JP4397038B2 - Toner for developing electrostatic image, developer, image forming method and image forming apparatus - Google Patents

Description

  The present invention relates to inorganic fine particles for electrostatic charge image developing toner, electrostatic charge image developing toner, developer, image forming method and image forming apparatus.

  In electrophotographic devices and electrostatic recording devices, toner is attached to an electrostatic latent image formed on a photoreceptor, transferred to a transfer material, and then fixed to the transfer material by heat to form a toner image. is doing. Also, full-color image formation is generally performed by using four color toners of black, yellow, magenta, and cyan. Each toner is developed, and each toner layer is superimposed on a transfer material. To obtain a full-color image.

  However, for users who are familiar with printing in general, images on full-color copiers are not yet satisfactory, and there is a demand for higher image quality that satisfies photography, high-definition, and high resolution. It is known to use a toner having a small particle size and a narrow particle size distribution to improve the image quality.

  Conventionally, an electrical or magnetic latent image has been visualized with toner. Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a polymerization method.

  In the pulverization method, a colorant, a charge control agent, an offset preventing agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle.

  Therefore, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, the particle size There is a disadvantage that the fine powder of 5 μm or less and the coarse powder of 20 μm or more must be removed by classification, resulting in a very low yield. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. The uneven dispersion of the compounding agent adversely affects the fluidity, developability, durability, image quality and the like of the toner.

  In recent years, in order to overcome these problems in the pulverization method, for example, toner particles are obtained by a suspension polymerization method (see Patent Document 1). However, although the toner particles obtained by the suspension polymerization method are spherical, there is a disadvantage that the cleaning property is inferior. In development and transfer with a low image area ratio, there is little transfer residual toner, and cleaning defects do not become a problem. However, if the image area ratio is high, such as photographic images, or if there is a paper feed failure, etc. The image-formed toner may be generated as a transfer residual toner on the photosensitive member, and if this is accumulated, the image may be soiled. In addition, the toner contaminates a charging roller for contacting and charging the photosensitive member, and the original charging ability cannot be exhibited. Also, the low temperature fixability is not sufficient, and a large amount of energy required for fixing is required, which is a problem.

  On the other hand, a method of obtaining irregular toner particles by associating resin fine particles obtained by an emulsion polymerization method is disclosed (see Patent Document 2). However, in the toner particles obtained by the emulsion polymerization method, a large amount of the surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of the toner charging is impaired. The amount distribution is widened, and the background stain of the obtained image becomes poor. In addition, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, and the like, and the original charging ability cannot be exhibited.

  On the other hand, in a fixing process using a contact heating method performed using a heating member such as a heat roller, the toner particles are required to release from the heating member (hereinafter referred to as “offset resistance”). Here, the offset resistance can be improved by the presence of a release agent on the toner particle surface. On the other hand, Patent Documents 3 and 4 disclose a method for improving offset resistance not only by containing resin fine particles in toner particles but also by unevenly distributing the resin fine particles on the surface of the toner particles. Yes. However, there is a problem that the lower limit fixing temperature is increased and the low temperature fixing property, that is, the energy saving fixing property is not sufficient.

  In addition, the following problems occur in the method of obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method. That is, when the release agent fine particles are associated with each other in order to improve the offset resistance, the release agent fine particles are taken into the toner particles, and as a result, the offset resistance can be sufficiently improved. Can not. Resin fine particles, release agent fine particles, colorant fine particles, etc. are randomly fused to constitute toner particles, so there is a variation in composition (content ratio of constituent components) and molecular weight of constituent resins among the obtained toner particles. As a result, the toner particles have different surface characteristics, and a stable image cannot be formed over a long period of time. Further, in a low-temperature fixing system that requires low-temperature fixing, there is a problem that fixing temperature range cannot be secured because fixing inhibition occurs due to resin fine particles unevenly distributed on the toner surface.

  On the other hand, a dissolution suspension method is known as a toner production method. In this method, there is a merit that a polyester resin that can be fixed at low temperature can be used, but in this method, since the high molecular weight component is added in the process of dissolving or dispersing the low temperature fixing resin and the colorant in the solvent, the liquid viscosity As a result, productivity problems will occur. Furthermore, in this dissolution suspension method, the toner surface shape is spherical and the surface is made uneven to improve the cleaning of the toner (see Patent Document 5). When a wax is added to the composition as a mold, the uniform dispersibility and dispersion state (surface presence) of the wax and the uniform dispersibility of the pigment are reduced as compared with the kneaded and pulverized toner. Since wax is particleized in a solvent, there are restrictions in terms of viscosity, so the degree of freedom in polymer design of the binder is reduced, and it is difficult to ensure releasability.

In addition, the suspension polymerization method, the emulsion polymerization method, and the dissolution suspension method generally use a styrene / acrylic resin, and the polyester resin has difficulty in particle formation, and the particle size, particle size distribution, and shape control. It was difficult. In addition, there was a limit to fixability when aiming at lower temperature fixing.
On the other hand, it is also known to use polyester modified with a urea bond for the purpose of heat-resistant storage and low-temperature fixing (see Patent Document 6). The problem was not sufficient in terms of strict environmental charge stability.

  In the field of electrophotography, high image quality has been studied from various angles, and among them, the recognition that toner diameter reduction and spheroidization are extremely effective is increasing. However, as the diameter of the toner is reduced, the transferability and the fixing property are lowered, and a tendency to become a poor image is observed. On the other hand, it is known that transferability is improved by making the toner spherical (see Patent Document 7). Under such circumstances, further speeding up of image formation is desired in the field of color copiers and color printers.

  The “tandem method” is effective for speeding up (see, for example, Patent Document 8). The “tandem method” is a method of obtaining a full-color image on a transfer sheet by sequentially superimposing and transferring an image formed by an image forming unit onto a single transfer sheet conveyed to a transfer belt. A tandem color image forming apparatus has a variety of transfer papers that can be used, has high quality of a full color image, and has excellent characteristics that a full color image can be obtained at a high speed. In particular, the characteristic that a full color image can be obtained at a high speed is a characteristic that is not found in other color image forming apparatuses. On the other hand, attempts have been made to achieve high speed while improving image quality using spherical toner. However, in order to cope with higher speeds, quick fixability is required, but a toner having both good fixability and low temperature fixability with a spherical toner has not been realized so far.

  Also, high temperature and high humidity, low temperature and low humidity environment during storage and transportation after toner production are harsh conditions for the toner, and the toner does not aggregate even after storage in the environment, charging characteristics, fluidity, transferability, fixing There has been a demand for a toner having no deterioration in properties or an extremely low storage stability, but no effective means has been found so far particularly for spherical toners.

On the other hand, in general, in terms of heat efficiency, simplicity of a fixing mechanism, and manufacturing cost of a fixing member, a fixing member such as a fixing roller or a fixing belt is directly pressed against an unfixed image to heat the toner to melt the paper. A method of fixing to an image carrier such as a hot pressure fixing method is preferably employed.
In particular, in recent years, a fixing mechanism using a belt-shaped heat transfer medium (hereinafter referred to as belt fixing) has been widely used for the purpose of energy saving and apparatus miniaturization.

  In such belt fixing, the contact time with the surface of the toner can be lengthened especially during fixing, and fixing at a lower temperature is possible. On the other hand, melting of the toner is further promoted so that the toner adheres to the surface of the belt. A so-called offset phenomenon is likely to occur. In particular, in color toners, an appropriate gloss is required in order to provide sufficient transparency and a high quality feeling, and the molecular weight of the binder resin is sharpened, and sharp melt characteristics are required. Thereby, melting of the toner is promoted at the time of fixing, and an offset phenomenon is likely to occur.

  As the fixing belt, an endless or endless belt made of heat-resistant resin is often used, and a problem associated with this is improvement of mechanical durability. In addition, toner external additives and other components may adhere to the belt-shaped heat transfer medium, resulting in belt wear and scratches, hot offset, and even the belt itself tearing. .

In order to solve the above problems, various proposals have been made so far in terms of a fixing mechanism and an electrophotographic toner.
On the other hand, as a fixing mechanism, several studies have been tried including the announcement in Non-Patent Document 1.
However, such examination and proposal of the fixing mechanism alone cannot be a fundamental solution to the above problem due to the same reason as described above.

  It is also known to add a fixing release material such as wax to the toner to prevent offset during fixing. However, if the characteristics of the wax and the state of dispersion in the toner are inappropriate, development is possible. With long-term use in the unit, phenomena such as wax detachment from the toner surface or exudation occur, and in the case of two-component developers, the carrier surface is contaminated. In the case of a one-component developer, the toner is often fused to a developing roller or a blade for thinning the toner, thereby hindering uniform development of the toner. Therefore, from the viewpoint of development, it is preferable that the addition of wax is as small as possible.

  Toners obtained by conventional kneading and pulverization methods are generally irregular in shape, have a broad particle size distribution, low fluidity, low transferability, high fixing energy, and charging between toner particles. There was a problem that the amount was not uniform and the charging stability was low. Particularly in the case of fixing, a kneading and pulverizing type toner produced by a pulverization method has a releasing effect because cracks due to pulverization occur at the interface of the releasing agent (wax), so that a large amount of the releasing agent exists on the surface of the toner. On the other hand, it tends to stick out to the carrier, the photoconductor and the blade, and the performance is unsatisfactory.

  On the other hand, attempts have been made to control the molecular weight distribution of THF (tetrahydrofuran) solubles or the ratio of insolubles as means for controlling fixability (see, for example, Patent Documents 9 to 11). For toners containing a large amount of toner, it is sufficient to control the amount of THF soluble matter (fixed upper and lower limit widths (hot offset property, cold offset property, wrapping property, friction strength after fixing, gloss, or trace offset). It was not possible to satisfy toner stains on paper, etc. Further, a development system with little carrier contamination by a small amount of toner spent component could not be obtained.

Japanese Patent Laid-Open No. 9-43909 Japanese Patent No. 2537503 JP 2000-292773 A JP 2000-292978 A (Japanese Patent Laid-Open No. 9-15903) Japanese Patent Laid-Open No. 11-133667 JP 9-258474 A JP-A-5-341617 Japanese Patent No. 3413024 Japanese Patent No. 3397661 JP 2002-351143 A Japan Hardcopy '94 (Electronic Society of Japan sponsored by 1994.6.23-24) “Examination of on-demand fixing technology” (A-11)

The object of the present invention is as follows.
1) Corresponding to a low-temperature fixing system, having a sufficient fixing temperature range, good offset resistance and wrapping property, sufficient friction peeling strength after fixing, sufficient gloss, and several To provide a fixing device and a toner, a developer, an image forming apparatus, and an image forming method that do not contaminate an image even after printing 10,000 sheets.
2) The charging ability of the toner is sufficiently high, the charging start-up property is good, and even if tens of thousands of images are output, there is little toner spent on the carrier, etc., high chargeability and fluidity can be maintained, and the background stain ( To provide an image forming apparatus and an image forming method capable of obtaining image quality with sufficient image density with less fogging.
3) To provide an image forming apparatus and an image forming method that form an image with excellent background stability and low background stain (fogging) in a high temperature and high humidity and low temperature and low humidity environment, and in which toner is less scattered in the apparatus.
4) To provide an image forming apparatus and an image forming method which are excellent in heat-resistant storage, humidity-resistant storage and stress-resistant storage, and have high durability and low maintenance as an image forming system.

As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have found that in a toner containing at least a colorant and a resin, the HFIP (hexafluoroisopropanol) -soluble component of the toner has the following relationship: 2000 ≦ Mn ≦ 7000, 1.5 ≦ Mw / Mn ≦ 10
(Where Mn is the number average molecular weight, Mw is the weight average molecular weight)
By using a toner for developing electrostatic images, it is compatible with a low-temperature fixing system, has a sufficient fixing temperature range, good offset resistance and wrapping property, and sufficient friction peeling strength after fixing. In addition, the present inventors have found that a toner, a developer, an image forming apparatus, and an image forming method that have sufficient gloss and do not contaminate the fixing device and the image can be provided.

The mechanism is currently being elucidated, but the following were inferred from some analysis data.
By using HFIP (hexafluoroisopropanol), which can sufficiently dissolve even highly crosslinked resin components, accurate molecular weight distribution evaluation to highly crosslinked components (high molecular weight components) that could not be evaluated with conventional solvents such as THF (tetrahydrofuran) is possible. It was. By adjusting the toner formulation and manufacturing process based on this evaluation method, it is compatible with low-temperature fixing systems, has a sufficient fixing temperature range, good offset resistance and wrapping property, and friction peeling strength after fixing It has been found that a toner, a developer, an image forming apparatus, and an image forming method can be provided which have sufficient gloss, sufficient gloss, and do not contaminate the fixing device and the image even after printing tens of thousands of sheets.

When Mn of the HFIP-soluble component is less than 2000, the hot offset property, the paper roll winding, and the carrier contamination property are not sufficient, which is not preferable. Moreover, when Mn exceeds 7000, it is not preferable from low temperature fixability and sufficient glossiness. Further, when Mw / Mn is less than 1.5, the molecular weight distribution becomes too narrow, and the fixing temperature range cannot be sufficiently obtained, which is not preferable. Further, when Mw / Mn exceeds 10, the molecular weight distribution becomes too wide, and it is not preferable because both low-temperature fixability and sufficient glossiness cannot be achieved.

Toners satisfying the above relationship are increased in molecular weight (Mn, Mw) of the low molecular weight polyester before the reaction, and the toner is formed by extending the distribution of the high cross-linking component and the low molecular weight component so as to become a sharper toner. It is possible to have a distribution. In order to sufficiently extend the reaction of the unreacted monomer or prepolymer, it is effective to give a sufficient aging time.
Mn is preferably 2400 or more and 12000 or less, and more preferably 5000 or more and 10,000 or less.
Further, Mw is preferably 7000 or more and 30000 or less, and more preferably 9000 or more and 20000 or less.
As described above, by increasing the molecular weight of the low molecular weight polyester before the reaction and giving sufficient aging time, the resulting toner is shifted to a higher molecular weight side compared to the conventional toner, thereby Particularly, contamination of the fixing device and the image after printing tens of thousands of sheets can be prevented.

  Further, since the toner is a toner for developing an electrostatic image having a molecular weight component of 100,000 or more of 0.5% to 18%, the frictional peel strength after fixing is sufficient, and a further minute offset amount is obtained. Thus, the fixing device and the fixing system with less image contamination can be obtained even after printing tens of thousands of sheets.

  Further, the toner is an electrostatic charge image developing toner comprising particles formed by dispersing an oil droplet of an organic solvent in which a toner composition containing a prepolymer is dissolved in an aqueous medium, and extending and / or crosslinking reaction. By being present, it is more preferable that the stretch crosslinking component can satisfy sufficient low-temperature fixability, hot offset property, and sufficient glossiness.

The toner is more preferably an electrostatic charge image developing toner containing at least a polyester resin in terms of gloss, fixability and chargeability control.
Further, it is more preferable that the toner is an electrostatic charge image developing toner containing at least a modified polyester resin, so that the low-temperature fixability and the frictional peel strength after fixing can be sufficiently maintained.

In addition, since the toner is a toner for developing an electrostatic charge image having an average circular diameter E of 0.90 to 0.99, the low temperature can be reduced in a short time from the viewpoint of thermal conductivity. Fixability can be secured, which is more preferable.
In addition, since the toner is an electrostatic charge image developing toner having a circularity SF-1 value of 100 to 150 and a circularity SF-2 value of 100 to 140, the thermal conductivity can be further improved for a short time. It is more preferable because it can ensure low-temperature fixability in

The toner is an electrostatic charge image developing toner having a volume average particle diameter Dv of 2 to 7 μm and a ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn of 1.25 or less. This ensures the toner's chargeability, transferability, fixability, and image quality, while ensuring the uniformity of the thermal conductivity due to the uniformity of the toner particles, the uniformity of the fixing temperature range, and the fixing after printing tens of thousands of sheets This is more preferable because it can ensure the stability.
In addition, by using a two-component developer containing a carrier composed of the toner and magnetic particles, it is possible to ensure sufficient start-up property by frictional charging in a short time while ensuring low-temperature fixability, It is more preferable that a sufficiently sharp charge amount distribution can be maintained without destroying the toner shape.

  Also, a recording medium comprising the toner, a heating element, one or more heat transfer media heated by the heating element, and a pressure member that presses the recording medium against one of the heat transfer media In the image forming method using the fixing method in which the toner image is heated and fixed, at least one of the heat transfer media is a belt-like heat transfer medium, and a certain amount of oil is applied or not applied on the belt. An image forming apparatus including a toner fixing method to be used is more preferable because low-temperature fixability and image stability can be secured.

Thus, according to the present invention, the following (1) to (14) are provided.
(1) In a toner comprising particles formed by an extension reaction and / or a crosslinking reaction in which oil droplets of an organic solvent in which a toner composition containing at least a colorant, a resin, and a prepolymer is dissolved are dispersed in an aqueous medium . An electrostatic charge image developing toner, wherein the HFIP (hexafluoroisopropanol) -soluble component of the toner has the following relationship:
2000 ≦ Mn ≦ 7000, 1.5 ≦ Mw / Mn ≦ 10
(Where Mn is the number average molecular weight, Mw is the weight average molecular weight)
(2) The toner for developing an electrostatic charge image according to (1) above, wherein the HFIP (hexafluoroisopropanol) -soluble component of the toner has the following relationship.
3000 ≦ Mn ≦ 7000, 1.5 ≦ Mw / Mn ≦ 10
(Where Mn is the number average molecular weight, Mw is the weight average molecular weight)
(3) The electrostatic image development of (1) and (2) above, wherein the molecular weight component of 100,000 or more in the HFIP (hexafluoroisopropanol) -soluble component of the toner is 0.5% to 18%. Toner.
( 4 ) The electrostatic image developing toner according to any one of (1) to ( 3 ) above, which contains at least a polyester resin.
( 5 ) The electrostatic image developing toner according to any one of (1) to ( 4 ) above, which contains at least a modified polyester resin.
( 6 ) The toner for developing an electrostatic charge image according to (1) to ( 5 ) above, wherein the toner particles have an average circularity E of 0.90 to 0.99.
( 7 ) The toner for developing an electrostatic charge image according to the above (1) to ( 6 ), wherein the toner has a circularity SF-1 value of 101 to 150 and a circularity SF-2 value of 101 to 140. .
( 8 ) The volume average particle diameter Dv of the toner particles is 2 to 7 μm, and the ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn is 1.25 or less. ) To ( 7 ) toners for developing electrostatic images.
( 9 ) A two-component developer comprising at least the toner for developing an electrostatic charge image of (1) to ( 8 ) and a carrier made of magnetic particles.
( 10 ) The electrostatic image on the electrostatic image bearing member is developed with a developer for developing an electrostatic image to form a toner image, and a transfer means is brought into contact with the surface of the electrostatic image bearing member via a transfer material. An image forming apparatus for electrostatically transferring an image onto a transfer material, wherein the developer is the two-component developer of ( 9 ).
( 11 ) A process cartridge which constitutes a part of the image forming apparatus and is detachable, and at least the electrostatic image carrier and the developing means are integrally supported inside, and the developing means A process cartridge comprising the toner for electrophotography according to any one of (1) to ( 8 ).
( 12 ) An image forming method comprising forming an image using the image forming apparatus according to ( 10 ).
( 13 ) Using the toner of the above (1) to ( 8 ), the heating medium, one or more heat transfer media heated by the heating element, and the recording medium is pressed against one of the heat transfer media In an image forming method using a fixing method in which a toner image on a recording medium is heated and fixed with a pressure member, at least one of the heat transfer media is a belt-like heat transfer medium, and a certain amount of the heat transfer medium is placed on the belt. An image forming method including a toner fixing method used with or without applying oil.
( 14 ) The image forming method according to ( 13 ), wherein the belt-like heat transfer medium has a belt thickness of 10 μm to 200 μm.

With the above configuration, the present invention has the following effects.
1) Corresponding to a low-temperature fixing system, having a sufficient fixing temperature range, good offset resistance and wrapping property, sufficient friction peeling strength after fixing, sufficient gloss, and several It is possible to provide a fixing device and a toner, a developer, an image forming apparatus, and an image forming method that do not contaminate an image even after printing 10,000 sheets.
2) The charging ability of the toner is sufficiently high, the charging start-up property is good, and even if tens of thousands of images are output, there is little toner spent on the carrier, etc., high chargeability and fluidity can be maintained, and the background stain ( It is possible to provide an image forming apparatus and an image forming method capable of obtaining image quality with a sufficient image density with less fogging.
3) It is possible to provide an image forming apparatus and an image forming method that form an image with excellent background stability and low background contamination (fogging) in a high-temperature, high-humidity, low-temperature, low-humidity environment, and that cause less toner scattering in the apparatus.
4) It is possible to provide an image forming apparatus and an image forming method that are excellent in heat-resistant storage, humidity-resistant storage, and stress-resistant storage, and have high durability and low maintenance as an image forming system.

  Hereinafter, the present invention will be described in detail. Here, the toner, the manufacturing method and material of the developer, and the overall system relating to the electrophotographic process that are used in the present invention can be used as long as the conditions are satisfied.

(HFIP dissolved GPC)
In the present invention, the molecular weight distribution of the toner is measured by GPC (gel permeation chromatography) under the following conditions.
The measurement conditions for HFIP dissolution GPC of the toner are as follows.
1) Equipment: Waters type 2695
2) Solvent: HFIP + 10 mM sodium trifluoroacetate 3) Column; Shodex HFIP-LG + HFIP-806M × 2 4) Temperature: 40 ° C.
5) Flow rate: 0.8 ml / min
6) Sample: Measurement after filtration in a 0.45 μm filter after dissolution in a solvent. Concentration 2 mg / ml, injection volume 500 μl
7) Detector; RI detector (RI-8011)

The molecular weight distribution is calculated using the molecular weight calibration curve prepared with the monodisperse polymethylmethacrylate standard sample when the molecular weight of the sample is calculated under the above conditions. In addition, it is more preferable to contain 5-20 mM sodium trifluoroacetate as a salt in the solvent in order to improve the dissolution / separation property. If it is less than 5 mM, the effect is not exhibited, which is not preferable. Moreover, when it contains exceeding 20 mM, it is unpreferable at a column damage or a soluble point.
The molecular weight distribution obtained here is preferably 2000 ≦ Mn ≦ 7000, 1.5 ≦ Mw / Mn ≦ 10 (Mn is the number average molecular weight, and Mw is the weight average molecular weight). More preferably, 2000 ≦ Mn ≦ 7000, 1.5 ≦ Mw / Mn ≦ 10, and more preferably 3500 ≦ Mn ≦ 6500, 4 ≦ Mw / Mn ≦ 9. Further, it is sufficient that the molecular weight component of 100,000 or more is 0.5% to 18%, preferably 1% to 10%, more preferably 1% to 5%. The amount of offset can be reduced, and a fixing device and a fixing system with less image contamination even after printing tens of thousands of sheets are more preferable.

(Average circularity E)
It is important that the toner in the present invention has a specific shape and shape distribution, and the average circularity E is preferably 0.90 to 0.99. The above range is more preferable from the viewpoint of thermal conductivity, because low temperature fixability in a short time can be secured. A toner having an irregular shape of 0.90 or less and too far from a spherical shape cannot provide satisfactory transferability and a high-quality image free from dust. On the other hand, if it exceeds 0.99, it becomes a perfect sphere, which is not preferable because of poor cleaning performance. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera.

  The average circularity E is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle. In order for the toner to form a high-definition image having a reproducibility with an appropriate density, the average circularity E is more preferably 0.94 to 0.99. If attention is paid to the ease of cleaning, it is more preferable that the average circularity E is 0.94 to 0.99 and the number of particles having a circularity of less than 0.94 is 10% or less.

  The apparatus can measure the average circularity E with a flow particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance. About 0.1 to 0.5 g. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

(Circularity SF-1, SF-2)
The shape factors SF-1 and SF-2, which are the circularity used in the present invention, are obtained by randomly sampling 300 SEM images of toner obtained by measurement with a FE-SEM (S-4200) manufactured by Hitachi, Ltd. The image information was introduced into an image analysis apparatus (Luzex AP) manufactured by Nireco through an interface and analyzed, and the values obtained from the following equations were defined as SF-1 and SF-2. The values of SF-1 and SF-2 are preferably values obtained by Luzex, but are not particularly limited to the FE-SEM device and the image analysis device as long as similar analysis results can be obtained.
SF-1 = (L ² / A) × (π / 4) × 100
SF-2 = (P ² / A) × (1 / 4π) × 100
(Here, L: absolute maximum length of toner, A: projected area of toner, P: maximum peripheral length of toner)
In the case of a true sphere, all become 100, and from a spherical shape to an indefinite shape as the value becomes larger than 100. In particular, SF-1 represents the shape of the entire toner (ellipse, sphere, etc.), and SF-2 is a shape factor indicating the degree of surface irregularities.
The SF-1 value is 101 to 150, more preferably 101 to 130.
The SF-2 value is 101 to 140, more preferably 101 to 128.

(Volume average particle diameter, Dv / Dn (volume average particle diameter / number average particle diameter ratio))
The volume average particle diameter (Dv) of the toner of the present invention is more preferably 2 to 7 μm, and the ratio (Dv / Dn) to the number average particle diameter (Dn) is 1.25 or less, preferably 1.10 to 1.25. The dry toner is excellent in heat-resistant storage stability, low-temperature fixability, and hot offset resistance, and particularly excellent in image gloss when used in a full-color copying machine. Even if the toner balance is extended, the fluctuation of the toner particle diameter in the developer is reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Further, when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner filming on the developing roller and the toner layer are made thin. There was no fusion of toner to a member such as a blade, and good and stable developability and images were obtained even during long-term use (stirring) of the developing device.

In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced, or the one-component development When used as an agent, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.
Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention.

On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.

(Modified polyester resin)
In the present invention, the following modified polyester resins can be used as the polyester resin. For example, a polyester prepolymer having an isocyanate group can be used. Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group further reacted with a polyisocyanate (3). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts.

  Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid).

  Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam, etc. And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate.

  The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the modified polyester after crosslinking and / or elongation becomes low, and the hot offset resistance deteriorates.
(Crosslinking agent and extender)
In the present invention, amines can be used as a crosslinking agent and / or an extender. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like.

  Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, the molecular weight of the modified polyester after completion of the reaction can be adjusted by terminating the crosslinking and / or elongation with a terminator if necessary. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

(Unmodified polyester)
In the present invention, it is important not only to use the modified polyester (A) alone, but also to contain the unmodified polyester (C) as a toner binder component together with the (A). By using (C) in combination, the low-temperature fixability and the glossiness when used in a full-color apparatus are improved. Examples of (C) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (A), and preferred ones are also the same as (A). (C) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with, for example, a urethane bond.

  It is preferable that (A) and (C) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (A) and (C) preferably have similar compositions. When (A) is contained, the weight ratio of (A) to (C) is usually 5/95 to 75/25, preferably 10/90 to 25/75, more preferably 12/88 to 25/75, Especially preferably, it is 12 / 88-22 / 78. If the weight ratio of (A) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (C) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (C) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (C) is usually from 0.5 to 40, preferably from 5 to 35. By having an acid value, it tends to be negatively charged. Further, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.

In the present invention, the glass transition point (Tg) of the toner is usually 40 to 70 ° C., preferably 45 to 55 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the crosslinked and / or elongated polyester resin, the toner for developing an electrostatic charge image of the present invention exhibits good storage stability even when the glass transition point is low, as compared with known polyester-based toners. As the storage elastic modulus of the toner, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10000 dyne / cm ² is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates.

  As the viscosity of the toner, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or less, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or more. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

(Coloring agent)
As the colorant of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide , Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithobon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

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

  This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet cake of a coloring agent, is a method of mixing and kneading an aqueous paste containing water of a coloring agent together with a resin and an organic solvent, transferring the coloring agent to the resin side, and removing moisture and organic solvent components. Can be used as it is, so that it is not necessary to dry and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
Further, a wax may be contained together with the toner binder and the colorant. Known waxes can be used in the present invention, such as polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbons (paraffin wax, sasol wax, etc.); carbonyl group-containing waxes, etc. Can be mentioned.

  Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18 -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.

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

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.

  Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

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

(External additive)
As an external additive for assisting fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles and hydrophobic treated inorganic fine particles can be used in combination with oxide fine particles. More preferably, the hydrophobic treated primary particles contain at least one kind of inorganic fine particles having an average particle size of 1 to 100 nm, more preferably 5 to 70 nm. Further, it is more preferable that the hydrophobized primary particles contain at least one kind of inorganic fine particles having an average particle diameter of 20 nm or less and at least one kind of inorganic fine particles of 30 nm or more. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

  Any of them can be used as long as the conditions are satisfied. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), fluoropolymers, and the like may be contained.

  Particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H 1303 (above Hoechst), and R972, R974, RX200, RY200, R202, R805, and R812 (above Nippon Aerosil). Further, as titania fine particles, P-25 (Nippon Aerosil), STT-30, STT-65C-S (above Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT-600B MT-150A (taker above). Particularly, the hydrophobized titanium oxide fine particles include T-805 (Nippon Aerosil), STT-30A, STT-65S-S (above Titanium Industry), TAF-500T, TAF-1500T (above Fuji Titanium Industry), MT -100S, MT-100T (above Taka), IT-S (Ishihara Sangyo), etc.

  In order to obtain hydrophobized oxide fine particles, silica fine particles, titania fine particles, and alumina fine particles, hydrophilic fine particles are treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, and amino-modified silicone. Oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and the like can be used.

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, quartz sand, clay, mica, and silica ash. Examples thereof include stone, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Of these, silica and titanium dioxide are particularly preferred.

  The addition amount can be 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the toner. The average particle size of the primary particles of the inorganic fine particles is 100 nm or less, preferably 3 nm or more and 70 nm or less. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor is undesirably damaged.

  Other polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, and thermosetting resin Examples include polymer particles.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

(Resin fine particles)
In the present invention, resin fine particles can be contained as required. The resin fine particles used have a glass transition point (Tg) of 40 to 100 ° C., a weight average molecular weight of 9000 to 200,000 is more preferable, and as described above, the glass transition point (Tg) is less than 40 ° C., and When the weight average molecular weight is less than 9,000, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the glass transition point (Tg) is 100 ° C. or higher and / or the weight average molecular weight is 200,000 or higher, the resin fine particles inhibit the adhesiveness to the fixing paper, and the minimum fixing temperature increases.

More preferably, the residual ratio with respect to the toner particles is 0.5 to 5.0 wt%. When the residual ratio is less than 0.5 wt%, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the residual amount is 5.0 wt% or more, the resin fine particles are not present. The exudation of the wax is obstructed, the effect of releasing the wax is not obtained, and the occurrence of offset is observed.
The residual rate of the resin fine particles can be measured by analyzing a substance caused by the resin fine particles, not by the toner particles, using a pyrolysis gas chromatograph mass spectrometer, and calculating from the peak area. The detector is preferably a mass spectrometer, but is not particularly limited.

  The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimides Examples thereof include resins, silicon-based resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.

  The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

(Prepolymer production method)
The toner binder can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group.

The dry toner of the present invention can be produced by the following method, but is not limited thereto.
(Toner production method in aqueous medium)
Resin fine particles are added in advance to the aqueous phase used in the present invention. The water used for the aqueous phase may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The toner particles are obtained by forming a dispersion composed of a polyester prepolymer (A) having an isocyanate group dissolved or dispersed in an organic solvent in an aqueous phase and reacting with amines (B). As a method for stably forming a dispersion comprising a polyester prepolymer (A) in an aqueous phase, a composition of a toner raw material comprising a polyester prepolymer (A) dissolved or dispersed in an organic solvent in an aqueous phase is added. And a method of dispersing by shearing force. Polyester prepolymer (A) dissolved or dispersed in an organic solvent and other toner composition (hereinafter referred to as toner raw material), colorant masterbatch, release agent, charge control agent, unmodified The polyester resin or the like may be mixed when forming the dispersion in the aqueous phase, but after the toner raw material is mixed in advance and dissolved or dispersed in an organic solvent, the mixture is added to the aqueous phase and dispersed. Is more preferable. In the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in the aqueous phase. It may be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the polyester prepolymer (A) has a low viscosity and is easy to disperse.

  The amount of the aqueous phase used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts of the toner composition containing the polyester prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino acids as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in the aqueous phase Amine salt types such as alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, and quaternary ammonium such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride Nonionic surfactants such as salt-type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N- Amphoteric surfactants such as ammonium betaine.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11). ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid And perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N mono ( 2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned,
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C 6 -C 10) sulfonamidopropyltrimethylammonium salt which right the fluoroalkyl group, Benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, trade names include Surflon S-21 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries Co., Ltd.) ), Megafuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-32 (Tochem Products Co., Ltd.), Footgent F 1300 (Neos Co., Ltd.), and the like.
Moreover, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, etc. can be used as an inorganic compound dispersant which is hardly soluble in water.

  Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and carboxyl groups For example, pinyl acetate, pinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine Homopolymers or copolymers such as those having a nitrogen atom or its heterocyclic ring, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  In addition, when an acid such as calcium phosphate salt or an alkali-soluble one is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as washing with water after dissolving the calcium phosphate salt with an acid such as hydrochloric acid. To do. It can also be removed by operations such as enzymatic degradation. When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

In order to remove the organic solvent from the obtained emulsified dispersion, a method can be employed in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely evaporated and removed. Alternatively, it is also possible to spray the emulsified dispersion in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and to evaporate and remove the aqueous dispersant together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used are generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.
Further, as a method for removing the organic solvent, air can be blown away by a rotary evaporator or the like.

Thereafter, rough separation is performed by centrifugal separation, the emulsified dispersion is washed in a washing tank, and the drying process is repeated in a hot air dryer, and the solvent is removed and dried to obtain a toner base.
Thereafter, a ripening step is further performed, so that the hollow state inside the toner can be controlled, which is more preferable. It is preferably 30 to 55 ° C. (more preferably 40 to 50 ° C.), and more preferably aging for 5 to 36 hours (more preferably 10 to 24 hours).

When the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

  Mixing or giving mechanical impact force to the powder mixture after drying with different types of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles By immobilizing and fusing on the surface, it is possible to prevent detachment of foreign particles from the surface of the resulting composite particle.

Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries Ltd.), automatic mortar, etc.
Finally, an external additive such as inorganic fine particles and a toner are mixed with a Henschel mixer or the like, and coarse particles are removed with an ultrasonic sieve or the like to obtain a final toner.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is 1 to 10 wt. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin.

  Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins.

Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(Intermediate transfer member)
In the present invention, an intermediate transfer member can also be used. One embodiment of the intermediate transfer member of the transfer system will be described. FIG. 1 is a schematic configuration diagram of a copying machine according to the present embodiment. Around a photosensitive drum (hereinafter referred to as a photosensitive member) 10 as an image carrier, a charging roller 20 as a charging device, an exposure device 30, a cleaning device 60 having a cleaning blade, a static elimination lamp 70 as a static elimination device, and development. An apparatus 40 and an intermediate transfer member 50 as an intermediate transfer member are provided. The intermediate transfer member 50 is suspended by a plurality of suspension rollers 51 and is configured to run endlessly in the direction of the arrow by a driving unit such as a motor (not shown). A part of the suspension roller 51 also serves as a transfer bias roller for supplying a transfer bias to the intermediate transfer member, and a predetermined transfer bias voltage is applied from a power source (not shown). A cleaning device 90 having a cleaning blade for the intermediate transfer member 50 is also provided. Further, a transfer roller 80 is provided as a transfer means for transferring the developed image onto the transfer paper 100 as the final transfer material, facing the intermediate transfer member 50, and the transfer roller 80 is transferred by a power supply device (not shown). Supplied. Around the intermediate transfer member 50, a corona charger 52 as a charge applying unit is provided.

The developing device 40 includes a developing belt 41 as a developer carrier, a black (hereinafter referred to as “Bk”) developing unit 45K, a yellow (hereinafter referred to as “Y”) developing unit 45Y, The developing unit 45M is hereinafter referred to as magenta and the cyan (hereinafter referred to as C) developing unit 45C. Further, the developing belt 41 is stretched between a plurality of belt rollers, and is configured to run endlessly in a direction indicated by an arrow by a driving unit such as a motor (not shown). Moves at approximately the same speed as 10.
Since the configuration of each developing unit is common, the following description will be given only for the Bk developing unit 50Bk, and for the other developing units 50Y, 50M, and 50C, the portions corresponding to those in the Bk developing unit 50Bk in the figure are as follows. Y, M, and C are appended to the numbers given to those in the unit, and the description is omitted.

The developing unit 50Bk is disposed so that a developing tank 42Bk containing a high-viscosity, high-concentration liquid developer containing toner particles and a carrier liquid component, and a lower part is immersed in the liquid developer in the developing tank 42Bk. And a coating roller 44Bk that thins the developer pumped from the pumping roller 43Bk and applies it to the developing belt 41. The application roller 44Bk has conductivity, and a predetermined bias is applied from a power source (not shown).
In addition to the apparatus configuration as shown in FIG. 1, the apparatus configuration of the copying machine according to the present embodiment is an apparatus configuration in which development units 45 for each color are provided around the photoconductor 10 as shown in FIG. It may be.

  Next, the operation of the copying machine according to the present embodiment will be described. In FIG. 1, the photosensitive member 10 is uniformly charged by the charging roller 20 while being driven to rotate in the direction of the arrow, and then the reflected light from the original is imaged and projected by an optical system (not shown) by the exposure device 30 on the photosensitive member 10. An electrostatic latent image is formed on the surface. This electrostatic latent image is developed by the developing device 40 to form a toner image as a visible image. The developer thin layer on the developing belt 41 is peeled off from the belt 41 in a thin layer state by contact with the photosensitive member in the developing region, and moves to a portion where a latent image is formed on the photosensitive member 10. The toner image developed by the developing device 40 is transferred to the surface of the intermediate transfer member 50 at the contact portion (primary transfer region) between the photosensitive member 10 and the intermediate transfer member 50 moving at a constant speed (primary transfer). Transcription). When transferring three or four colors to be superimposed, this process is repeated for each color to form a color image on the intermediate transfer member 50.

  The corona charger 52 for applying an electric charge to the superimposed toner image on the intermediate transfer member is provided at a contact facing portion between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is installed on the downstream side and on the upstream side of the contact facing portion between the intermediate transfer member 50 and the transfer paper 100. The corona charger 52 gives the toner image a true charge having the same polarity as the charge polarity of the toner particles forming the toner image, and is sufficient for good transfer to the transfer paper 100. Charge is applied to the toner image. The toner image is charged by the corona charger 52, and then transferred to the transfer paper 100 conveyed in the direction of the arrow from a paper supply unit (not shown) by a transfer bias from the transfer roller 80 (two). Next transfer). Thereafter, the transfer paper 100 onto which the toner image has been transferred is separated from the photoconductor 10 by a separation device (not shown), and after a fixing process is performed by a fixing device (not shown), the transfer paper 100 is discharged from the device. On the other hand, after the transfer, the untransferred toner is collected and removed by the cleaning device 60, and the residual charge is discharged by the discharging lamp 70 in preparation for the next charging.

As described above, the static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably from several Ωcm to 10 ³ Ωcm. When the volume resistance is set to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means hardly remains on the intermediate transfer member. Transfer unevenness can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

The material of the intermediate transfer member is not particularly limited, and all known materials can be used. An example is shown below.
(1) A material having a high Young's modulus (tensile modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT ( Polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, PC / PAT blend material, carbon black dispersed thermosetting polyimide, and the like. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and registration is not likely to occur particularly during color image formation.

(2) A belt having a two- or three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery thereof. Therefore, the line image has a performance capable of preventing the line image from being lost.

(3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the width of the belt is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .

  Conventionally, fluorine-based resin, polycarbonate resin, polyimide resin, and the like have been used for the intermediate transfer belt, but in recent years, an elastic belt in which the entire belt layer or a part of the belt is an elastic member has been used. The transfer of a color image using a resin belt has the following problems.

  A color image is usually formed with four colored toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet), and the cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has high hardness and does not deform in accordance with the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely to occur.

  Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a sheet with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. When the transfer pressure at the secondary transfer portion is increased to improve the adhesion, the condensing power of the toner layer is increased, and the above-described character void is generated.

  The elastic belt is used for the following purposes. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, since the elastic belt deforms following local unevenness, the paper does not have excessive flatness and has good adhesion without excessively increasing the transfer pressure against the toner layer. The transfer image with excellent uniformity can be obtained.

  Resin for elastic belt is polycarbonate, fluorine resin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer Polymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer and styrene-phenyl acrylate copolymer), styrene-methacrylic acid ester copolymer (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer) Coalesce etc.), styrene-α-chloroacryl Styrenic resin (monopolymer or copolymer containing styrene or styrene-substituted product), methyl methacrylate resin, butyl methacrylate resin, acrylic resin, such as methyl phosphate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer Ethyl acid resin, butyl acrylate resin, modified acrylic resin (silicone modified acrylic resin, vinyl chloride resin modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate Polymer, rosin-modified maleic resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polyurethane resin, silicone resin, ketone resin, Len - ethyl acrylate copolymer, may be used xylene resin and polyvinyl butyral resin, polyamide resin, one kind or two kinds or more selected from the group consisting of modified polyphenylene oxide resin. However, it is natural that the material is not limited to the above materials.

  Elastic rubbers and elastomers include butyl rubber, fluorine rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene rubber natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene ter Polymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, silicone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, hydrogenated nitrile Selected from the group consisting of rubber, thermoplastic elastomers (eg polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, polyurea, polyester, fluororesin) It is possible to use one kind or two or more kinds that. However, it is natural that the material is not limited to the above materials.

  There are no particular restrictions on the conductive agent for adjusting the resistance value. For example, carbon black, graphite, metal powder such as aluminum or nickel, tin oxide, titanium oxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite Conductive metal oxides such as oxide (ATO), indium oxide-tin oxide composite oxide (ITO), and conductive metal oxides are coated with insulating fine particles such as barium sulfate, magnesium silicate, and calcium carbonate But you can. Of course, the conductive agent is not limited to the above.

  The surface layer material for forming the surface layer of the elastic material includes the prevention of contamination of the photosensitive member by the sex material, the surface friction resistance to the surface of the transfer belt is reduced, the toner adhesion is reduced, and the cleaning property and the secondary transfer property The thing which raises is required. For example, materials that use one or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and increase lubricity, such as fluororesin, fluorine compound, fluorocarbon, titanium dioxide, silicon carbide powder It can be used by dispersing one or more types of particles, particles, or particles with different particle sizes, and by performing heat treatment like a fluorine-based rubber material, a surface rich in fluorine can be formed by forming a fluorine-rich layer on the surface. You can also use a smaller one

Although the manufacturing method of a belt is not limited, For example, the following methods can be used, However, It is not limited to these, It is common to manufacture a belt combining several manufacturing methods.
(1) Centrifugal molding method in which material is poured into a rotating cylindrical mold to form a belt (2) Spray coating method in which a liquid paint is sprayed to form a film (3) The cylindrical mold is immersed in a solution of the material (4) Casting method for pouring into inner and outer molds (5) Method of wrapping a compound around a cylindrical mold and performing vulcanization polishing

As a method of preventing the elastic belt from stretching, there are a method of forming a rubber layer in a core resin layer with little elongation, a method of putting a material for preventing elongation into the core layer, and the like.
Examples of the material constituting the core layer for preventing elongation include natural fibers such as cotton and silk, polyester fibers, nylon fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, and polyvinylidene chloride fibers. 1 type selected from the group consisting of synthetic fibers such as polyurethane fiber, polyacetal fiber, polyfluoroethylene fiber and phenol fiber, inorganic fibers such as carbon fiber, glass fiber and boron fiber, and metal fibers such as iron fiber and copper fiber, or Two or more kinds of woven fabrics or yarns can be used. Of course, the material is not limited to the above.

The yarn may be twisted in any manner, such as one or a plurality of filaments twisted, a single twisted yarn, various twisted yarns, a double yarn or the like. Further, for example, fibers of a material selected from the above material group may be blended. Of course, the yarn can be used after being subjected to an appropriate conductive treatment.
On the other hand, the woven fabric can be any woven fabric such as knitted weave. Of course, a woven fabric that has been woven can also be used, and naturally conductive treatment can be applied.

The production method for providing the core layer is not particularly limited, for example, a method of providing a woven fabric woven in a cylindrical shape on a mold and the like, and providing a coating layer thereon, the woven fabric woven in a cylindrical shape is a liquid rubber And a method of providing a coating layer on one side or both sides of the core layer, and a method of winding a thread spirally around a mold at an arbitrary pitch and providing a coating layer thereon.
The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur in the surface layer. Moreover, it is not preferable to be too thick because the amount of expansion and contraction is large and the image is greatly stretched, but is preferably about 1 mm or more.

(Tandem color image forming device)
The present invention can also be used as a tandem color image forming apparatus. An example of an embodiment of a tandem type color image forming apparatus will be described. As shown in FIG. 3, the tandem type electrophotographic apparatus includes a direct transfer system in which an image on each photoconductor 1 is sequentially transferred onto a sheet s conveyed by a sheet conveying belt 3 by a transfer apparatus 2; As shown in FIG. 4, the images on the respective photoconductors 1 are once sequentially transferred to the intermediate transfer member 4 by the primary transfer device 2, and then the images on the intermediate transfer member 4 are transferred to the sheet s by the secondary transfer device 5. There are indirect transfer systems that perform batch transfer. The transfer device 5 is a transfer conveyance belt, but there is also a roller-shaped method.

Comparing the direct transfer type and the indirect transfer type, the former has a sheet feeding device 6 arranged upstream of the tandem type image forming apparatus T in which the photoreceptors 1 are arranged, and a fixing device 7 arranged downstream. There is a disadvantage that the size increases in the sheet conveyance direction.
On the other hand, the latter can set the secondary transfer position relatively freely.
The sheet feeding device 6 and the fixing device 7 can be arranged so as to overlap with the tandem image forming apparatus T, and there is an advantage that downsizing is possible.

In the former, in order not to increase the size in the sheet conveying direction, the fixing device 7 is arranged close to the tandem type image forming apparatus T. Therefore, the fixing device 7 cannot be disposed with a sufficient margin that the sheet s can bend, and an impact when the leading edge of the sheet s enters the fixing device 7 (particularly with a thick sheet), There is a drawback that the fixing device 7 tends to affect image formation on the upstream side due to the speed difference between the sheet conveyance speed when passing through the fixing device 7 and the sheet conveyance speed by the transfer conveyance belt.
On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that allows the sheet s to bend, so that the fixing device 7 can hardly affect the image formation.
In view of the above, recently, an indirect transfer type of tandem type electrophotographic apparatus has attracted attention.

  In this type of color electrophotographic apparatus, as shown in FIG. 4, the transfer residual toner remaining on the photoreceptor 1 after the primary transfer is removed by the photoreceptor cleaning device 8 to clean the surface of the photoreceptor 1. In preparation for another image formation. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 5 shows an embodiment of the present invention, which is a tandem indirect transfer type electrophotographic apparatus. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) mounted thereon. The copying machine main body 100 is provided with an endless belt-shaped intermediate transfer member 10 at the center.

Then, as shown in FIG. 5, in the illustrated example, it is wound around three support rollers 14, 15, and 16 so that it can be rotated and conveyed clockwise in the figure.
In this illustrated example, an intermediate transfer body cleaning device 17 for removing residual toner remaining on the intermediate transfer body 10 after image transfer is provided on the left of the second support roller 15 among the three.
Further, among the three images, four images of yellow, cyan, magenta, and black are arranged on the intermediate transfer member 10 stretched between the first support roller 14 and the second support roller 15 along the conveyance direction. The tandem image forming apparatus 20 is configured by arranging the forming units 18 side by side.

An exposure device 21 is further provided on the tandem image forming apparatus 20 as shown in FIG. On the other hand, a secondary transfer device 22 is provided on the side opposite to the tandem image forming apparatus 20 with the intermediate transfer body 10 interposed therebetween. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23, and is pressed against the third support roller 16 via the intermediate transfer body 10. The image on the intermediate transfer body 10 is transferred to a sheet.
A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt.

The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. Of course, a transfer roller or a non-contact charger may be disposed as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveyance function together.
In the illustrated example, a sheet reversing device 28 for reversing the sheet so as to record an image on both sides of the sheet is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. Is provided.

  Now, when making a copy using this color electrophotographic apparatus, a document is set on the document table 30 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it.

When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34, and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.
When a start switch (not shown) is pressed, one of the support rollers 14, 15, and 16 is driven to rotate by a drive motor (not shown), and the other two support rollers are driven to rotate to convey the intermediate transfer member 10. To do. At the same time, the individual image forming means 18 rotates the photoconductors 40 to form black, yellow, magenta, and cyan monochrome images on the photoconductors 40, respectively. Then, along with the conveyance of the intermediate transfer member 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer member 10.

On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, the sheet is fed out from one of the paper cassettes 44 provided in the paper bank 43 in multiple stages, and the separation roller 45 Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped.
Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.
Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer member 10, the sheet is fed between the intermediate transfer member 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.

  The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge roller. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.

On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for another image formation.
Here, the registration roller 49 is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.
Now, in the tandem image forming apparatus 20 described above, the individual image forming means 18 includes, for example, a charging device 60, a developing device 61, and a primary device around a drum-shaped photoconductor 40 as shown in FIG. The image forming apparatus includes a transfer device 62, a photoconductor cleaning device 63, a charge removal device 64, and the like.

(Belt fixing system)
An example of the fixing device used in the image forming method of the present invention is shown in FIG. In FIG. 7, 2 is a fixing roller in which a metal (aluminum, iron, etc.) metal core is covered with an elastic body (silicon rubber, etc.), and 1 is a metallic (pipe made of aluminum, iron, copper, stainless steel, etc.) hollow cylinder It is a heating roller made of a cored bar and having a heating source 5 inside. Reference numeral 7 denotes a temperature sensor for measuring the surface temperature of the fixing belt 3 in contact with the heating roller 1 portion. A fixing belt 3 is stretched between the fixing roller 2 and the heating roller 1. The fixing belt 3 has a small heat capacity, and on a substrate (thickness of about 30 to 150 μm such as nickel or polyimide), a release layer (thickness of 50 to 300 μm for silicon rubber or 10 to 50 μm for fluororesin). Etc.).

Reference numeral 4 denotes a pressure roller in which an elastic body is coated on a metal core, and the nip between the fixing belt 3 and the pressure roller 4 is pressed by pressing the fixing roller 2 from below through the fixing belt 3. Forming part. Moreover, the dimension of each member is set by various conditions required.
These are only examples, and for example, it is possible to provide a heat source inside the fixing roller 2 or the pressure roller 4. In the present invention, a fixing device using a fixing belt in a configuration other than this example is also applied. Is done.

  The fixing belt is preferably excellent in heat resistance, releasability, and durability. In the present invention, a thin belt having a total thickness of 10 to 200 μm, more preferably 20 to 150 μm, has low temperature fixability (thermal conductivity). It is more preferable from the point. As the fixing belt, for example, a single layer film of a heat resistant resin such as polyimide, polyetherimide, PES (polyether sulfide), PFA (tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin), or a composite layer film, for example, 20 μm. Thick belt with a release coating layer with a conductive material added to fluororesin such as PTFE (tetrafluoroethylene resin) and PFA on at least the image contact surface side, fluorine rubber, silicon rubber, etc. Those having an elastic layer are more preferable.

[Example]
EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
Hereinafter, a part shows a weight part.

(Evaluation of two-component developer)
When evaluating an image with a two-component developer, a ferrite carrier having an average particle diameter of 35 μm coated with a silicone resin at an average thickness of 0.5 μm is used as follows, and toner 7 of each color is used with respect to 100 parts by weight of the carrier. The developer was prepared by uniformly mixing and charging the parts by weight using a tumbler mixer of the type in which the container rolls and stirs.

(Carrier production)
・ Core material Mn ferrite particles (weight average diameter: 35 μm) 5000 parts ・ Coating material Toluene 450 parts Silicone resin SR2400 450 parts (Toray, Dow Corning, silicone, nonvolatile content 50%)
Aminosilane SH6020 (manufactured by Toray Dow Corning Silicone) 10 parts Carbon black 10 parts The coating material is dispersed with a stirrer for 10 minutes to prepare a coating solution, and the coating solution and the core material are placed in a fluidized bed with a rotating bottom plate disk The coating liquid was applied to the core material by applying the coating liquid while forming a swirling flow provided with stirring blades. The obtained coated product was baked in an electric furnace at 250 ° C. for 2 hours to obtain the carrier.

<Synthesis of organic fine particle emulsion>
(Production Example 1)
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, 110 butyl acrylate Parts and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and an aqueous dispersion of vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). [Fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 58 ° C., and the weight average molecular weight was 130,000.

<Preparation of aqueous phase>
(Production Example 2)
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

<Synthesis of low molecular weight polyester>
(Production Example 3)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C. for 11 hours at normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 44 parts of trimellitic anhydride into the reaction vessel, and at 180 ° C. at normal pressure. By reacting for 4 hours, [low molecular weight polyester 1] was obtained. [Low molecular polyester 1] had a number average molecular weight of 7,800, a weight average molecular weight of 16,500, a Tg of 46 ° C., and an acid value of 25.

<Synthesis of intermediate polyester>
(Production Example 4)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 3200, a weight average molecular weight of 10300, Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Synthesis of ketimine>
(Production Example 5)
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

<Synthesis of master batch (MB)>
(Production Example 6)
1200 parts of water, 540 parts of carbon black (manufactured by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1200 parts of [low molecular weight polyester 1] are added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Then, the mixture was kneaded at 110 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

<Production of oil phase>
(Production Example 7)
In a container equipped with a stirring bar and a thermometer, 378 parts of [Low molecular weight polyester 1], Carnauba WAX10O part, 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

<Emulsification => Solvent removal>
(Production Example 8)
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was charged into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 40 ° C. for 24 hours to obtain [Dispersion slurry 1].

<Washing->Drying>
(Production Example 9)
[Dispersion slurry 1] After filtering 100 parts under reduced pressure, [filter cake 1] was obtained by the following steps.
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 1O parts of 10% sodium hydroxide aqueous solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was. The obtained [Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, sieved with a mesh of 75 μm, [Toner Base Particle 1] was obtained.
Thereafter, 100 parts of [toner base particle 1] and 1 part of hydrophobized silica were mixed with a Henschel mixer to obtain a toner. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.

In Example 1, a toner was obtained in the same manner as in Example 1 except that the oil phase preparation step was changed to the following conditions. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
<Production of oil phase>
(Production Example 10)
In a container equipped with a stir bar and a thermometer, 378 parts of [low molecular weight polyester 1], carnauba / rice wax (weight ratio 7: 3) WAX10O part, 947 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining at 80 ° C. for 3 hours, it was cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 2].

  [Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80 vol% Carbon black and WAX were dispersed under conditions of filling and 7 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by 4 passes using a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 2]. The solid content concentration of [Pigment / WAX Dispersion 2] (130 ° C., 30 minutes) was 50%.

A toner was obtained in the same manner as in Example 1 except that the steps from emulsification to solvent removal were changed to the following conditions. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
<Emulsification => Solvent removal>
(Production Example 11)
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) for 3 minutes at 5,000 rpm After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at 13,000 rpm for 10 minutes to obtain [Emulsified Slurry 2].
[Emulsion slurry 2] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 6 hours, aging was carried out at 45 ° C. for 10 hours to obtain [Dispersion slurry 2].

A toner was obtained in the same manner as in Example 1 except that the steps from emulsification to solvent removal were changed to the following conditions. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
A toner was obtained in the same manner as in Example 1 except that the steps from emulsification to solvent removal were changed to the following conditions. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
<Emulsification => Solvent removal>
(Production Example 12)
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at 13,000 rpm for 40 minutes to obtain [Emulsified Slurry 3].
[Emulsified slurry 3] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C for 7 hours, aging was carried out at 45 ° C for 7 hours to obtain [Dispersed slurry 3].

In Example 1, a toner was obtained in the same manner as in Example 1 except that the oil phase process was changed to the following conditions. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
<Production of oil phase>
(Production Example 13)
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular weight polyester 1], 130 parts of carnauba / rice wax (weight ratio 7: 3) WAX, 947 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining at 80 ° C. for 4 hours, it was cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 2 hours to obtain [Raw material solution 3].

  [Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80 vol% Carbon black and WAX were dispersed under conditions of filling and 7 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and the mixture was subjected to 4 passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 3]. The solid content concentration of [Pigment / WAX Dispersion 3] (130 ° C., 30 minutes) was 50%.

In Example 1, a toner was obtained in the same manner as in Example 1 except that the oil phase process was changed to the following conditions. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
<Production of oil phase>
(Production Example 14)
378 parts of [Low molecular polyester 1], Carnauba wax WAX40O part, and 947 parts of ethyl acetate were charged in a container equipped with a stirring bar and a thermometer, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 4 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 2 hours to obtain [Raw material solution 6].
[Raw material solution 6] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 7 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by 4 passes through the bead mill under the above conditions to obtain [Pigment / WAX Dispersion 6]. The solid content concentration of [Pigment / WAX Dispersion 6] (130 ° C., 30 minutes) was 50%.

In Example 1, a toner was obtained in the same manner as in Example 1 except that the oil phase preparation step was changed to the following conditions. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
A toner was obtained in the same manner as in Example 1 except that the steps from emulsification to solvent removal were changed to the following conditions. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
<Emulsification => Solvent removal>
(Production Example 15)
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous Phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 1 hour and 30 minutes to obtain [Emulsified Slurry 5].
[Emulsion slurry 5] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C for 8 hours, aging was carried out at 45 ° C for 10 hours to obtain [Dispersion slurry 5].

In Example 1, a toner was obtained in the same manner as in Example 1 except that the oil phase preparation step was changed to the following conditions. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
A toner was obtained in the same manner as in Example 1 except that the steps from emulsification to solvent removal were changed to the following conditions. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
<Emulsification => Solvent removal>
(Production Example 16)
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and [Aqueous Phase 1] 1200 parts are added to the container. And mixing at 13,000 rpm for 1 hour to obtain [Emulsion slurry 5].
[Emulsion slurry 5] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C for 8 hours, aging was carried out at 45 ° C for 10 hours to obtain [Dispersion slurry 5].

A toner was obtained in the same manner as in Example 1 except that the low molecular polyester used in Example 1 was changed to the following. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
<Synthesis of low molecular weight polyester>
(Production Example 17)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react for 11 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then put 44 parts of trimellitic anhydride into the reaction vessel at 175 ° C. under normal pressure. By reacting for 3 hours, [low molecular weight polyester 2] was obtained. [Low molecular polyester 2] had a number average molecular weight of 6,200, a weight average molecular weight of 10,300, a Tg of 46 ° C., and an acid value of 25.

[Comparative Example 1]
In Example 1, a toner was obtained in the same manner as in Example 1 except that the conditions were changed as follows. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.

<Synthesis of low molecular weight polyester>
(Production Example 18)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 7 hours at normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. By reacting for 3 hours, [low molecular polyester 3] was obtained. [Low molecular weight polyester 3] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, a peak molecular weight of 3,100, a Tg of 43 ° C., and an acid value of 25.

<Production of oil phase>
(Production Example 19)
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular polyester 3], 100 parts of Carnauba WAX, and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 5].
[Raw material solution 2] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 2] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 5]. The solid content concentration of [Pigment / WAX Dispersion 5] (130 ° C., 30 minutes) was 50%.

<Emulsification => Solvent removal>
(Production Example 20)
[Pigment / WAX Dispersion 5] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and allowed to stand for 1 hour to obtain [Emulsified Slurry 6].
[Emulsion slurry 6] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Dispersion slurry 6]. Subsequent aging was not performed.

[Comparative Example 2]
<First step>
(Preparation of dispersion (1))
Styrene ... 370g
nButyl acrylate ... 30g
Acrylic acid ... 8g
Dodecanethiol ... 24g
Carbon tetrabromide ... 4g

  After mixing and dissolving the above, 6 g of nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and 10 g of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) were ionized. Dispersed in 550 g of exchange water, dispersed in a flask, emulsified, and slowly mixed for 10 minutes, charged with 50 g of ion exchange water in which 4 g of ammonium persulfate was dissolved, and after nitrogen substitution, While stirring in the flask, the contents were heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a dispersion liquid (1) was prepared by dispersing resin particles having an average particle diameter of 155 nm, a glass transition point of 59 ° C., and a weight average molecular weight (Mw) of 12,000.

(Preparation of dispersion (2))
Styrene ... 280g
n-Butyl acrylate ... 120g
Acrylic acid ... 8g

  The above mixture was dissolved, and 6 g of a nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and 12 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) were ionized. Dispersed in 550 g of exchange water, dispersed in a flask, emulsified, and slowly mixed for 10 minutes, charged with 50 g of ion exchange water in which 3 g of ammonium persulfate was dissolved, and after nitrogen replacement, While stirring in the flask, the contents were heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. The average particle size was 105 nm, the glass transition point was 53 ° C., and the weight average molecular weight (Mw) was 550. A dispersion liquid (2) was prepared by dispersing resin particles having a molecular weight of 1,000.

(Preparation of colorant dispersion (1))
Carbon black ... 50g
(Cabot Corporation: Mogal L)
Nonionic surfactant ... 5g
(Sanyo Kasei Co., Ltd .: Nonipol 400)
Ion exchange water ... 200g

  The above is mixed, dissolved, and dispersed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to disperse a colorant (carbon black) having an average particle size of 250 nm (carbon black) 1) was prepared.

(Preparation of release agent dispersion (1))
Paraffin wax ... 50g
(Nippon Seiwa Co., Ltd .: HNP0190, melting point 85 ° C.)
Cationic surfactant ... 7g
(Manufactured by Kao Corporation: Sanizol B50)
Ion exchange water ... 200g

  The above was heated to 95 ° C. and dispersed using a homogenizer (IKA: Ultra Turrax T50), and then dispersed with a pressure discharge homogenizer to disperse a release agent having an average particle size of 550 nm. A release agent dispersion (1) was prepared.

(Preparation of aggregated particles)
Dispersion liquid (1) ... 120g
Dispersion liquid (2) ... 80g
Colorant dispersion (1) ... 30g
Release agent dispersion (1) 40g
Cationic surfactant ... 1.5g
(Manufactured by Kao Corporation: Sanizol B50)

The above was mixed and dispersed in a round stainless steel flask using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then heated to 48 ° C. while stirring the inside of the flask in an oil bath for heating. After maintaining at 48 ° C. for 30 minutes, observation with an optical microscope confirmed that aggregated particles (volume: 95 cm ³ ) having an average particle diameter of about 5 μm were formed.

<Second step>
(Preparation of adhered particles)
To this, 60 g of the dispersion liquid (1) as the resin-containing fine particle dispersion liquid was gradually added. The volume of the resin particles contained in the dispersion liquid (1) is 25 cm ^3. And the temperature of the heating oil bath was raised to 50 degreeC, and was hold | maintained for 1 hour.

<Third step>
Then, after adding 3 g 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 up to 105 ° C. Heated and held for 3 hours. Then, after cooling, the reaction product was filtered, thoroughly washed with ion exchange water, and then dried to obtain a toner base. Thereafter, 100 parts of toner base particles were mixed with 1 part of hydrophobic silica and 1 part of hydrophobic titanium oxide using a Henschel mixer to obtain a toner. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.

[Comparative Example 3]
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube and reacted at 230 ° C. for 8 hours at normal pressure. The reaction was further carried out at a reduced pressure of 10 to 15 mmHg for 5 hours, followed by cooling to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Subsequently, it cooled to 80 degreeC and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the isocyanate containing prepolymer (1) was obtained.

  Next, 267 parts of prepolymer (1) and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain urea-modified polyester (1) having a weight average molecular weight of 64,000. In the same manner as above, 724 parts of bisphenol A ethylene oxide 2 mol adduct, 138 parts of terephthalic acid and 138 parts of isophthalic acid were polycondensed at 230 ° C. for 6 hours under normal pressure, and then reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. An unmodified polyester (a) having a peak molecular weight of 2300, a hydroxyl value of 55, and an acid value of 1 was obtained. 200 parts of urea-modified polyester (1) and 800 parts of unmodified polyester (a) are dissolved and mixed in 1000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and an ethyl acetate / MEK solution of toner binder (1) is mixed. Got.

  In a reaction vessel equipped with a condenser, a stirrer and a thermometer, 942 parts of water and 58 parts of a 10% suspension of hydroxyapatite (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) are placed, and the toner binder (1 1000 parts of ethyl acetate / MEK solution was added and dispersed. The temperature was raised to 98 ° C., the organic solvent was distilled off, and after cooling, filtered from water, washed and dried to obtain the toner binder (1) of the present invention. The toner binder (1) had a Tg of 52 ° C., Tη of 123 ° C., and TG ′ of 132 ° C.

  100 parts of the toner binder (1), 7 parts of glycerin tribehenate and 4 parts of cyanine blue KRO (manufactured by Sanyo Dye Co., Ltd.) were converted into a toner by the following method. First, after premixing using a Henschel mixer (FM10B manufactured by Mitsui Miike Chemical Co., Ltd.), the mixture was kneaded using a biaxial kneader (PCM-30 manufactured by Ikegai Co., Ltd.). Then, after finely pulverizing using a supersonic jet pulverizer, Labo Jet (manufactured by Nippon Pneumatic Industry Co., Ltd.), the toner base particles are classified by an airflow classifier (MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.). Obtained. Thereafter, 100 parts of toner base particles were mixed with 1 part of hydrophobic silica and 1 part of hydrophobic titanium oxide using a Henschel mixer to obtain a toner. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.

[Comparative Example 4 ]
(Production of polymer A)
Two flasks equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube were charged with 300 g of methanol, 100 g of toluene, 570 g of styrene, 30 g of 2-acrylamido-2-methylpropanesulfonic acid, and 12 g of lauroyl peroxide, and the mixture was stirred while introducing nitrogen. The solution was polymerized at a temperature of 10 ° C. for 10 hours, the contents were taken out from the flask, dried under reduced pressure, and then pulverized with a jet mill to produce a polymer A (Mw = 3000).

Toner formulation Styrene 183 parts 2-ethylhexyl acrylate 17 parts Polymer A 0.1 part C.I. I. Pigment Yellow 17 7 parts Paraffin wax (melting point 155 ° F. (manufactured by Taisei Kosan)) 32 parts Initiator (V-601 (manufactured by Wako Pure Chemical Industries)) 10 parts

The above formulation was heated to 65 ° C. and uniformly dissolved or dispersed to obtain a monomer composition.
Separately, 0.3 g of a silane coupling agent [KBE903 (manufactured by Shin-Etsu Silicone)] was uniformly dispersed in 1200 ml of ion-exchanged water, and 6 g of colloidal silica [Aerosil # 200 (manufactured by Aerosil Japan)] was added and further uniformly dispersed. This dispersion was adjusted to pP = 6 with HCl to prepare a dispersion medium system.
The monomer composition was charged into this dispersion medium, and stirred at 6500 rpm for 60 minutes at 70 ° C. under a nitrogen atmosphere to granulate the monomer composition. Thereafter, polymerization was performed at 75 ° C. for 8 hours while stirring with a paddle stirring blade.
After the completion of the polymerization reaction, the reaction product was cooled, 42 g of 20 wt% NaOH aqueous solution was added and alkali treatment was performed overnight, the dispersant was dissolved, washed excessively, washed with water, and dried to obtain a polymerization method toner.
The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.

[Comparative Example 5 ]
A toner was obtained in the same manner as in Example 1 except that the low molecular polyester used in Example 1 was changed to the following. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
<Synthesis of low molecular weight polyester>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 7 hours at normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. By reacting for 3 hours, [low molecular weight polyester 4] was obtained. [Low molecular polyester 4] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, a peak molecular weight of 3,100, a Tg of 43 ° C., and an acid value of 25.

[Comparative Example 6 ]
A toner was obtained in the same manner as in Example 1 except that the low molecular polyester used in Example 1 was changed to the following. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.
<Synthesis of low molecular weight polyester>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 243 parts of bisphenol A ethylene oxide 2-mole adduct, 543 parts of bisphenol A propylene oxide 3-mole adduct, 172 parts terephthalic acid, 51 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C. for 10 hours at normal pressure, and further react for 7 hours under reduced pressure of 10-15 mmHg, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C. at normal pressure. By reacting for 4 hours, [low molecular weight polyester 5] was obtained. [Low molecular polyester 5] had a number average molecular weight of 13,000, a weight average molecular weight of 34,000, Tg of 49 ° C., and an acid value of 25.

<Evaluation items>
1) Fixability (hot offset resistance, low temperature fixability)
A belt fixing method by remodeling Ricoh's imgio Neo 450, with a solid image and 1.0 ± 0.1mg / mm on a plain paper and cardboard transfer paper (type 6200 made by Ricoh and copy printing paper <135> made by NBS Ricoh) Fixing evaluation was performed with a toner adhesion amount of cm ² . The fixing test was conducted by changing the temperature of the fixing belt, and the upper limit temperature at which hot offset did not occur on plain paper was defined as the upper limit temperature for fixing. Further, the minimum fixing temperature was measured with a thick paper. The lower limit fixing temperature was defined as the fixing lower limit temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more. It is desirable that the fixing upper limit temperature is 200 ° C. or higher and the fixing lower limit temperature is 140 ° C. or lower.

2) Gloss Ricoh's imagio Neo 450 was remodeled as a belt fixing system, and the fixing evaluation was performed with a solid image on plain paper (Ricoh Type 6200) with a toner adhesion amount of 0.4 ± 0.05 mg / cm ² . About images
Using a gloss meter (VG-1D) (manufactured by Nippon Denshoku Co., Ltd.), set the light projection angle and light reception angle to 60 °, S and S / 10 switch SW to S, use 0 preparation and standard plate Measurements were made after the standard settings had been made. From those having good glossiness, ◎: 6 or more, ◯: 4 or more and less than 6, Δ: 3 or more and less than 4 and x: less than 3.

3) Apparatus and image contamination Using an evaluation machine that was tuned by remodeling Ricoh's IPSiO Color 8100 into an oilless fixing system, an image area ratio 5% chart continuous 100,000 sheet output durability test was conducted. Dirt caused by toner dropping, a small amount of hot offset, etc. was evaluated. X indicates that there is a lot of contamination on the image, △ indicates that the contamination on the image is very slight, ◯ indicates that no contamination is observed on the image but the inside of the device is dirty, ○ contamination in the device Also, ◎ is the one with less.

4) Friction peelability Ricoh Type 6200 with a solid image and a toner adhesion amount of 0.8 ± 0.05 mg / cm ² using an evaluation machine that was tuned by remodeling Ricoh's IPSiO Color 8100 into an oilless fixing system. An image is created by fixing at 140 ° C. on plain paper. The image was rubbed 100 times with cotton, and the state of image peeling at that time was judged visually. The state where there was a lot of peeling was rated as x, the state where it was peeled slightly, Δ, the case where there was almost no peeling, the cotton was slightly colored, and the state where there was no peeling at all.

5) Transferability After transferring a 20% image area ratio chart from the photoconductor to the paper, the transfer residual toner on the photoconductor immediately before cleaning is transferred to white paper with Scotch tape (manufactured by Sumitomo 3M Co., Ltd.), and it is reflected by Macbeth reflection. Measured with a densitometer RD514 type, ◎ if the difference from the blank is less than 0.005, ○ if 0.005 to 0.010, △ if 0.011 to 0.02, and 0.02. Those exceeding were evaluated as x.

6) Charging stability Using an evaluation machine in which Ricoh's IPSiO Color 8100 was remodeled into an oil-less fixing system and tuned, an image area ratio 5% chart continuous 100,000 sheet output durability test was carried out. Changes in charge amount were evaluated. 1 g of developer was weighed and the change in charge amount was determined by the blow-off method. When the change in the charge amount was 5 μc / g or less, it was evaluated as ◯, when it was 10 μc / g or less, Δ when it exceeded 10 μc / g.

7) Image graininess and sharpness Using an evaluation machine tuned by remodeling Ricoh's IPSiO Color 8100 to an oilless fixing system, a photographic image was output in a single color, and the degree of graininess and sharpness was visually evaluated. . Evaluations were made from GOOD, ◎, ○, Δ, and ×.並 is equivalent to offset printing, ◯ is slightly worse than offset printing, Δ is much worse than offset printing, and × is very bad compared to conventional electrophotographic images.

8) Fog In an environment with a temperature of 10 ° C and a humidity of 15%, using an evaluation machine that has been tuned by remodeling the Ricoh IPSiO Color 8100 into an oil-less fixing system, output 100000 images in a continuous 5% chart using each toner. The degree of toner contamination on the transfer paper upper surface after the durability test was visually evaluated (loupe). Evaluations were made from GOOD, ◎, ○, Δ, and ×. ◎: Toner contamination is not observed at all and is in a good state ○: Slight contamination is not a problem Δ: Slight contamination is observed ×: There is very contamination outside the allowable range

9) Toner scattering In an environment with a temperature of 40 ° C. and a humidity of 90%, using an evaluation machine that was tuned by remodeling Ricoh's IPSiO Color 8100 into an oil-less fixing system, an image area ratio 5% chart continuous 100,000 sheets using each toner The toner contamination state in the copying machine after the output durability test was visually evaluated. ◎ indicates that the toner stains are not observed at all and is in a good state, ○ indicates that only slight stains are observed, △ indicates that the stains are slightly observed, and × indicates that the contamination is not within the allowable range. There is a problem with dirt.

10) Environmental preservation (blocking resistance)
Weigh 10 g of toner, put it in a 20 ml glass container, tap the glass bottle 100 times, leave it in a thermostatic bath set at a temperature of 50 ° C. and a humidity of 80% for 24 hours, and then check the penetration with a penetration meter. It was measured. The toner stored in a low-temperature and low-humidity (10 ° C., 15%) environment was similarly evaluated for penetration, and the value with the lower penetration was employed in a high-temperature and high-humidity and low-temperature and low-humidity environment. From the favorable ones, ◎: 20 mm or more, ◯: 15 mm or more and less than 20 mm, Δ: 10 mm or more to less than 15 mm, x: less than 10 mm.

  The toner of the present invention has a sufficient fixing temperature range, good anti-offset property and wrapping property, sufficient friction peeling strength after fixing, sufficient gloss, fixing device and image Therefore, it is highly usable as a toner of an image forming apparatus such as a full-color copying machine.

1 is a schematic configuration diagram illustrating an example of a color copying machine using a developing belt. FIG. 2 is a schematic configuration diagram illustrating an example of a color copying machine in which development units for each color are provided around a photoconductor. 1 is a schematic configuration diagram illustrating an example of a tandem type electrophotographic apparatus. 1 is a schematic configuration diagram showing an example of a tandem type electrophotographic apparatus using an intermediate transfer member. 1 is a schematic configuration diagram of a tandem indirect transfer type electrophotographic apparatus. FIG. 6 is an enlarged view showing individual image forming means of the tandem image forming apparatus of FIG. 1 is a schematic configuration diagram illustrating an example of a fixing device of an image forming apparatus.

Explanation of symbols

(About FIGS. 1-4)
DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Transfer device 3 Sheet conveyance belt 4 Intermediate transfer body 5 Transfer device 10 Photoconductor 20 Charging roller 30 Exposure device 40 Development device 41 Development belt 42 Development tank 43 Pumping roller 44 Application roller 45 Development unit 50 Intermediate transfer body 51 Suspension Roller 52 Corona charger 53 Constant current source 60 Cleaning device 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 100 Transfer paper (About FIGS. 5 and 6)
DESCRIPTION OF SYMBOLS 10 Intermediate transfer body 14,15,16 Support roller 17 Intermediate transfer body cleaning apparatus 18 Image forming means 20 Tandem image forming apparatus 21 Exposure apparatus 22 Secondary transfer apparatus 23 Roller 24 Secondary transfer belt 25 Fixing apparatus 26 Fixing belt 27 Pressure Roller 28 Sheet reversing device 30 Document table 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Photosensitive body 42 Paper feed roller 43 Paper bank 44 Paper feed cassette 45 Separating roller 46 Paper feed path 47 Conveying roller 48 Paper feed path 49 Registration roller 50 Paper feed roller 51 Manual feed tray 52 Separating roller 53 Paper feed path 55 Switching claw 56 Ejection roller 57 Ejection tray 60 Charging device 61 Developing device 62 Primary transfer device,
63 photoconductor cleaning device,
64 Static eliminator 100 Copier body 200 Paper feed table 300 Scanner 400 Automatic document feeder (About Fig. 7)
DESCRIPTION OF SYMBOLS 1 Heating roller 2 Fixing roller 3 Fixing belt 4 Pressure roller 5 Heating source 7 Temperature sensor

Claims (14)

In a toner comprising particles formed by an extension reaction and / or a crosslinking reaction in which oil droplets of an organic solvent in which a toner composition containing at least a colorant, a resin, and a prepolymer is dissolved are dispersed in an aqueous medium . An electrostatic charge image developing toner, wherein HFIP (hexafluoroisopropanol) -dissolved components exhibit the following relationship:
2000 ≦ Mn ≦ 7000, 1.5 ≦ Mw / Mn ≦ 10
(Where Mn is the number average molecular weight, Mw is the weight average molecular weight) The electrostatic charge image developing toner according to claim 1, wherein the HFIP (hexafluoroisopropanol) -soluble component of the toner has the following relationship.
3000 ≦ Mn ≦ 7000, 1.5 ≦ Mw / Mn ≦ 10
(Where Mn is the number average molecular weight, Mw is the weight average molecular weight)   The electrostatic image developing toner according to claim 1 or 2, wherein a molecular weight component of 100,000 or more in an HFIP (hexafluoroisopropanol) -soluble component of the toner is 0.5% to 18%.   The electrostatic image developing toner according to claim 1, comprising at least a polyester resin.   The electrostatic image developing toner according to claim 1, comprising at least a modified polyester resin. 6. The electrostatic image developing toner according to claim 1, wherein the toner particles have an average circularity E of 0.90 to 0.99.   7. The electrostatic image developing toner according to claim 1, wherein the toner has a circularity SF-1 value of 101 to 150 and a circularity SF-2 value of 101 to 140.   8. The volume average particle diameter Dv of the toner particles is 2 to 7 μm, and the ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn is 1.25 or less. The toner for developing an electrostatic image according to any one of the above.   A two-component developer comprising at least the electrostatic image developing toner according to claim 1 and a carrier made of magnetic particles.   The electrostatic image on the electrostatic image bearing member is developed with a developer for developing an electrostatic image to form a toner image, and a transfer means is brought into contact with the surface of the electrostatic image bearing member via a transfer material so that the toner image is An image forming apparatus for electrostatic transfer to a transfer material, wherein the developer is the two-component developer according to claim 9.   A process cartridge which constitutes a part of the image forming apparatus and is detachable, and at least an electrostatic charge image carrier and a developing unit are integrally supported inside, and the developing unit is claimed in claim 1. A process cartridge comprising the toner for electrophotography according to any one of -8.   An image forming method comprising forming an image using the image forming apparatus according to claim 10.   A toner according to any one of claims 1 to 8, wherein the heating element, one or more heat transfer media heated by the heating element, and a recording medium is pressed against one of the heat transfer media. In an image forming method using a fixing method in which a toner image on a recording medium is heated and fixed by a pressure member, at least one of the heat transfer media is a belt-like heat transfer medium, and a certain amount of oil is placed on the belt. An image forming method including a toner fixing method used with or without applying the toner.   The image forming method according to claim 13, wherein the belt-like heat transfer medium has a belt thickness of 10 μm to 200 μm.

Images