JP2010160374A - Method of manufacturing toner particle or toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of stably manufacturing toner that maintains high-quality images and having proper fixing properties that allow the toner to be fixed to various mediums. <P>SOLUTION: The toner-manufacturing method has a surface modification process of a toner particle which includes a binder resin and a colorant; the surface modification process is performed, by using a surface modification device and the surface modification device includes a classification means for performing the discharge and removal to the outside of the device and a surface modification means using mechanical impact force, wherein the classification means has a plurality of blades and each blade is arranged so as to form a specified angle &theta;, with respect to a straight line that connects the center of a classification rotor with the top end of the blade; if the angle &theta; satisfies the relation 20&deg;&le;&theta;&le;65&deg;, and the circle-equivalent number is the mean diameter Da (&mu;m) of the toner particle satisfies the relation: 4.0&le;Da&le;8.0 and, if the average circularity of the toner particle is set to Ca and the average circularity of the toner particle at circle-equivalent degree mean diameter of Da/2 is set to Ca/2, the relation : 0&le;¾Ca-Ca/2¾&le;0.004 holds. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention forms a toner image on a photoreceptor using a two-component developer, and transfers the toner image to a recording material to obtain an image. For example, toner particles or toner of an electrophotographic system or an electrostatic recording system It relates to the manufacturing method.

  In recent years, copying machines and printers have been sought to be smaller, lighter, faster, and more reliable due to demands for space saving and higher speed. The copying machine itself is simpler in various ways. It has come to be composed of. As a result, the performance required for the developer becomes higher, and if the improvement in the performance of the developer cannot be achieved, a more excellent main body configuration cannot be realized. For example, among the main body elements, miniaturization of the motor and reduction of the motor are also points. Since full-color machines have many colors, a large number of motors are inevitably required compared to black-and-white machines. Therefore, multiple work with the same motor can contribute to power saving and space saving. As an example, it is also an effective means to drive the development configuration and the transfer configuration with the same motor. On the other hand, a considerable number of gears are required to move different ones with the same motor, and there is a drawback in that the drive accuracy is reduced due to amplification of the deviation caused by the crossing of gears. For example, during the transfer, the fluctuation in the peripheral speed difference between the transfer member and the photosensitive member becomes large, and the transferability is reduced. The so-called hollowing out of the thin line in the transfer property is sensitive to the difference in the peripheral speed between the transfer member and the photosensitive member, so that the toner needs to be improved.

  Conventionally, it is considered that the void in the transfer is sensitive to the roundness of the toner, that is, the circularity. Various methods such as mechanical impact and thermal spheronization have been proposed as methods for spheroidizing toner. Although the thermal spheronization can be uniformly rounded, the release agent oozes out on the surface, causing the negative effects of broadening the charge and fogging. On the contrary, in the spheronization by a simple mechanical impact, the pulverization is likely to be over-pulverized, and the fine powder generated by the over-pulverization has caused adverse effects such as contamination of members. Therefore, proposals have been made to remove fine powder while making it spherical (see, for example, Patent Documents 1, 2, and 3). However, even with the proposed toner with a small amount of fine powder and a high degree of circularity, if the fluctuation in the peripheral speed difference between the transfer member and the photosensitive member becomes large, the occurrence of voids cannot be sufficiently suppressed, and improvement is achieved. I needed it.

  In recent years, there has been an increasing need for printing on various media such as envelopes, recycled paper, and coated paper, and it is desired that fixing can be performed even with a simple and small fixing machine. To enable fixing on various media, a toner having a wide fixing area is required. In order to achieve a wide fixability, it is considered that a toner having both a soft component and a hard component is necessary. To pass thick paper (a large amount of heat) through a fixing machine at a constant temperature, a toner that is easily melted, that is, a toner having a soft component is required. When passing thin paper (with a small amount of heat), so-called hot offset that causes the fixing member to be contaminated occurs because only the easily soluble toner melts too much. Therefore, a toner having a hard component to such an extent that it does not hinder easiness of dissolution is preferable.

  A toner having both a soft component and a hard component as described above is difficult to stably produce while increasing the circularity. The reason is that the desired sphericity cannot be obtained due to a hard component with a weak impact force. On the other hand, when a strong impact force is applied, the sphericity increases, but the temperature of the toner surface partially rises due to the impact force no matter how much the manufacturing apparatus is cooled. As the temperature rises, a soft component of the toner causes fusing and adhesion in the manufacturing apparatus, which causes a problem that stable production cannot be achieved.

JP 2002-233787 A JP 2003-103187 A JP 2003-233218 A

  The present invention solves the above-mentioned problems of the prior art.

  In other words, the object of the present invention is to use a two-component developer, maintain a high-quality image even in a configuration in which the peripheral speed difference between the transfer member and the photosensitive member is large, and fixability that can be fixed on various media. It is an object of the present invention to provide a production method capable of stably producing good toner particles or toner.

  As a result of intensive studies, the present inventors have found a manufacturing method that enables stable production while maintaining uniform toner particle diameter and circularity even with desired toner softness. The present invention has been reached.

  That is, the present invention is characterized by the following configuration.

(1) In a toner manufacturing method including a toner particle or toner surface modification step containing at least a binder resin and a colorant,
The surface modification step is performed using a surface modification device, and the surface modification device includes at least a classification unit for continuously discharging and removing out of the device, a surface modification unit using mechanical impact force, and A guide means for partitioning a space between the classification means and the surface modification means into a first space and a second space;
1) The classification means has a plurality of blades arranged at regular intervals on the same circumference, and each blade forms a constant angle θ with respect to a straight line connecting the center of the classification rotor and the tip of the blade. Classifying means arranged in such a manner that the angle θ is 20 ° ≦ θ ≦ 65 °,
2) The circle equivalent number average diameter Da (μm) 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) of the toner particles is 4.0 ≦ Da ≦ 8.0,
3) The circularity 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) of the toner particles is 0.200 or more and 1.000 or less. The average circularity of the toner particles or toner in the range of 1.99 μm or more and less than 39.69 μm analyzed by dividing into 800 degrees is Ca, and the average circularity of the toner particles or toner in the equivalent circle diameter of half of Da is defined as Ca. A method for producing toner particles or toner, wherein Ca / 2 and Ca / 2 have the relationship of Formula A when Ca / 2 is used.
0 ≦ | Ca−Ca / 2 | ≦ 0.004 Formula A

  (2) The method for producing toner particles or toner according to (1), wherein a Vickers hardness Hv of a blade surface of the classification rotor is 800 ≦ Hv ≦ 5000.

  (3) Manufacture of toner particles or toner according to (1) or (2), wherein the surface roughness Ra (μm) of the blades of the classification rotor is 0.2 ≦ Ra ≦ 1.5. Method.

(4) In the measurement of the toner particles with a flow tester, the outflow start temperature in the measurement with a cylinder pressure of 9.81 × 10 ⁵ Pa and an orifice hole diameter of 1.0 mm is 77.0 ° C. or more and 88.0 ° C. or less. The method for producing toner particles or toner according to (1) to (3), wherein the THF insoluble content in the toner particles is 5.0 mass% or more and 20.0 mass% or less.

  According to the present invention, it is possible to stably obtain a toner having excellent transferability and fixability for various media even in a copying apparatus having a large fluctuation in peripheral speed difference between the transfer member and the photosensitive member. .

  As described above, in order to be able to print on various media, it is necessary to achieve fixing performance with a wide fixing area. For this purpose, a toner having both a soft component and a hard component is required. The physical properties of the soft component have a correlation with the outflow start temperature of the toner particles by the flow tester. The physical properties of the hard component correlate with the THF insoluble content of the toner particles. Fixability is formed by the relationship between the outflow start temperature and the THF insoluble matter.

  Specifically, the toner physical properties of a toner outflow start temperature of 77.0 ° C. and a THF insoluble content of 5.0% by mass are considered as the lower limit of soft toner particles. Further softening tends to cause contamination (hot offset) of the fixing member. This is because, when fixing using thin paper, only a little heat is taken away by the paper, so that the viscosity of the toner is too low and the toner adheres not only to the paper but also to the fixing member and is easily contaminated. On the other hand, the toner physical properties of the toner starting temperature of 88.0 ° C. and the THF insoluble content of 20.0% by mass are considered as the upper limit of the hard toner particles. This is because when heat is fixed using thick paper, a lot of heat is taken away by the paper, so that the amount of heat received by the toner decreases. For this reason, if the toner is too hard, it becomes difficult for the toner to melt and the toner cannot be sufficiently fixed on the paper (cold offset). Therefore, the toner particles according to the present invention preferably have an outflow start temperature of 77.0 ° C. or more and 88.0 ° C. or less and a THF insoluble content of 5.0% by mass or more and 20.0% by mass or less.

  A toner having an outflow start temperature of toner of less than 77.0 ° C. and a THF insoluble content of less than 5.0% by mass may be further problematic. The first problem is that toner fusing to the manufacturing apparatus is likely to occur during manufacturing. The second problem is that the circularity distribution is widened and a void is generated. Specifically, it will be described with reference to the apparatus 1 shown in FIG. The apparatus 1 is a surface modification apparatus that removes fine powder while making it spherical, and has been proposed to improve (eg, Japanese Patent Application Laid-Open No. 2007-148077).

  First, the surface modification apparatus will be described in detail with reference to FIG. 1 includes a cylindrical main body casing 30, a top plate 43 installed to be openable and closable at the top of the main body casing; a fine powder discharge portion 44 having a fine powder discharge casing and a fine powder discharge pipe; cooling water Or it has the cooling jacket 31 which can flow antifreeze liquid. Further, as a surface modification means using a mechanical impact force, a disc-like shape that has a plurality of dispersion hammers 33 on the upper surface and is attached to the central rotating shaft in the main body casing 30 and rotates at high speed in a predetermined direction. The dispersion rotor 32 is a rotating body; and the liner 34 is fixedly disposed around the dispersion rotor 32 at a constant interval and provided with a number of grooves on the surface facing the dispersion rotor 32. Further, a classification rotor 35 for continuously discharging and removing fine powder and ultrafine powder having a predetermined particle size or less in the finely pulverized product; a cold air inlet 46 for introducing cold air into the main body casing 30; ), A feed pipe having a raw material feed port 37 and a raw material feed port 39 formed on the side surface of the main body casing 30; a product discharge port for discharging the toner particles after the surface modification treatment to the outside of the main body casing 30 40 and a product discharge pipe having a product extraction port 42; an openable and closable raw material supply valve 38 installed between the raw material input port 37 and the raw material supply port 39 so that the surface modification time can be freely adjusted; and the product A product discharge valve 41 is provided between the discharge port 40 and the product extraction port 42. A guide ring 36 that is a guide means for partitioning the space between the classifying means and the surface modifying means into a first space 47 and a second space 48 is also provided.

  The first problem is that long-term stable production cannot be achieved due to the growth of toner fusion to the manufacturing apparatus. The desired particle size, circularity, and circularity distribution of the toner particles cannot be obtained as the fusion grows. As described above, the device 1 can obtain a high degree of circularity without increasing the fine powder. However, when a toner having a soft component and a hard component is used, it is no longer an apparatus that can satisfy long-term stable production. In order to obtain a high degree of circularity, it is necessary to rotate the 32 dispersion rotors at a high speed to give a high impact force. Furthermore, high circularity can be obtained by passing the toner particles through 49 surface modification zones many times. In order to pass the toner particles many times, it is necessary to increase the flow rate of the toner particles. Increasing the flow rate of the toner particles can be achieved by introducing a high air volume into the apparatus. However, when the flow rate of the toner particles is increased, the toner particles easily enter the 35 classification rotor, resulting in a very poor classification yield. Further, in the configuration in which the toner particles are likely to jump into the classification rotor of 35, the circularity tends to be low. This is presumed to be because the toner does not circulate efficiently in the 49 surface modification zones and tends to stay in the 50 classification zones. In order to prevent the toner particles from jumping into the 35 classification rotor, it is essential to rotate the 35 classification rotor at a high speed. Although there is no problem in the initial operation, toner fusion occurs in the 35 classification rotors after long-term production. As a result of toner fusion, the opening area of the 35 classification rotors changes, and the particle size distribution and the circularity change successively. In addition, the melted material is peeled off successively to generate coarse particles. Therefore, the present inventors have confirmed that the fusion can be suppressed by adjusting the blade angle θ of the 35 classification rotor shown in FIG. Although the configuration is different, there is one previously proposed to adjust the blade angle (for example, Japanese Patent Laid-Open No. 9-179345), and the effect is a high-precision classification different from the present invention. It is considered that by making the individual blade angle θ of the classification rotor 20 ° or more, the impact force on the toner particles is weakened and toner fusion can be prevented. As shown in FIG. 2, in a plurality of blades arranged at regular intervals on the same circumference, an angle θ formed by a straight line connecting the center of the classification rotor 35 and the tip of the blade and the blade. That is, an angle ABC formed by the straight line OA and the straight line BC is defined as θ.

  The second problem is a problem that occurs in all toners that have a soft component and a hard component. Among them, a soft toner having a toner outflow start temperature of less than 77.0 ° C. and a THF-insoluble content of less than 5.0% by mass becomes a more serious problem. Due to the impact force during pulverization, the soft component of the toner is easily broken and the hard component is hard to break. Therefore, many parts which are easy to be broken and become small particles during pulverization occur. When it becomes small particles, it is difficult for the impact force to be transmitted in the apparatus, and the shape tends to be distorted. Therefore, in the toner in which the toner has a soft component and a hard component, the circularity is likely to be different between the small particle portion and the central particle size portion. When the fluctuation of the peripheral speed difference between the transfer member and the photosensitive member is small, if the circularity of the whole toner is high to a certain degree, no void is generated. However, when the fluctuation in the peripheral speed difference between the transfer member and the photosensitive member becomes large, the difference in circularity between the small particle portion and the central particle size portion has a great influence on the hollow. When the peripheral speed difference between the transfer member and the photosensitive member increases, the toner is moved to the left and right while being compressed between the transfer member and the photosensitive member. Toner rearrangement occurs, increasing the chance of small particles coming into contact with the photoreceptor. If the difference in circularity between the small particle portion and the central particle size portion is large, the adhesion force to the photoconductor is different, resulting in a problem that the small particles remain without being transferred from the photoconductor side. Therefore, it is considered that the difference in circularity between the small particle portion and the central particle size portion needs to be reduced and made uniform.

More specifically, Ca is the average circularity when the toner particle or toner circle equivalent number average diameter Da measured by the flow type particle image measuring device is used. Let Ca / 2 be the average circularity of the toner particles or toner at the equivalent circle diameter of half of Da. When Ca and Ca / 2 have the relationship of the formula A, even if the fluctuation of the peripheral speed difference between the transfer member and the photosensitive member is large, no void occurs.
0 ≦ | Ca−Ca / 2 | ≦ 0.004 Formula A

  In order to satisfy Formula A, it was necessary to control the physical properties of the toner along with improvements in the apparatus 1. In the apparatus 1, it is necessary to adjust the blade angle θ of the 35 classification rotor described above, and it is necessary to adjust the outflow start temperature and the THF-insoluble matter as described above for the physical properties of the toner.

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

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

  When the particle image is circular, the degree of circularity is 1, and the degree of unevenness on the outer periphery of the particle image increases, and the degree of circularity decreases. After calculating the circularity of each particle, the circularity range of 0.200 or more and 1.000 or less is divided into 800, an arithmetic average value of the obtained circularity is calculated, and the value is set as the average circularity.

  It was found that the value of | Ca−Ca / 2 | varies greatly depending on the blade angle θ in the toner having a soft component and a hard component. When the blade angle θ was less than 20 °, | Ca−Ca / 2 |> 0.005, and the hollow hole was not satisfactory. A preferred range is 20 ° ≦ θ ≦ 65 °. Although the reason is not clear, it is considered that if the blade angle θ is less than 20 °, small particles stay in the 50 classification zones and do not efficiently go to the 49 surface modification zones. More specifically, there are many small particles near the 35 classification rotor. If the blade angle θ is less than 20 °, the impact force to the toner particles by the classification rotor of 35 is strong, and the small particles cause irregular movement due to the impact force, and as a result, they do not go efficiently to the surface modification zone of 49. I believe. In addition, a toner having both a soft component and a hard component becomes prominent because of the large difference in circularity between the small particle portion and the central particle size portion during pulverization. On the contrary, when the blade angle θ is larger than 65 °, the swirl flow is increased inside the 35 classification rotor, and the toner particles are easily swirled inside the classification rotor. As a result, toner particles adhere to the inside of the classification rotor, and the particle size distribution and the circularity are successively changed.

  In addition, the toner particle or toner circle equivalent number average diameter Da also affects | Ca-Ca / 2 |. When 4.0> Da, the particle size becomes too small as described above, and it is difficult for the impact force to be transmitted to small toner particles in the apparatus, and the shape is further distorted. On the other hand, when Da> 8.0, the difference between Da and the particle size of half of Da increases, so that the difference in circularity is likely to occur. Therefore, 4.0 ≦ Da ≦ 8.0 is preferable. Furthermore, as an improvement of the apparatus 1, it is preferable that the Vickers hardness Hv of the blade surface in the 35 classification rotor is 800 ≦ Hv ≦ 5000.

And it is preferable that surface roughness Ra (micrometer) of the blade | wing of the said classification rotor is 0.2 <= Ra <= 1.5. These are all effective means for preventing toner fusion and adhesion. If 800> Hv, the releasability is lowered, and if 0.2> Ra, the mirror surface becomes too much, and the fusion is promoted together. On the other hand, when Ra> 1.5, the unevenness becomes excessively large and toner particles are likely to be deposited, and the particle size distribution and the circularity are likely to change sequentially. As the base material of the classification rotor, carbon steel such as S45C or chromium molybdenum steel such as SCM material is often used. By blasting here with various abrasive particles, the surface of the base material is made into a surface having uniform irregularities. By coating the surface of the base material with a chromium alloy, the surface hardness is high, the wear resistance is increased, and the life is long. In addition, chromium carbide (Cr ₂₃ C ₆ ), which exists in the chromium alloy and has a strong intermolecular bonding force, exists from the surface layer to a certain depth or more, specifically, to a depth of 5 μm or more, so that it adheres to the base material surface. The frequency of occurrence of phenomena such as peeling and cracking can be reduced as much as possible. Further, the coating of the chromium alloy containing chromium carbide on the surface of the base material can be processed by “plating” to finish the surface uniformly and smoothly, to reduce the friction coefficient and to improve the wear resistance. An example of such a plating process is a brasstron process (Chiyoda Daiichi Kogyo Co., Ltd.). In order to make Hv ≧ 2000, a hydrocarbon gas such as benzene is introduced into a vacuum chamber, and hydrocarbon ions are generated in a DC arc discharge plasma. This hydrocarbon ion is suitable for treatment with a so-called diamond-like carbon which collides with a coating material having a negative voltage with energy corresponding to the voltage to solidify and form a film.

  An example of the toner used in the present invention will be given.

  The toner used in the present invention is a toner having toner particles containing a resin mainly composed of a polyester unit and a colorant. “Polyester unit” refers to a part derived from polyester, and “resin mainly composed of polyester unit” means a resin in which many of the repeating units constituting the resin are repeating units having an ester bond. However, these will be described in detail later.

  The polyester unit is formed by condensation polymerization of ester monomers. Examples of the ester-based monomer include a polyhydric alcohol component and a carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester having two or more carboxyl groups.

  The following are mentioned as a dihydric alcohol component among a polyhydric alcohol component. For example, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene ( 2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, poly Alkylene oxide adducts of bisphenol A such as oxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol 1,4-butanediol, neopentyl glycol, 1,4-bute Examples include diol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, and hydrogenated bisphenol A. .

  Examples of the trihydric or higher alcohol component among the polyhydric alcohol components include the following. For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol And glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.

  The following are mentioned as a carboxylic acid component which comprises a polyester unit. For example, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; alkyl groups having 6 to 12 carbon atoms And succinic acid or anhydride thereof substituted with an unsaturated dicarboxylic acid such as fumaric acid, maleic acid and citraconic acid, or an anhydride thereof.

  Preferable examples of the resin having a polyester unit contained in the toner particles include the following. That is, a bisphenol derivative typified by the structure represented by the formula (1) as an alcohol component, a carboxylic acid component consisting of a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof (for example, fumaric acid, This is a polyester resin obtained by polycondensation of maleic acid, maleic anhydride, phthalic acid, terephthalic acid, dodecenyl succinic acid, trimellitic acid, pyromellitic acid) as carboxylic acid components. This polyester resin has good charging characteristics. The charging characteristics of this polyester resin work more effectively when used as a resin contained in a color toner contained in a two-component developer.

〔式中、Ｒはエチレン基及びプロピレン基から選ばれる１種以上であり、ｘ及びｙはそれぞれ１以上の整数であり、且つｘ＋ｙの平均値は２以上１０以下である。〕

[In the formula, R is one or more selected from an ethylene group and a propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 or more and 10 or less. ]

  A preferable example of the resin having a polyester unit contained in the toner particles includes a polyester resin having a cross-linked site. The polyester resin having a crosslinking site can be obtained by subjecting a polyhydric alcohol and a carboxylic acid component containing a trivalent or higher polyvalent carboxylic acid to a condensation polymerization reaction. Examples of the trivalent or higher polyvalent carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7. -Naphthalene tricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and acid anhydrides and ester compounds thereof. The content of the trivalent or higher polyvalent carboxylic acid component contained in the ester monomer to be polycondensed is preferably 0.1 mol% or more and 1.9 mol% or less based on the total monomers.

  Furthermore, preferable examples of the resin having a polyester unit contained in the toner particles include (a) a hybrid resin having a polyester unit and a vinyl polymer unit, and (b) a mixture of the hybrid resin and the vinyl polymer. (C) A mixture of a polyester resin and a vinyl polymer, (d) a mixture of a hybrid resin and a polyester resin, and (e) a mixture of a polyester resin, a hybrid resin, and a vinyl polymer.

  The hybrid resin is formed by a transesterification reaction between a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer component having a carboxylic ester group such as an acrylic ester. Examples of the hybrid resin include a graft copolymer or a block copolymer in which a vinyl polymer is a trunk polymer and a polyester unit is a branch polymer.

  The vinyl polymer unit refers to a portion derived from a vinyl polymer. A vinyl polymer unit or a vinyl polymer can be obtained by polymerizing a vinyl monomer described later.

  Any of the image forming methods using the toner of the present invention is preferably used in an electrophotographic process employing oilless fixing. Therefore, the toner used in the present invention preferably contains a release agent.

  Examples of the release agent include the following. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax; oxidation of aliphatic hydrocarbon wax such as oxidized polyethylene wax Or block copolymers thereof; waxes based on fatty acid esters such as carnauba wax, montanate wax, and behenyl behenate; partially or fully deoxidized fatty acid esters such as deoxidized carnauba wax The thing which was done is mentioned.

  Suitable release agents include hydrocarbon waxes and paraffin waxes. The toner has one or more endothermic peaks in the temperature range of 30 ° C. or more and 200 ° C. or less in the endothermic curve of the toner in differential scanning calorimetry measurement, and the maximum endothermic peak temperature in the endothermic peak is 50 ° C. or more and 110 ° C. or less. As a result, the toner can have good low-temperature fixability and durability.

  The content of the release agent in the chromatic color toner and the transparent toner used in the present invention is preferably 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner particles. More preferably, it is 10 parts by mass or less. When the content of the release agent is 1 part by mass or more and 15 parts by mass or less, good transferability can be exhibited during oilless fixing.

  The toner used in the present invention may contain a charge control agent. Examples of the charge control agent include organometallic complexes, metal salts, and chelate compounds. Examples of the organometallic complex include a monoazo metal complex, an acetylacetone metal complex, a hydroxycarboxylic acid metal complex, a polycarboxylic acid metal complex, and a polyol metal complex. Other examples include carboxylic acid derivatives such as metal salts of carboxylic acids, carboxylic acid anhydrides, and esters, and condensates of aromatic compounds. Also, phenol derivatives such as bisphenols and calixarenes can be used as the charge control agent. The charge control agent contained in the toner of the present invention is preferably a metal compound of an aromatic carboxylic acid from the viewpoint of improving the charge rising of the toner.

  The content of the charge control agent in the toner is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, and is 0.2 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferably. Since the toner has a charge control agent of 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the binder resin in the toner particles, the toner can be used in a wide range of environments from high temperature and high humidity to low temperature and low humidity. The change in the charge amount can be reduced.

  The toner used in the present invention has a colorant. Here, the colorant may be a pigment or a dye, or a combination thereof.

  Examples of the dye include the following. For example, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modern Tread 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modern Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Basic green 6 is listed.

  Examples of the pigment include the following. For example, Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Tartrazine Lake, Molybdenum Orange, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake , Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, Pigment Green B, Malachite Green Lake And Final Yellow Green G.

  Further, when the toner of the present invention is used as a developer for forming a full-color image, it can contain a magenta color pigment. Examples of the magenta coloring pigment include the following. For example, 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, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, 238, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35 are mentioned.

  The toner particles may contain only a magenta color pigment. However, when a dye and a pigment are combined, the clarity of the developer can be improved and the image quality of a full-color image can be improved. Examples of the magenta dye include the following. For example, C.I. 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 Disperse Violet 1; 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, and 28 may be mentioned.

  Examples of the color pigment for cyan include the following. For example, C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 16, 17; I. Acid Blue 6; I. Examples include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of the color pigment for yellow include the following. For example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 93, 97, 155, 180, C. I. Bat yellow 1, 3, and 20 are mentioned.

  Examples of the black pigment include carbon powder such as furnace black, channel black, acetylene black, thermal black, and lamp black, and magnetic powder such as magnetite and ferrite.

  Further, the color may be adjusted by combining a magenta dye and a pigment, a yellow dye and a pigment, a cyan dye and a pigment, and the carbon black may be used in combination.

  The toner used in the present invention may be externally added with external additives which are fine particles. By externally adding fine particles, fluidity and transferability can be improved. The external additive externally added to the toner particle surface preferably contains inorganic fine particles of titanium oxide, alumina oxide, and silica fine particles. The surface of the inorganic fine particles contained in the external additive is preferably subjected to a hydrophobic treatment. The hydrophobizing treatment is preferably performed by a coupling agent such as various titanium coupling agents and silane coupling agents; fatty acids and metal salts thereof; silicone oils; or a combination thereof. Among various combinations, it is preferable to add inorganic fine particles having a number average particle diameter of 80 nm or more and less than 300 nm as one of the inorganic fine particles. The reason is that the adhesion force with the carrier can be reduced, and even if the toner has a high charge, it can be developed efficiently. Examples of the material include silica, alumina, and titanium oxide. In the case of silica, any silica produced by using a conventionally known technique such as a gas phase decomposition method, a combustion method, or a deflagration method can be used.

  Examples of the titanium coupling agent for hydrophobizing the inorganic fine particles contained in the external additive include the following. For example, tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecyl benzene sulfonyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate can be mentioned.

  Moreover, the following are mentioned as a silane coupling agent. For example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) ) Γ-aminopropyltrimethoxysilane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane , Phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, and p-methylphenyltrimethoxysilane.

  Examples of the fatty acid for hydrophobizing the inorganic fine particles include the following. For example, long chain fatty acids such as undecyl acid, lauric acid, tridecyl acid, dodecyl acid, myristic acid, palmitic acid, pentadecylic acid, stearic acid, heptadecylic acid, arachidic acid, montanic acid, oleic acid, linoleic acid, arachidonic acid It is done. Examples of the metal of the fatty acid metal salt include zinc, iron, magnesium, aluminum, calcium, sodium, and lithium.

  Examples of the silicone oil for performing the hydrophobizing treatment include dimethyl silicone oil, methylphenyl silicone oil, and amino-modified silicone oil.

  In the hydrophobic treatment, the inorganic fine particles are coated by adding a hydrophobic treatment agent of 1% by mass to 30% by mass (more preferably 3% by mass to 7% by mass) with respect to the inorganic fine particles. Is preferably carried out by

  The content of the external additive in the toner is preferably 0.1% by mass or more and 5.0% by mass or less, and more preferably 0.5% by mass or more and 4.0% by mass or less. The external additive may be a combination of a plurality of types of fine particles.

  When the two-component developer is prepared by mixing the toner of the present invention and the magnetic carrier, the mixing ratio is 2% by mass or more and 15% by mass or less, preferably 4% by mass or more and 13% as the toner concentration in the developer. Good results are usually obtained when the content is less than or equal to mass%. 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.

  The measurement method according to the present invention will be described below.

<Measurement of weight average particle diameter (D4) of toner>
The weight average particle diameter (D4) of the toner is a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube, and measurement condition setting. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for measurement data analysis, the measurement data is analyzed with 25,000 effective measurement channels. Calculated.

  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, dedicated software was set up as follows.

  In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. 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 flash 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, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.

  (2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion exchange water is added.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and a predetermined amount is placed in a water tank of an ultrasonic disperser “Ultrasonic Disposition System Tetora 150” (manufactured by Nikka Machine Bios) with an electric output of 120 W Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this 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%. . The 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) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measurement of molecular weight of resin by GPC>
The molecular weight distribution by gel permeation chromatography (GPC) can be measured under the following conditions.

Resin prepared by stabilizing the column in a heat chamber at 40 ° C., and flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min to the column at this temperature to prepare a sample concentration of 0.05 to 0.6% by mass 50 to 200 μl of THF sample solution is injected and measured. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns in order to accurately measure a molecular weight region of 1 × 10 ³ or more and 2 × 10 ⁶ or less. As a combination of such commercially available polystyrene gel columns, for example, a combination of μ-styragel 500, 103, 104, 105 manufactured by Waters, or shodex KA-801, 802, 803, 804, 805, 806 manufactured by Showa Denko KK , 807 are preferred.

In measuring the molecular weight of the resin, which is a sample, the molecular weight distribution of the resin is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ are used. It is appropriate to use at least about 10 standard polystyrene samples.

<Measuring method of toner particles and toner Ca, Da, Ca / 2>
The average circularity (Ca) and the equivalent circle number average diameter (Da) of the toner particles and the toner are measured and analyzed under calibration conditions by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation). taking measurement. 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 dispersant with ion-exchanged water about 3 times by mass is added. 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. A predetermined amount of ion-exchanged water is placed in the water tank, and about 2 ml of the contamination N is added to the water tank.

  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 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%, and the analysis particle diameter is limited to a circle equivalent diameter of 1.99 μm or more and less than 39.69 μm. The toner particles and the circle equivalent number average diameter (Da) of the toner are obtained.

  Prior to the start of measurement, standard latex particles (for example, “RESEARCHANDTESTPARTICLESLATEX Microsphere Suspensions 5200A” manufactured by Duke Scientific) are used for automatic focus adjustment with standard latex particles (diluted with ion-exchanged water). It is preferable to adjust the focus.

  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. The measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.99 μm or more and less than 39.69 μm.

  The circularity at each equivalent circle diameter was determined by dividing the equivalent circle diameter of 1.99 μm or more to 39.69 μm at intervals of about 0.5 μm. The circularity in the range of about 0.5 μm where the particle diameter of the circle-equivalent number average diameter (Da) is entered is determined as the average circularity (Ca). Further, a circularity in the range of about 0.5 μm where a particle size half of Da is contained is determined as Ca / 2.

<Measurement method of THF-insoluble content of toner particles>
The THF-insoluble content of the resin component in the toner is measured as follows.

  About 1.0 g of toner is weighed (W1 g), put in a pre-weighed cylindrical filter paper (for example, trade name No. 86R (size 28 × 100 mm), manufactured by Advantech Toyo Co., Ltd.), and set in a Soxhlet extractor. Then, extraction is performed for 16 hours using 200 ml of tetrahydrofuran (THF) as a solvent. At this time, extraction is performed at a reflux rate such that the solvent extraction cycle is about once every 5 minutes. After the extraction is completed, the cylindrical filter paper is taken out and air-dried, and then vacuum-dried at 40 ° C. for 8 hours. The mass of the cylindrical filter paper including the extraction residue is weighed, and the mass of the extraction residue is subtracted from the mass of the cylindrical filter paper ( W2g) is calculated.

And a THF insoluble content can be calculated | required by subtracting content (W3g) of components other than a resin component like following formula (1).
THF insoluble matter (mass%) = {(W2-W3) / (W1-W3)} × 100 (1)

  Content of components other than a resin component can be measured by a well-known analysis means. When the analysis is difficult, the content of components other than the resin component (incineration residual ash content (W3′g)) in the toner is estimated as follows, and the THF-insoluble content is obtained by subtracting the content. be able to.

The incineration residual ash content in the toner is obtained by the following procedure. About 2 g of toner is weighed (Wag) into a 30 ml magnetic crucible weighed in advance. Place the crucible in an electric furnace, heat at about 900 ° C for about 3 hours, let it cool in the electric furnace, let it cool in a desiccator at room temperature for more than 1 hour, weigh the mass of the crucible containing the incineration residual ash, and crucible The incineration residual ash content (Wbg) is calculated by subtracting the mass of. And the mass (W3'g) of the incineration residual ash content in sample W1g is computed by following formula (2).
W3 ′ = W1 × (Wb / Wa) (2)

In this case, the THF-insoluble matter is obtained by the following formula (3).
THF-insoluble matter (mass%) = {(W2-W3 ′) / (W1-W3 ′)} × 100 (3)

<Measurement method of toner outflow start temperature>
The toner outflow start temperature is measured using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the apparatus. 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 outflow start point by the “temperature raising method” described in the manual attached to the “flow characteristic evaluation apparatus flow tester CFT-500D” is used (a schematic diagram of the flow curve is shown in FIG. 3).

  As a measurement sample, about 1.0 g of toner is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising 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): 9.81 × 10 ⁵ Pa (10.0 kgf)
Preheating time: 300 seconds Orifice hole diameter: 1.0 mm
Orifice length: 1.0 mm

<Measurement of Vickers hardness>
The Vickers hardness in the present invention can be measured using, for example, Shimadzu Corporation, a dynamic micro hardness tester DVH-200, and was measured under a condition of holding a load of 0.4903 N for 30 seconds.

<Measurement of surface roughness>
The surface roughness (Ra) was measured with a laser focus displacement meter LF8100 (manufactured by Keyence Corporation) that can be measured in a non-contact manner. It measured using surface shape measurement software Tres-ValleLite (made by Mitani Corp.), measured several times each shifting the measurement point at random, and calculated | required from the average value. At this time, the measurement was performed with the reference length set to 8 mm and the cut-off value set to 0.8 mm. The reference length L is extracted from the roughness curve in the direction of the center line, the center line of the extracted portion is the X axis, the direction of the vertical magnification is the Z axis, and the roughness curve is expressed by Z = f (x). Is determined by the following formula.
Ra = (1 / L) · ∫│f (x) │dx

  Hereinafter, the present invention will be described more specifically with reference to specific production examples and examples. However, the present invention is not limited to these examples.

<Resin A production example (hybrid resin)>
As a vinyl polymer, 2.9 mol of styrene, 0.91 mol of 2-ethylhexyl acrylate, 0.15 mol of fumaric acid, 0.03 mol of α-methylstyrene dimer, and 0.05 mol of dicumyl peroxide were put into a dropping funnel. . In addition, 7.0 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane; 0 mol, 3.0 mol of terephthalic acid, 0.9 mol of trimellitic anhydride, 3.0 mol of fumaric acid and 0.8 g of tin hexanoate are placed in a glass 4-liter four-necked flask, a thermometer, a stir bar, a condenser and nitrogen The introduction tube was installed and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and while stirring at a temperature of 145 ° C., the monomer of the vinyl resin, the crosslinking agent and the polymerization initiator were added from the previous dropping funnel. It was dripped over 5 hours. Subsequently, the temperature was raised to 200 ° C. and reacted for 3.5 hours to obtain a hybrid resin (resin A). Table 1 shows the results of molecular weight measurement by GPC (gel permeation chromatography). In Table 1, Mw is a weight average molecular weight, Mn is a number average molecular weight, and Mp is a peak molecular weight.

<Example of resin B production (hybrid resin)>
As a vinyl polymer, 4.5 mol of styrene, 1.21 mol of 2-ethylhexyl acrylate, 0.15 mol of fumaric acid, 0.03 mol of α-methylstyrene dimer, and 0.05 mol of dicumyl peroxide were placed in a dropping funnel. . In addition, 7.0 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane; 0 mol, 3.0 mol of terephthalic acid, 3.3 mol of trimellitic anhydride, 7.0 mol of fumaric acid and 0.8 g of tin hexanoate are placed in a 4-liter 4-necked flask made of glass, thermometer, stirring rod, condenser and nitrogen The introduction tube was installed and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and while stirring at a temperature of 145 ° C., the monomer of the vinyl resin, the crosslinking agent and the polymerization initiator were added from the previous dropping funnel. It was dripped over 5 hours. Next, the temperature was raised to 200 ° C. and reacted for 4.5 hours to obtain a hybrid resin (resin B). Table 1 shows the results of molecular weight measurement by GPC (gel permeation chromatography).

[Production of Toner 1]
-Resin A 60 parts by mass-Cyan pigment (Pigment Blue 15: 3) 40 parts by mass The above formulation was melt-kneaded with a kneader mixer to prepare a cyan master batch.

Resin A 36.2 parts by mass Resin B 44.6 parts by mass Refined paraffin wax (maximum endothermic peak: 70 ° C., Mw = 450, Mn = 32)
5.0 parts by mass · Cyan masterbatch (40% by mass of colorant) 14.0 parts by mass · 0.2 parts by mass of di-tert-butylsalicylic acid aluminum compound (charge control agent) The mixture was preliminarily mixed and melt kneaded with a twin screw extrusion kneader so that the kneaded product temperature was 140 ° C. After cooling, it was roughly crushed to about 1 to 2 mm using a hammer mill. Further, a finely pulverized product was prepared to about 7 μm using a turbo mill (RS rotor / SNB liner) manufactured by Turbo Industry. Using apparatus 1, spheroidization was performed simultaneously with classification under the operating conditions shown in Table 2 to obtain cyan particles (toner particles 1). Table 3 shows toner physical properties and long run productivity.

To 100 parts by mass of the cyan particles (toner particles 1), 1.0 part by mass of anatase-type titanium oxide fine powder (BET specific surface area 80 m ² / g, isobutyltrimethoxysilane 12% by mass treatment), and oil-treated silica ( BET specific surface area 95 m ² / g, silicone oil 15 mass% treatment) 1.0 part by mass, sol-gel silica (BET specific surface area 24 m ² / g, number average particle size (D1): 110 nm) 0.7 part by mass Thus, cyan toner 1 was externally added using a Henschel mixer.

[Production of Toners 2 to 7, 10 to 16]
The toner was manufactured under the operating conditions shown in Table 2 in substantially the same manner as toner particles 1.

[Production of Toner 8]
The toner was manufactured in the same manner as the toner particles 1 with the following blending ratio.
-Resin A 60 parts by mass-Cyan pigment (Pigment Blue 15: 3) 40 parts by mass The above formulation was melt-kneaded with a kneader mixer to prepare a cyan master batch.

Resin A 68.3 parts by mass Resin B 12.5 parts by mass Refined paraffin wax (maximum endothermic peak: 70 ° C., Mw = 450, Mn = 32)
5.0 parts by mass · Cyan masterbatch (40% by mass of colorant) 14.0 parts by mass · 0.2 parts by mass of aluminum compound of di-tert-butylsalicylic acid (charge control agent)

[Production of Toner 9]
The toner was manufactured in the same manner as the toner particles 1 with the following blending ratio.
-Resin A 60 parts by mass-Cyan pigment (Pigment Blue 15: 3) 40 parts by mass The above formulation was melt-kneaded with a kneader mixer to prepare a cyan master batch.

Resin A 3.2 parts by mass Resin B 77.6 parts by mass Refined paraffin wax (maximum endothermic peak: 70 ° C., Mw = 450, Mn = 32)
5.0 parts by mass · Cyan masterbatch (40% by mass of colorant) 14.0 parts by mass · 0.2 parts by mass of aluminum compound of di-tert-butylsalicylic acid (charge control agent)

[Production of Toner 17]
The toner was manufactured in the same manner as the toner particles 10 with the following blending ratio.
-Resin A 60 parts by mass-Cyan pigment (Pigment Blue 15: 3) 40 parts by mass The above formulation was melt-kneaded with a kneader mixer to prepare a cyan master batch.

Resin A 80.8 parts by mass Refined paraffin wax (maximum endothermic peak: 70 ° C., Mw = 450, Mn = 32)
5.0 parts by mass · Cyan masterbatch (40% by mass of colorant) 14.0 parts by mass · 0.2 parts by mass of aluminum compound of di-tert-butylsalicylic acid (charge control agent)

[Production of Toner 18]
The toner was manufactured in the same manner as the toner particles 10 with the following blending ratio.
-Resin B 60 parts by mass-Cyan pigment (Pigment Blue 15: 3) 40 parts by mass The above formulation was melt-kneaded with a kneader mixer to prepare a cyan master batch.

-Resin B 80.8 parts by mass-Refined paraffin wax (maximum endothermic peak: 70 ° C, Mw = 450, Mn = 32)
5.0 parts by mass · Cyan masterbatch (40% by mass of colorant) 14.0 parts by mass · 0.2 parts by mass of aluminum compound of di-tert-butylsalicylic acid (charge control agent)

[Manufacture of carrier 1]
A carrier core 1 of Mn—Mg—Sr ferrite was used. Average particle size of 38 μm, cut to 22 μm or less by air classification. A coated carrier 1 was prepared by coating 100 parts by mass of ferrite with a silicone resin containing an amino-modified silicon coupling material.

[Production of developer]
10 parts by mass of toner 1 and 90 parts by mass of carrier 1 were mixed to obtain a two-component developer 1. Similarly, toners 2 to 18 and carrier 1 were mixed to form two-component developers 2 to 18, respectively.

[Examples 1 to 9, Comparative Examples 1 to 9]
Evaluation items and evaluation criteria are shown below. The obtained evaluation results are shown in Table 3.

<Toner dropout evaluation>
Using LBP-5900 (manufactured by Canon Inc.), the development contrast is adjusted so that the amount of toner on the paper becomes 1.0 mg / cm ² in a high-temperature and high-humidity environment (30 ° C./80%) in the single color mode. An image was formed so that fine lines existed in both the vertical and horizontal directions, and 2 to 10 dot lines were printed. The peripheral speed difference between the photosensitive member and the transfer member was adjusted to 1.5%.
A: Image with almost no voids even by magnified observation in 2 dot lines B: Image with slight voids observed by magnified observation in 2 dot lines and not visually observed C: Image voids visually observed in 2 dot lines An image in which a void is not visually observed in a 4-dot line.
D: An image in which voids are observed visually at 4 dot lines, and voids are not observed visually at 6 dot lines.

<Fixability evaluation>
First, an A4 image (printing ratio: 20%) as shown in FIG. 4 and 105 g / m ² paper were used as the recording material. An image was output while adjusting the developing bias so that the toner loading on the recording material was 1.2 mg / cm ² . The paper was passed while the temperature of the fixing belt was increased by 5 ° C. in the range of 130 to 200 ° C. The passed image was folded and opened in a cross shape by reciprocating a cylindrical roller (brass: 798 g) having a diameter of 60 mm × 40 mm in the toner image portion 5 times. Thereafter, a Sylbon paper (Dasper K3-half cut, manufactured by Ozu Sangyo Co., Ltd.) was wrapped around the section of a 22 mm × 22 mm × 47 mm square column weight (made of brass: 198 g) and rubbed 10 times. The temperature at which the toner image peeling rate was 25% or less was determined as the temperature at which there was no problem with cold offset. An image processing system (PersonalIAS) was used for the measurement of the peeling rate.

Next, A4 images (printing ratio: 15%) as shown in FIG. 5 and 64 g / m ² paper were used as the recording material. An image was output while adjusting the development bias so that the amount of toner applied on the recording material was 0.2 mg / cm ² . The paper was passed while the temperature of the fixing belt was increased by 5 ° C. in the range of 130 to 200 ° C. The fogged density measurement was performed on the passed image in an area other than the toner image portion. For the fog density measurement, a reflection densitometer (TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.) was used. It was determined that the temperature at which (maximum value of reflection density) − (minimum value of reflection density) was 0.5 or less was a temperature at which hot offset was not a problem.

The level was judged in the temperature range where there was no problem of cold offset and hot offset.
A: Excellent with a fixing range of 45 ° C. or higher.
B: 35 ° C. or more and less than 45 ° C. and a fixing range may be good.
C: There is a fixing range of 25 ° C. or more and less than 35 ° C.
D: The fixing range is only below 25 ° C.

It is a schematic diagram which shows an example of the manufacturing apparatus 1 of this invention. It is a schematic diagram which shows an example of the classification rotor of this invention. It is a schematic diagram which shows an outflow curve. It is explanatory drawing of the image used by evaluation of cold offset. It is explanatory drawing of the image used by evaluation of hot offset.

30 Main body casing 31 Cooling jacket 32 Dispersion rotor 33 Dispersion hammer 34 Liner 35 Classification rotor 36 Guide ring 37 Material input port 38 Material supply valve 39 Material supply port 40 Product discharge port 41 Product discharge valve 42 Product extraction port 43 Top plate 44 Fine powder discharge Part 45 Fine powder outlet 46 Cold air inlet 47 First space 48 Second space 49 Surface modification zone 50 Classification zone 51 Blade

Claims (4)

In a toner production method having toner particle or toner surface modification step containing at least a binder resin and a colorant,
The surface modification step is performed using a surface modification device, and the surface modification device includes at least a classification unit for continuously discharging and removing out of the device, a surface modification unit using mechanical impact force, and A guide means for partitioning a space between the classification means and the surface modification means into a first space and a second space;
1) The classification means has a plurality of blades arranged at regular intervals on the same circumference, and each blade forms a constant angle θ with respect to a straight line connecting the center of the classification rotor and the tip of the blade. Classifying means arranged in such a manner that the angle θ is 20 ° ≦ θ ≦ 65 °,
2) The circle equivalent number average diameter Da (μm) 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) of the toner particles is 4.0 ≦ Da ≦ 8.0,
3) The circularity 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) of the toner particles is 0.200 or more and 1.000 or less. The average circularity of the toner particles or toner in the range of 1.99 μm or more and less than 39.69 μm analyzed by dividing into 800 degrees is Ca, and the average circularity of the toner particles or toner in the equivalent circle diameter of half of Da is defined as Ca. A method for producing toner particles or toner, wherein Ca / 2 and Ca / 2 have the relationship of Formula A when Ca / 2 is used.
0 ≦ | Ca−Ca / 2 | ≦ 0.004 Formula A   2. The toner particle or toner manufacturing method according to claim 1, wherein a Vickers hardness Hv of a blade surface of the classification rotor is 800 ≦ Hv ≦ 5000.   3. The method for producing toner particles or toner according to claim 1, wherein the surface roughness Ra (μm) of the blades of the classification rotor is 0.2 ≦ Ra ≦ 1.5. In the measurement of the toner particles by the flow tester, the outflow start temperature in the measurement of the cylinder pressure of 9.81 × 10 ⁵ Pa and the orifice hole diameter of 1.0 mm is 77.0 ° C. or more and 88.0 ° C. or less, and the toner The method for producing toner particles or toner according to claim 1, wherein THF-insoluble matter in the particles is 5.0% by mass or more and 20.0% by mass or less.

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