by externally adding 0.1 part by mass of titanium oxide. Table 1 shows the physical properties of Toner (4-1).

  Measurement of the molecular weight distribution of the obtained toner (4-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (4-1) was set in a process cartridge of a modified laser beam printer (Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Example 5>
Toner particles 5 were obtained in the same manner as in Example 1 except for the raw materials shown in Table 1.

For toner particles 5 (100.0 parts by mass), 0.8 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by BET method and titanium oxide 0 having a specific surface area of 100 m ² / g by BET method Toner (5-1) was obtained by externally adding 1 part by mass. Table 1 shows the physical properties of Toner (5-1).

  Measurement of the molecular weight distribution of the obtained toner (5-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (5-1) was set in a process cartridge of a modified laser beam printer (Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Example 6>
Toner particles 6 were obtained in the same manner as in Example 1 except for the raw materials shown in Table 1.

For toner particles 6 (100.0 parts by mass), 0.8 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by BET method and titanium oxide 0 having a specific surface area of 100 m ² / g by BET method Toner (6-1) was obtained by externally adding 1 part by mass. Table 1 shows the physical properties of Toner (6-1).

  Measurement of the molecular weight distribution of the obtained toner (6-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (6-1) was set in a process cartridge of a modified laser beam printer (Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Example 7>
Toner particles 7 were obtained in the same manner as in Example 1 except for the raw materials shown in Table 1.

The toner particles 7 (100.0 parts by weight), titanium oxide specific surface area by BET method specific surface area by 0.8 part by weight of hydrophobic silica and a BET method is 200 meters ² / g is 100 m ² / g 0 Toner (7-1) was obtained by externally adding 1 part by mass. Table 1 shows the physical properties of Toner (7-1).

  Measurement of the molecular weight distribution of the obtained toner (7-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (7-1) was set in a process cartridge of a modified laser beam printer (manufactured by Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Example 8>
To the slurry 1 (100.0 parts by mass) obtained in Example 1, a ferrite carrier (500.0 parts by mass) having a particle size of 40 μm and surface-coated with a styrene-methyl methacrylate copolymer was added, and a stirring blade was added. The mixture was stirred at 60 ° C. for 1 hour with uniform stirring. After cooling to 30 ° C., dilute hydrochloric acid was added to remove the dispersion stabilizer. Further, the toner particles 8 were obtained by filtration, washing and drying.

For toner particles 8 (100.0 parts by mass), 0.8 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by BET method and titanium oxide 0 having a specific surface area of 100 m ² / g by BET method Toner (8-1) was obtained by externally adding 1 part by mass. Table 1 shows the physical properties of Toner (8-1).

  Measurement of the molecular weight distribution of the obtained toner (8-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (8-1) was set in a process cartridge of a modified laser beam printer (Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Comparative Example 1>
Styrene resin (4) 40.0 parts by mass Styrene resin (5) 160.0 parts by mass (styrene-n-butyl acrylate copolymerization ratio 80:20 (mass ratio), Mw = 290000, Mw / Mn = 12. .40)
Polyester resin (1) 10.0 parts by mass (terephthalic acid-propylene oxide modified bisphenol A (2 mol adduct) -ethylene oxide modified bisphenol A (2 mol adduct) (molar ratio 51:30:20); acid value 9; Glass transition point 60 ° C. Mw = 10000, Mw / Mn = 3.20)
Copper phthalocyanine pigment 13.0 parts by mass Negative charge control agent (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.8 parts by mass Wax [Fischer-Tropsch wax (1), melting point 78.0 ° C.] 15.0 parts by mass

  After the above materials are mixed with a Henschel mixer, melt kneading is performed with a twin-screw kneading extruder at 130 ° C., and the kneaded product is cooled. The cooled kneaded material is roughly pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and further classified with an air classifier, whereby toner particles 9 having a weight average particle diameter of 6.7 μm are obtained. Got.

With respect to the obtained toner particles 9 (100.0 parts by mass), 2.0 parts by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g and a specific surface area by the BET method of 100 m ² / g Toner (9-1) was obtained by externally adding 0.1 part by mass of titanium oxide. Table 1 shows the physical properties of Toner (9-1).

  Measurement of the molecular weight distribution of the obtained toner (9-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (9-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Comparative example 2>
Toner particles 10 were obtained in the same manner as in Comparative Example 1 except for the raw materials shown in Table 1.

With respect to the obtained toner particles 10 (100.0 parts by mass), 2.0 parts by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g and a specific surface area by the BET method of 100 m ² / g Toner (10-1) was obtained by externally adding 0.1 part by mass of titanium oxide. Table 1 shows the physical properties of Toner (10-1).

  Measurement of the molecular weight distribution of the obtained toner (10-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (10-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Comparative Example 3>
Toner particles 11 were obtained in the same manner as in Comparative Example 1 except for the raw materials shown in Table 1.

With respect to the obtained toner particles 11 (100.0 parts by mass), 2.0 parts by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g and a specific surface area by the BET method of 100 m ² / g Toner (11-1) was obtained by externally adding 0.1 part by mass of titanium oxide. Table 1 shows the physical properties of Toner (11-1).

  Measurement of the molecular weight distribution of the obtained toner (11-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (11-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Comparative example 4>
Except for the raw materials shown in Table 1, toner particles 12 were obtained in the same manner as in Example 1.

With respect to the obtained toner particles 12 (100.0 parts by mass), 2.0 parts by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g and a specific surface area by the BET method of 100 m ² / g Toner (12-1) was obtained by externally adding 0.1 part by mass of titanium oxide. Table 1 shows the physical properties of Toner (12-1).

  Measurement of the molecular weight distribution of the obtained toner (12-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3. The molecular weight distribution chart measured by GPC of the THF soluble content of the toner (12-1) obtained at this time is shown in FIG.

  In the same manner as in Example 1, the toner (12-1) was set in a process cartridge of a laser beam printer (manufactured by Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Comparative Example 5>
Toner particles 13 were obtained in the same manner as in Example 1 except for the raw materials shown in Table 1.

With respect to the obtained toner particles 13 (100.0 parts by mass), 2.0 parts by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g and a specific surface area by the BET method of 100 m ² / g Toner (13-1) was obtained by externally adding 0.1 part by mass of titanium oxide. Table 1 shows the physical properties of Toner (13-1).

  Measurement of the molecular weight distribution of the obtained toner (13-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (13-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Comparative Example 6>
Except for the raw materials shown in Table 1, toner particles 14 were obtained in the same manner as in Example 1.

The toner particles (100.0 parts by weight), titanium oxide specific surface area by BET method specific surface area by hydrophobic silica 0.8 parts by weight and the BET method is 200 meters ² / g is 100m ² / g 0. 1 part by mass was externally added to obtain a toner (14-1). Table 1 shows the physical properties of Toner (14-1).

  Measurement of the molecular weight distribution of the obtained toner (14-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (14-1) was set in a process cartridge of a modified laser beam printer (Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Comparative Example 7>
Toner particles 15 were obtained in the same manner as in Example 1 except for the raw materials shown in Table 1.

The toner particles (100.0 parts by weight), titanium oxide specific surface area by BET method specific surface area by hydrophobic silica 0.8 parts by weight and the BET method is 200 meters ² / g is 100m ² / g 0. Toner (15-1) was obtained by externally adding 1 part by mass. Table 1 shows the physical properties of Toner (15-1).

  Measurement of the molecular weight distribution of the obtained toner (15-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (15-1) was set in a process cartridge of a modified laser beam printer (Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Comparative Example 8>
[Preparation of dispersion of colorant fine particles]
Sodium dodecyl sulfate “Adeka Hope LS-90” (manufactured by Asahi Denka Co., Ltd.) 0.90 parts by mass and 10.0 parts by mass of ion-exchanged water were charged into a resin container, and this system was stirred to prepare sodium n-dodecyl sulfate. An aqueous solution of was prepared. While stirring this aqueous solution, 1.2 parts by mass of carbon black “Regal 330R” (manufactured by Cabot) was gradually added. After the addition, the mixture was stirred for 1 hour, and then the dispersion treatment of carbon black was continuously performed for 20 hours using a medium-type disperser, whereby a dispersion of colorant fine particles (hereinafter referred to as “colorant dispersion [C]”). Prepared). When the particle diameter of the colorant fine particles in this colorant dispersion [C] was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the weight average particle diameter was 122 nm. . Moreover, the solid content concentration of the colorant dispersion liquid [C] measured by a gravimetric method by standing drying was 16.6% by mass.

[Preparation of dispersion of release agent fine particles]
Using polypropylene (PP) produced by a usual synthesis method, thermal decomposition was carried out in the state of being melted by heat to obtain release agent fine particles of polypropylene 1.

  1.05 kg of the obtained (polypropylene 1) is added to 2.45 kg of an aqueous solution of a surfactant (nonylphenoxyethanol), and the pH is adjusted to 9 using potassium hydroxide. By raising the temperature of the system to a temperature equal to or higher than the softening point of the release agent under pressure and performing an emulsification dispersion treatment of the release agent, a dispersion of release agent particles having a solid content of 30% by mass is obtained. Produced. This dispersion was designated as “release agent dispersion W1”.

[Preparation of aqueous solution of surfactant]
[Preparation Example (S-1)] 0.055 parts by mass of sodium dodecylbenzenesulfonate (manufactured by Kanto Chemical Co., Ltd.), which is an anionic surfactant, and 4.0 parts by mass of ion-exchanged water were charged in a stainless steel pot. . And the aqueous solution (henceforth "surfactant solution (S-1)") of an anionic surfactant was prepared by stirring this system at room temperature.

  [Preparation Example (S-2)] 0.014 parts by mass of a nonionic surfactant “New Coal 565C” (manufactured by Nippon Emulsifier Co., Ltd.) and 4.0 parts by mass of ion-exchanged water were charged into a stainless steel pot. And the aqueous solution (henceforth "surfactant solution (S-2)") of nonionic surfactant was prepared by stirring this system at room temperature.

  [Preparation Example (S-3)] 1.00 parts by mass of a nonionic surfactant “FC-170C” (manufactured by Sumitomo 3M Limited) and 1000 parts by mass of ion-exchanged water were charged into a glass beaker. And the aqueous solution (henceforth "surfactant solution (S-3)") of nonionic surfactant was prepared by stirring this system at room temperature.

[Preparation of aqueous solution of polymerization initiator]
[Preparation Example (P-1)] 200.7 parts by mass of potassium persulfate (manufactured by Kanto Chemical Co., Ltd.), which is a polymerization initiator, and 12,000 parts by mass of ion-exchanged water were charged into a enamel pot. And the aqueous solution (henceforth "initiator solution (P-1)") of a polymerization initiator was prepared by stirring this system at room temperature.

  [Preparation Example (P-2)] 223.8 parts by mass of potassium persulfate (manufactured by Kanto Chemical Co., Ltd.), which is a polymerization initiator, and 12000 parts by mass of ion-exchanged water were charged into a enamel pot. And the aqueous solution (henceforth "initiator solution (P-2)") of a polymerization initiator was prepared by stirring this system at room temperature.

[Preparation of aqueous solution of sodium chloride]
An aqueous solution of sodium chloride was prepared by charging 5.36 parts by mass of sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) as a salting-out agent and 20.0 parts by mass of ion-exchanged water into a stainless steel pot and stirring the system at room temperature. (Hereinafter referred to as “sodium chloride solution (N)”).

[Manufacture of toner particles]
[Production Example (1)]
(I) Preparation of dispersion of resin fine particles [A]: A reaction vessel having a temperature sensor, a cooling pipe, a nitrogen introducing device and a stirring blade, and having a glass lining treatment on the inner surface and having an internal volume of 100 liters was prepared. Charge 4.0 liters of surfactant solution (S-1) and 4.0 liters of surfactant solution (S-2) to the reaction kettle, and add 44.0 liters of ion-exchanged water while stirring at room temperature. The system was heated. When the temperature of the system reached 75 ° C., 12.0 liters of the initiator solution (P-2) was added. Then, while controlling the temperature of the system to 75 ° C. ± 1 ° C., a monomer mixture consisting of 12.0 kg of styrene, 2.9 kg of n-butyl acrylate, 1.0 kg of methacrylic acid and 550 g of t-dodecyl mercaptan was quantitatively determined. It added over 180 minutes with the liquid feeding pump with a meter. The system was stirred for 5 hours while controlling the temperature of the system at 80 ° C. ± 1 ° C. Thereafter, the system is cooled to a temperature of 40 ° C. or lower, stirring is stopped, and the scale (foreign matter) is removed by filtration using a pole filter, whereby a dispersion of resin fine particles [A] made of a low molecular weight resin (hereinafter referred to as “low molecular weight resin”). And “low molecular weight latex [A]”). The weight average particle diameter of the resin fine particles constituting the low molecular weight latex [A] was 105 nm.

  (Ii) Preparation of dispersion of resin fine particles [B]: A reaction vessel having an internal volume of 100 liters, which was equipped with a temperature sensor, a cooling tube, a nitrogen introducing device, and a stirring blade and was subjected to glass lining treatment on its inner surface was prepared. The reaction kettle was charged with 4.0 liters of a surfactant solution (S-1) and 4.0 liters of a surfactant solution (S-2), and the ion-exchanged water 44. 0 liter was added and the system was heated. When the temperature of the system reached 70 ° C., 12.0 liters of the initiator solution (P-1) was added. A monomer mixture comprising 11.0 kg of styrene, 4.00 kg of n-butyl acrylate, 1.0 kg of methacrylic acid, and 9.0 g of t-dodecyl mercaptan while controlling the temperature of the system at 70 ° C. ± 1 ° C. Was added over 180 minutes by a liquid feed pump equipped with a meter. Then, the system was stirred for 5 hours while controlling the temperature of the system at 72 ° C. ± 2 ° C., and further stirred for 12 hours while controlling the temperature of the system at 80 ° C. ± 2 ° C. Thereafter, the system is cooled to a temperature of 40 ° C. or lower, stirring is stopped, and scale (foreign matter) is removed by filtration with a pole filter, whereby a dispersion of resin fine particles [B] made of a high molecular weight resin (hereinafter referred to as “liquid dispersion”) And “high molecular weight latex [B]”). The weight average particle diameter of the resin fine particles constituting the high molecular weight latex [B] was 102 nm.

  (Iii) Manufacture of toner particles (salting out / fusion process): A stainless steel reaction vessel having an internal volume of 100 liters equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, a comb baffle and a stirring blade (anchor blade) is prepared. I made it. In the reaction vessel, 20.0 kg of low molecular weight latex [A], 5.0 kg of high molecular weight latex [B], 0.4 kg of colorant dispersion [C], 1.02 kg of release agent dispersion (W1), Then, 20.0 kg of ion-exchanged water was charged, and the system was stirred at room temperature. The temperature of the system was heated to 40 ° C., and 20 liters of sodium chloride solution (N), 6.00 kg of isopropyl alcohol (manufactured by Kanto Chemical Co., Ltd.), and 1.0 liter of surfactant solution (S-3), They were added in this order. The system was allowed to stand for 10 minutes and then heated, heated to 85 ° C. over 60 minutes, and stirred at 85 ° C. ± 2 ° C. for 6 hours. Thus, toner particles were formed by salting out / fusion of resin fine particles made of high molecular weight resin, resin fine particles made of low molecular weight resin, colorant fine particles, and release agent fine particles (PP1 for the present invention). . After cooling until the temperature of the system reached 40 ° C. or less and stirring was stopped, aggregates were removed by filtration with a filter having an opening of 45 μm to obtain a dispersion of toner particles. Next, a wet cake (aggregate of toner particles) was separated from the obtained dispersion by vacuum filtration using a Nutsche, and this was washed with ion-exchanged water. The wet cake that has been washed is taken out from Nutsche, spread over 5 sheets of all-pads while being finely crushed, covered with kraft paper, and then dried in a blow dryer at 40 ° C. for 100 hours. An aggregate of toner particles was obtained. Next, this aggregate was pulverized with a Henschel pulverizer, whereby toner particles 16 were obtained.

The toner particles (100.0 parts by weight), titanium oxide specific surface area by BET method specific surface area by hydrophobic silica 0.8 parts by weight and the BET method is 200 meters ² / g is 100m ² / g 0. Toner (16-1) was obtained by externally adding 1 part by mass. Table 5 shows the physical properties of Toner (16-1).

  Measurement of the molecular weight distribution of the obtained toner (16-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 3.

  As in Example 1, the toner (16-1) was set in the process cartridge of a modified laser beam printer (manufactured by Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Comparative Example 9>
Using polyethylene (PE), thermal decomposition was carried out in the state of being melted by heat to obtain a release agent fine particle polyethylene 1.

  1.05 kg of the obtained (polyethylene 1) is added to 2.45 kg of an aqueous solution of a surfactant (nonylphenoxyethanol), and the pH is adjusted to 9 using potassium hydroxide. By raising the temperature of the system to a temperature equal to or higher than the softening point of the release agent under pressure and performing an emulsification dispersion treatment of the release agent, a dispersion of release agent particles having a solid content of 30% by mass is obtained. Produced. This dispersion was designated as “release agent dispersion W2.”

  Toner particles in the same manner as in Comparative Example 8, except that 1.02 kg of the release agent dispersion (W2) was used instead of the release agent dispersion (W1) in the salting out / fusion process of Comparative Example 8. 17 was obtained.

The toner particles (100.0 parts by weight), titanium oxide specific surface area by BET method specific surface area by hydrophobic silica 0.8 parts by weight and the BET method is 200 meters ² / g is 100m ² / g 0. Toner (17-1) was obtained by externally adding 1 part by mass. Table 5 shows the physical properties of Toner (17-1).

  The physical properties and molecular weight distribution of the obtained toner (17-1) were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

  In the same manner as in Example 1, the toner (17-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 4.

<Example 9>
[Production of hydrophobic magnetic iron oxide 1]
An aqueous solution containing ferrous hydroxide was prepared by mixing 1.0 to 1.05 equivalent of a caustic soda solution with respect to iron ions in an aqueous ferrous sulfate solution. While maintaining the aqueous solution at pH 8, air was blown in, and an oxidation reaction was performed at 85 to 90 ° C. to prepare a slurry liquid for generating seed crystals. Next, after adding 0.9 to 1.15 equivalent of ferrous sulfate aqueous solution with respect to the initial alkali amount (sodium component of caustic soda), the slurry liquid was maintained at pH = 8. Then, the oxidation reaction was advanced while blowing air, the pH was adjusted to about 6 at the end of the oxidation reaction, and the oxidation reaction was terminated. The produced iron oxide particles were washed and filtered out, and redispersed in another water without drying. The pH of the redispersed liquid was adjusted, and 2.5 parts by mass of n-hexyltrimethoxysilane coupling agent was added to 100 parts by mass of magnetic iron oxide with sufficient stirring, followed by thorough stirring. The produced hydrophobic iron oxide particles were washed, filtered and dried, and then the aggregated particles were crushed to obtain hydrophobic magnetic iron oxide 1 having an average particle size of 0.17 μm.

While adding 710 parts by weight of ion-exchanged water and 460 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution in a four-necked container, while stirring at 11,000 rpm using a high-speed stirring device TK-homomixer, Maintained at 60 ° C. To this, 68 parts by mass of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 124.0 parts by mass n-butyl acrylate 36.0 parts by mass Hydrophobic magnetic iron oxide 1 190.0 parts by mass Styrenic resin (1) 40.0 parts by mass (Mw = 3200, Mw / Mn = 1.19) )
Polyester resin (1) 10.0 parts by mass (terephthalic acid-propylene oxide modified bisphenol A (2 mol adduct) -ethylene oxide modified bisphenol A (2 mol adduct) (molar ratio 51:30:20); acid value 9; Glass transition point 60 ° C. Mw = 10000, Mw / Mn = 3.20)
Negative charge control agent (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.8 parts by mass Wax [Fischer-Tropsch wax (1), melting point 78.0 ° C.] 15.0 parts by mass

  The monomer mixture 2 was dispersed for 3 hours using an attritor. Then, a polymerizable monomer obtained by adding 8 parts by mass of 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate (toluene solution 50%) as a polymerization initiator to the monomer mixture 2 was used. The monomer composition was put into an aqueous dispersion medium. And it granulated for 5 minutes, maintaining the rotation speed of a stirrer at 10,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 80 ° C., and the reaction was allowed to proceed for 8 hours while slowly stirring. Table 1 shows the raw materials and Table 2 shows the physical properties of the styrene resin (1).

  Next, the inside of the container was gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain slurry 2. Dilute hydrochloric acid was added to the container containing the slurry 2 to remove the dispersion stabilizer. Further, filtration, washing, and drying were performed to obtain polymer particles (toner particles 18) having a weight average particle diameter of 6.1 μm.

To the obtained toner particles 18 (100.0 parts by mass), 1.0 part by mass of hydrophobic silica having a specific surface area of 120 m ² / g by BET method is externally added to obtain a toner (18-1). It was. Other toner properties of the toner (18-1) were measured and are shown in Table 1.

  Table 3 shows the measurement result of the molecular weight distribution chart measured by GPC of the THF-soluble component of the toner (18-1).

  As an image forming apparatus, a fixing device of LBP-2160 (manufactured by Canon) was removed, and a modified LBP-2160 machine with a process speed of 120 mm / sec was used. . For the unfixed image, a modified LBP-2160 machine was used, and for the fixing, the LBP-2510 (Canon) fixing unit was modified so that the fixing temperature could be adjusted in the same manner as in Example 1. This was done with a fixing device.

  500 g of toner (18-1) is filled in a process cartridge, and low temperature and low humidity (16 ° C./15% RH), normal temperature and normal humidity (24 ° C./60% RH), high temperature and high humidity (30 ° C./76% RH) It was printed out and evaluated in the environment. Specifically, an image having a printing ratio of 2% was printed up to 8000 sheets, and the solid image density at the initial stage and when outputting 8000 sheets was evaluated. The results are shown in Table 4. Next, fixing evaluation was performed, and the results are also shown in Table 4.

<Example 10>
While adding 710 parts by weight of ion-exchanged water and 850 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution in a four-necked container, while stirring at 12,000 rpm using a high-speed stirring device TK-homomixer, Maintained at 60 ° C. To this, 68 parts by mass of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 160.0 parts by mass n-butyl acrylate 40.0 parts by mass Copper phthalocyanine pigment 13.0 parts by mass Polyester resin (1) 10.0 parts by mass (terephthalic acid-propylene oxide modified bisphenol A (2 mol adduct) -Ethylene oxide modified bisphenol A (2 mol adduct) (molar ratio 51:30:20); acid value 9; glass transition point 60 ° C. Mw = 10000, Mw / Mn = 3.20)
Negative charge control agent (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.8 parts by mass Wax [Fischer-Tropsch wax (1), melting point 78.0 ° C.] 15.0 parts by mass

  The monomer mixture 3 was dispersed for 3 hours using an attritor. To the monomer mixture 3, 15.0 parts by weight of a polymerization initiator t-butylperoxyneodecanoate (70% toluene solution) and 1,1,3,3-tetramethylbutylperoxy-2-ethyl 10.0 parts by mass of hexanoate (toluene solution 50%) was added. The obtained polymerizable monomer composition was put into an aqueous dispersion medium. And it granulated for 5 minutes, maintaining the rotation speed of a stirrer at 10,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, and the reaction was carried out at 60 ° C. for 3 hours while slowly stirring. Furthermore, the internal temperature was raised to 70 ° C. and reacted for 2 hours with slow stirring. The raw materials are shown in Table 1.

  Next, the temperature in the container was raised to 80 ° C. and maintained for 4 hours, and then gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain slurry 3. Dilute hydrochloric acid was added to the container containing the slurry 3 to remove the dispersion stabilizer. Further, filtration, washing, and drying were performed to obtain polymer particles (toner particles 19) having a weight average particle diameter of 6.4 μm.

With respect to the obtained toner particles 19 (100.0 parts by mass), 2.0 parts by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g and a specific surface area by the BET method of 100 m ² / g Toner (19-1) was obtained by externally adding 0.1 part by mass of titanium oxide. Other toner properties of the toner (19-1) were measured and are shown in Table 1.

  Table 3 shows the measurement results of a chart of molecular weight distribution measured by GPC of the THF-soluble component of toner (19-1).

  200 g of toner (19-1) is filled in a process cartridge, and low temperature and low humidity (16 ° C./15% RH), normal temperature and normal humidity (24 ° C./60% RH), high temperature and high humidity (30 ° C./76% RH) It was printed out and evaluated in the environment. Specifically, an image having a printing ratio of 2% was printed up to 8000 sheets, and the solid image density at the initial stage and when outputting 8000 sheets was evaluated. The results are shown in Table 4. Next, fixing evaluation was performed, and the results are also shown in Table 4.

It is a figure which shows an example of the chart of the molecular weight distribution measured by GPC of the THF soluble part of a toner. FIG. 2 is a view showing a chart of molecular weight distribution measured by GPC of a THF soluble part of the toner shown in FIG. 1 when a main peak height is 1.00. FIG. 2 is a view showing a chart of molecular weight distribution measured by GPC of a THF soluble part of the toner shown in FIG. 1 when a main peak height is 1.00. It is a figure which shows an example of the chart of the molecular weight distribution measured by GPC of the THF soluble part of a toner. FIG. 5 is a diagram illustrating an example of a chart of molecular weight distribution measured by GPC of a THF soluble portion of the toner illustrated in FIG. 4 when a main peak height is 1.00. FIG. 5 is a diagram illustrating an example of a chart of molecular weight distribution measured by GPC of a THF soluble portion of the toner illustrated in FIG. 4 when a main peak height is 1.00. It is a figure which shows an example of the endothermic chart measured by DSC of a toner. FIG. 10 is a view showing a chart of molecular weight distribution measured by GPC of a THF soluble part of toner (12-1) used in Comparative Example 4.

Claims (13)

A toner having toner particles containing at least a binder resin, a colorant and a wax,
In the chart of molecular weight distribution measured by gel permeation chromatography (GPC) of tetrahydrofuran (THF) soluble content of the toner,
i) having a main peak in the region of molecular weight 16000 or more and 60,000 or less,
ii) When the molecular weight of the main peak is M1, the height of the molecular weight M1 is H (M1), the height of the molecular weight 4000 is H (4000), and the height of the molecular weight 15000 is H (15000) H (4000), H (15000) and H (M1) are as follows: H (4000): H (15000): H (M1) = (0.10 or more and 0.95 or less) :( 0.20 More than 0.90): 1.00
Satisfied,
The weight-average molecular weight (Mw) of the THF soluble content of the toner determined by GPC is 15000 or more and 80000 or less,
In the endothermic chart measured by differential scanning calorimetry (DSC), the toner is
i) the endothermic main peak is in the range of 40 ° C. or higher and 130 ° C. or lower;
ii) A toner having an integral value of heat expressed by a peak area of the endothermic main peak of 10 J or more and 35 J or less per 1 g of toner.   2. The toner according to claim 1, wherein the toner has a sub-peak in a region having a molecular weight of 600 or more and 2000 or less in a molecular weight distribution chart measured by GPC of THF-soluble matter of the toner.   3. The toner according to claim 1, wherein the toner has at least a maximum point P (M3) in a region having a molecular weight of 2500 or more and less than 15000 in a molecular weight distribution chart measured by GPC of a THF-soluble component of the toner. . In the molecular weight distribution chart measured by GPC of the THF soluble part of the toner, the height of the local maximum point P (M3) is H (M3), and between the local maximum point P (M3) and the main peak. H (M3), H (L1), and H (M1) satisfy the following conditions, where H (L1) is the height of the minimum point P (L1) when the existing minimum point P (L1) is set. H (M3): H (L1): H (M1) = (0.10 or more and 0.95 or less): (0.20 or more and 0.99 or less): 1.00
The toner according to claim 3, wherein:   In the chart of molecular weight distribution measured by GPC of the THF soluble part of the toner, the integral value (S1) in the region having a molecular weight of 500 to 2500, the integral value (S2) of the molecular weight 2500 to 15000, and the molecular weight 15000 or more. The ratio with the integral value (S3) of 1 million or less is S1: S2: S3 = (0.15 or more and 0.95 or less): 1.00: (1.50 or more and 8.00 or less). The toner according to claim 1.   6. The toner according to claim 1, wherein the toner has an average circularity of 0.970 or more and 1.000 or less and a mode circularity of 0.98 or more and 1.00 or less in particles of 3 μm or more. Toner according to.   The toner particles are obtained by dispersing a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a wax, and a low molecular weight resin in an aqueous medium, and forming droplets of the polymerizable monomer composition. The toner particles according to any one of claims 1 to 6, wherein the toner particles are produced through at least a granulating step for producing and a polymerization step for polymerizing the polymerizable monomer in the droplets. toner.   8. The toner according to claim 7, wherein a weight-average molecular weight (Mw) of a THF-soluble component of the low molecular weight resin obtained by GPC is 2,000 or more and 6,000 or less.   The toner according to claim 7 or 8, wherein the glass transition point of the low molecular weight resin is 40 ° C or higher and 100 ° C or lower. A granulating step for producing a droplet of the polymerizable monomer composition by dispersing a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a wax and a low molecular weight resin in an aqueous medium. A toner production method for producing toner particles through at least a polymerization step of polymerizing the polymerizable monomer in the droplets,
The resulting toner is a toner having toner particles containing at least a binder resin, a colorant and a wax,
In the chart of molecular weight distribution measured by gel permeation chromatography (GPC) of tetrahydrofuran (THF) soluble content of the toner,
i) having a main peak in the region of molecular weight 16000 or more and 60,000 or less,
ii) When the molecular weight of the main peak is M1, the height of the molecular weight M1 is H (M1), the height of the molecular weight 4000 is H (4000), and the height of the molecular weight 15000 is H (15000) H (4000), H (15000) and H (M1) are as follows: H (4000): H (15000): H (M1) = (0.10 or more and 0.95 or less) :( 0.20 More than 0.90): 1.00
Satisfied,
The weight-average molecular weight (Mw) of the THF soluble content of the toner determined by GPC is 15000 or more and 80000 or less,
In the endothermic chart measured by differential scanning calorimetry (DSC), the toner is
i) the endothermic main peak is in the range of 40 ° C. or higher and 130 ° C. or lower;
ii) A method for producing toner, wherein an integral value of heat expressed by a peak area of the endothermic main peak is 10 J or more and 35 J or less per 1 g of toner.   11. The method for producing a toner according to claim 10, wherein a weight-average molecular weight (Mw) of a THF soluble portion of the low molecular weight resin obtained by GPC is 2000 or more and 6000 or less.   12. The toner production method according to claim 10, wherein the low molecular weight resin has a glass transition point of 40 ° C. or more and 100 ° C. or less. The method for producing a toner according to any one of claims 10 to 12, wherein the toner is the toner according to any one of claims 2 to 9.

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