JP5966517B2 - Image forming method and image forming apparatus using the image forming method - Google Patents

Description

  The present invention relates to an image forming method and an image forming apparatus in electrophotography.

In recent years, image forming methods using electrophotography require not only high-quality image formation but also energy saving and high speed.

Energy saving is generally achieved by improving the low-temperature fixability of the toner and reducing the energy consumed for fixing the image. However, if the speed of image formation is increased, the image quality deteriorates.

Various factors are related to the degradation of image quality due to image formation at higher speeds. Among them, the greatest contribution is the influence of fixing defects in the fixing process.

  In the fixing process, an unfixed toner image on a recording medium typified by paper is fixed on the recording medium by heat and pressure to form a fixed image. An unfixed toner image cannot obtain a sufficient amount of heat in the process, and as a result, fixing failure occurs, the surface of the final toner image becomes rough, and an afterimage phenomenon called cold offset occurs, resulting in a defective image. Or

Therefore, when the system speed is increased, it is necessary to raise the fixing temperature so as not to deteriorate the image quality, and it is difficult to achieve both energy saving and high speed. A toner that can be fixed is required.

A toner that can be fixed at low temperature can be produced by using a binder resin having a low glass transition temperature (Tg) or softening temperature (T1 / 2), for example. In addition to low offset resistance, toner particles are soft, and in high-speed image formation, the toner is stressed and adheres to the surface of the developing sleeve, and the developing sleeve is contaminated.
When the developing sleeve is contaminated in this way, the potential of the developer or the like fluctuates, and a ghost (a phenomenon in which the next image takes over the previous image history) may occur.

In the two-component development method, a magnetic brush is formed by a magnet in a developing sleeve, and development is performed by rubbing an electrostatic latent image formed on the image carrier in a development region facing the image carrier. The developer separation region where the magnetic force is almost zero is created by providing an odd number of magnets and a magnet pair having the same polarity at a position below the rotation axis of the developing sleeve. The developer is peeled off from the developing sleeve by naturally dropping the developer.

In such a two-component development system, a counter charge is generated in the magnetic carrier at the time of toner consumption in the immediately preceding image, so that a mirror image force is generated between the carrier and the development sleeve, and is provided inside the development sleeve. At the developer separation pole where the magnetic force is almost zero, the developer does not leave normally, and the developer with low development ability, in which the toner is consumed and the toner density is reduced, is transported again to the development area, so that the previous image formation An abnormal image in which the image density at the portion becomes lighter occurs.
That is, an image with a normal density can be formed for one round of the sleeve, but a ghost (a phenomenon in which the next image takes over the previous image history) occurs in the second and subsequent rounds, in which the image density becomes lighter in the immediately preceding image forming unit. End up.

A ghost also occurs when toner adheres to the developing sleeve according to the immediately preceding image history and the toner development amount of the next image varies according to the potential of the toner.
In other words, toner adhesion to the developing sleeve occurs when the toner is developed on the developing sleeve because a bias is applied in the direction of the developing sleeve during non-image formation, and the toner developed on the developing sleeve has a potential. For this reason, at the time of printing, the developing potential is increased by the potential of the toner on the developing sleeve, and the toner development amount increases.

In addition, since the toner on the developing sleeve is consumed according to the formed image, the amount of toner on the developing sleeve varies depending on the history of the formed image. When the toner is uniformly supplied to the developing sleeve, the amount of toner on the developing sleeve increases and the image density increases in the case where the immediately preceding image is a non-image or in the place immediately after the interval between the sheets. On the contrary, when the immediately preceding image is an image having a large image area, the toner on the developing sleeve is consumed and the image density is decreased.

In order to solve this problem, for example, in Japanese Patent Application Laid-Open No. 11-65247 of Patent Document 1, a pumping roll having a magnet inside is arranged in the vicinity of the peeling region on the developing sleeve, and development is performed with the magnetic force. A configuration in which the developer is peeled later is described.
The developer peeled from the developing sleeve by the scooping roll is further pumped by another scooping roll and then conveyed to a developer stirring chamber having a screw, where the toner density is readjusted and the toner is charged. It has a configuration.

  The ghost may occur not only in the two-component development method but also in the hybrid development method and the one-component development method, but the ghost generation in these methods is due to different mechanisms.

The hybrid development system is based on a one-component development system and has improved development capability. The development system is opposed to an image carrier such as a photoconductor and a toner, and is opposed to the development sleeve. And a developer conveying roll carrying a two-component developer containing toner and a magnetic carrier, and a large amount of developer is supplied to the developing sleeve by a magnetic brush formed on the developer conveying roll. A toner layer is formed.
In such a hybrid developing system, only toner is supplied to the developing sleeve, and no counter charge is generated in the magnetic carrier in the developing area, as in the one-component developing system.

The occurrence of a ghost in the hybrid development system is that a constant amount of toner is always supplied to the developing sleeve regardless of the toner consumed from the developing sleeve, so the amount of toner on the developing sleeve varies depending on the amount of toner consumed. It is caused by that.

That is, when the previous image prints an image with low toner consumption, the amount of residual toner on the developing sleeve is large, and after toner supply, the amount of toner on the developing sleeve is greater than the desired amount, resulting in a dark image density. On the other hand, after printing an image with high toner consumption, the amount of residual toner on the developing sleeve is small, and even if toner is supplied, the amount of toner on the developing sleeve is less than the desired amount and the image density becomes light.

As described above, in the ghost image in the hybrid development, when the toner is transferred from the developer conveying roll onto the developing sleeve, the toner is developed and the toner is removed from the developing sleeve, and the toner is not developed and the developing sleeve is developed. This is because it is difficult to re-apply the toner amount in the part where the toner remains as it is, and the toner amount on the developing sleeve at the time of printing the next image varies depending on the history of the previous image. doing.

In order to solve this problem, for example, Japanese Patent No. 3356948 of Patent Document 2, Japanese Patent Application Laid-Open No. 2005-157002 of Patent Document 3, and Japanese Patent Application Laid-Open No. 11-231652 of Japanese Patent Application Laid-Open No. It has been proposed that the toner is scraped off by a scraper or a toner collecting roll after the development and before the toner resupply.

Japanese Patent Application Laid-Open No. 7-72733 of Patent Document 5 uses the space between copies or between papers to collect the remaining toner on the developing sleeve on a magnetic roll by a potential difference, and to adjust the amount of toner on the developing sleeve. A method for stabilizing the above has been proposed.

Furthermore, as a countermeasure against a hysteresis phenomenon when a magnetic brush is formed on a developer conveying roll, Japanese Patent Application Laid-Open No. 7-128983 of Patent Document 6 discloses a method in which a full width at half maximum of the magnetic flux density of the magnetic roll is set. There have been proposals to collect and supply toner on the developing roll.

Japanese Patent Application Laid-Open No. 7-92913 of Patent Document 7 uses a non-spherical carrier as a carrier for charging toner on a developer transport roll, so that charge is injected to the carrier at the tip of the magnetic brush and developed. By narrowing the substantial gap between the sleeve and the developing sleeve, the toner supply amount to the developing sleeve is increased at one time, and the toner is supplied up to the toner saturation amount on the developing sleeve, thereby affecting the history of the previous image. A method has been proposed in which the toner amount on the developing sleeve is kept constant without being affected.

Japanese Patent Application Laid-Open No. 7-281517 of Patent Document 8 discloses a method for suppressing ghost by providing a coating film made of molybdenum on the surface of a developing sleeve of a one-component developing system. However, this method prevents an increase in the amount of charge due to the developer being carried around the developing sleeve and being rubbed against the developing sleeve many times. Absent.

Japanese Patent Application Laid-Open No. 2003-76132 of Patent Document 9 discloses a high wear-resistant plating layer that prevents unevenness on the surface of a developer-carrying member subjected to a roughening treatment for one-component development from being reduced by wear. In order to prevent the substrate from undergoing thermal deformation and the gap between the electrostatic latent image carrier and the developer carrying member from partially varying, an electro-Cr plated layer and an electroless layer are formed on the aluminum substrate. By using a developing sleeve provided with a Ni-P layer, however, this method is not an effective solution for the afterimage of the two-component developing system.

Japanese Patent Application Laid-Open No. 2007-121561 of Patent Document 10 discloses a method of providing a metal layer having a specular gloss on the surface of a substrate in order to control the roughness of the developing sleeve, and that the effect can be obtained even with a two-component developer. Is described. However, Patent Document 10 only describes an example of a one-component development system, and also describes that “in general, image density increases as the chargeability of the surface layer increases”. Therefore, the present invention relates to the one-component development method, and is not an effective solution to the afterimage generation of the two-component development method.

Further, in the hybrid development method and the one-component development method, the developer is prevented from slipping on the developing sleeve rotating at high speed by performing sandblasting or groove formation on the outer surface of the developing sleeve. This prevents a decrease in image density caused by a stagnation of the developer due to a slight slip.

However, since the unevenness formed on the outer surface is very fine, the unevenness is gradually scraped by a developer or the like, and as a result, the development sleeve subjected to the sandblasting process described above increases as the number of printed sheets increases. That is, the above-described unevenness is shaved and flattened due to aging. Therefore, the developing sleeve subjected to the sandblasting process described above has a problem that the amount of developer transport is gradually reduced and the formed image is gradually thinned. Thus, the developing sleeve subjected to sandblasting has a problem of durability. The developing sleeve can be made of high-hardness stainless steel or the surface can be hardened, but this is not desirable because it increases costs.

  As for the toner, the pulverized toner has a broad particle size distribution and a large amount of fine powder compared to the polymerized toner, so that the surface of the developing sleeve is easily stained and a ghost image is likely to be generated. From the viewpoint of cost reduction of toner, development of a pulverized toner that is excellent in low-temperature fixability and heat-resistant storage stability and that does not generate afterimages is desired.

  Conventionally, various studies have been made in order to improve toner fixability. For example, in order to improve the toner fixing performance, a method of controlling the thermal characteristics of the resin itself, represented by the glass transition temperature (Tg) and the softening temperature (T1 / 2), is known.

However, a decrease in the glass transition temperature of the resin causes a deterioration in heat-resistant storage stability, and a decrease in the softening temperature due to a decrease in the molecular weight of the resin causes problems such as the occurrence of hot offset.
Therefore, by controlling the thermal characteristics of a single resin, it is not possible to obtain a toner having all of low-temperature fixability, heat-resistant storage stability, and hot offset resistance.

  In order to cope with the low-temperature fixing, an attempt has been made to use a polyester resin having excellent low-temperature fixability and relatively good heat-preserving stability in place of the conventionally used styrene-acrylic resins (see Patent Document 11). Japanese Patent Application Laid-Open No. 60-90344, Japanese Patent Application Laid-Open No. 64-15755, Japanese Patent Application Laid-Open No. Hei 2-82267, Japanese Patent Application Laid-Open No. 2-229264, Japanese Patent Application Laid-Open No. (Kaihei 3-41470, JP-A-11-305486).

In addition, there has been an attempt to add a specific non-olefinic crystalline polymer having sharp melt properties at the glass transition temperature to the binder for the purpose of improving low-temperature fixability (Japanese Patent Laid-Open No. 62-63940). is there. However, these cannot be said to have been optimized for molecular structure and molecular weight.

  In Japanese Patent No. 2931899 of Patent Document 18 and Japanese Patent Application Laid-Open No. 2001-222138 of Patent Document 19, a crystalline polyester having a sharp melt property is used for the toner in the same manner as the specific non-olefinic crystalline polymer described above. Thus, a technique for improving the fixing property is disclosed.

However, the toner using the crystalline polyester described in Patent Document 18 has a low acid value and a hydroxyl value of 5 or less and 20 or less, respectively, and has a low affinity for paper and the crystalline polyester. I don't have it.
Further, the toner using the crystalline polyester described in Patent Document 19 is not optimized with respect to the molecular weight of the finally obtained toner and the presence state of the crystalline polyester. For this reason, the toner using the crystalline polyester described in Patent Document 19 does not always exhibit the excellent low-temperature fixability and heat-resistant storage stability caused by the crystalline polyester after it is actually converted into a toner. In addition, no countermeasure against hot offset is taken, and a temperature range in which a good image can be fixed is not always secured.

  Japanese Patent Application Laid-Open No. 2004-46095 of Patent Document 20 proposes a technique in which an incompatible crystalline polyester resin and an amorphous polyester resin have a sea-island phase separation structure. However, the toner described in Patent Document 20 uses three types of resins including a crystalline polyester resin as a resin. If an attempt is made to maintain the sea-island structure of the crystalline polyester resin with this technique, the crystalline polyester resin is used. The dispersion diameter of the toner may become too large, which may hinder heat-resistant storage stability, or the electrical resistance may be too low, resulting in a transfer failure in the transfer process, which may cause a rough image.

In Japanese Patent Application Laid-Open No. 2007-33773 of Patent Document 21, in the DSC curve measured by a differential scanning calorimeter, the existence state of the crystalline polyester resin is controlled by defining the endothermic amount of the peak appearing on the endothermic side. Therefore, a technique has been proposed in which the effect of the crystalline polyester resin is significantly exhibited, and the toner is imparted with low-temperature fixability and heat-resistant storage stability.
However, in Patent Document 21, it is assumed that a resin having a relatively high softening temperature is used as the amorphous polyester resin used in combination with the crystalline polyester resin, and the role of low-temperature fixability is guaranteed by the crystalline polyester resin. Therefore, the amount of the crystalline polyester resin used is inevitably increased, and the risk of deterioration in heat resistant storage stability due to the compatibility with the amorphous resin is increased.

  Japanese Patent Application Laid-Open No. 2005-338814 of Patent Document 22 proposes a technique in which a toner contains a large amount of crystalline polyester resin. However, since the amount of crystalline polyester resin is very large, compatibility with an amorphous resin is caused. There is a high risk of deterioration in heat-resistant storage stability.

  In Japanese Patent No. 4118498 of Patent Document 23, a technique for defining the peak and half-value width of the toner, the amount of chloroform insolubles, and using two or more resins having different softening temperatures as the binder resin is disclosed. Has been proposed. However, since no crystalline polyester resin is used, the low-temperature fixability is insufficient as compared with the case where a crystalline polyester resin is used.

The present invention has been made in view of the current state of the above-described prior art, that is, the toner consumption of the immediately preceding image is compatible with both excellent excellent low temperature fixability, high hot offset resistance, and good storage stability. An image forming method capable of developing a stable toner amount without being affected by the history, obtaining a uniform image excellent in color reproducibility over a long period of time, and forming a high-quality image over the long term An object of the present invention is to provide an image forming apparatus.

The said subject is solved by following (1)-(14) of this invention.
(1) “a process of forming an electrostatic latent image on an image carrier, a process of developing the electrostatic latent image with a developer containing toner for developing an electrostatic image, and a toner image; An image forming method comprising a step of transferring onto a transfer body and a step of fixing a toner image on the transfer body,
The developing step is to form a toner image using a developing sleeve having a coat layer on a substrate,
The toner is
It has a toner binder including a crystalline resin, an amorphous resin, and a composite resin,
The crystalline resin is a polyester resin (A) having crystallinity,
The amorphous resin includes an amorphous resin (B) containing a chloroform-insoluble component, an amorphous resin (C) having a softening temperature (T1 / 2) lower than that of the amorphous resin (B) by 25 ° C. or more. The absolute value | Tgc−Tgb | of the difference between the glass transition temperature (Tgc) of the amorphous resin (C) and the glass transition temperature (Tgb) of the amorphous resin (B) is 10 ° C. or less. ,
The composite resin is a composite resin (D) having a condensation polymerization resin unit and an addition polymerization resin unit,
The toner has a main peak in which the molecular weight distribution by GPC determined by THF-soluble content is between 1000 and 10,000, and the half-value width of the molecular weight distribution is 15000 or less ",
(2) “The coating layer contains elements of Groups 2-6 and 12-16 of the Periodic Table of Elements and has a surface roughness (Ra) of 10 μm or less. The image forming method according to item 1), "
“The image forming method according to (1) or (2), wherein the coating layer has a surface roughness (Ra) of 8 μm or less”,
"The image forming method according to any one of (1) to (3), wherein the coat layer has TiN on a surface thereof",
(5) “The image forming method according to any one of (1) to (4) above, wherein the toner has inorganic fine particles on its surface”;
(6) "The image forming method according to any one of (1) to (5) above, wherein the toner contains a fatty acid amide compound",
(7) "The image forming method according to any one of (1) to (6) above, wherein the toner contains a metal salicylic acid compound",
(8) Any one of (1) to (7) above, wherein the toner has an endothermic peak in a range of 90 to 130 ° C. in an endothermic peak measurement by DSC. Described image forming method ",
(9) “The toner has an endothermic peak of 1 J / g or more and 15 J / g or less in the endothermic peak measurement by DSC. Image forming method according to
(10) The items (1) to (9), wherein the crystalline polyester (A) contains an ester bond represented by the following general formula (1) in the molecular main chain. An image forming method according to any one of the above;

（式中、Ｒは炭素数２〜２０の直鎖状不飽和脂肪族２価カルボン酸残基を示し、ｎは２〜２０の整数を示す。）」、
（１１）「前記非結晶性樹脂（Ｂ）が、クロロホルム不溶分を５〜４０質量％含有することを特徴とする前記第（１）項乃至第（１０）項のいずれかに記載の画像形成方法」、
（１２）「前記非結晶性樹脂（Ｃ）が、ＴＨＦ可溶分により求められたＧＰＣによる分子量分布が１０００〜１００００の間にメインピークを有し、該分子量分布の半値幅が１５０００以下であることを特徴とする前記第（１）項乃至第（１１）項のいずれかに記載の画像形成方法」、
（１３）「前記複合樹脂（Ｄ）が、ポリエステルの縮重合系樹脂ユニットとビニル系樹脂の付加重合系ユニットを有する複合樹脂であることを特徴とする前記第（１）項乃至第（１２）項のいずれかに記載の画像形成方法」、
（１４）「像担持体上に静電潜像を形成する手段と、静電潜像を静電荷像現像用トナーを含む現像剤で現像してトナー画像を形成する手段と、トナー画像を被転写体上に転写する手段と、被転写体上のトナー画像を定着する手段とを有する画像形成装置であって、
前記現像手段は、基体上にコート層を有する現像スリーブを有するものであり、
前記トナーは、
結晶性樹脂、非結晶性樹脂、及び複合樹脂を含むトナーバインダーを有するものであり、
前記結晶性樹脂は、結晶性を有するポリエステル樹脂（Ａ）であり、
前記非結晶性樹脂は、クロロホルム不溶分を含有する非結晶性樹脂（Ｂ）と該非結晶性樹脂（Ｂ）よりも軟化温度（Ｔ１/２）が２５℃以上低い非結晶性樹脂（Ｃ）とを含み、前記非結晶性樹脂（Ｃ）のガラス転移温度（Ｔｇｃ）と前記該非結晶性樹脂（Ｂ）のガラス転移温度（Ｔｇｂ）の差の絶対値｜Ｔｇｃ−Ｔｇｂ｜が１０℃以下であり、
前記複合樹脂は、縮重合系樹脂ユニットと付加重合系樹脂ユニットとを有する複合樹脂（Ｄ）であり、
前記トナーは、ＴＨＦ可溶分により求められたＧＰＣによる分子量分布が１０００〜１００００の間にメインピークを有し、該分子量分布の半値幅が１５０００以下であることを特徴とする画像形成装置」。

(Wherein R represents a linear unsaturated aliphatic divalent carboxylic acid residue having 2 to 20 carbon atoms, and n represents an integer of 2 to 20). "
(11) “Image formation according to any one of items (1) to (10), wherein the amorphous resin (B) contains 5 to 40% by mass of chloroform-insoluble matter. Method",
(12) “The non-crystalline resin (C) has a main peak between GPC molecular weight distributions determined by THF-soluble content of 1000 to 10,000 and the half-value width of the molecular weight distribution is 15000 or less. The image forming method according to any one of Items (1) to (11),
(13) The items (1) to (12), wherein the composite resin (D) is a composite resin having a polyester condensation polymerization resin unit and a vinyl resin addition polymerization unit. The image forming method according to any one of items
(14) “Means for forming an electrostatic latent image on the image carrier, means for developing the electrostatic latent image with a developer containing toner for developing an electrostatic image, and forming a toner image; An image forming apparatus having means for transferring onto a transfer body and means for fixing a toner image on the transfer body,
The developing means has a developing sleeve having a coat layer on a substrate,
The toner is
It has a toner binder including a crystalline resin, an amorphous resin, and a composite resin,
The crystalline resin is a polyester resin (A) having crystallinity,
The amorphous resin includes an amorphous resin (B) containing a chloroform-insoluble component, an amorphous resin (C) having a softening temperature (T1 / 2) lower than that of the amorphous resin (B) by 25 ° C. or more. The absolute value | Tgc−Tgb | of the difference between the glass transition temperature (Tgc) of the amorphous resin (C) and the glass transition temperature (Tgb) of the amorphous resin (B) is 10 ° C. or less. ,
The composite resin is a composite resin (D) having a condensation polymerization resin unit and an addition polymerization resin unit,
The image forming apparatus, wherein the toner has a main peak in a molecular weight distribution by GPC determined by THF-soluble content of 1000 to 10,000, and a half width of the molecular weight distribution is 15000 or less.

As will be understood from the following detailed and specific description, according to the present invention, low temperature fixability, high hot offset resistance, and good storage stability are compatible, and the influence of the toner consumption history of the immediately preceding image. Image forming method and image forming apparatus capable of developing a stable toner amount without being affected, and obtaining a uniform image excellent in color reproducibility over a long period of time and forming a high-quality image over the long term Is provided.

It is a graph which shows the X-ray-diffraction result of crystalline polyester resin a6 used in the Example. 42 is an example of a graph showing an X-ray diffraction result of the toner obtained in Example 32. 1 is a schematic diagram illustrating an example of an electrophotographic developing device according to the present invention. It is the schematic which shows an example of the image development apparatus used by this invention. FIG. 5 is a diagram illustrating an example of an image forming apparatus having the developing device of FIG. 4. It is a figure which shows the other example of the image forming apparatus used by this invention. It is a figure which shows an example of the process cartridge of this invention. It is a figure which shows the longitudinal belt chart used for evaluation of a ghost image.

Toners with low temperature fixability for energy saving have a lower fixing minimum temperature. In general, in the two-component development system, heat tends to accumulate in the toner due to the stirring of the developer, and the toner components tend to dissolve out. It is in. Therefore, there is a problem that the toner component easily adheres to the groove or the like of the developing sleeve and a ghost image is generated.
In order to achieve both low-temperature fixability and prevention of ghost image generation, countermeasures from both the toner and process aspects are required.

The toner of the present invention will be described.
To simply fix the toner at a low temperature, the toner binder may have a low softening temperature (T1 / 2). However, if the softening temperature is lowered, the glass transition temperature is lowered and the heat resistant storage stability is deteriorated.
In addition, since the lower limit of the fixable temperature (fixing lower limit temperature) at which no problem occurs in image quality is lowered, the upper limit of fixing temperature (fixing upper limit temperature) is also lowered, so that the hot offset resistance is also impaired. The heat resistant storage stability is also lowered.
For this reason, it is a very difficult proposition for designers of electrophotographic image forming toners to achieve both low-temperature fixability, heat-resistant storage stability, and hot offset resistance.

As a result of intensive studies on the above propositions, the present inventors have a toner binder including a crystalline resin, an amorphous resin, and a composite resin, and the crystalline resin is a polyester resin having crystallinity. (A), the non-crystalline resin is a non-crystalline resin (B) containing a chloroform-insoluble component and a non-crystalline resin having a softening temperature (T1 / 2) lower than that of the non-crystalline resin (B) by 25 ° C. or more. The absolute value of the difference between the glass transition temperature (Tgc) of the non-crystalline resin (C) and the glass transition temperature (Tgb) of the non-crystalline resin (B) | Tgc -Tgb | is 10 ° C. or less, the composite resin is a composite resin (D) having a condensation polymerization resin unit and an addition polymerization resin unit, and the toner is a GPC determined by THF soluble content. Molecular weight distribution by 1000-1 It has been found that by using a toner having a main peak between 0000 and a half-value width of the molecular weight distribution of 15000 or less, it is possible to save energy, increase the speed, and form a high-quality image over a long period of time.

The toner binder of the present invention will be described.
By using the crystalline polyester (A), the toner binder can impart low-temperature fixability and heat-resistant storage stability to the toner due to the sharp melt property due to the crystallinity.
However, when the crystalline polyester (A) is used alone as a toner binder, the hot offset resistance becomes very poor, and the fixing temperature width becomes very narrow and cannot be practically used.

Therefore, by using an amorphous resin (B) containing a chloroform-insoluble component together with the crystalline polyester resin (A), it is possible to improve hot offset resistance and widen the fixable temperature range.
However, when only the crystalline polyester (A) and the amorphous resin (B) are formulated, the effect of the crystalline polyester (A) decreases when the amount of the amorphous resin (B) increases, and the low-temperature fixability decreases. On the other hand, if the amount of the crystalline polyester (A) is large, the crystalline polyester (A) is compatible with components other than the chloroform-insoluble component of the amorphous resin (B) when melt-kneaded. Due to the decrease in the glass transition temperature of the crystalline resin (B), the heat-resistant storage stability is extremely deteriorated.

  As a result of studies by the present inventors, when only the crystalline polyester (A) and the amorphous resin (B) are prescribed, how the distribution of the crystalline polyester (A) and the amorphous resin (B) changes. Even if it is made, energy saving can be achieved in combination with the fixing device, and there is no mixing ratio that satisfies all of the low-temperature fixing property, heat-resistant storage property, and hot-offset resistance.

  Therefore, by further using the amorphous resin (C) whose softening temperature is 25 ° C. or more lower than that of the amorphous resin (B), the distribution of the crystalline polyester (A) is reduced, and the crystalline polyester ( A) is suppressed from lowering the glass transition temperature due to the compatibility of the amorphous resin (B) with components other than the chloroform-insoluble component, and the low-temperature fixability of the crystalline polyester (A) is reduced to the amorphous resin ( It was found that the hot offset resistance due to the amorphous resin (B) was not inhibited by assisting with C).

However, even when the amorphous resin (C) is used in addition to the crystalline polyester (A) and the amorphous resin (B), the heat resistant storage stability cannot be satisfied.
That is, even if the compatibility between the crystalline polyester (A) and the components other than the chloroform-insoluble component of the amorphous resin (B) is suppressed, and the glass transition temperature decrease of the toner binder is suppressed, the crystalline polyester (A) However, if the dispersion diameter remains large, the interface between the crystalline polyester (A) and the amorphous resin tends to be crushed during the pulverization step, and as a result, the crystalline polyester (A) appears on the toner particle surfaces. It becomes easy.

Since the crystalline polyester (A) is a sharp melt material, when it is present inside the toner particles, it exhibits excellent heat storage stability as described above, but when it is present on the toner particle surface, the glass transition of the toner binder. Since the crystals are slightly broken even at temperatures below the temperature, the crystalline polyester (A) acts as a binder between the toner particles, and as a result, the heat resistant storage stability of the toner is deteriorated. This phenomenon is particularly remarkable in a crystalline polyester resin having a low crystallinity.

  In addition, when the amorphous resin (C) is added to suppress the compatibility of the crystalline polyester (A) with the components other than the chloroform-insoluble component of the amorphous resin (B), the crystalline polyester (A) becomes amorphous during melt kneading. Since the viscosity of the resin (C) is low, the toner material containing the amorphous resin (C) is less likely to be sheared, and the dispersion diameter of the crystalline polyester resin (A) tends to increase.

The crystalline polyester resin (A) has a relatively low electrical resistance, and other toner materials such as a colorant, a release agent, and a resistance adjuster are included in the domain of the crystalline polyester resin (A). Since it cannot enter the toner, it will be present in the amorphous resin (B) and the amorphous resin (C) in a relatively high concentration state. If the dispersion diameter of the crystalline polyester resin (A) is increased, the toner Nonuniformity in the particles occurs, and the particles of the crystalline polyester resin (A) may be unevenly distributed in either the amorphous resin (B) or the amorphous resin (C), resulting in a decrease in electrical resistance. It becomes difficult to control the toner characteristics.

However, by prescribing the composite resin (D) having a condensation polymerization resin unit and an addition polymerization resin unit, the composite resin (D) is harder than the non-crystalline resin resin (C) and is suitable for melt kneading. The dispersion of the crystalline polyester (A) is improved and the glass transition temperature (Tgc) of the amorphous resin (C) and the glass transition of the amorphous resin (B) are increased. When the absolute value | Tgc−Tgb | of the difference in temperature (Tgb) is 10 ° C. or less, the amorphous resin (C) and the amorphous resin in the toner material are cooled after the toner material is melt-kneaded. The glass transition with (B) occurs almost at the same time, and the particles of the crystalline polyester resin (A) can be maintained in a finely dispersed state without being biased in either resin, and non-uniformity is prevented and electric resistance is prevented. To prevent deterioration, toner Sex control becomes easy.

In addition, since the composite resin (D) is hard and easily appears at the interface during pulverization, the probability that the amorphous resin (C) having a low softening temperature appears on the toner particle surface is reduced, contributing to improvement in heat resistant storage stability. Adherence to the developing sleeve is prevented.

  In addition, by prescribing the composite resin (D), the hardness of the toner particle surface is increased, so that toner deterioration due to physical stress is prevented, and external additives such as a charge imparting agent and a fluidity imparting agent are added. In this case, the embedding of the external additive in the toner particles is prevented, the change in the toner characteristics such as the charging characteristics due to the stress is reduced, the sticking to the developing sleeve is reduced by the inorganic fine particles, and the image quality is stable over a long period of time. It becomes possible to provide.

  As described above, the toner binder in the present invention is complemented by the crystalline polyester resin (A), the non-crystalline resin (B), the non-crystalline resin (C), and the composite resin (D). , Heat-resistant storage stability, and hot offset resistance, the toner has a main peak between 1000 and 10,000 in terms of molecular weight distribution by GPC determined by THF-soluble matter, and has a molecular weight distribution. It is necessary that the full width at half maximum is 15000 or less.

In particular, when the chain of molecules insoluble in chloroform contained in the amorphous resin (B) is short and the molecular weight distribution of the entire toner binder becomes broad, the low temperature due to the amorphous resin (C) having a low softening temperature. Fixability will be reduced.

Next, each resin constituting the toner binder will be described.
<Crystalline polyester A>
As the crystalline polyester resin (A) in the present invention, a conventionally known one can be used, but an aromatic dicarboxylic acid can be used by using a linear unsaturated aliphatic dicarboxylic acid as the acid component. There is an advantage that it is easier to form a crystal structure than in the case where it is present, and the function of the crystalline polyester resin can be exhibited more effectively.

  The polyester resin (A) is composed of, for example, (i) a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (an acid anhydride, a lower alkyl ester having 1 to 4 carbon atoms, an acid halide, etc.). A polyvalent carboxylic acid component and (ii) a polyhydric alcohol component composed of a linear aliphatic diol can be produced by a polycondensation reaction and represented by the following general formula (1) in the molecular main chain. It is preferable to contain an ester bond.

（式中、Ｒは炭素数２〜２０の直鎖状不飽和脂肪族２価カルボン酸残基を示し、ｎは２〜２０の整数を示す。）
一般式（１）の構造の存在は固体Ｃ^１３ＮＭＲにより確認することができる。

(In the formula, R represents a linear unsaturated aliphatic divalent carboxylic acid residue having 2 to 20 carbon atoms, and n represents an integer of 2 to 20).
The presence of the structure of the general formula (1) can be confirmed by solid C ¹³ NMR.

Specific examples of the linear unsaturated aliphatic group include linear unsaturated divalent carboxylic acids such as maleic acid, fumaric acid, 1,3-n-propene dicarboxylic acid, and 1,4-n-butene dicarboxylic acid. Examples include acid-derived linear unsaturated aliphatic groups.
In the general formula (1), (CH ₂ ) _n represents a linear aliphatic dihydric alcohol residue. Specific examples of the linear aliphatic dihydric alcohol residue in this case include linear aliphatic 2 such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Those derived from a monohydric alcohol.

In addition to the polyvalent carboxylic acid component, a small amount of other polyvalent carboxylic acid may be added as necessary.
Examples of the other polyvalent carboxylic acid include (i) unsaturated aliphatic divalent carboxylic acid having a branched chain, (ii) saturated aliphatic divalent carboxylic acid, and saturated aliphatic trivalent carboxylic acid. Examples include polyvalent carboxylic acids, (iii) aromatic polyvalent carboxylic acids such as aromatic divalent carboxylic acids and aromatic trivalent carboxylic acids, such as malonic acid, succinic acid, glutaric acid, adipic acid, and suberic acid. Divalent carboxylic acids such as sebacic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid; trimetic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2, 4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1, 7,8 etc. trivalent or higher-valent carboxylic acid such as octane tetracarboxylic acid.

  The addition amount of these other polyvalent carboxylic acids is usually 30 mol% or less, preferably 10 mol% or less with respect to the total carboxylic acid, and is suitably added within the range in which the resulting polyester has crystallinity. .

In addition to the polyhydric alcohol component, other polyhydric alcohol components may be added as necessary. Examples of the other polyhydric alcohol components include aliphatic branched dihydric alcohols and cyclic dihydric alcohols, 3 Examples thereof include polyhydric alcohols having a valency or higher, such as 1,4-bis (hydroxymethyl) cyclohexane, polyethylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, and glycerin.
The addition amount of these other polyhydric alcohol components is 30 mol% or less, preferably 10 mol% or less, based on the total alcohol, and is appropriately added within the range where the resulting polyester has crystallinity.

The molecular weight distribution of the crystalline polyester resin (A) of the present invention is preferably sharp from the viewpoint of low-temperature fixability.
In the molecular weight distribution diagram in which the horizontal axis is log (M: molecular weight) and the vertical axis is mass%, the crystalline polyester resin (A) used in the present invention is in the range of 3.5 to 4.0 (mass%). It is preferable to have a molecular weight peak and that the half width of the peak is 1.5 or less.

  In addition, the molecular weight of the crystalline polyester resin (A) of the present invention is preferably a relatively low molecular weight, and the weight average molecular weight (Mw) is 5500 to 5 in the molecular weight distribution by GPC of soluble o-dichlorobenzene. 6500, the number average molecular weight (Mn) is 1300 to 1500, and the Mw / Mn ratio is preferably 2 to 5.

GPC (gel permeation chromatography) is measured as follows.
The column was stabilized in a heat chamber at 40 ° C., and THF was added to the column at this temperature as a solvent at a flow rate of 1 ml / min. Is measured by injecting 50 to 200 μl.
In measuring the molecular weight of the sample (toner), the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the prepared calibration curve and the number of counts using several types of monodisperse polystyrene standard samples.
As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Or molecular weight made by Toyo Soda Industry Co., Ltd. is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. It is suitable to use x10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

In the crystalline polyester resin (A) of the present invention, the glass transition temperature (Tg) and the softening temperature (T1 / 2) are desirably low as long as the heat resistant storage stability of the toner is not deteriorated.
The Tg of the crystalline polyester resin (A) is preferably 80 to 130 ° C, and more preferably 80 to 125 ° C.
The softening temperature (T1 / 2) of the crystalline polyester resin (A) is preferably 80 to 130 ° C, and more preferably 80 to 125 ° C.
When the glass transition temperature (Tg) and the softening temperature (T1 / 2) are higher than the above ranges, the fixing lower limit temperature of the toner is increased, and the low-temperature fixability is deteriorated.

The softening temperature (T1 / 2) of the binder resin is as follows: an elevated flow tester CFT-500 (manufactured by Shimadzu Corporation), a die hole diameter of 1 mm, a pressure of 20 kg / cm ² , and a temperature increase rate of 6 ° C./min. The temperature is measured at a temperature corresponding to ½ from the outflow start point to the outflow end point when a 1 cm ² sample is melted out.
A method for measuring the glass transition temperature Tg will be described later.

Whether or not the polyester resin in the present invention has crystallinity can be confirmed by whether or not a peak exists in the X-ray diffraction pattern by the powder X-ray diffractometer.
The crystalline polyester resin (A) used in the present invention has at least one diffraction peak at a position where 2θ is 19 ° to 25 ° in the diffraction pattern, and more preferably 2θ is (i) 19 ° to 20 °. It is preferable that diffraction peaks exist at positions of °, (ii) 21 ° to 22 °, (iii) 23 ° to 25 °, and (iv) 29 ° to 31 °.
Even after toner formation, a diffraction peak exists at a position of 2θ = 19 ° to 25 °, that is, it indicates that the crystalline polyester resin (A) maintains the crystallinity, and the crystalline polyester resin ( The function of A) can be surely exhibited.

The powder X-ray diffraction measurement was carried out using a Rigaku Electric RINT1100, using a wide-angle goniometer under the conditions that the tube was Cu and the tube voltage-current was 50 kV to 30 mA.
FIG. 1 shows an X-ray diffraction result of the crystalline polyester resin a6 used in the example, and FIG. 2 shows an X-ray diffraction result of the toner 35 obtained in the example.

<Amorphous resin>
The amorphous resin of the present invention comprises an amorphous resin (B) containing a chloroform-insoluble component and an amorphous resin (C) whose softening temperature (T1 / 2) is 25 ° C. or lower lower than that of the amorphous resin (B). The absolute value | Tgc−Tgb | of the difference between the glass transition temperature (Tgc) of the amorphous resin (C) and the glass transition temperature (Tgb) of the amorphous resin (B) is 10 ° C. It is as follows.

The non-crystalline resin achieves both offset resistance and low-temperature fixability, and the glass transition between the non-crystalline resin (C) and the non-crystalline resin (B) occurs almost simultaneously, and the crystalline polyester resin (A) It becomes possible to finely disperse the particles without unevenness, and by bringing the glass transition temperature of the amorphous resin (B) close to the glass transition temperature of the amorphous resin (C) effective for the lower limit of fixing, Lower temperature fixability is improved.

When the absolute value of the glass transition temperature difference is 10 ° C. or less, uneven distribution of the crystalline polyester resin (A) can be prevented and fine dispersion can be achieved, and sharp melt property and low temperature fixability can be improved. When the absolute value of the glass transition temperature difference is greater than 10 ° C., the cooling state of the amorphous resin (C) and the amorphous resin (B) in the toner during kneading and cooling differs, and the crystalline polyester resin (A ) Agglomeration occurs, resulting in deterioration of heat resistant storage stability and electrical resistance.

  As the non-crystalline resin (B) and the non-crystalline resin (C), the content of chloroform insolubles and the magnitude relationship between the softening temperature of the non-crystalline resin (B) and the non-crystalline resin (C), and glass If the range of the absolute value | Tgc−Tgb | of the difference in transition temperature is satisfied, a conventionally known material can be used.

For example, polystyrene, chloropolystyrene, poly α-methylstyrene, styrene / chlorostyrene copolymer, styrene / propylene copolymer, styrene / butadiene copolymer, styrene / vinyl chloride copolymer, styrene / vinyl acetate copolymer Styrene / maleic acid copolymer, styrene / acrylic acid ester copolymer (styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / octyl acrylate) Copolymer, styrene / phenyl acrylate copolymer, etc.), styrene / methacrylate copolymer (styrene / methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer). , Styrene / Phenyl methacrylate copolymer ), Styrene resins such as styrene / α-methyl acrylate copolymer, styrene / acrylonitrile / acrylate ester copolymer (homopolymer or copolymer containing styrene or styrene-substituted product), vinyl chloride resin Styrene / vinyl acetate copolymer, rosin modified maleic acid resin, phenol resin, epoxy resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene / ethyl acrylate copolymer, xylene resin, Polyvinyl butyral resin, etc., petroleum-based resins, hydrogenated petroleum-based resins, and the like can be mentioned. These resins are not limited to single use but can be used in combination of two or more. A resin is preferred.

  Moreover, the manufacturing method of these resin is not specifically limited, Any of block polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be utilized.

As the polyester resin, those usually obtained by condensation polymerization of alcohol and carboxylic acid can be used.

  Examples of the alcohol include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol, ethylated bisphenols such as 1.4-bis (hydroxymethyl) cyclohexane and bisphenol A, and other dihydric alcohols. Mention may be made of monomers and trihydric or higher polyhydric alcohol monomers.

  Examples of the carboxylic acid include divalent organic acid monomers such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid, and 1,2,4-benzenetricarboxylic acid. 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2- Mention may be made of trivalent or higher polyvalent carboxylic acid monomers such as methylenecarboxypropane and 1,2,7,8-octanetetracarboxylic acid.

When the non-crystalline resin is a polyester resin, the glass transition temperature Tg is preferably 55 ° C. or higher, more preferably 60 ° C. or higher and 80 ° C. or lower from the viewpoint of heat-resistant storage stability.

The amorphous resin (B) of the present invention contains a chloroform-insoluble component and improves hot offset resistance.
The content of the chloroform-insoluble component is preferably 5 to 40% by mass because hot offset resistance is easily developed.

Further, it is preferable that the amount of insoluble chloroform in the toner is 2 to 20% by mass after the toner is formed, because distribution of resins other than the amorphous resin (B) can be secured while maintaining hot offset resistance. . When the chloroform insoluble content in the toner is less than 2% by mass, the hot offset resistance due to the chloroform insoluble content becomes dilute, and when it exceeds 20% by mass, the distribution of the binder resin that contributes to the low-temperature fixing property. Therefore, the low-temperature fixability deteriorates.

The chloroform insoluble matter is measured as follows.
About 1.0 g of toner (or binder resin) is weighed, and about 50 g of chloroform is added thereto. The sufficiently dissolved solution is separated by centrifugation, and filtered at room temperature using JIS standard (P3801) type 5 C qualitative filter paper. The filter paper residue is an insoluble component, and the ratio of the used toner mass to the filter paper residue mass (% by mass) represents the content of the chloroform insoluble component.
When measuring the insoluble matter in chloroform when the toner is used, about 1.0 g of the toner is weighed out in the same manner as the binder resin, but solid matter such as pigment is present in the filter paper residue. Therefore, it is obtained separately by thermal analysis.

The amorphous resin (C) of the present invention assists the low temperature fixability of the crystalline polyester resin (A) and contributes to the low temperature fixability.
The non-crystalline resin (C) has a softening temperature (T1 / 2) lower than that of the non-crystalline resin (B) by 25 ° C. or more, and preferably 35 ° C. or more and 50 ° C. or less.

The amorphous resin (C) preferably has a main peak in which the molecular weight distribution by GPC determined from the THF soluble content is 1000 to 10,000, and the half width of the molecular weight distribution is preferably 15000 or less.
Since such an amorphous resin (C) exhibits very good low-temperature fixability, it can sufficiently assist low-temperature fixability even when the amount of the crystalline polyester resin (A) is reduced when formulated into a toner. it can.
Further, paradoxically, even when the amorphous resin (C) having the above-described molecular weight distribution is used, the toner has a main peak between 1000 and 10,000 in the molecular weight distribution, and the half width is 15000 or less. In this case, the proportion of the non-crystalline resin (C) in the binder resin constituting the toner becomes high.

<Composite resin>
The composite resin (D) is a resin (also referred to as a hybrid resin) in which a condensation polymerization monomer and an addition polymerization monomer are chemically bonded, and dispersion of the crystalline polyester (A) and other toner materials. In addition, the toner particles are hardened by the composite resin (D) and contamination of the developing sleeve can be prevented.
In the composite resin (D), the condensation polymerization monomer and the addition polymerization monomer are chemically bonded to each other so that the site derived from the condensation polymerization monomer component and the site derived from the addition polymerization monomer are uniformly dispersed. The Tg of the composite resin (D) expresses sharp melt properties without being divided into Tg of the site derived from the condensation polymerization monomer component and Tg of the site derived from the addition polymerization monomer.

  The composite resin (D) is obtained by performing a polycondensation monomer and an addition polymerization monomer as a raw material in the same reaction vessel by simultaneously performing a polycondensation reaction and an addition polymerization reaction in parallel, It can be obtained by sequentially performing an addition polymerization reaction, or an addition polymerization reaction and a condensation polymerization reaction.

  Polycondensation monomers in the composite resin (D) include polyhydric alcohols and polycarboxylic acids that form polyester resin units, polyhydric carboxylic acids and amines that form polyamide resin units or polyester-polyamide resin units, and amino acids. However, a composite resin having a polyester condensation polymerization resin unit and a vinyl resin addition polymerization unit has an affinity for the polyester resin and is excellent in dispersibility in toner particles. The function (D) can be exhibited more effectively, which is preferable.

As the polyhydric alcohol, a dihydric alcohol, a trihydric or higher alcohol can be used. Examples of the dihydric alcohol include 1,2-propanediol, 1,3-propanediol, ethylene glycol, and propylene glycol. 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl Examples include -1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ether such as ethylene oxide and propylene oxide with bisphenol A.
Examples of the trivalent or higher alcohols include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1 , 2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, etc. It is done.
Among these, hydrogenated bisphenol A or alcohol components having a bisphenol A skeleton such as diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A impart heat-resistant storage stability and mechanical strength to the resin. Therefore, it can be suitably used.

As the polyvalent carboxylic acid, a divalent carboxylic acid, a trivalent or higher carboxylic acid can be used. Examples of the divalent carboxylic acid include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and the like. Anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid Maleic anhydride, citraconic anhydride, itaconic anhydride, unsaturated dibasic acid anhydrides such as alkenyl succinic anhydride, and the like.
Examples of the trivalent or higher polyvalent carboxylic acid include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1, 2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) Examples include methane, 1,2,7,8-octanetetracarboxylic acid, emporic trimer acid, or anhydrides thereof, partially lower alkyl esters, and the like.
Among these, aromatic polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid are preferably used from the viewpoints of heat resistant storage stability and mechanical strength of the resin.

  As the amine component or amino acid component, for example, diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of B1 to B5 are blocked. (B6) and the like.

Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.) and alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diaminocyclohexane, isophorone diamine, etc.), 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 the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid, aminocaproic acid, and ε-caprolactam.
(B6) obtained by blocking the amino group of (B1) to (B5) (K6) obtained from the amines of (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) And oxazolidine compounds.

The molar ratio of the condensation polymerization monomer component in the composite resin (D) is preferably 5 mol% to 40 mol%, more preferably 10 mol% to 25 mol%.
When the molar ratio is less than 5 mol%, the dispersibility with the polyester-based resin deteriorates, and when it exceeds 50 mol%, the dispersion of the release agent tends to deteriorate.
Further, an esterification catalyst or the like may be used when performing the condensation polymerization reaction.

  There is no restriction | limiting in particular as an addition polymerization type monomer in the said composite resin (D), Although it can select suitably according to the objective, A vinyl type monomer is typical.

  Examples of the vinyl monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and pn-amylstyrene. , Styrene vinyl monomers such as p-tert-butylstyrene, pn-hexylstyrene, pn-4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; acrylic acid, acrylic Methyl acid, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-nomer acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid n-butyl, isobutyl methacrylate, methacryl Methacrylic vinyl monomers such as n-octyl, n-dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; other vinyl monomers or co-polymers Other monomers that form a polymer, and the like.

Examples of other vinyl monomers or other monomers that form a copolymer include monoolefins such as ethylene, propylene, butylene, and isobutylene; polyenes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, vinyl bromide, Vinyl halides such as vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, Vinyl ketones such as methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; Vinyl naphthalenes; Acrylonitrile, methacrylonitrile Acrylic acid or methacrylic acid derivatives such as acrylamide; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride Unsaturated dibasic acid anhydrides such as alkenyl succinic anhydride; maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, citraconic acid monobutyl ester, Monoesters of unsaturated dibasic acids such as itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, and mesaconic acid monomethyl ester; unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid An α, β-unsaturated acid such as crotonic acid and cinnamic acid; an α, β-unsaturated acid anhydride such as crotonic acid anhydride and cinnamic anhydride; and the α, β-unsaturated acid and a lower fatty acid Monomers having a carboxyl group such as anhydrides, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these acid anhydrides or monoesters thereof; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate Acrylic acid or methacrylic acid hydroxyalkyl esters such as 4- (1-hydroxy-1-methylbutyl) styrene, monomers having a hydroxy group such as 4- (1-hydroxy-1-methylhexyl) styrene, and the like. It is done.
Among these, styrene, acrylic acid, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, n-butyl methacrylate, 2-ethylhexyl methacrylate and the like are preferably used, and a combination containing at least styrene and acrylic acid Is particularly preferable because the dispersibility of the release agent is extremely good.

Furthermore, a crosslinking agent for addition polymerization monomers can be added as necessary.
Examples of the crosslinking agent include the following crosslinking agents.

Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene.

  Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6. And xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of these compounds with methacrylate.

Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.
Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond.

  Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds in place of methacrylate, triallyl cyanide. Examples include nurate and triallyl trimellitate.

  The addition amount of the crosslinking agent is preferably 0.01 parts by mass to 10 parts by mass, and more preferably 0.03 parts by mass to 5 parts by mass with respect to 100 parts by mass of the addition polymerization monomer used.

  There is no restriction | limiting in particular as a polymerization initiator used when superposing | polymerizing an addition polymerization type monomer, According to the objective, it can select suitably, For example, 2,2'- azobisisobutyronitrile, 2,2 Azo polymerization initiators such as' -azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile); methyl ethyl ketone peroxide, acetylacetone peroxide, 2, Peroxide polymerization initiators such as 2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, benzoyl peroxide, n-butyl-4,4-di- (tert-butylperoxy) valerate Is mentioned.

  These may be used in combination of two or more for the purpose of adjusting the molecular weight and molecular weight distribution of the resin.

  The addition amount of the polymerization initiator is preferably 0.01 parts by mass to 15 parts by mass, and more preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the addition polymerization monomer used.

In order to chemically bond the condensation polymerization resin unit and the addition polymerization resin unit, for example, a monomer that can be reacted by either condensation polymerization or addition polymerization is used.
Examples of such bireactive monomers include unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof; and hydroxy groups. Examples thereof include vinyl monomers.
The addition amount of the both reactive monomers is preferably 1 part by mass to 25 parts by mass, and more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the addition polymerization monomer used.

  As long as the composite resin (D) is in the same reaction vessel, both the condensation polymerization reaction and the addition polymerization reaction proceed and / or complete at the same time, and each reaction temperature and time are selected independently. The progress of the reaction can be completed.

For example, a mixture of an addition polymerization monomer and a polymerization initiator is added dropwise to a mixture of condensation polymerization monomers in a reaction vessel in advance, and the addition polymerization is first completed by a radical polymerization reaction, and then the reaction temperature is increased. There is a method of performing condensation polymerization by raising the temperature.
In this way, it is possible to effectively disperse and combine two types of resin units by advancing two independent reactions in the reaction vessel.

As a softening temperature (T1 / 2) of the said composite resin (D), 90 to 130 degreeC is preferable and 100 to 120 degreeC is more preferable.
When the softening temperature (T1 / 2) is lower than 90 ° C., heat resistant storage stability and offset resistance may be deteriorated, and when it is higher than 130 ° C., low temperature fixability may be deteriorated.

  Further, the glass transition temperature of the composite resin (D) is preferably 45 ° C. to 80 ° C., more preferably 50 ° C. to 70 ° C., and further 53 ° C. to 65 ° C. from the viewpoints of fixability, storage stability and durability. preferable.

  The acid value of the composite resin (D) is preferably 5 mgKOH / g to 80 mgKOH / g, and more preferably 15 mgKOH / g to 40 mgKOH / g, from the viewpoints of chargeability and environmental stability.

The toner binder of the present invention is a combination of a crystalline polyester resin (A), an amorphous resin (B), an amorphous resin (C), and a composite resin (D), and a toner binder containing these resins The balance is best when the proportion of the amorphous resin (B) is increased, and there are side effects due to excessive crystalline polyester resin and excessive THF insoluble matter, and the lower limit of fixing due to the hardness of the composite resin (D). Adverse effects do not become apparent, the functions of the respective resins are effectively exhibited, and low-temperature fixability, heat-resistant storage stability, and hot offset resistance are improved.

Accordingly, the content of the crystalline polyester (A) in the toner binder is preferably 1 to 15% by mass, more preferably 1 to 10% by mass, and the content of the amorphous resin (B) is 10 to 10% by mass. 40% by mass is preferable, the content of the amorphous resin (C) is preferably 50 to 90% by mass, and the content of the composite resin (D) is preferably 3 to 20% by mass.

  In the toner of the present invention, a colorant, a release agent, a charge control agent, a fatty acid amide compound, and the like can be used as necessary.

  Examples of the colorant include carbon black, lamp black, iron black, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6C lake, calco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, tri Any conventionally known dyes and pigments such as dyes and pigments such as allylmethane dyes can be used singly or in combination, and can be used as a black toner or a full color toner.

In particular, carbon black has a good black coloring power. However, at the same time, since it is also a good conductive material, if it is used in a large amount or if it is present in an agglomerated state in the toner particles, the electrical resistance is lowered, causing a transfer failure in the transfer process.
In particular, when used in combination with the crystalline polyester resin (A), the carbon black particles cannot enter the domain of the crystalline polyester resin, so that when the crystalline polyester resin is present in the toner with a large dispersion diameter, the crystalline polyester It exists in a relatively high concentration in a resin other than the resin. For this reason, the aggregate is easily confined in the toner particles, and the resistance is likely to be excessively reduced.

  In the case of this invention, since it uses together with composite resin (D), dispersion | distribution of carbon also becomes favorable and said risk can be reduced. In addition, when carbon black is contained, the viscosity of the melted toner can be increased when fixing the toner to the recording medium. Therefore, when a large amount of the amorphous resin (C) is formulated, the viscosity is lowered. The effect that the hot offset which arises can be suppressed can also be provided.

  The amount of these colorants to be used is generally 1-30% by mass, preferably 3-20% by mass, based on the toner resin component.

  A conventionally well-known thing can be used as said mold release agent. For example, low molecular weight polyethylene, low molecular weight polypropylene and other low molecular weight polyolefin waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, beeswax, carnauba wax, candelilla wax, rice wax, montan wax and other natural waxes, Examples include petroleum waxes such as paraffin wax and microcrystalline wax, higher fatty acids such as stearic acid, palmitic acid, and myristic acid, metal salts of higher fatty acids, higher fatty acid amides, synthetic ester waxes, and various modified waxes thereof.

  Among these release agents, carnauba wax and its modified wax, polyethylene wax, and synthetic ester wax are preferably used. In particular, carnauba wax is very suitable because it is easily finely dispersed in a polyester resin or polyol resin, and can easily be a toner excellent in hot offset resistance, transferability and durability. Further, when used in combination with a fatty acid amide compound, the effect of staying on the fixed image surface becomes very strong, and smear resistance is further improved.

These release agents can be used alone or in combination of two or more. The amount of these release agents used is preferably 2 to 15% by mass with respect to the toner. If it is less than 2% by mass, the effect of preventing hot offset is insufficient, and if it exceeds 15% by mass, transferability and durability are deteriorated.
The melting point of the release agent is preferably 70 to 150 ° C. When the temperature is lower than 70 ° C., the heat resistant storage stability of the toner is lowered. If it is higher than 150 ° C., the releasability cannot be sufficiently achieved.

  Examples of the charge control agent include modified products of nigrosine and fatty acid metal salts, onium salts such as phosphonium salts and lake lakes thereof, triphenylmethane dyes and lake lake pigments, metal salts of higher fatty acids; dibutyltin oxide, dioctyltin Diorganotin oxides such as oxide and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate and dicyclohexyltin borate, organometallic complexes, chelate compounds, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids And aromatic dicarboxylic acid metal complexes, quaternary ammonium salts, salicylic acid metal compounds, and the like. In addition, there are aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, phenol derivatives such as bisphenol, etc., and any of these conventionally known polarity control agents can be used alone or Can be mixed and used. The use amount of these polarity control agents is 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to the toner resin component.

Among these charge control agents, the inclusion of a metal salicylic acid compound is preferable because it can improve hot offset resistance at the same time. In particular, a complex having a tri- or higher-valent metal capable of a hexacoordinate configuration reacts with a highly reactive part of the resin and wax to form a light cross-linked structure, and thus has a large effect on hot offset resistance. Moreover, dispersibility improves by using together with resin (D), and the function of charge polarity control can be exhibited more effectively.
Here, examples of the trivalent or higher metal include Al, Fe, Cr, and Zr.
As the salicylic acid metal compound, a compound represented by the following formula can be used, and examples of the metal complex in which M is zinc include Bontron E-84 manufactured by Orient Chemical Industry Co., Ltd.

（式中、Ｒ^２、Ｒ^３及びＲ^４はそれぞれ独立して水素原子、直鎖又は分枝鎖状の炭素数１〜１０のアルキル基又は炭素数２〜１０のアルケニル基、Ｍはクロム、亜鉛、カルシウム、ジルコニウム又はアルミニウム、ｍは２以上の整数、ｎは１以上の整数を示す）

(Wherein R ² , R ³ and R ⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, M is chromium, Zinc, calcium, zirconium or aluminum, m is an integer of 2 or more, and n is an integer of 1 or more)

The toner of the present invention preferably contains a fatty acid amide compound.
When a fatty acid amide compound is blended with a crystalline polyester resin in a pulverized toner including a melt-kneading process at the time of toner production, recrystallization in the kneaded product is accelerated when the crystalline polyester resin melted at the time of kneading is cooled. Therefore, the compatibility with the resin is reduced, and the decrease in the glass transition temperature of the toner can be suppressed, so that the heat resistant storage stability can be improved. Further, when used in combination with a release agent, it becomes possible to keep the release agent on the surface of the fixed image, and therefore it is resistant to rubbing (improved smear resistance).
The content of the fatty acid amide compound in the toner is preferably 0.5 to 10% by mass.

  As the fatty acid amide compound, a compound represented by the following general formula (I) and an alkylene bis fatty acid amide can be used, and an alkylene bis fatty acid amide is preferable.

一般式（I）中、Ｒ^１は、炭素数１０〜３０の脂肪族炭化水素基であり、Ｒ^２、Ｒ^３は各々独立して水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基、又は炭素数７〜１０のアラルキル基である。ここで、Ｒ^２、Ｒ^３のアルキル基、アリール基、アラルキル基は、フッ素原子、塩素原子、シアノ基、アルコキシ基、アルキルチオ基等の通常不活性な置換基で置換されていても良い。より好ましくは無置換のものである。

In general formula (I), R ¹ is an aliphatic hydrocarbon group having 10 to 30 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 6 carbon atoms. Or an aryl group having 10 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Here, the alkyl group, aryl group, and aralkyl group of R ² and R ³ may be substituted with a generally inactive substituent such as a fluorine atom, a chlorine atom, a cyano group, an alkoxy group, or an alkylthio group. More preferably, it is unsubstituted.

Specific examples include stearic acid amide, stearic acid methylamide, stearic acid diethylamide, stearic acid benzylamide, stearic acid phenylamide, behenic acid amide, behenic acid dimethylamide, myristic acid amide, palmitic acid amide, and the like. It can be preferably used.
The alkylene bis fatty acid amide is a compound represented by the following general formula (II).

（式中Ｒ^１、Ｒ^３は炭素数５〜２１のアルキル基またはアルケニル基、Ｒ^２は炭素数１〜２０のアルキレン基を示す。）

(Wherein R ¹ and R ³ represent an alkyl group or alkenyl group having 5 to 21 carbon atoms, and R ² represents an alkylene group having 1 to 20 carbon atoms.)

  Examples of the alkylene bis saturated fatty acid amide represented by the general formula (II) include methylene bis stearic acid amide, ethylene bis stearic acid amide, methylene bis palmitic acid amide, ethylene bis palmitic acid amide, methylene bis behenic acid amide, and ethylene. Examples thereof include bisbehenic acid amide, hexamethylene bisstearic acid amide, hexaethylene bispalmitic acid amide, hexamethylene bisbehenic acid amide, and the like. Of these, ethylene bis stearamide is most preferred.

  These fatty acid amide compounds can also serve as a release agent on the surface of the fixing member when the softening temperature (T1 / 2) is lower than the temperature of the surface of the fixing member at the time of fixing.

  Specific examples of alkylene bis fatty acid amide compounds that can be used in addition to the above include propylene bis stearic acid amide, butylene bis stearic acid amide, methylene bis oleic acid amide, ethylene bis oleic acid amide, propylene bis oleic acid amide, Butylene bis oleic acid amide, methylene bis lauric acid amide, ethylene bis lauric acid amide, propylene bis lauric acid amide, butylene bis lauric acid amide, methylene bis myristic acid amide, ethylene bis myristic acid amide, propylene bis myristic acid amide, butylene bis Myristic acid amide, Propylene bispalmitic acid amide, Butylene bispalmitic acid amide, Methylene bispalmitoleic acid amide, Ethylene bispalmitoleic acid amide, Propylene vinyl Palmitoleic acid amide, butylene bispalmitoleic acid amide, methylene bisarachidic acid amide, ethylene bisarachidic acid amide, propylene bisarachidic acid amide, butylene bisarachidic acid amide, methylene biseicosenoic acid amide, ethylene biseicosenoic acid Amide, Propylene biseicosenoic acid amide, Butylene biseicosenoic acid amide, Methylene bis behenic acid amide, Ethylene bis behenic acid amide, Propylene bis behenic acid amide, Butylene bis behenic acid amide, Methylene bis Mention may be made of alkylene bis fatty acid amide compounds of saturated or monovalent unsaturated fatty acids such as erucic acid amide, ethylene biserucic acid amide, propylene biserucic acid amide, butylene biserucic acid amide.

  The electrophotographic image forming toner in the present invention preferably has an endothermic peak due to the crystalline polyester resin (A) in the range of 90 to 130 ° C. as measured by DSC. When the endothermic peak due to the crystalline polyester resin (A) is in the range of 90 to 130 ° C., the crystalline polyester resin does not melt at room temperature, and the toner melts in a relatively low fixing temperature range, and recording is performed. Since it can be fixed on a medium, heat storage stability and low-temperature fixability can be expressed more effectively.

The endothermic amount of the endothermic peak is preferably 1 J / g or more and 15 J / g or less.
If the endothermic amount is less than 1 J / g, the amount of the crystalline polyester resin that works effectively in the toner particles is too small, so that the function of the crystalline polyester resin is not sufficiently exhibited. If the endothermic amount is more than 15 J / g, the amount of the crystalline polyester resin effective in the toner particles is excessive, so that the absolute amount compatible with the amorphous polyester resin increases and the glass transition temperature of the toner decreases. In addition, the heat resistant storage stability is reduced.

The DSC measurement (endothermic peak, glass transition temperature Tg) in the present invention is measured by using a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation) and increasing the temperature to 20 to 150 ° C. at 10 ° C./min. .
In the present invention, the endothermic peak derived from the crystalline polyester is present in the vicinity of 80 to 130 ° C., which is the melting point of the crystalline polyester, and the endothermic amount is determined from the area surrounded by the baseline and the endothermic curve. Generally, the endothermic amount in DSC measurement is often measured by increasing the temperature twice, but the endothermic peak and glass transition temperature in the present invention are derived using the endothermic curve at the first temperature increase. .
When the endothermic peak derived from the crystalline polyester (A) overlaps the endothermic peak of the wax, the endothermic amount of the wax is subtracted from the endothermic amount of the overlapped peak. The endothermic amount of the wax is calculated from the endothermic amount of the wax alone and the wax content in the toner.

The particle size of the toner of the present invention is not particularly limited, but the volume average particle size is preferably 4 to 10 μm in order to obtain a high image quality excellent in fine line reproducibility and the like.
If it is smaller than 4 μm, the cleaning property in the development process and the transfer efficiency in the transfer process are hindered, and the image quality is deteriorated. When it is larger than 10 μm, the fine line reproducibility of the image is lowered.

  Here, the volume average particle diameter of the toner can be measured by various methods. In the present invention, Coulter Counter TAII manufactured by Coulter Electronics, USA is used.

The toner of the present invention is preferably a pulverized toner manufactured using a so-called pulverization method in which the manufacturing process includes at least a melt-kneading process.
In the pulverization method, a toner material containing at least a crystalline polyester resin (A), an amorphous resin (B), an amorphous resin (C), a composite resin (D), a colorant, and a release agent is dry-mixed. In this method, melted and kneaded by a kneader and pulverized to obtain a pulverized toner.

  First, toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial continuous kneader, a biaxial continuous kneader, or a batch kneader using a roll mill can be used. Specific examples include KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay, PCM type twin screw extruder manufactured by Ikekai Iron Works, A Kneader manufactured by KK is preferably used.

The melt-kneading is preferably performed under appropriate conditions that do not cause the molecular chain of the binder resin to be broken. Specifically, the melt kneading temperature is performed with reference to the softening point of the binder resin. If the temperature is higher than the softening point, the molecular chain is severely cut, and if the temperature is too low, the dispersion may not proceed.

  In the pulverization step, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification step, the pulverized product obtained in the pulverization step is classified and adjusted to particles having a predetermined particle size. Classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like.
After the pulverization and classification are completed, the pulverized product is classified in an air stream with a centrifugal force or the like to produce a toner having a predetermined particle size.

  The toner of the present invention is a pulverized toner that undergoes a melt-kneading process in the manufacturing process. If the thickness of the kneaded product is 2.5 mm or more in the cooling step after melt-kneading the raw materials, the kneaded product is cooled. Since the speed is reduced and the time for recrystallization of the crystalline polyester resin (A) melted in the kneaded product is increased, recrystallization is promoted and the function of the crystalline polyester resin (A) is more effective. Can be demonstrated. In order to promote recrystallization, it is an effective means to add a fatty acid amide as described above, but the effect can also be obtained by adjusting the production process in this way. There is no upper limit to the thickness of the kneaded product, but if it is thicker than 8 mm, the efficiency is remarkably lowered in the pulverization step.

  In order to enhance the fluidity, storage stability, developability, and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner base particles produced as described above.

For mixing such additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, for example, the additive may be added in the middle or gradually.
You may change suitably the rotation speed, rolling speed, time, temperature, etc. of a mixer. Further, a strong load may be applied first, and then a relatively weak load may be applied, or vice versa.
Examples of mixing equipment that can be used in the external additive mixing step include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, and a Henschel mixer.
After performing the mixing step, coarse particles and aggregated particles may be removed by passing through a sieve of 250 mesh or more.

  When the toner of the present invention is used as a developer, it may be used as a one-component developer composed only of toner, or may be mixed with a carrier and used as a two-component developer. When used in a high-speed printer or the like corresponding to the recent improvement in information processing speed, it is developed by using a two-component development method in which a magnet as a magnetic field generating means is formed and a magnetic brush is formed on a development sleeve. The developer can be transported even if the surface roughness of the sleeve surface is reduced, and it is preferably used as a two-component developer from the viewpoints of contributing to the prevention of contamination of the developing sleeve, high charging ability, and improvement in life. .

The image forming apparatus of the present invention will be described.
The image forming apparatus of the present invention includes a means for forming an electrostatic latent image on an image carrier, a means for developing the electrostatic latent image with a developer containing an electrostatic charge image developing toner, and forming a toner image. The image forming apparatus includes means for transferring a toner image onto a transferred material and means for fixing the toner image on the transferred material, and the developing means includes a developing sleeve having a coat layer on a substrate.

By coating the developing sleeve, it is possible to fill the sleeve groove where the toner particles and the scale are close to each other, reduce the catch between the sleeve and the toner particles, and reduce the deterioration of the toner. The effect is particularly remarkable in low image area printing using a two-component development type high-speed printer.

When the toner having a weight average particle diameter of 4 to 10 [mu] m is used, the surface roughness (Ra) of the sleeve is set to 10 [mu] m or less, so that the toner particles can be prevented from being caught and the toner can be prevented from being deteriorated, and the ghost image can be prevented from being generated. .
The surface roughness (Ra) of the sleeve is preferably 8 μm or less, and more preferably 0.1 μm or more and 4 μm or less. When the thickness is less than 0.1 μm, the toner is hardly caught and an effect corresponding to an increase in manufacturing cost cannot be obtained.
In addition, the surface roughness (Ra) in this invention says the average value which measured the predetermined location (100 locations) extracted at random using the surface roughness measuring device.

The coating method may be any method as long as the developing sleeve can be coated and the sleeve groove can be filled, but metal spraying is preferable.

An Al base tube, a SUS cylinder, or the like can be used as the substrate.
The surface treatment material of the substrate is not particularly limited as long as it has wear resistance, but it is preferable to have an element of group 2-6 or 12-16 of the periodic table of elements, TiN, More preferred is MoO ₂ or Cr.
As toner external additives, those containing Ti and Si are often used, and toner particle-development is achieved by coating the surface of the developing sleeve with a material containing an element having a relatively close electronegativity to Ti or Si. The electrostatic force between the sleeves is reduced, and toner sticking can be prevented.

An example of the electrophotographic developing apparatus in the present invention is shown in FIG.
In FIG. 3, reference numeral (101A) is a driving roller, (101B) is a driven roller, (102) is a photosensitive belt, (103) is a charger, (104) is a laser writing system unit, (105A) to (105D). Development units for storing toners of respective colors of yellow, magenta, cyan and black, (106) a paper feed cassette, (107) an intermediate transfer belt, (107A) a drive shaft roller for driving the intermediate transfer belt, 107B) is a driven shaft roller that supports the intermediate transfer belt, (108) is a cleaning device, (109) is a fixing roller, (109A) is a pressure roller, (110) is a paper discharge tray, and (113) is a paper transfer roller. Is shown.

  In this color image forming apparatus, a flexible intermediate transfer belt (107) is used for the transfer drum, and the intermediate transfer belt (107), which is an intermediate transfer member, is paired with a drive shaft roller (107A). The belt is stretched around the driven shaft roller (107B) and circulated in the clockwise direction, and the belt surface between the pair of driven shaft rollers (107B) faces the photosensitive belt (102) on the outer periphery of the drive roller (101A). It is in a state of contacting from the horizontal direction.

During normal color image output, each color toner image formed on the photosensitive belt (102) is transferred to the intermediate transfer belt (107) each time it is formed, and a color toner image is synthesized. The transfer paper conveyed from the paper feed cassette (106) is collectively transferred by the paper transfer roller (113), and the transferred transfer paper is transferred between the fixing roller (109) and the pressure roller (109A) of the fixing device. After being conveyed and fixed by the fixing roller (109) and the pressure roller (109A), the paper is discharged onto a paper discharge tray (110).

  When the developing units (105A) to (105E) develop toner, the toner concentration of the developer contained in the developing unit is lowered. A decrease in the toner density of the developer is detected by a toner density sensor (not shown). When a decrease in toner density is detected, a toner replenishing device (not shown) connected to each developing unit operates to replenish the toner and increase the toner density. At this time, the replenished toner may be a so-called trickle developing system developer in which a carrier and toner are mixed as long as the developing unit has a developer discharging mechanism.

  In FIG. 3, an image is formed by superimposing a toner image on the intermediate transfer belt. However, the electrophotography of the present invention is similarly applied to a system that directly transfers from a transfer drum to a recording medium without using an intermediate transfer belt. An image forming apparatus can be obtained.

FIG. 4 is a diagram showing an example of the developing device used in the present invention, and modifications as will be described later also belong to the category of the present invention.
In FIG. 4, a developing device (40) disposed opposite to the photosensitive member (20) as a latent image carrier includes a developing sleeve (41) as a developer carrier, a developer containing member (42), It is mainly composed of a doctor blade (43) as a regulating member, a support case (44) and the like.
A toner hopper (45) serving as a toner accommodating portion for accommodating the toner (21) is joined to the support case (44) having an opening on the photosensitive member (20) side. In the developer accommodating portion (46) for accommodating the developer composed of the toner (21) and the carrier (23) adjacent to the toner hopper (45), the toner (21) and the carrier (23) are agitated. A developer stirring mechanism (47) is provided for imparting friction / release charges to (21).

  Inside the toner hopper (45), a toner agitator (48) and a toner replenishing mechanism (49) are disposed as toner supplying means rotated by a driving means (not shown). The toner agitator (48) and the toner replenishing mechanism (49) send out the toner (21) in the toner hopper (45) toward the developer container (46) while stirring.

  A developing sleeve (41) is disposed in the space between the photoconductor (20) and the toner hopper (45). The developing sleeve (41) driven to rotate in the direction of the arrow by a driving means (not shown) is arranged in a relative position relative to the developing device (40) in order to form a magnetic brush by the carrier (23). A magnet (not shown) is provided as magnetic field generating means.

  A doctor blade (43) is integrally attached to the developer accommodating member (42) on the side facing the side attached to the support case (44). In this example, the doctor blade (43) is disposed in a state where a certain gap is maintained between the tip thereof and the outer peripheral surface of the developing sleeve (41).

  Using such a device without limitation, the image forming method of the present invention is performed as follows. That is, with the above configuration, the toner (21) sent out from the toner hopper (45) by the toner agitator (48) and the toner replenishing mechanism (49) is transported to the developer accommodating portion (46), where the developer agitation is performed. By stirring by the mechanism (47), a desired friction / peeling charge is imparted, and is carried on the developing sleeve (41) as a developer together with the carrier (23) and faces the outer peripheral surface of the photoreceptor (20). The toner image is formed on the photoconductor (20) by being electrostatically coupled to the electrostatic latent image formed on the photoconductor (20) only by being conveyed to the position.

  FIG. 5 is a diagram illustrating an example of an image forming apparatus having the developing device of FIG. Around the drum-shaped photoreceptor (20), a charging member (32), an image exposure system (33), a developing device (40), a transfer device (50), a cleaning device (60), and a static elimination lamp (70) are arranged. In this example, the surface of the charging member (32) is in a non-contact state with a surface of about 0.2 mm from the surface of the photoreceptor (20), and the photoreceptor is driven by the charging member (32). When charging (20), charging unevenness is reduced by charging the photosensitive member (20) with an electric field in which an alternating current component is superimposed on a direct current component by a voltage applying means (not shown) on the charging member (32). It is possible and effective. The image forming method including the developing method is performed by the following operation.

A series of image forming processes can be described as a negative-positive process. The photoconductor (20) represented by a photoconductor (OPC) having an organic photoconductive layer is neutralized by a static elimination lamp (70) and is uniformly negatively charged by a charging member (32) such as a charging charger or a charging roller. A latent image is formed by laser light emitted from an image exposure system (33) such as a laser optical system (in this example, the absolute value of the exposed portion potential is lower than the absolute value of the non-exposed portion potential). Is called.
Laser light is emitted from a semiconductor laser and scans the surface of the photoconductor (20) in the direction of the rotation axis of the photoconductor (20) by a polygonal polygonal mirror (polygon) that rotates at high speed. The latent image formed in this way is developed with a developer composed of a mixture of toner and carrier supplied on a developing sleeve (41) which is a developer carrying member in the developing device (40), and the toner image is developed. It is formed. At the time of developing the latent image, a DC voltage of an appropriate magnitude or an AC voltage is applied to the developing sleeve (41) from a voltage application mechanism (not shown) between the exposed portion and the non-exposed portion of the photosensitive member (20). A developing bias with a superimposed voltage is applied.

  On the other hand, a transfer medium (for example, paper) (80) is fed from a paper feed mechanism (not shown), and is synchronized with the leading edge of the image by a pair of upper and lower registration rollers (not shown), so that the photoconductor (20). And the transfer device (50) to transfer the toner image. At this time, it is preferable that a potential having a polarity opposite to the polarity of toner charging is applied to the transfer device (50) as a transfer bias. Thereafter, the transfer medium (80) is separated from the photoreceptor (20) to obtain a transfer image.

The toner remaining on the photoconductor (20) is collected in a toner collection chamber (62) in the cleaning device (60) by a cleaning blade (61) as a cleaning member.
The collected toner may be transported to the developer container (46) and / or the toner hopper (45) by a toner recycling means (not shown) and reused.
The image forming apparatus may be a device in which a plurality of the developing devices described above are arranged, and the toner images are sequentially transferred onto the transfer medium, then sent to the fixing mechanism, and the toner is fixed by heat or the like. An apparatus may be used in which a plurality of toner images are transferred to a transfer medium and transferred together onto a transfer medium and fixed in the same manner.

  FIG. 6 shows another example of the image forming apparatus used in the present invention. The photosensitive member (20) is provided with at least a photosensitive layer on a conductive support, driven by driving rollers (24a) and (24b), charged by a charging member (32), and by an image exposure system (33). Image exposure, development by developing device (40), transfer using transfer device (50), exposure before cleaning by exposure light source (26) before cleaning, cleaning by brush-like cleaning means (64) and cleaning blade (61), discharge lamp The charge removal according to (70) is repeated. In 69, the photosensitive body (20) (of course, the support is translucent in this case) is subjected to pre-cleaning exposure from the support side.

FIG. 7 shows an example of the process cartridge of the present invention. This process cartridge uses the developer of the present invention, as a photoconductor (20), a proximity brush-like charging means (32), a developing means (40) for storing the developer of the present invention, and a cleaning means. This is a process cartridge that integrally supports a cleaning means having at least a cleaning blade (61) and is detachable from the main body of the image forming apparatus. In the present invention, the above-described components can be integrally combined as a process cartridge, and the process cartridge can be configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

Hereinafter, the present invention will be described with reference to examples and comparative examples. In addition, this invention is not limited to the Example illustrated here. In the following, “parts” represents parts by mass.

<Production of development sleeve>
(Development sleeve production example 1)
A surface coating treatment was performed by metal spraying a Zn / Al alloy on the surface of an aluminum cylinder having a diameter of 25 mm, thereby producing a developing sleeve 1 having a surface roughness Ra of 8 μm.

(Development sleeve production example 2)
The surface of the aluminum cylinder having a diameter of 25 mm is thermally sprayed with a Zn / Al alloy and subjected to a surface coating treatment. Further, the surface roughness Ra of the titanium nitride layer is formed by vapor deposition so that the developing sleeve is 8 μm. 2 was produced.

(Development sleeve production example 3)
A surface of the aluminum cylinder having a diameter of 25 mm is sprayed with a Zn / Al alloy and subjected to surface coating, and the surface is formed by physical vapor deposition so that the surface roughness Ra of the titanium nitride layer is 10 μm or less. Thus, a developing sleeve 3 to be a developing sleeve was produced.

(Development sleeve production example 4)
A surface of the aluminum cylinder having a diameter of 25 mm is sprayed with a Zn / Al alloy and subjected to surface coating, and the surface is formed by physical vapor deposition so that the surface roughness Ra of the titanium nitride layer is 8 μm or less. Thus, a developing sleeve 3 to be a developing sleeve was produced.

(Development sleeve production example 5)
Zn / Al alloy is metal sprayed on the surface of an aluminum cylinder with a diameter of 25 mm, and surface coating is applied.
Further, the surface of the molybdenum oxide layer was formed so as to have a surface roughness Ra of 10 μm or less by a physical vapor deposition method, thereby producing a developing sleeve 5 serving as a developing sleeve.

(Development sleeve production example 6)
Zn / Al alloy is metal sprayed on the surface of an aluminum cylinder with a diameter of 25 mm, and surface coating is applied.
Further, the surface was formed by physical vapor deposition so that the surface roughness Ra of the molybdenum oxide layer was 8 μm or less, thereby producing a developing sleeve 6 serving as a developing sleeve.

(Development sleeve production example 7)
By coating the surface of a SUS cylinder with a diameter of 25 mm with a metal spray of Zn / Al alloy and applying a surface coating treatment, the surface is formed by physical vapor deposition so that the surface roughness Ra of the titanium nitride layer is 8 μm or less. A developing sleeve 4 to be a developing sleeve was produced.

(Development sleeve production example 8)
By subjecting the surface of a SUS cylinder with a diameter of 25 mm to a surface blasting treatment by sandblasting, and further forming the surface by physical vapor deposition so that the surface roughness Ra of the titanium nitride layer is 8 μm or less, A developing sleeve 8 to be a developing sleeve was produced.

(Development sleeve production example 9)
By subjecting the surface of a SUS cylinder with a diameter of 25 mm to surface blasting by sandblasting, and further forming the surface by physical vapor deposition so that the surface roughness Ra of the titanium nitride layer is 10 μm or less, A developing sleeve 8 to be a developing sleeve was produced.

(Development sleeve production example 10)
The surface of a SUS cylinder with a diameter of 25 mm is subjected to roughening treatment by sandblasting,
Further, a titanium nitride layer was applied to the surface by physical vapor deposition, and further burr polishing was performed so that the surface roughness Ra was 8 μm or less, thereby producing a developing sleeve 10 serving as a developing sleeve.

(Development sleeve production example 11)
The developing sleeve 11 was made of a SUS cylinder having a diameter of 25 mm.

<Crystalline polyester resin>

A compound selected from 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol as the alcohol component, and selected from fumaric acid, succinic acid, trimellitic acid and terephthalic acid as the carboxylic acid component Crystalline polyesters a1 to a6 were obtained using the compound.

It was confirmed that the crystalline polyesters a1 to a6 were crystalline polyesters having at least one diffraction peak at a position of 2θ = 19 ° to 25 ° in an X-ray diffraction pattern by a powder X-ray diffractometer. The X-ray diffraction result of the crystalline polyester resin a6 is shown in FIG.
Table 1 shows the glass transition temperatures (Tg) and softening temperatures (T1 / 2) of the crystalline polyesters a1 to a6.

<Amorphous resin>
(Preparation of non-crystalline resins b1 to b5 and c1 to c3)
After an aromatic diol component and a monomer selected from ethylene glycol, glycerin, adipic acid, terephthalic acid, isophthalic acid, and itaconic acid are subjected to an esterification reaction under conditions of 170 to 260 ° C. and no catalyst under normal pressure, 400 ppm of antimony trioxide is added to the total carboxylic acid component in the reaction system, and polycondensation is performed at 250 ° C. while removing glycol out of the system under a vacuum of 3 Torr to obtain amorphous resins b1 to b10 and c1 to 3. It was.
The crosslinking reaction was carried out until the stirring torque reached 10 kg · cm (100 ppm), and the reaction was stopped by releasing the reduced pressure state of the reaction system.

Amorphous resins b1 to b10 and c1 to c3 were confirmed to be non-crystalline by the X-ray diffraction pattern without a diffraction peak.
Tables 2 and 3 show the physical properties of the amorphous resins b1 to b10 and c1 to c3.

(Preparation of composite resin d1)
As the condensation polymerization monomer, terephthalic acid, fumaric acid, trimetic anhydride, bisphenol A (2,2) propylene oxide, bisphenol A (2,2) ethylene oxide are used, and styrene, acrylic acid, 2 -Using ethylhexyl acrylate, in an inert gas atmosphere, in the presence of an esterification catalyst, a polymerization inhibitor, etc., in the presence of a polycondensation at a temperature of about 180-250 ° C, softening temperature 115 ° C, glass transition A composite resin d1 having a temperature of 58 ° C. and an acid value of 25 mgKOH / g was obtained.

(Preparation of composite resin d2)
As the condensation polymerization monomer, hexamethylenediamine and ε-caprolactam are used, and addition polymerization monomer: styrene, acrylic acid, 2-ethylhexyl acrylate, and in an inert gas atmosphere, if necessary, an esterification catalyst, In the presence of a polymerization inhibitor or the like, condensation polymerization was performed at a temperature of about 180 to 250 ° C. to obtain a composite resin d2.

<Master batch production>
Amorphous resin: c3 100 parts by weight Colorant: p2 50 parts by weight Pure water 50 parts by weight

Pre-kneading was performed using the above materials to prepare a master batch.

[Example 1]
Crystalline polyester resin: a1 4 parts by weight Amorphous resin: b1 35 parts by weight Amorphous resin: c1 55 parts by weight Composite resin: d1 10 parts by weight Colorant: p1 (carbon black) 14 parts by weight Release agent: Carna Uba wax (melting point: 81 ° C.) 6 parts by mass Charge control agent: monoazo metal complex (chromium complex dye (Bontron S-34, manufactured by Orient Chemical Co., Ltd.) 2 parts by mass

The toner raw materials are premixed using a Henschel mixer (Mitsui Miike Kako Co., Ltd., FM20B), and then a biaxial kneader (Ikegai Co., Ltd., PCM-30) at a temperature of 100 to 130 ° C. The mixture was melted and kneaded under a feed rate of 140 to 160 kg / h. The obtained kneaded material was rolled to a thickness of 2.8 mm with a roller, cooled to room temperature with a belt cooler, and coarsely pulverized to 200 to 300 μm with a hammer mill.
Subsequently, after finely pulverizing using a supersonic jet pulverizer lab jet (manufactured by Nippon Pneumatic Industry Co., Ltd.), the weight average particle diameter is 5. Classification was performed while appropriately adjusting the louver opening so as to be 6 ± 0.2 μm to obtain toner base particles. Next, 1.0 part by mass of an additive (HDK-2000, manufactured by Clariant Co., Ltd.) was mixed with 100 parts by mass of the toner base particles with a Henschel mixer to prepare a pulverized toner 1.

  The pulverized toner developer 1 was prepared by uniformly mixing 5% by mass of the pulverized toner 1 and 95% by mass of the coated ferrite carrier with a tumbler mixer (manufactured by Willy et Bacchofen (WAB)) for 5 minutes at 48 rpm. Was made.

[Examples 1 to 39, Comparative Examples 1 to 11]
Except for replacing the raw materials shown in Table 5 below, melting and kneading were conducted in the same manner as in Example 1 to obtain toners 1 to 42 (toner production examples 1 to 42), and developers 1 to 42 were produced. Also,
In addition, the metal complex (Bontron E-84 manufactured by Orient Chemical Industry Co., Ltd.), which is a zinc salicylate compound, was used for the metal salt of salicylate as the charge control agent used in the toners 38 to 42.
Further, in the toner 31, since the dispersion of the pigment in the resin is poor, a toner using a master batch was prepared. In forming the toner, the amount of the amorphous resin c3 contained in the master batch was calculated backward, and the final raw material ratio was adjusted to the amount shown in Table 5.
The molecular weight main peak of the prepared pulverized toner, the half-value width of the molecular weight distribution, the DSC peak temperature and endothermic amount in the range of 90 to 130 ° C. due to the crystalline polyester resin (A), and the range of 19 to 25 ° in the X-ray diffraction measurement Table 6 shows the presence / absence of a diffraction peak and the volume average particle diameter.

The pulverized toner developers 1 to 42 were accommodated in the developing unit 105D shown in FIG. The developing units 105A to 105C were not used.

Table 7 shows combinations of toner production examples and sleeve production examples.

<Low temperature fixability, hot offset resistance, fine line reproducibility (initial)>
Using the image forming apparatus, images of the pulverized toner developers 1 to 43 were output. A solid image having an adhesion amount of 0.4 mg / cm ² was output on paper (Type 6200 manufactured by Ricoh) through the exposure, development, and transfer processes. The linear speed of fixing was 160 mm / second. The fixing temperature was sequentially output in increments of 5 ° C., and the lower limit temperature at which no cold offset occurred (fixing lower limit temperature: low temperature fixability) and the upper limit temperature at which hot offset did not occur (fixing upper limit temperature: hot offset resistance) were measured. The NIP width of the fixing device was 11 mm. Separately, a character chart (image size of about 2 mm × 2 mm) with an image area ratio of 5% by pulverized toner is output at a fixing lower limit temperature + 20 ° C., and fine lines are reproduced by visual judgment. The sex was evaluated.

◆ Low temperature fixability ◎: Less than 130 ° C. ○: 130 ° C. or more and less than 140 ° C. □: 140 ° C. or more and less than 150 ° C. Δ: 150 ° C. or more and less than 160 ° C. x: 160 ° C. or more ◆ Hot offset resistance ◎: 200 ° C. or more ○: 190 ° C or higher and lower than 200 ° C □: 180 ° C or higher and lower than 190 ° C △: 170 ° C or higher and lower than 180 ° C ×: Less than 170 ° C ◆ Fine wire reproducibility ◎: Very good ○: Good □: General level △: Practical No problem ×: Not acceptable

<Smear resistance>
At the minimum fixing temperature, a halftone image with a toner coverage of 0.40 ± 0.1 mg / cm ² and an image area ratio of 60% is output on paper (Ricoh Type 6200 paper), and the fixed image portion is clocked. Using a meter, rubbing with a white cotton cloth (JIS L0803 cotton No. 3) 10 times, and the ID of dirt adhering to the cloth (hereinafter referred to as smear ID) was measured. The smear ID was measured with a colorimeter (X-Rite 938). The pulverized toner 31 was measured with cyan, and the other toners were measured with black.
A: Smear ID is 0.20 or less B: Smear ID is 0.21 to 0.35
Δ: Smear ID is 0.36 to 0.55
×: Smear ID is 0.56 or more

<Reproducibility of fine lines (over time)>
After evaluating the initial fine line reproducibility, a chart with an image area ratio of 5% was continuously output while replenishing the toner, and 100 k sheets of charts were continuously output. A 5% character chart (the size of one character is about 2 mm × 2 mm) is output, and visual judgment is performed to evaluate reproducibility of fine lines over time. The criterion was the same as the initial thin line reproducibility evaluation.

<Heat resistant storage stability>
10 g of each toner is put into a 30 ml screw vial, tapped 100 times with a tapping machine, stored in a constant temperature bath at 50 ° C. for 24 hours, returned to room temperature, and then penetrated with a penetration testing machine. It measured and it was set as the heat-resistant preservation | save evaluation.
◎: Penetrating ○: 20 mm or more □: 15 mm or more and less than 20 mm △: 10 mm or more and less than 15 mm ×: Less than 10 mm

<Image stability>
For how to evaluate ghost images,
After printing 100K copies of a character chart with an image area of 8% (size of one character: about 2mm x 2mm), print the vertical band chart shown in Fig. 8 and print the density for one sleeve (a) and one cycle (b). The difference was determined by X-Rite938 (manufactured by X-Rite), and the average density difference of the three measurements at the center, rear, and front was taken as ΔID, and the following ranking was made.
A: Very good, B: Good, B: Acceptable, B: Unusable for practical use A: B, B, C: Passed and x: Fail.
A: 0.01 ≦ ΔID
○: 0.01 <ΔID ≦ 0.03
Δ: 0.03 <ΔID ≦ 0.06
×: 0.06 <ΔID
The results of each evaluation are shown in Table 8.

(About Figure 3)
DESCRIPTION OF SYMBOLS 101A Drive roller 101B Follower roller 102 Photoconductor belt 103 Charger 104 Laser writing system unit 105A-105D Development unit which accommodates toner of each color of yellow, magenta, cyan, and black 106 Paper feed cassette 107 Intermediate transfer belt 107A Intermediate transfer belt Drive shaft roller for driving 107B Driven shaft roller for supporting the intermediate transfer belt 108 Cleaning device 109 Fixing roller 109A Pressure roller 110 Paper discharge tray 113 Paper transfer roller (about FIG. 4)
DESCRIPTION OF SYMBOLS 20 Photoconductor 21 Toner 23 Carrier 41 Developing sleeve 42 Developer accommodating member 43 Developer supply regulating member 44 Support case 45 Toner hopper 46 Developer accommodating portion 47 Developer agitating mechanism 48 Toner agitator 49 Toner replenishing mechanism (FIG. 5)
DESCRIPTION OF SYMBOLS 20 Photoconductor 32 Charging member 33 Image exposure system 40 Developing device 41 Developing sleeve 45 Toner hopper 47 Developer stirring mechanism 50 Transfer device 60 Cleaning device 61 Cleaning blade 62 Toner recovery chamber 70 Static elimination lamp 80 Transfer medium (about FIG. 6)
DESCRIPTION OF SYMBOLS 20 Photoconductor 24a Drive roller 24b Drive roller 26 Exposure light source before cleaning 32 Charging member 33 Image exposure system 40 Developing device 50 Transfer device 61 Cleaning blade 64 Brush-like cleaning means 70 Static elimination lamp (about FIG. 7)
20 Photosensitive member 32 Charging unit 40 Developing unit 61 Cleaning unit

Japanese Patent Laid-Open No. 11-65247 Japanese Patent No. 3356948 JP 2005-157002 A JP 11-231652 A Japanese Unexamined Patent Publication No. 7-72733 JP 7-128983 A Japanese Patent Laid-Open No. 7-92913 JP-A-7-281517 JP 2003-76132 A JP 2007-121561 A JP 60-90344 A JP-A 64-15755 Japanese Patent Laid-Open No. 2-82267 JP-A-3-229264 JP-A-3-41470 JP-A-11-305486 Japanese Patent No. 2931899 JP 2001-222138 A JP 2004-46095 A JP 2007-33773 A JP 2005-338814 A Japanese Patent No. 4118498

Claims (8)

A step of forming an electrostatic latent image on the image carrier, a step of developing the electrostatic latent image with a developer containing a toner for developing an electrostatic image, and forming a toner image; An image forming method including a step of transferring and a step of fixing a toner image on a transfer target,
The developing step, it der to form a toner image using a developing sleeve having a coating layer on a substrate, wherein the coating layer are those having a TiN on the surface,
The toner is
It has a toner binder including a crystalline resin, an amorphous resin, and a composite resin,
The crystalline resin is a polyester resin (A) having crystallinity,
The amorphous resin includes an amorphous resin (B) containing a chloroform-insoluble component, an amorphous resin (C) having a softening temperature (T1 / 2) lower than that of the amorphous resin (B) by 25 ° C. or more. The absolute value | Tgc−Tgb | of the difference between the glass transition temperature (Tgc) of the amorphous resin (C) and the glass transition temperature (Tgb) of the amorphous resin (B) is 10 ° C. or less. ,
The composite resin is a composite resin (D) having a condensation polymerization resin unit and an addition polymerization resin unit,
The image forming method, wherein the toner has a main peak having a molecular weight distribution by GPC determined by THF-soluble content of 1000 to 10,000, and a half width of the molecular weight distribution is 15000 or less. The image forming method according to claim 1, wherein the coat layer has a surface roughness (Ra) of 8 μm or less. The image forming method according to claim 1, wherein the toner has inorganic fine particles on a surface thereof. The image forming method according to claim 1, wherein the toner contains a fatty acid amide compound. The image forming method according to claim 1, wherein the toner contains a salicylic acid metal compound. The image forming method according to claim 1, wherein the toner has an endothermic peak in a range of 90 to 130 ° C. in an endothermic peak measurement by DSC. 7. The image forming method according to claim 1, wherein the toner has an endothermic peak with an endothermic peak of 1 J / g or more and 15 J / g or less as measured by DSC. Means for forming an electrostatic latent image on the image carrier, means for developing the electrostatic latent image with a developer containing toner for developing an electrostatic image, and forming a toner image on the image receiving member. An image forming apparatus having a means for transferring and a means for fixing a toner image on a transfer object,
The developing means has a developing sleeve having a coating layer on a substrate, and the coating layer has TiN on the surface,
The toner is
It has a toner binder including a crystalline resin, an amorphous resin, and a composite resin,
The crystalline resin is a polyester resin (A) having crystallinity,
The amorphous resin includes an amorphous resin (B) containing a chloroform-insoluble component, an amorphous resin (C) having a softening temperature (T1 / 2) lower than that of the amorphous resin (B) by 25 ° C. or more. The absolute value | Tgc−Tgb | of the difference between the glass transition temperature (Tgc) of the amorphous resin (C) and the glass transition temperature (Tgb) of the amorphous resin (B) is 10 ° C. or less. ,
The composite resin is a composite resin (D) having a condensation polymerization resin unit and an addition polymerization resin unit,
2. The image forming apparatus according to claim 1, wherein the toner has a main peak in a molecular weight distribution by GPC determined by THF-soluble content of 1000 to 10,000, and a half width of the molecular weight distribution is 15000 or less.

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