JP2009294374A - Toner, and two-component developer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner and a two-component developer which have high transferring performance and excellent retransfer performance wherein scattering is prevented at transfer in a secondary color, and the lowering of image density caused by the deterioration of the electrostatic charging performance of the toner is alleviated. <P>SOLUTION: The toner comprises: toner particles each containing at least a binder resin, a colorant and wax; and an external additive. When dispersion where the toner is dispersed is irradiated with an ultrasonic wave at a frequency of 20 kHz in 50 W/10 cm<SP>3</SP>, the measured value C1 of the particles of 0.50 to 2.00 μm measured by a flow particle image measuring apparatus having an image-processing resolution of 512×512 pixels (0.37 μm×0.37 μm per a pixel), is ≤40.0% by number. A surface tension index of the toner for a 45 vol% aqueous solution of methanol measured by a capillary suction time method is 5.0×10<SP>-3</SP>to 1.0×10<SP>-1</SP>N/m. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner and a two-component developer used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system.

  In recent years, as a transfer material for full-color printers, full-color copiers, and full-color multifunction devices, in addition to plain paper and overhead projector film (OHT), it can handle a variety of materials such as glossy paper, cardboard, and postcards. It has been demanded. Therefore, a transfer method using an intermediate transfer member has become mainstream.

  Usually, in a transfer method using an intermediate transfer member, it is necessary to transfer a toner image visualized on an image carrier to the intermediate transfer member and then transfer the toner image from the intermediate transfer member onto a transfer material. Therefore, the number of times of transfer increases as compared with the conventional method, and it is desired that the toner has higher transfer efficiency.

  As one method for increasing the transfer efficiency, the formation of a spherical toner has been studied.

  For example, polymerized toners such as suspension polymerization and emulsion polymerization (see Patent Documents 1, 2, and 3) have been proposed. However, although the polymerization toner improves the transfer efficiency, the scattering in the secondary color at the time of transfer sometimes worsens.

  Further, the image density of the polymerized toner may be lowered when a large number of sheets are used. In the polymerized toner, resin fine particles and the like generated at the time of polymerization are attached to the surface of the toner particles, and the resin fine particles are peeled off from the toner, and the amount of particles of 0.60 μm or more and 2.00 μm or less is increased. There was a case where the image density was lowered when many sheets were used.

  In view of this, there has been proposed a toner (see Patent Document 4) in which the ratio of toner particles of 0.60 μm or more and 2.00 μm or less in a dispersion liquid in which the toner is dispersed with ultrasonic waves is controlled to improve durability. However, although the toner described above can achieve good transfer efficiency and suppress a decrease in image density, it has not yet solved the secondary color scattering during transfer.

  As a toner spheronization method, a toner obtained by spheroidizing a pulverized toner has been proposed. As a specific example of the spheroidizing treatment of the pulverized toner, there is a method of spheronizing with a mechanical impact force (see Patent Document 5). However, in the case of a mechanical type, there is a limit to spheroidization, and sufficient transfer efficiency is obtained. Has not reached.

  In addition, a method of spheroidizing with hot air (see Patent Document 6) has been proposed.

  However, although the toner has good transferability, the retransferability may deteriorate when printing in a room temperature and low humidity environment or when printing an image with a high area ratio.

As described above, various proposals have been made. However, there is still room for improvement, transfer efficiency is high, retransferability is good, and scattering during transfer of secondary colors is suppressed, and image density reduction due to toner chargeability is reduced. There is a long-awaited provision of toner and developer.
JP-A-6-282105 Japanese Patent Laid-Open No. 3-84558 JP 2005-49853 A JP-A-10-333356 JP 2004-295101 A JP 2004-138691 A

  It is an object of the present invention to provide a toner and a toner having high transfer efficiency, good retransferability, suppression of scattering during transfer of secondary colors, and reduction in image density reduction due to toner chargeability reduction. It is to provide a component developer.

According to the present invention, in a toner having toner particles containing at least a binder resin, a colorant, and a wax and an external additive, an ultrasonic wave of 20 kHz and 50 W / 10 cm ³ is applied to the dispersion liquid in which the toner is dispersed for 5 minutes. The measured value C1 of particles of 0.50 μm or more and 2.00 μm or less measured by a flow type particle image measuring apparatus having an image processing resolution of 512 × 512 pixels (0.37 μm × 0.37 μm per pixel) is 40. The toner has a surface tension index of 45 × 10 ⁻³ N / m or more and 1.0 × 10 ⁻¹ N / m with respect to a 45 volume% aqueous methanol solution measured by the capillary suction time method. The present invention relates to a toner characterized by being m or less.

The present invention also provides a two-component developer containing a magnetic carrier and a toner.
The toner has toner particles containing at least a binder resin, a colorant, and a wax, and an external additive,
Flow type particle image measurement with an image processing resolution of 512 × 512 pixels (0.37 μm × 0.37 μm per pixel) when the toner dispersion is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 5 minutes. The measured value C1 of particles of 0.50 μm or more and 2.00 μm or less measured by the apparatus is 40.0% by number or less,
The toner has a surface tension index of 45 × 10 ⁻³ N / m or more and 1.0 × 10 ⁻¹ N / m or less with respect to a 45 volume% aqueous methanol solution measured by a capillary suction time method. To a two-component developer.

  According to the present invention, a toner and a two-component system having high transfer efficiency, good retransferability, suppression of scattering during transfer in a secondary color, and reduction in image density reduction due to reduction in toner chargeability A developer can be provided.

  In the present invention, the measured value C1 needs to be 40.0% by number or less in order to achieve good retransferability. In order to achieve better retransferability and suppression of image density reduction, the measured value C1 is preferably 1.0% by number or more and 30.0% by number or less, more preferably 1.0% by number. More than 15.0% by number.

  In the case of a full-color image forming method using an intermediate transfer member, a plurality of color toners are transferred onto the intermediate transfer member. At this time, there may occur a phenomenon (so-called retransfer) in which the toner previously transferred onto the intermediate transfer member moves from the intermediate transfer member to the photosensitive member during transfer of another color. The retransfer is remarkable at the time of endurance, particularly when an image having a high area ratio is printed.

The present inventors have found that this phenomenon is 0.50 μm or more measured by the flow type particle image measuring apparatus when the dispersion liquid in which the toner is dispersed is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 5 minutes. It was found that there is a correlation with the measured value C1 of particles of 00 μm or less.

  And it was found that the retransferability at the time of durability can be improved by controlling the measured value C1 to 40.0% by number or less.

  As a method for controlling the measured value C1 to 40.0% by number or less, small particles of 2.00 μm or less are removed by classification treatment, or particles of 2.00 μm or less are combined by surface smoothing treatment with hot air. There are methods such as reducing the number.

  When the measured value C1 is more than 40.0% by number, retransfer is likely to occur.

  If the measured value C1 is less than 1.0% by number, the charge amount of the toner may increase and the image density may decrease in a low humidity environment. Therefore, the measured value C1 may be set to 1.0% by number or more. More preferred.

Further, measured values of particles of 0.50 μm or more and 2.00 μm or less measured by the flow type particle image analyzer when the dispersion liquid in which toner is dispersed is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 1 minute. By controlling C2, the retransferability when an image with a high area ratio is printed can be further improved.

  The reason is not clear, but the present inventors consider as follows.

  When an image with a high area ratio is printed, excess toner is replenished.

  The toner of 0.50 μm or more and 2.00 μm or less contained in the toner that has just been replenished is not easily developed from the developing sleeve to the photosensitive member, and remains in the developing machine. For this reason, as the number of printed sheets increases, the amount of toner of 0.50 μm or more and 2.00 μm or less in the developing unit increases, and developability further decreases.

  Therefore, by setting the measured value C2 to 0.5% by number or more and 20.0% by number or less, developability can be maintained even when a large number of images having such a high area ratio are printed. .

  When the measured value C2 is greater than 20.0% by number, the developability decreases, and the density may decrease when a large number of high area ratio images are printed.

  On the other hand, if the measured value C2 is less than 0.5% by number, the toner charge amount may increase in a low humidity environment and the image density may decrease.

  In order to control the measured value C2 to the above range, a method of removing small particles of 2.00 μm or less by classification treatment or combining small particles by surface smoothing treatment with hot air to reduce the number of particles of 2.00 μm or less. Can be achieved. In particular, classification is preferably performed after surface smoothing treatment with hot air.

  The toner of the present invention preferably has a weight average particle diameter (D4) of 3.0 μm or more and 8.0 μm or less, and more preferably 4.0 μm or more and 7.0 μm or less. By setting the weight average diameter (D4) of the toner within the above range, high image quality can be achieved.

  When the weight average particle diameter (D4) of the toner is less than 3.0 μm, the fluidity of the toner is deteriorated, the mixing property in the developing device is deteriorated, and a high image quality may not be obtained.

  On the other hand, when the weight average particle diameter (D4) of the toner exceeds 8.0 μm, toner scattering may be visually perceived. The weight average particle diameter (D4) of the toner can be adjusted by classifying the toner particles at the time of toner production.

  The toner of the present invention has an average circularity of 0 and divided into 800 in the range of the circularity of 0.200 or more and 1.000 or less of particles having an equivalent circle diameter of 2.00 μm or more and 200.00 μm or less. It is preferable that it is 950 or more and 1.000 or less. More preferably, they are 0.955 or more and 0.990 or less, More preferably, they are 0.955 or more and 0.985 or less. By setting the average circularity of the toner within the above range, good transfer efficiency can be achieved. When the circularity of the toner is less than 0.950, the transfer efficiency may be deteriorated. The circularity in the present invention is a value measured by a flow type particle image measuring apparatus having an image processing resolution of 512 × 512 pixels (0.37 μm × 0.37 μm per pixel).

  Further, the inventors have found that it is necessary to control the surface tension index of the toner with respect to the 45 volume% aqueous methanol solution measured by the capillary suction time method as well as the measured value C1 in order to suppress a decrease in image density. Found.

Specifically, the toner has a surface tension index of 5.0 × 10 ⁻³ N / m or more and 1.0 × 10 ⁻¹ N / m or less with respect to a 45 volume% aqueous methanol solution measured by a capillary suction time method. Preferably they are 6.0 * 10 < ^-3 > N / m or more and 6.0 * 10 ^<-2 > N / m or less.

The surface tension index (N / m) of the toner is determined by measuring the capillary pressure of the toner with respect to a 45 volume% aqueous methanol solution measured by the capillary suction time method as Pα (N / m ² ) and the specific surface area of the toner as A (m ² / g). ), When the true density of the toner is B (g / cm ³ ), it is calculated from the following equation (1).
Formula (1): Surface tension index of toner = Pα / (A × B × 10 ⁶ )
In the present invention, the surface tension index of the toner is used as an index of the adhesion force on the toner surface.

  The reason is not clear, but the inventors think as follows.

  The toner of the present invention has a measured value C1 of particles of 0.50 μm or more and 2.00 μm or less of 40.0% by number or less. Usually, the toner charge amount is larger for the toner having a small particle diameter. For this reason, a toner having a C1 larger than 40.0% by number has a large amount of small-size toner having a high charge amount, so that the charge amount of the toner as a whole becomes high. As a result, the decrease in the charge amount due to the desorption of the external additive is not likely to be significant.

  However, in the toner of the present invention, C1 is 40.0% by number in order to ensure good retransferability. For this reason, there are few high-charged small-diameter toners, the toner charge amount is low, and when the external additive is detached from the toner particle surface, the toner charge amount is significantly reduced. A decrease may occur.

A toner having a surface tension index of 45 × 10 ⁻³ N / m or more and 1.0 × 10 ⁻¹ N / m or less with respect to a 45 volume% aqueous methanol solution measured by the capillary suction time method is the above-mentioned. Even when the amount of the small particle toner is small, it is possible to suppress the detachment of the external additive from the toner particle surface. In addition, it is possible to reduce a decrease in image density due to a decrease in toner charge amount.

  In addition, by controlling the surface tension index of the toner within the above range, the adhesion force of the toner is increased, so that scattering at the time of transfer particularly in the secondary color can be reduced.

When the surface tension index of the toner exceeds 1.0 × 10 ⁻¹ N / m, an excessive amount of wax may be eluted from the toner, and the toner may be charged due to adhesion of the toner to the charging member. May fall.

Further, when the surface tension index of the toner is less than 5.0 × 10 ⁻³ N / m, the adhesion force on the toner surface is reduced, and the scattering at the time of transfer in the secondary color may be deteriorated.

  In the toner of the present invention, the surface tension index can be adjusted to the above range by hydrophobizing the surface of the toner.

  Examples of the hydrophobic treatment method include treating the toner surface with a known hydrophobic substance. As the treating agent, a coupling agent, wax, oil, varnish, organic compound and the like can be used.

  The toner of the present invention can be obtained, for example, by subjecting the toner particles to a surface smoothing treatment using hot air and simultaneously performing a hydrophobic treatment on the toner particle surfaces using wax. More preferably, the toner has been subjected to a surface smoothing treatment using hot air containing 3 to 20 parts by weight of wax with respect to 100 parts by weight of the binder resin.

  In the surface smoothing treatment of the toner particles using the hot air, if an excessive amount of heat is applied to the surface of the toner, the excessive amount of wax may be transferred to the surface of the toner particles or the wax in the toner particles may be removed. Distribution may be non-uniform. For this reason, it is important to control the production conditions such as the temperature of hot air and the temperature of cooling air, thereby controlling the amount and distribution of wax and controlling the toner surface tension index within the above range.

  As a specific example of the surface smoothing treatment using hot air, the surface of the toner particles is melted by instantaneously blowing high-temperature hot air on the surface of the toner particles in a state where the toner particles are diffused in the air. A surface smoothing treatment may be performed by instantaneously cooling with cold air.

  The surface smoothing treatment of the toner particles by the above method can be performed uniformly without giving excessive heat to the toner particles. In addition, it is possible to prevent the raw material components from being altered and to smooth the surface of only the toner particles. Therefore, it is possible to prevent the excessive amount of wax from being transferred to the surface of the toner particles and the localization of the wax due to heat, and to achieve reduction in reduction in chargeability of the toner.

  As the binder resin used in the toner of the present invention, a known resin can be used.

  For example, the following are mentioned. Polyester, polystyrene; polymer of styrene derivatives such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic Acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, Styrene copolymers such as styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, modified phenol resin, maleic resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin; Polyester resins having as structural units monomers selected from aliphatic polyhydric alcohols, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, aromatic dialcohols and diphenols; polyurethane resins, polyamide resins, polyvinyl butyral, terpenes Resin, coumarone indene resin, petroleum resin.

  Among these, polyester resins and styrene acrylic resins are preferable from the viewpoints of fixability and developability.

  In addition, it is preferable to use a binder resin that can reduce particles of 0.50 μm or more and 2.00 μm or less during the toner surface smoothing process using hot air.

  Specifically, it is preferable to use at least a low softening point resin having a softening point of 70 ° C. or higher and 100 ° C. or lower, or a resin having crystallinity of a melting point of 80 ° C. or higher and 120 ° C. or lower as the binder resin. The term “having crystallinity” as used herein refers to a resin in which the difference between the softening point of the resin and the peak temperature of the maximum endothermic peak of the resin is 10 ° C. or less.

  When the above resin is used, since the specific surface area is large at the time of thermal spheroidization, fine particles having a size of 2.00 μm or less that are susceptible to heat are effectively combined. As a result, it is preferable because the amount of particles of 2.00 μm or less can be reduced.

  If a resin having a softening point of less than 70 ° C. or a resin having a crystallinity of a melting point of less than 80 ° C. is used, the storage stability of the toner may be lowered.

  In addition, if a resin having a softening point higher than 100 ° C. or a resin having a melting point higher than 120 ° C. is used, the amount of particles of 2.00 μm or less may not be sufficiently reduced.

  Furthermore, by using together with the above resin a high softening point resin having a softening point of 100 ° C. or higher and 200 ° C. or lower, it is possible to moderately suppress coalescence of particles larger than 2.00 μm and to suppress generation of excessive coalescence particles. Is preferable.

  If the resin has a softening point of less than 100 ° C., the formation of excessive coalescence particles cannot be suppressed, and if a resin having a softening point higher than 200 ° C. is used, the fixability may deteriorate.

  More preferably, the difference between the softening point of the low softening point resin and the high softening point resin, or the difference between the melting point of the resin having crystallinity and the softening point of the high softening point resin is 10 ° C. or more and 100 ° C. or less. This is preferable because the amount of particles of 2.00 μm or less can be reduced and coalescence of particles larger than 2.00 μm can be effectively suppressed.

If the difference in softening point is less than 10 ° C., it may be impossible to reduce both particles of 2.00 μm or less and to suppress coalescence of particles larger than 2.00 μm.
On the other hand, if the difference between the softening points is greater than 100 ° C., the mixing property of the resin deteriorates, and as a result, the chargeability may decrease.

  Examples of the wax used in the toner of the present invention include the following.

  Oxides of aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or Block copolymers of the above: Deoxidized part or all of fatty acid esters such as carnauba wax, behenic ester behenate wax, montanate ester wax, and deoxygenated carnauba wax thing. Furthermore, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid; and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, Esters of alcohols such as melyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscaprin Saturated fatty acid bisamides such as amide, ethylene bislauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N ′ dioleyl Unsaturated fatty acid amides such as sebacic acid amide; aromatic bisamides such as m-xylene bis-stearic acid amide, N, N ′ distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts (generally referred to as metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides Price And methyl ester compounds having a hydroxyl group obtained by and hydrogenated vegetable oils; call partial ester.

  Examples of the wax particularly preferably used in the present invention include aliphatic hydrocarbon waxes and esterified products which are esters of fatty acids and alcohols. For example, low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure with Ziegler catalyst or metallocene catalyst under low pressure; alkylene polymer obtained by thermal decomposition of high molecular weight alkylene polymer; synthesis containing carbon monoxide and hydrogen It is a synthetic hydrocarbon wax obtained from the distillation residue of hydrocarbons obtained by gas from the gas or by hydrogenation of these.

  Further, those obtained by fractionating hydrocarbon wax by press sweating, solvent method, vacuum distillation or fractional crystallization are more preferably used. The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems) [for example, the Jintol method, the Hydrocol method (the fluidized catalyst bed Hydrocarbon compounds synthesized by use); hydrocarbons with up to several hundred carbon atoms obtained by the age method (using the identified catalyst bed) from which a large amount of wax-like hydrocarbons can be obtained; alkylene such as ethylene by Ziegler catalyst Polymerized hydrocarbons are preferred because they are linear hydrocarbons with little branching, small and long saturation. In particular, a wax synthesized by a method that does not rely on polymerization of alkylene is also preferred from its molecular weight distribution. Paraffin wax is also preferably used.

  Further, the wax used for the toner has a peak temperature of a maximum endothermic peak in a temperature range of 30 ° C. or higher and 200 ° C. or lower in an endothermic curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus. It is preferable that it is in the range of not lower than 140 ° C and lower than 140 ° C. More preferably, it is the range of 65 degreeC or more and 100 degrees C or less.

  When the peak temperature of the maximum endothermic peak of the wax is in the range of 45 ° C. or more and 140 ° C. or less, the surface tension index of the toner is preferably within the above range, and at the same time, good fixability is achieved. On the other hand, when the peak temperature of the maximum endothermic peak is less than 45 ° C., the blocking resistance of the toner deteriorates, and when the peak temperature of the maximum endothermic peak exceeds 140 ° C., the fixability tends to deteriorate.

  The content of the wax is preferably 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferably, they are 3 to 10 mass parts.

  It is preferable to use the wax content within the above range because the surface tension index of the toner can be used within the range of the present invention.

  When the content of the wax is less than 3 parts by mass with respect to 100 parts by mass of the binder resin, it is not preferable because the effect of releasing the wax during fixing is hardly exhibited, and the hot offset resistance is deteriorated.

  Further, when the wax content exceeds 20 parts by mass, excessive amount of wax may be eluted from the toner when the surface treatment is performed with hot air, and the toner adheres to the charging member. As a result, the chargeability of the toner may decrease, which is not preferable.

  The following are mentioned as a coloring agent used by this invention. In the colorant, the pigment may be used alone, but it is preferable from the viewpoint of the image quality of the full color image that the dye and the pigment are used in combination to improve the sharpness.

  Examples of the black colorant include carbon black; a magnetic material; a black colorant prepared using a yellow colorant, a magenta colorant, and a cyan colorant.

Examples of the color pigment for magenta toner include the following.
Examples include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.

  Specifically, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, 269; I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35 are mentioned.

  Examples of the magenta toner dye include the following. C. I solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the color pigment for cyan toner include the following.
C. I. Pigment Blue 1, 2, 3, 7, 15: 2, 15: 3, 15: 4, 16, 17, 60, 62, 66; I. Bat Blue 6, C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyls are substituted on the phthalocyanine skeleton.

Examples of the color pigment for yellow include the following.
Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal compounds, methine compounds, allylamide compounds. Specifically, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 155, 168, 174, 180, 181, 185, 191; I. Bat yellow 1, 3, and 20 are mentioned. In addition, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6 and Solvent Yellow 162 can also be used.

  In the toner, it is preferable to use a toner obtained by previously mixing a colorant with a binder resin to form a master batch. Then, the colorant can be favorably dispersed in the toner by melt-kneading the colorant master batch and other raw materials (binder resin, wax, etc.).

  When a colorant is mixed with the binder resin to make a master batch, even if a large amount of colorant is used, the dispersibility of the colorant is not deteriorated, and the dispersibility of the colorant in the toner particles is improved. Excellent color reproducibility such as color mixing and transparency. Further, a toner having a large covering power on the transfer material can be obtained. Further, since the dispersibility of the colorant is improved, it is possible to obtain an image having excellent durability stability of toner chargeability and maintaining high image quality.

  The amount of the colorant used is preferably 0.1 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

  In the toner of the present invention, a known charge control agent can be used in order to stabilize the charging property. The charge control agent varies depending on the type of the charge control agent and the physical properties of other toner constituent materials, but is preferably contained in an amount of 0.1 to 10.0 parts by mass per 100 parts by mass of the resin in the toner. More preferably, it is contained in an amount of 0.1 to 5 parts by mass. As such a charge control agent, there are known one that controls the toner to be negatively charged and one that controls the toner to be positively charged. One or two kinds of various kinds of charge control agents are used depending on the kind and use of the toner. The above can be used. The charge control agent may be added internally or externally to the toner.

Examples of the negatively chargeable charge control agent include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, An example is calix arene.
On the other hand, examples of the positively chargeable charge control agent include quaternary ammonium salts, polymer compounds having a quaternary ammonium salt in the side chain, guanidine compounds, and imidazole compounds.

  In particular, the charge control agent is preferably an aromatic metal carboxylic acid compound that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount.

  In the present invention, for the purpose of improving the performance of the toner, external additives are mixed with the toner particles with a mixer such as a Henschel mixer for the purpose of improving fluidity, transferability, charging stability and the like. As the external additive, known ones can be used, but the following fine powder can be preferably used.

  For example, fluororesin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder; fine powder silica such as titanium oxide fine powder, alumina fine powder, wet process silica, dry process silica; and silane compound, organic Treated silica surface-treated with a silicon compound, titanium coupling agent, and silicone oil.

  If the titanium oxide fine powder is used, the fine powder of titanium oxide obtained by low-temperature oxidation (thermal decomposition, hydrolysis) of sulfuric acid method, chlorine method, volatile titanium compounds such as titanium alkoxide, titanium halide, titanium acetylacetonate is used. It is done. As the crystal system, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.

  If it is the above-mentioned alumina fine powder, buyer method, improved buyer method, ethylene chlorohydrin method, underwater spark discharge method, organoaluminum hydrolysis method, aluminum alum pyrolysis method, ammonium aluminum carbonate pyrolysis method, aluminum chloride flame Alumina fine powder obtained by a decomposition method is used. As the crystal system, α, β, γ, δ, ξ, η, θ, κ, χ, ρ type, any of these mixed crystal types and amorphous types can be used. Α, δ, γ, θ, mixed crystal A mold or an amorphous material is preferably used.

  More preferably, the surface of the fine powder is subjected to a hydrophobic treatment with a coupling agent or silicone oil. The method of hydrophobizing the surface of the fine powder is a method of chemically or physically treating with an organosilicon compound that reacts or physically adsorbs with the fine powder.

  A preferable method for the hydrophobic treatment is a method in which silica fine particles produced by vapor phase oxidation of a silicon halogen compound are treated with an organosilicon compound. Examples of the organosilicon compound used in such a method include the following. Hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloro Ethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyl Disiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane Examples thereof include siloxane and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and one hydroxyl group in the terminal Si unit. These are used alone or in a mixture of two or more.

The external additive has a specific surface area by nitrogen adsorption measured by BET method of 30 m ² / g or more, preferably 50 m ² / g or more from the viewpoint of imparting characteristics. The addition amount of the external additive is 0.1 parts by mass or more and 8.0 parts by mass or less, preferably 0.1 parts by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

  The toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, thereby improving developable dot reproducibility.

  The present inventors consider that this is due to the following reason.

  When a two-component developer having a magnetic carrier and a toner is used, a spike of the two-component developer can be formed on the developing sleeve. As a result, the opportunity for development increases, and the toner easily moves from the developing sleeve to the photosensitive member.

  Examples of the magnetic carrier include oxidized iron powder with oxidized or unoxidized surface; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth, alloy particles thereof or oxidized Magnetic particles such as ferrite; a magnetic material containing a magnetic material; a magnetic material-dispersed resin carrier (so-called resin carrier) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state;

  When the toner of the present invention is used as a two-component developer, the toner and carrier mixing ratio is preferably 2% by mass or more and 15% by mass or less, more preferably 4% by mass as the toner concentration in the developer. % Or more and 13% by mass or less. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  Next, the procedure for producing the toner of the present invention will be described, but the present invention should not be limited to this production method. In the toner of the present invention, a binder resin, a colorant, a wax, and an arbitrary material are melt-kneaded, cooled and pulverized, and a pulverized product is spheroidized, surface-smoothed, and classified as necessary. It is possible to manufacture by processing and mixing this with an external additive. Specific examples are shown below.

  First, in the raw material mixing step, at least a binder resin, a colorant, and a wax are weighed and mixed and mixed. Examples of the mixing apparatus used here include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.

  Further, the mixed toner raw materials are melt-kneaded to melt the resins and disperse the colorant and the like therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Kay C.K. The Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.

  In general, the cooled colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed with a crusher, a hammer mill, a feather mill or the like, and further, pulverization is performed with a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nissin Engineering Co., Ltd., or the like to obtain a pulverized product.

  After that, if necessary, classification is performed using a classifier such as an inertia class elbow jet (manufactured by Nippon Steel Mining Co., Ltd.) or a centrifugal classifier turboplex (manufactured by Hosokawa Micron Co., Ltd.) to obtain a classified product. .

  The toner of the present invention can be obtained by obtaining the above pulverized product, performing surface smoothing treatment with hot air using, for example, the surface smoothing device shown in FIG. 1, and then classifying. Or it can obtain by performing the surface smoothening process by a hot air what was classified beforehand. Thus, it can be obtained by any method.

  Here, an outline of the surface smoothing device used for obtaining the toner of the present invention will be described with reference to FIGS.

  FIG. 1 is a schematic cross-sectional view of a surface smoothing device used in the present invention, and FIG. 2 is a schematic cross-sectional view of a toner supply port and an airflow ejecting member in the surface smoothing device.

  The toner 114 supplied from the toner supply port 100 is accelerated by the injection air injected from the high-pressure air supply nozzle 115 and travels toward the airflow injection member 102 located below the toner 114. As shown in FIG. 2, diffused air 110 is ejected from the airflow ejecting member 102, and the diffused air 110 diffuses the toner upward and outward. At this time, the diffusion state of the toner can be controlled by adjusting the flow rate of the injection air and the flow rate of the diffusion air.

Further, a cooling jacket 106 is provided on the outer periphery of the toner supply port 100, the outer periphery of the surface smoothing device, and the outer periphery of the transfer pipe 116 for the purpose of preventing toner fusion. In addition, it is preferable to pass cooling water (preferably antifreeze such as ethylene glycol) through the cooling jacket.
The toner diffused by the diffusion air is melted and smoothed by the hot air supplied from the hot air supply port 101. At this time, the temperature C (° C.) of the hot air supply port is preferably 100 ≦ C ≦ 450.

When the temperature is less than 100 ° C., the toner smoothness may vary, which is not preferable in terms of toner transferability. Further, when the temperature exceeds 450 ° C., the toner may be coalesced due to excessive progress of the melted state, and the toner may be coarsened or fused.
The toner whose surface is smoothed by hot air is cooled by cold air supplied from a cold air supply port 103 provided on the outer periphery of the upper part of the apparatus. At this time, cold air may be introduced from the second cold air supply port 104 provided on the side surface of the main body of the apparatus for the purpose of managing the temperature distribution in the apparatus and controlling the surface state of the toner. The outlet of the second cold air supply port 104 can use a slit shape, a louver shape, a perforated plate shape, a mesh shape, etc., and the introduction direction can be selected according to the purpose, horizontal to the center direction and along the device wall surface It is.

At this time, the temperature E (° C.) in the cold air supply port and the second cold air supply port is preferably −20 ≦ E ≦ 10. The cold air is preferably dehumidified cold air. Specifically, the absolute water content is preferably 5 g / m ³ or less. This is important for controlling the surface tension index of the toner surface within the range of the present invention.

  When the temperature of the cold air is less than −20 ° C., the temperature in the apparatus is excessively lowered, and the smoothing process by heat, which is the original purpose, is not sufficiently performed, so that the toner transfer performance cannot be improved. There is. When the temperature exceeds 10 ° C., the control of the hot air zone in the apparatus becomes insufficient, the coalescence of the particles proceeds, and the powder particles may be coarsened.

  Next, the airflow injection member provided in the surface modification apparatus used in the present invention will be described with reference to FIG. As shown in FIG. 2, the toner supplied from the upper part of the toner supply port 100 by the metering feeder is accelerated by the injection air in the same pipe toward the outlet, and by the diffusion air from the airflow injection member 102 installed in the apparatus. Spreads outward. Note that the lower end of the airflow ejecting member 102 is provided at a position of 5 mm to 150 mm from the toner supply port 100. When the lower end of the airflow injection member is connected to a position less than 5 mm from the outlet, if the amount of toner to be introduced into the apparatus is set to be large, clogging or poor modification may occur. On the other hand, when the diameter exceeds 150 mm, the effect of hot air for modifying the toner diffused by the diffusion air may not be obtained uniformly, and the toner modification may vary. It is not preferable.

  Further, on the outer periphery of the toner supply port 100, an air flow supply port 111 for the purpose of preventing condensation may be provided between the toner supply port 100 and the cooling jacket 106. This air flow for preventing condensation may be introduced from diffused air or a supply device common to the cold air and the second cold air, or the outside air may be taken in with the intake port opened. It is also possible to operate the apparatus with the intake port closed as buffer air.

  Further, if necessary, surface modification and spheronization may be further performed using, for example, a hybridization system manufactured by Nara Machinery Co., Ltd. or a mechano-fusion system manufactured by Hosokawa Micron. In such a case, if necessary, a sieving machine such as a wind-type sieve high voltor (manufactured by Shin Tokyo Machine Co., Ltd.) may be used. Furthermore, as a method of externally adding the external additive, a predetermined amount of classified toner and various known external additives are blended, and a high-speed stirrer that gives a shearing force to the powder such as a Henschel mixer or a super mixer is removed. A method of stirring and mixing can be used as an accessory.

  A method for measuring various physical properties of the toner will be described below.

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

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

  Prior to measurement and analysis, the dedicated software was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

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

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for the Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Then, measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

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

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

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

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

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

<Measurement Values C1 and C2 of Toner Particles of 0.50 μm to 2.00 μm>
The measured value C1 of the toner particles of 0.50 μm or more and 2.00 μm or less of the toner was measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.

The specific measurement method is as follows. To 20 ml of ion-exchanged water, 0.01 g of a surfactant, preferably sodium dodecylbenzenesulfonate, was added as a dispersant. Thereafter, 0.02 g of a measurement sample is added, and an ultrasonic dispersing device STM UH-50 is used for 5 minutes (at the time of C1 measurement) or 1 minute (at the time of C2 measurement) at an oscillation frequency of 20 kHz and 50 W / 10 cm ^3. Time) Distributed processing was performed. In that case, it cooled suitably so that the temperature of a dispersion liquid might be 10 degreeC or more and 40 degrees C or less.

  The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure was introduced into the flow type particle image analyzer, and 3000 toner particles were measured in the total count mode in the HPF measurement mode. The binarization threshold at the time of particle analysis is 85%, and the number% of particles of 0.50 μm or more and 2.00 μm or less with respect to all analysis particles (0.50 μm or more and 200.00 μm or less) is measured value C1 and measurement value C2. .

<Measurement of surface tension index of toner>
About 5.5 g of toner is gently put into the measurement cell, and a tapping operation is performed for 1 minute at a tapping speed of 30 times / min using a tapping machine PTM-1 (manufactured by Sankyo Piotech Co., Ltd.). This is set in a measuring device (manufactured by Sankyo Piotech Co., Ltd .: WTMY-232A wet tester) and measured.

The capillary pressure Pα (N / m ² ) was determined by the constant flow method. Each condition is as follows.
Solvent: 45% by volume methanol aqueous solution Measurement mode: Constant flow method (A2 mode)
Liquid flow rate: 2.4 ml / min
Cell: Y-type measurement cell The toner surface tension index (N / m) is the capillary pressure measured by the capillary capillary suction time method, Pα (N / m ² ), and the specific surface area of the toner is A (m ² / g). ), When the true density of the toner is B (g / cm ³ ), it is calculated from the following formula (2).
Formula (2): Toner surface tension index = Pα / (A × B × 10 ⁶ )

<Measurement of BET specific surface area of toner and external additive>
The BET specific surface area of the toner and the external additive is measured according to JIS Z8830 (2001). A specific measurement method is as follows.

  As the measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method is used. Setting of measurement conditions and analysis of measurement data are performed using dedicated software “TriStar3000 Version 4.00” attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe are connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas is defined as the BET specific surface area in the present invention.

  The BET specific surface area is calculated as follows.

First, nitrogen gas is adsorbed to the toner or external additive, and the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g ⁻¹ ) of the toner or external additive at that time are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g ⁻¹ ) is plotted on the vertical axis. The adsorption isotherm is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g ⁻¹ ), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the toner or external additive, is determined by applying the following BET formula.
Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)
The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 1 / (Vm × C)
When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept value of the straight line can be calculated. Vm and C can be calculated by solving the above slope and intercept simultaneous equations using these values.

Further, the BET specific surface area S (m ² · g ⁻¹ ) of the toner and the external additive is calculated from the calculated Vm and the molecular occupation cross-sectional area (0.162 nm ² ) of the nitrogen molecule based on the following formula. To do.
S = Vm × N × 0.162 × 10 ⁻¹⁸
(N is Avogadro's number (mol- ¹ ).)
The measurement using this apparatus follows the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus, and specifically, the measurement is performed according to the following procedure.

  Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 ml) that has been thoroughly cleaned and dried. A toner (about 1.5 g) or an external additive (about 0.3 g) is put into the sample cell using a funnel.

  The sample cell containing the toner or external additive is set in a “pretreatment device Bacrepep 061 (manufactured by Shimadzu Corporation)” connected to a vacuum pump and a nitrogen gas pipe, and vacuum degassing is performed at 23 ° C. for about 10 hours. continue. During vacuum deaeration, the toner or external additive is gradually deaerated while adjusting the valve so that the vacuum pump does not suck the toner or the external additive. The pressure in the cell gradually decreases with deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the exact mass of the toner or external additive is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber stopper during weighing so that the toner or the external additive in the sample cell is not contaminated by moisture in the atmosphere.

  Next, a dedicated “isothermal jacket” is attached to the stem portion of the sample cell containing toner or an external additive. Then, a dedicated filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member having an inner surface made of a porous material and an outer surface made of an impermeable material capable of sucking liquid nitrogen to a certain level by capillary action.

  Subsequently, the free space of the sample cell including the connection tool is measured. The free space is measured by measuring the volume of the sample cell with helium gas at 23 ° C., and subsequently measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen using helium gas. Calculated from the difference in volume. The saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.

  Next, after performing vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum deaeration. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules to the toner. At this time, the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, and the adsorption isotherm is converted into a BET plot. Note that the points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Further, using the value of Vm, the BET specific surface area of the toner or the external additive is calculated as described above.

<Measurement of true density of toner and magnetic carrier>
The true density of the toner and magnetic carrier is measured by a dry automatic densimeter autopycnometer (manufactured by Yuasa Ionics). The conditions are as follows.
Cell SM cell (10ml)
Sample amount About 2.0 g (toner), about 5.0 g (magnetic carrier)
This measurement method measures the true density of a solid / liquid based on a gas phase substitution method. Similar to the liquid phase replacement method, it is based on Archimedes' principle, but uses a gas (argon gas) as a replacement medium, and therefore has high accuracy for micropores.

<Measurement of peak temperature of maximum endothermic peak of wax and resin>
The maximum endothermic peaks of the wax and resin are measured according to ASTM D3418-82 using a differential scanning calorimetry (DSC) apparatus “Q1000” (TA Instruments). That is, the temperature detection of the device detection unit uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium.

  Specifically, about 5 mg of wax or resin is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the measurement temperature range is 30 to 200 ° C. Measurement is performed at a temperature elevation rate of 10 ° C./min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The peak temperature of the maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is the peak temperature of the maximum endothermic peak of the endothermic curve in the DSC measurement of the toner and resin of the present invention. .

<Measurement method of softening point of resin>
The softening point of the resin is measured by using a constant load extrusion type capillary rheometer “flow characteristic evaluation device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of descending piston is the sum of X and Smin in the flow curve is the melting temperature in the 1/2 method.

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

<Measurement Method of Volume Distribution Standard 50% Particle Size of Magnetic Carrier>
The particle size distribution was measured with a laser diffraction / scattering particle size distribution measuring apparatus “Microtrack MT3300EX” (manufactured by Nikkiso Co., Ltd.).

  The volume distribution standard 50% particle size (D50) of the magnetic carrier was measured by mounting a sample feeder “One Shot Dry Sample Conditioner Turbotrac” (manufactured by Nikkiso Co., Ltd.) for dry measurement. As the supply conditions of Turbotrac, a dust collector was used as a vacuum source, the air volume was about 33 liters / sec, and the pressure was about 17 kPa. Control is automatically performed on software. As for the particle size, 50% particle size (D50) and 90% particle size (D90), which are cumulative values based on volume, are obtained. Control and analysis are performed using attached software (version 10.3.3-202D).

The measurement conditions are as follows.
SetZero time: 10 seconds Measurement time: 10 seconds Number of measurements: 1 time Particle refractive index: 1.81
Particle shape: Non-spherical measurement upper limit: 1408 μm
Measurement lower limit: 0.243 μm
Measurement environment: 23 ° C / 50% RH

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples.

(Resin Production Example 1)
1,2-propylene glycol 33.9 parts by mass Terephthalic acid 60.0 parts by mass Adipic acid 5.9 parts by mass Tetrabutoxy titanate 0.2 parts by mass The above is a reactor equipped with a cooling tube, a stirrer and a nitrogen introduction tube It was put in, and it was made to react at 180 degreeC under nitrogen stream for 8 hours. Next, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while distilling off water under a nitrogen stream, and further reacted under a reduced pressure of 6.7 × 10 ² or more and 2.7 × 10 ³ Pa to soften. It was taken out when the point reached 72 ° C. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as resin (A-1).

(Resin Production Example 2)
Except that the reaction time at 180 ° C. was changed from 8 hours to 10 hours, it was taken out when the softening point reached 98 ° C. in the same manner as in Production Example 1 of the resin. This is designated as resin (A-2).

(Production Example 3 of Resin)
Bisphenol A ethylene oxide 2-mole adduct 34.3 parts by mass Bisphenol A propylene oxide 2-mole adduct 35.8 parts by mass Terephthalic acid 29.7 parts by mass Tetrabutoxy titanate 0.2 parts by mass The reaction vessel was placed in a reaction vessel equipped with a nitrogen introduction tube and reacted at 210 ° C. for 7 hours while distilling off the water produced under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 6.7 * 10 < ² > or more and 2.7 * 10 < ³ > Pa, and it took out when the softening point became 75 degreeC. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as resin (A-3).

(Resin Production Example 4)
Bisphenol A ethylene oxide 2-mole adduct 35.8 parts by mass Bisphenol A propylene oxide 2-mole adduct 37.4 parts by mass Terephthalic acid 23.8 parts by mass Trimellitic anhydride 2.8 parts by mass Tetrabutoxy titanate 0.2 parts by mass The above was placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted for 9 hours at 210 ° C. while distilling off the water produced in a nitrogen stream. Next, the reaction was performed under a reduced pressure of 6.7 × 10 ² or more and 2.7 × 10 ³ Pa, and the mixture was taken out when the softening point reached 82 ° C. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as resin (A-4).

(Resin Production Example 5)
1,2-propylene glycol 37.0 parts by mass terephthalic acid 60.0 parts by mass trimellitic anhydride 2.8 parts by mass tetrabutoxy titanate 0.2 parts by mass The above was equipped with a condenser, a stirrer and a nitrogen inlet tube It put into the reaction tank and made it react for 12 hours, distilling off the water produced | generated under nitrogen stream at 210 degreeC. Subsequently, it was made to react under the reduced pressure of 6.7 * 10 < ² > or more and 2.7 * 10 < ³ > Pa, and it took out when the softening point became 112 degreeC. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as resin (A-5).

(Resin Production Example 6)
Styrene 77.6 parts by weight n-butyl acrylate 19.6 parts by weight Methacrylic acid 2.0 parts by weight 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane
0.8 parts by mass The above components were thoroughly substituted with nitrogen while stirring 200 parts by mass of xylene in a four-necked flask and the temperature was raised to 125 ° C., and then the above components were added dropwise over 4 hours. did. Furthermore, the polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure. The softening point of the resin was 112 ° C. The resin thus obtained is referred to as “resin (A-6)”.

(Resin Production Example 7)
1,2-propylene glycol 32.9 parts by mass terephthalic acid dimethyl ester 58.7 parts by mass tetrabutoxy titanate 0.2 parts by mass The above was placed in a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube. The reaction was carried out for 16 hours while distilling off the produced methanol under a nitrogen stream at ℃.
Next, 6.9 parts by mass of trimellitic anhydride was added, and the reaction was performed in a nitrogen stream while gradually raising the temperature to 230 ° C., and then the reaction was performed under a reduced pressure of 6.7 × 10 ^{2 to} 2.7 × 10 ³ Pa. When the softening point reached 172 ° C., it was taken out. The taken-out resin was cooled to room temperature and then pulverized into particles. This is Resin (B-1).

(Resin Production Example 8)
Of the resin production example 7, the reaction time under reduced pressure of 6.7 × 10 ² or more and 2.7 × 10 ³ Pa after addition of trimellitic anhydride was extended, and the resin was taken out when the softening point reached 192 ° C. It was. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as resin (B-2).

(Resin Production Example 9)
1,2-propylene glycol 31.8 parts by mass terephthalic acid dimethyl ester 56.8 parts by mass tetrabutoxy titanate 0.2 parts by mass The above was placed in a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube. The reaction was carried out for 24 hours while distilling off the methanol produced under nitrogen flow at ℃.
Next, 9.7 parts by mass of trimellitic anhydride was added, the reaction was carried out under a nitrogen stream while gradually raising the temperature to 230 ° C., and then the reaction was performed under a reduced pressure of 6.7 × 10 ^{2 to} 2.7 × 10 ³ Pa. The resin taken out when the softening point reached 203 ° C. was cooled to room temperature and then pulverized into particles. This is designated as resin (B-3).

(Resin Production Example 10)
Bisphenol A ethylene oxide 2-mole adduct 34.8 parts by mass Bisphenol A propylene oxide 2-mole adduct 36.4 parts by mass Terephthalic acid 23.2 parts by mass Tetrabutoxy titanate 0.2 parts by mass The reaction vessel was placed in a reaction vessel equipped with a nitrogen introduction tube and reacted at 210 ° C. for 7 hours while distilling off the water produced under a nitrogen stream.
Next, 5.4 parts by mass of trimellitic anhydride was added, and the reaction was performed in a nitrogen stream while gradually raising the temperature to 230 ° C., and further under reduced pressure of 6.7 × 10 ^{2 to} 2.7 × 10 ³ Pa. The reaction was allowed to take out when the softening point reached 132 ° C. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as resin (B-4).

(Resin Production Example 11)
Among the resin production examples 8, the reaction time under reduced pressure of 6.7 × 10 ² or more and 2.7 × 10 ³ Pa after addition of trimellitic anhydride is reduced, and the resin is taken out when the softening point becomes 126 ° C. It was. The taken-out resin was cooled to room temperature and then pulverized into particles. This is Resin (B-5).

(Resin Production Example 12)
1,4-butanediol 43.2 parts by mass Succinic acid 56.6 parts by mass Tetrabutoxy titanate 0.2 parts by mass The above was placed in a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube at 180 ° C. The reaction was carried out for 6 hours while distilling off the water produced under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 6.7 * 10 < ² > or more and 2.7 * 10 < ³ > Pa. When the glass transition point of this resin was measured using a differential scanning calorimetry (DSC) apparatus “Q1000”, the peak temperature of the maximum endothermic peak of the resin was 121 ° C. and the softening point was 123 ° C. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as crystalline resin (C-1).

(Cyan toner production example 1)
Resin A-1 50.0 parts by mass Resin B-1 50.0 parts by mass Paraffin wax (maximum endothermic peak peak temperature 75 ° C.) 5.0 parts by mass 3,5-di-t-butylsalicylate aluminum compound 1.0 Mass part C.I. I. Pigment Blue 15: 3 5.0 parts by mass After the above formulation was mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), a twin-screw kneader (PCM-30 type, Kneaded by Ikekai Tekko Co., Ltd. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely pulverized product was pulverized with a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.) to obtain cyan pulverized particles.

  The cyan pulverized particles were subjected to a surface smoothing process in the surface smoothing apparatus shown in FIG.

The operating conditions were as follows.
Feed amount = 5 kg / hr
Hot air temperature C = 200 ° C
Hot air flow rate = 6m ³ / min
Cold air temperature E = 5 ℃
Cold air flow rate = 4m ³ / min
Second cold air flow rate = 1 m ³ / min
Blower air volume = 20m ³ / min
Injection air flow rate = 1m ³ / min
Diffusion air = 0.4m ³ / min
Further, classification was performed by a multi-division classifier using the Coanda effect to obtain toner particles C1.

To 100 parts by mass of the obtained surface smoothed toner particles C1, 0.8 parts by mass of titanium oxide fine particles having a specific surface area of 100 m ² / g surface-treated with isobutyltrimethoxysilane, and a specific surface area of 300 m ² treated with hexamethyldisilazane. / G hydrophobic silica fine particles (0.8 parts by mass) were added and mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain toner C1. Table 1 shows the physical properties of Toner C1 obtained.

(Cyan toner production example 2)
In Cyan Toner Production Example 1, the toner formulation is 50.0 parts by mass of resin A-4, 50.0 parts by mass of resin B-4, paraffin wax (peak temperature of maximum endothermic peak: 75 ° C.), 5.0 parts by mass. I. Pigment Blue 15: 3 Changed to 5.0 parts by weight,
The rotor speed of the mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.) was changed, and among the surface smoothing conditions, the hot air temperature C was changed from 200 ° C. to 160 ° C., and the hot air flow rate was changed from 6 m ³ / min. Toner C2 was obtained in the same manner except for changing to 5 m ³ / min. Table 1 shows the physical properties of Toner C2 obtained.

(Cyan toner production example 3)
In the cyan toner production example 1, the toner formulation is 50.0 parts by mass of resin A-3, 50.0 parts by mass of resin B-5, paraffin wax (peak temperature of maximum endothermic peak 67 ° C.) 8.0 parts by mass of 3,5- Di-t-butylsalicylate aluminum compound 1.0 part by mass C.I. I. Pigment Blue 15: 3 Changed to 5.0 parts by weight,
The rotor speed of the mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.) was changed, and among the surface smoothing conditions, the hot air temperature C was changed from 200 ° C. to 240 ° C., and the hot air flow rate was changed from 6 m ³ / min. Toner C3 was obtained in the same manner except that it was changed to 8 m ³ / min. Table 1 shows the physical properties of Toner C3 obtained.

(Cyan toner production example 4)
In Cyan Toner Production Example 1, the toner formulation is Resin A-2 50.0 parts by mass Resin B-2 50.0 parts by mass Fischer-Tropsch wax (maximum endothermic peak temperature 105 ° C.)
3.2 parts by mass 3,5-di-t-butylsalicylic acid aluminum compound 1.0 part by mass C.I. I. Pigment Blue 15: 3 Changed to 5.0 parts by weight,
The rotor speed of the mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.) was changed, and among the surface smoothing conditions, the hot air temperature C was changed from 200 ° C. to 160 ° C., and the hot air flow rate was changed from 6 m ³ / min. Toner C4 was obtained in the same manner except that it was changed to 4 m ³ / min. Table 1 shows the physical properties of Toner C4 obtained.

(Cyan toner production example 5)
In cyan toner production example 1, the toner formulation is resin A-6 100.0 parts by mass paraffin wax (maximum endothermic peak peak temperature 57 ° C.) 9.5 parts by mass 3,5-di-t-butylsalicylate aluminum compound 1 0.0 parts by mass C.I. I. Pigment Blue 15: 3 Toner C5 was obtained in the same manner except that the rotation speed of the rotor of a mechanical pulverizer (T-250, manufactured by Turbo Industry Co., Ltd.) was changed. Table 1 shows the physical properties of Toner C5 obtained.

(Cyan toner production example 6)
In the cyan toner production example 1, the toner formulation is 50.0 parts by mass of resin A-5, 50.0 parts by mass of behenate behenate (peak temperature of maximum endothermic peak is 71 ° C.) 8.0 parts by mass 3, 5-di-t-butylsalicylic acid aluminum compound 1.0 parts by mass C.I. I. Pigment Blue 15: 3 Changed to 5.0 parts by weight,
In the same manner, except that the rotational speed of the rotor of a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.) was changed and the hot air temperature C was changed from 200 ° C. to 220 ° C. among the surface smoothing treatment conditions. C6 was obtained. Table 1 shows the physical properties of Toner C6 obtained.

(Cyan toner production example 7)
In Cyan Toner Production Example 1, the toner formulation is 90.0 parts by mass of resin A-5 10.0 parts by mass of crystalline resin C-1 paraffin wax (peak temperature of maximum endothermic peak 75 ° C.) 5.0 parts by mass 3, 5-di-t-butylsalicylic acid aluminum compound 1.0 parts by mass C.I. I. Pigment Blue 15: 3 Changed to 5.0 parts by weight,
In the same manner, except that the rotational speed of the rotor of a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.) was changed and the hot air temperature C was changed from 200 ° C. to 220 ° C. among the surface smoothing treatment conditions. C7 was obtained. Table 1 shows the physical properties of Toner C7 obtained.

(Cyan toner production example 8)
In cyan toner production example 1, the toner formulation is 90.0 parts by mass of resin A-1 10.0 parts by mass of crystalline resin C-1 paraffin wax (peak temperature of maximum endothermic peak 75 ° C.) 5.0 parts by mass of C.I. I. Pigment Blue 15: 3 Changed to 5.0 parts by weight,
Toner C8 was obtained in the same manner except that the rotational speed of the rotor of a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.) was changed and the surface smoothing treatment was not performed. Table 1 shows the physical properties of Toner C8 obtained.

(Cyan toner production example 9)
In the cyan toner production example 1, the toner formulation is 90.0 parts by mass of resin A-3 10.0 parts by mass of resin B-5 paraffin wax (peak temperature of 43 ° C. at the maximum endothermic peak) 20.0 parts by mass of C.I. I. Pigment Blue 15: 3 Changed to 5.0 parts by weight,
Toner C9 was similarly prepared except that the rotational speed of the rotor of the mechanical pulverizer (T-250, manufactured by Turbo Industry Co., Ltd.) was changed and the hot air temperature C was changed from 200 ° C. to 220 ° C. in the surface smoothing treatment conditions. Got. Table 1 shows the physical properties of Toner C9 obtained.

(Cyan toner production example 10)
In cyan toner production example 1, the toner formulation is 90.0 parts by mass of resin A-1 10.0 parts by mass of resin B-1 polypropylene wax (peak temperature of maximum endothermic peak 135 ° C.) 5.0 parts by mass I. Pigment Blue 15: 3 Changed to 5.0 parts by weight,
Toner C10 was obtained in the same manner except that the rotational speed of the rotor of a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.) was changed and the surface smoothing treatment was not performed. Table 1 shows the physical properties of Toner C10 thus obtained.

(Cyan toner production example 11)
<Dispersion A>
Styrene 350.0 parts by mass n-butyl acrylate 100.0 parts by mass Acrylic acid 25.0 parts by mass t-dodecyl mercaptan 10.0 parts by mass The above formulations were mixed and dissolved to prepare a monomer mixture.
100 parts by mass of paraffin wax dispersion (peak temperature of maximum endothermic peak 75 ° C., solid content concentration 30%, dispersed particle size 0.14 μm)
1.2 parts by weight of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
0.5 parts by weight of nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400)
1530.0 parts by mass of ion-exchanged water The above composition was dispersed in a flask, and heating was started while performing nitrogen substitution. When the liquid temperature reached 70 ° C., a solution prepared by dissolving 6.56 parts by mass of potassium persulfate with 350 parts by mass of ion-exchanged water was added thereto. While maintaining the liquid temperature at 70 ° C., the monomer mixture is charged and stirred, the liquid temperature is raised to 80 ° C. and emulsion polymerization is continued for 6 hours. After that, the liquid temperature is adjusted to 40 ° C. and then filtered and dispersed. Liquid A was obtained. Thus, the particles in the obtained dispersion have a number average particle size of 0.16 μm, a glass transition point of solid content of 60 ° C., a weight average molecular weight (Mw) of 15,000, and a peak molecular weight of 12, 000. Paraffin wax was contained in the polymer in an amount of 6% by mass. As a result of observing a thin piece of this solid content with a transmission electron microscope, it was confirmed that the polymer particles encapsulated the wax particles.

<Dispersion B>
C. I. Pigment Blue 15: 3 12.0 parts by mass Anionic surfactant 2.0 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
86.0 parts by mass of ion-exchanged water The above composition was mixed and dispersed using a bead mill (Ultra Apex Mill, manufactured by Kotobuki Industries Co., Ltd.) to obtain Colorant Dispersion Liquid B.

  300 parts by mass of the dispersion A and 25 parts by mass of the dispersion B were charged into a 1 liter separable flask equipped with a stirrer, a cooling tube and a thermometer, and stirred. As a flocculant, 180 parts by mass of a 10% by mass sodium chloride aqueous solution was dropped into this mixed solution, and the flask was heated to 54 ° C. while stirring the inside of the flask. After maintaining at 48 ° C. for 1 hour, it was confirmed by observation with an optical microscope that aggregated particles having a diameter of about 5 μm were formed.

  In the subsequent fusion process, after adding 3 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC), the stainless steel flask was sealed and stirring was continued using a magnetic seal. While heating to 100 ° C., it was held for 3 hours. Then, after cooling, the reaction product was filtered, thoroughly washed with ion exchange water, and then dried to obtain toner particles C11.

To 100 parts by mass of the obtained toner particles C11, 1.0 part by mass of titanium oxide fine particles having a specific surface area of 120 m ² / g surface-treated with isobutyltrimethoxysilane, and a specific surface area of 300 m ² / g hydrophobically treated with hexamethyldisilazane. 0.5 parts by mass of silica fine particles and 1.2 parts by mass of hydrophobic silica fine particles having a specific surface area of 50 m ² / g subjected to a surface treatment with hexamethyldisilazane were added, and a Henschel mixer (FM-75 type, Mitsui Miike Chemical Co., Ltd. ) To obtain toner C11. Table 1 shows the physical properties of Toner C11 thus obtained.

(Cyan toner production example 12)
To 710 parts by mass of ion-exchanged water, 450 parts by mass of a 0.12 mol / l-Na ₃ PO ₄ aqueous solution was added and heated to 60 ° C. to obtain an aqueous solution obtained from a TK homomixer (manufactured by Special Machine Industries). Was stirred at 15,000 rpm. To this, 68 parts by mass of a 1.2 mol / l-CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .
Styrene 160.0 parts by mass n-butyl acrylate 30.0 parts by mass Behenic acid behenyl ester wax (maximum endothermic peak temperature 72 ° C.)
20.0 parts by mass 1,4-di-t-butylsalicylic acid aluminum compound 0.5 parts by mass saturated polyester (terephthalic acid-propylene oxide modified bisphenol A; acid value 15, peak molecular weight 6000) 10.0 parts by mass C.I. I. Pigment Blue 15: 3 10.0 parts by mass was heated to 60 ° C., and uniformly dissolved and dispersed at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). In this, 10 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

The obtained polymerizable monomer composition was put into the aforementioned aqueous medium. The obtained mixture was stirred at 15,000 rpm for 10 minutes at 60 ° C. in a nitrogen atmosphere using a TK homomixer to granulate the polymerizable monomer composition. Then, it heated up at 80 degreeC, stirring with a paddle stirring blade, and was made to react for 10 hours. After completion of the polymerization reaction, the remaining monomer was distilled off under reduced pressure. After cooling, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ . The resulting solution was filtered, and the filtered product was washed with water and dried to obtain toner particles C12.

100 parts by mass of toner particles C12, 0.8 parts by mass of titanium oxide fine particles having a specific surface area of 120 m ² / g surface-treated with isobutyltrimethoxysilane, and 300 m ² / g of hydrophobic silica having a specific surface area of hexamethyldisilazane surface-treated 0.8 parts by mass of fine particles were added and mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain toner C12. Table 1 shows the physical properties of Toner C12 thus obtained.

(Magnetic carrier production example 1)
Water was added to 100 parts by mass of Fe ₂ O ₃ ; the mixture was pulverized with a ball mill for 15 minutes to prepare a magnetic core having a 50% particle size of 36.1 μm.

Next, a mixed solution of 3 parts by mass of a straight silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd .: KR271), 0.5 part by mass of γ-aminopropyltriethoxysilane, and 96.5 parts by mass of toluene is added to 100 parts by mass of the magnetic core. The solution was then dried under reduced pressure at 70 ° C. for 5 hours while stirring and mixing with a solution vacuum kneader to remove the solvent. Then, it baked at 140 degreeC for 2 hours, and sieved with the sieve shaker (300MM-2 type | mold, Tsutsui physics and chemistry machine: 75 micrometers opening), and the magnetic carrier was obtained. The obtained magnetic carrier had a 50% particle size of 38.2 μm based on volume distribution and a true specific gravity of 5.0 g / cm ³ .

<Example 1>
10 parts by mass of the toner C1 obtained in the toner production example 1 and 90 parts by mass of the magnetic carrier 1 obtained in the magnetic carrier production example 1 were mixed by a V-type mixer to obtain a two-component developer C1.

  The main body was a Canon full-color copying machine iRC5180 modified using a developing device that can use a two-component developer and modified so that the process conditions can be changed.

The two-component developer C1 was placed in a cyan position developer.
Endurance image evaluation under normal temperature and normal humidity (N / N) (23 ° C., 50% RH), normal temperature and low humidity (N / L) (23 ° C., 10% RH) environment (A4 horizontal, 30% printing ratio, 50,000 Sheet).

  Items for image evaluation and evaluation criteria after the first sheet (initial stage) and after passing 50,000 sheets are shown below. The evaluation results of the following (1) to (6) are shown in Tables 2 and 3.

(1) Image Density The development voltage was adjusted so that the toner loading of the image was 0.6 mg / cm ^2, and the density was measured using the X-Rite color reflection densitometer described above. The difference in image density at the initial stage of durability and after 50,000 sheets was evaluated.
(Evaluation criteria)
A: Very good (less than 0.05)
B: Good (0.05 or more and less than 0.10)
C: Normal (0.10 or more and less than 0.20)
D: Bad (over 0.20)

(2) Transfer efficiency (transfer residual density)
A solid image was output, and the transfer residual toner on the photoconductor at the time of solid image formation was removed by taping with a transparent polyester adhesive tape. The density difference was calculated by subtracting the density of the adhesive tape only on the paper from the density of the adhesive tape that had been peeled off. And it judged as follows from the value of the density difference. The density was measured with the X-Rite color reflection densitometer described above.
(Evaluation criteria)
A: Very good (less than 0.05)
B: Good (0.05 or more, less than 0.10)
C: Normal (0.10 or more, less than 0.20)
D: Bad (over 0.20)

(3) Transfer scattering The development voltage was adjusted so that the toner loading amount was 1.0 mg / cm ² .
At the development voltage, a lattice pattern (interval of 1 cm) on 100 μm (latent image) lines was printed, and the scattering was visually evaluated using an optical microscope.
(Evaluation criteria)
A: Very good (the lines are very sharp with almost no scattering)
B: Good (the line is relatively sharp with only slight scattering)
C: Normal (Slightly splattering and the lines feel dull)
D: Poor (below C level)

(4) Retransferability A developing unit in which no developer was put in the black position was set, the developing voltage was adjusted so that the amount of cyan toner applied was 0.6 mg / cm ^2, and an image was output.
The toner to be retransferred to the photosensitive member of the developing device at the black position was collected with a tape, and was removed by taping with a transparent polyester adhesive tape. The density difference was calculated by subtracting the density of the adhesive tape only on the paper from the density of the adhesive tape that had been peeled off. And it judged as follows from the value of the density difference. The density was measured with the X-Rite color reflection densitometer described above.
A: Very good (less than 0.05)
B: Good (0.05 or more, less than 0.10)
C: Normal (0.10 or more, less than 0.20)
D: Bad (over 0.20)

<Examples 2-7 and Comparative Examples 1-5>
Examples 2 to 7 and Comparative Examples 1 to 5 were evaluated in the same manner as in Example 1 except that the toner C1 used in Example 1 was changed to toners C2 to C12, respectively. Tables 2 and 3 show the evaluation results.

1 is a schematic cross-sectional view of a surface smoothing device of the present invention. FIG. 3 is a schematic cross-sectional view of a toner supply port and an airflow ejection member in the surface smoothing device of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Toner supply port 101 Hot-air supply port 102 Airflow injection member 103 Cold-air supply port 104 Second cold-air supply port 106 Cooling jacket 110 Diffusion air 111 Air-flow supply port for the purpose of dew condensation 112 Diffusion member with a plurality of holes 113 Air-flow injection Hole through which member shaft passes 114 Toner 115 High-pressure air supply nozzle 116 Transfer piping

Claims (6)

In a toner having an external additive and toner particles containing at least a binder resin, a colorant and a wax,
Flow-type particle image with an image processing resolution of 512 × 512 pixels (0.37 μm × 0.37 μm per pixel) when a 20 kHz, 50 W / 10 cm ³ ultrasonic wave is irradiated to the dispersion liquid in which the toner is dispersed for 5 minutes. The measured value C1 of the particles of 0.50 μm or more and 2.00 μm or less measured by the measuring device is 40.0% by number or less,
The toner has a surface tension index of 45 × 10 ⁻³ N / m or more and 1.0 × 10 ⁻¹ N / m or less with respect to a 45 volume% aqueous methanol solution measured by a capillary suction time method. Toner. The toner has particles of 0.50 μm or more and 2.00 μm or less measured by the flow type particle image analyzer when an ultrasonic wave of 20 kHz and 50 W / 10 cm ³ is irradiated to the dispersion liquid in which the toner is dispersed for 5 minutes. 2. The toner according to claim 1, wherein the measured value C <b> 1 is 1.0% by number or more and 30.0% by number or less. The toner has particles of 0.50 μm or more and 2.00 μm or less measured by the flow type particle image analyzer when an ultrasonic wave of 20 kHz and 50 W / 10 cm ³ is irradiated to the dispersion liquid in which the toner is dispersed for 1 minute. 3. The toner according to claim 1, wherein the measured value C2 of the toner is 0.5% by number or more and 20.0% by number or less.   The toner according to claim 1, wherein the toner particles are obtained by performing a surface smoothing treatment with hot air. In a two-component developer containing a magnetic carrier and a toner,
The toner has toner particles containing at least a binder resin, a colorant, and a wax, and an external additive,
Flow type particle image measurement with an image processing resolution of 512 × 512 pixels (0.37 μm × 0.37 μm per pixel) when the toner dispersion is irradiated with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 5 minutes. The measured value C1 of particles of 0.50 μm or more and 2.00 μm or less measured by the apparatus is 40.0% by number or less,
The toner has a surface tension index of 45 × 10 ⁻³ N / m or more and 1.0 × 10 ⁻¹ N / m or less with respect to a 45 volume% aqueous methanol solution measured by a capillary suction time method. A two-component developer.   The two-component developer according to claim 5, wherein the toner is the toner according to claim 2.

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