JP4813332B2 - Image forming method and non-contact heat fixing toner used therefor - Google Patents

Description

  The present invention relates to an image forming method using a one-pass type multi-station printer in the field of electrophotographic electrostatic recording, and more particularly to a non-contact heat fixing toner used in the image forming method and a method for manufacturing the same.

  The fixing of the powder toner electrophotographic process can be broadly divided into (1) a non-heating fixing method using pressure and a solvent, and (2) an oven fixing method in which heated air is supplied to the toner image holding member for fixing. There are three types, a non-contact heating fixing method that does not directly heat a toner image represented by a radiation fixing method that supplies heat by (3), and a contact heating method that supplies heat and pressure simultaneously with a heat roll. Many of copiers and printers using an electrophotographic process have been widely used in the heat roll fixing, which is a representative example of the contact heating method from the viewpoint of thermal efficiency. However, in the heat roll fixing, (1) heating Since the toner layer is crushed during pressurization, it is not suitable for output of fine images formed with dots, and (2) it is not suitable for fixing unfixed images on both sides simultaneously. Alternatively, in the field of copying, the non-contact heat fixing method is mainstream. However, in the non-contact heat fixing method, unlike the heat roll fixing, the fixing pressure is not applied to the toner. This phenomenon occurred remarkably when the fixing temperature was lowered in order to obtain a so-called matte low gloss image. In addition, when used in an image forming method in which two or more layers of different color toners are combined to reproduce multiple colors, color reproducibility and the like are deteriorated, which is a serious problem.

  In electrophotographic technology, a one-pass type multi-station multicolor printer using the non-contact heat fixing method is well known, and forms an image on a photoconductive belt, transfers it to continuous paper, and transfers the transferred toner. It is known that after fixing an image, the continuous paper is cut into a sheet containing a desired print. Patent Document 1 discloses an electrophotographic printer in which a plurality of image forming units are arranged so that toner images are superimposed on an endless belt driven by a motor, and the superimposed images are transferred from the endless belt to a paper sheet. However, each image forming unit is driven by a motor in synchronization with the endless belt. However, these methods are very complicated, and it is desirable to transfer a plurality of toner images directly onto a continuous paper as a transfer material in a single path through a printer, and then fix them by non-contact heating such as an oven. . One of these methods is disclosed in Patent Document 2, in which a continuous paper as a transfer material is guided while being in contact with a latent image carrier that can be rotated over a certain winding angle, and the continuous paper is conveyed while applying tension. Thus, the toner image is transferred. According to this method, since an image can be formed without using a transfer belt or the like, the structure becomes simple. By arranging the rotatable latent image carriers in a staggered arrangement (FIG. 1), a compact space can be obtained. Thus, one-pass simultaneous duplex printing can be performed. Furthermore, there is a merit that non-contact heat fixing can fix the formed toner image with high image quality.

On the other hand, it has been proposed to reduce the toner particle size in response to the demand for higher image quality. The effects of the toner having a reduced particle size include not only the improvement of dot reproducibility and sharpness, but also the advantage that the same image density can be obtained even if the amount of adhesion is reduced by finely filling the toner of the toner image. . However, in the method disclosed in Patent Document 2 suitable for the above-described one-pass simultaneous double-sided printing, when the toner is transferred from the latent image carrier to the transfer material, the tension applied to the transfer material is sandwiched between the toners. Due to the nature of being applied to the latent image carrier as a pressure, particularly when transferring to thick paper exceeding 190 g / m ² , the pressure applied to the toner layer increases and transfer defects (so-called worm-eaten images) occur. When the amount of toner adhesion is reduced as the particle size is reduced, transfer defects are particularly noticeable, and when multiple colors are superimposed, the color reproducibility deteriorates. It was a very big problem in improving image quality.

As a method for improving the transfer failure, Patent Document 3, Patent Document 4 and the like specify parameters indicating the degree of circularity of the toner and the relationship between the additive and the toner particles. In particular, the toner volume average particle diameter is 7 μm. In the case where the toner adhesion amount of the solid image portion is 5.0 g / m ² , the effect is insufficient.
Further, for example, Patent Literature 4, Patent Literature 5, Patent Literature 6, Patent Literature 7 and the like have been disclosed as toners suitable for the non-contact fixing method, and the toner volume average particle diameter is particularly 7 μm or less. In such a case, the above-described transfer failure occurs, and it is impossible to obtain a printed matter with a desired high image quality and excellent fixability and color reproducibility simply by defining the thermal characteristics and the like.

Patent Document 8 discloses a non-contact heat fixing toner containing a needle-like polyolefin wax. According to the present invention, smear quality as an image after fixing by non-contact heating is improved, but transfer defect is not improved, and particularly when the toner adhesion amount is reduced by reducing the particle size, the image quality becomes high. Could not be obtained.
Patent Document 9 discloses the coverage and gloss of the rheometer and additives, but even in this invention, the expected effect is not obtained in the problem area where high image quality is obtained with a small particle size toner.

In particular, in the printing field where high image quality is required, an image forming method with no fluctuation in print quality is required. In particular, in an image forming method in which the toner adhesion amount is reduced by reducing the particle size of the toner, charging over time is required. When there is a variation in the amount of toner adhering due to fluctuations or the like, the influence on the image quality appears remarkably, so that further improvement in charging fluctuation is necessary.
US Pat. No. 5,160,946 Patent No. 3009994 JP 2001-222132 A JP 2002-23409 A Japanese Patent No. 3415909 JP 2001-1000045 A JP 2001-1000045 A Japanese Patent Laid-Open No. 9-134027 JP-A-10-39539

  SUMMARY OF THE INVENTION An object of the present invention is an image forming method for forming an image on a transfer material while driving a latent image carrier suitable for a one-pass type multi-station printer by the close contact of the continuous transfer material. Is to provide an image forming method capable of obtaining a simple printed material with a small amount of toner adhesion on one side or both sides, and furthermore, it is possible to obtain a high quality printed material with excellent fixing quality even in non-contact heat fixing. An object of the present invention is to provide an image forming method, a non-contact heat fixing toner, and a manufacturing method thereof. It is another object of the present invention to provide a stable image forming method with little quality variation with time.

（式中、Ｘⁿ⁺はカチオン、ｎは１又は２の整数を示す）
（４）「荷電制御剤が着色粒子１００重量部に対し０．５〜５．０重量部の範囲で配合されていることを特徴とする前記（１）〜（３）のいずれかに記載の画像形成方法」、
（５）「平均一次粒子径が８０〜２００ｎｍの大粒径シリカが、着色粒子１００重量部に対し０．３〜１．５重量部の範囲で外添されていることを特徴とする前記（１）〜（４）のいずれかに記載の画像形成方法」、
（６）「使用されるトナーの体積平均粒径（Ｄｖ）が５〜７μｍであることを特徴とする前記（１）〜（５）のいずれかに記載の画像形成方法」、
（７）「使用されるトナーの体積平均粒径（Ｄｖ）と個数平均粒子径（Ｄｎ）との比Ｄｖ／Ｄｎが１．１０〜１．２５であることを特徴とする前記（１）〜（６）のいずれかに記載の画像形成方法」、
（８）「前記着色粒子に占めるワックスの重量比率が１〜５重量％の範囲であることを特徴とする前記（１）〜（７）のいずれかに記載の画像形成方法」、
（９）「使用されるトナーのフローテスターで測定した１／２溶融温度が１００〜１１５℃であることを特徴とする前記（１）〜（８）のいずれかに記載の画像形成方法」、
によって達成される。 The above-described problem is (1) “image forming method for forming an image on a transfer material while driving the latent image carrier by close contact with the continuous transfer material, wherein the toner used is at least a polyol resin, A large particle size silica having an average primary particle size of 80 to 200 nm is externally added to colored particles having an average circularity of 0.93 to 0.97 consisting of a charge control agent, a colorant and a wax. An image forming method characterized in that fixing is performed by a non-contact heat fixing method ",
(2) “Image formation according to (1) above, wherein the latent image carrier is cylindrical, and one-pass simultaneous double-sided image formation is performed by an image forming apparatus arranged in a staggered manner with a continuous transfer material interposed therebetween. Method",
(3) The image forming method according to (1) or (2), wherein the charge control agent is an organoboron compound represented by the following formula (I):

(Wherein, X ^{n +} represents a cation, and n represents an integer of 1 or 2)
(4) “The charge control agent is blended in an amount of 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the colored particles,” according to any one of (1) to (3), Image forming method ",
(5) The above-mentioned, wherein the large primary silica having an average primary particle size of 80 to 200 nm is externally added in the range of 0.3 to 1.5 parts by weight with respect to 100 parts by weight of the colored particles ( The image forming method according to any one of 1) to (4) ",
(6) “The image forming method according to any one of (1) to (5) above, wherein the toner used has a volume average particle diameter (Dv) of 5 to 7 μm”;
(7) The ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner used is 1.10 to 1.25. The image forming method according to any one of (6) ",
(8) “Image forming method according to any one of (1) to (7) above, wherein the weight ratio of the wax to the colored particles is in the range of 1 to 5% by weight”;
(9) “Image forming method according to any one of (1) to (8) above, wherein the ½ melting temperature measured with a flow tester of the toner used is 100 to 115 ° C.”,
Achieved by:

  According to the present invention, there is provided an image forming method on a continuous transfer material capable of obtaining a high-quality printed material free from defective transfer and simultaneously with a small amount of toner adhesion on both sides. Furthermore, it is possible to provide an image forming method, a non-contact heat fixing toner, and a method for producing the same, which are excellent in fixing quality even in non-contact heat fixing and can obtain a high-quality printed matter. Furthermore, it is possible to provide a stable image forming method with little quality variation with time.

The present invention is described in detail below.
The first of the present invention is an image forming method for forming an image on a transfer material while driving the latent image carrier by the close contact of the continuous transfer material, and the toner used is at least a polyol resin, a charge control agent, Large particles of silica having an average primary particle size of 80 to 200 nm are externally added to colored particles having an average circularity of 0.93 to 0.97, which are composed of a colorant and a wax, and the fixing is non-contact. An image forming method is performed by a heat fixing method.

  According to the present invention, double-sided simultaneous printing (simplification of the apparatus) can be achieved by combining the image forming method of the non-contact fixing and heating method with the image forming method of driving the latent image carrier with at least the contact of the continuous transfer material. An image forming method capable of copying) is obtained. In the field of printing (copying) using the recent electrophotographic process, not only high image quality comparable to offset printing, but also high copying speed and printing speed equivalent to offset printing are required. On the other hand, a certain degree of result has been obtained for speeding up on one side, but speeding up on both sides is still insufficient. In particular, in the method of fixing and fixing a toner image on one side of paper or the like and then transferring and fixing the toner image on the remaining side, it takes about twice as long as the printing time on only one side. .

In view of this, studies have been made on a system in which a toner image is transferred onto both sides before fixing and then fixed. Among them, a method has been studied in which latent image carriers are installed in stages on both sides of a transfer material such as paper and the other side (back side) is transferred immediately after the transfer on one side (front side) is completed. It was.
This method is roughly divided into two types depending on the means for driving the latent image carrier. One is a method in which the latent image carrier itself is provided with a rotation mechanism such as a motor or a belt and is driven, and the other is a method in which the latent image carrier is driven by adhesion of a transfer material such as paper without providing a rotation mechanism.
Due to the nature of the former, it is difficult to control the printing timing on both sides due to the nature of the rotation mechanism. To achieve more precise control, the precision and complexity of the equipment is inevitable, increasing costs and making the equipment larger. I have it. In particular, in an apparatus capable of obtaining a multicolor image, not only the misalignment of the printing timing on both sides but also the color misalignment peculiar to the multicolor image is likely to occur, and the burden on the apparatus for controlling these is only the monochromatic image. More than the resulting device.

  In the latter, the latent image carrier is driven by the adhesion of the transfer material, electrostatic force, etc., that is, driven by the transfer material. Printing timing and color misregistration are unlikely to occur, and the apparatus can be simplified. FIG. 1 shows a typical image forming method of the present invention, and FIG. 2 shows an enlarged view of an image forming portion. The transfer material described in the present invention refers to a transfer material that directly transfers a toner image from a latent image carrier, and the transfer material itself becomes a fixing medium. Specifically, it refers to paper, an OHP sheet, and the like.

As described above, several methods for forming an image on a continuous transfer material by a one-pass type multi-station printer have been proposed, but the method in which the rotatable latent image carriers shown in FIG. preferable. As a feature of this method, the latent image carrier is driven by bringing the transfer material into close contact with each other in order to convey and transfer the toner image while substantially synchronizing the latent image carrier and the continuous paper as the transfer material. It is mentioned. Although this image forming method can be realized by adopting this method, there is a drawback that the transfer quality of the toner image from the latent image carrier to the transfer material is easily affected by the paper. This problem is particularly noticeable as a solid image unevenness when the toner adhesion amount is reduced by reducing the particle size of the toner, and particularly when the toner adhesion amount is 5.0 g / m ² or less, The technology failed to improve transfer defects.

  According to the present invention, the toner used for image formation is a colored particle having an average circularity of 0.93 to 0.97 composed of at least a polyol resin, a charge control material, a colorant and a wax, and an average primary particle diameter of 80. It is characterized by the external addition of silica having a large particle diameter of .about.200 nm, and the degree of circularity of the colored particles is specified, and further, the external addition of the large particle diameter silica is applied when transferring from the latent image carrier to the transfer material. The pressure can be uniformly distributed, and transfer defects can be eliminated even at a portion where the toner adhesion amount is large, such as an edge portion. If the average circularity is less than 0.93, the effect on the uniform dispersion of pressure is insufficient, and in particular, the transfer failure of the second color is likely to occur when multiple colors are superimposed, and if the circularity exceeds 0.97, the transferability is improved. However, since an abnormal image is generated due to poor cleaning by a blade or the like, the range is preferably 0.93 to 0.97, and more preferably 0.94 to 0.96.

  If the average primary particle size of the large particle size silica is smaller than 80 nm, the spacer effect between the toner particles is insufficient, causing transfer failure. If the average primary particle size exceeds 200 nm, the spacer effect can be exerted, but the release is likely to occur. In this case, the range of 80 nm to 200 nm is preferable, and the range of 100 nm to 180 nm is more preferable.

  Further, in the present invention, in order to fix the toner image formed on the transfer material with high image quality without applying pressure, the toner image is fixed by non-contact heating using an oven or the like. The presence of the toner particles may interfere with the melt-bonding between the toner particles and leave the toner in an unmelted state. However, since the wax component is contained in the toner particles, the wax exudes even at low temperature fixing. As a result, the melt-bonding of the toner particles can be promoted, and the desired glossiness and further the smear quality after fixing can be improved.

（式中、Ｘⁿ⁺はカチオン、ｎは１又は２の整数を示す）
で表される有機ホウ素化合物が好ましく用いられる。式（Ｉ）においてＸⁿ⁺で示されるカチオンとしては、カリウム、ナトリウム等のアルカリ金属、アルカリ土類金属、アンモニウムイオン等が挙げられ、これらの中では、帯電安定性の観点からアルカリ金属が好ましく用いられる。また、式（Ｉ）で表される有機ホウ素化合物の市販品としては、「ＬＲ−１４７」（日本カーリット社製、ベンジル酸ホウ素化合物、Ｘⁿ⁺：カリウム（Ｋ⁺））等がある。 The toner of the present invention contains a charge control agent.
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified quaternary salts). Secondary charge control agents such as alkyl amides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts and metal salts of salicylic acid derivatives, and organic boron compounds. These may be used alone or in combination depending on the chargeability of the toner, but in the present invention, particularly from the standpoint of charge rise and charge stability over time,
Formula (I):

(Wherein, X ^{n +} represents a cation, and n represents an integer of 1 or 2)
An organic boron compound represented by the formula is preferably used. Examples of the cation represented by X ^{n +} in formula (I) include alkali metals such as potassium and sodium, alkaline earth metals, ammonium ions, etc. Among these, alkali metals are preferably used from the viewpoint of charging stability. It is done. Moreover, as a commercial item of the organoboron compound represented by a formula (I), there exists "LR-147" (The Nippon Carlit Co., Ltd. make, benzyl acid boron compound, ^{Xn +} : potassium (K ⁺ )).

The binder resin of the toner of the present invention is characterized by containing at least a polyol resin. Polyol resin has heat characteristics as a non-contact heat fixing toner, but is tougher than other resins, and in particular, it is difficult to generate fine powder during continuous stirring of developer, and the additive is not easily buried. And has excellent charging stability over time.
As the polyol resin used in the present invention, the end of the epoxy resin is capped from the viewpoints of environmental stability of charging, fixing stability, color reproducibility, gloss stability, anti-curling property after fixing, and the main chain. Those having a polyoxyalkylene moiety are preferred. For example, it can be obtained by reacting an epoxy resin having a glycidyl group at both ends and an alkylene oxide adduct of a dihydric phenol having both glycidyl groups with a dihalide, isocyanate, diamine, diol, polyhydric phenol or dicarboxylic acid. Of these, it is most preferable to react divalent phenol in terms of reaction stability. Moreover, it is also preferable to use polyhydric phenols and polyhydric carboxylic acids in combination with dihydric phenols as long as they do not gel.
Examples of the alkylene oxide adduct of a dihydric phenol having both glycidyl groups used in the present invention include the following. Examples thereof include reaction products of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof with bisphenols such as bisphenol A and bisphenol F. The obtained adduct may be used after glycidylation with epichlorohydrin or β-methylepichlorohydrin.

In particular, glycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following chemical formula (II) is preferable.

The number average molecular weight of the polyol resin used in the present invention is preferably in the range of 1000 to 5000 and more preferably in the range of 1500 to 3500 in order to obtain stable fixing characteristics and gloss in the non-contact heating method. When the molecular weight is lower than 1000, the gloss may be excessively high or the storage stability may be deteriorated. When the molecular weight is higher than 5000, the gloss may be insufficient, or the fixability may be deteriorated.
The Mw / Mn ratio of the polyol resin used in the present invention is preferably in the range of 2.0 to 5.0, more preferably in the range of 2.0 to 4.0 from the viewpoint of non-contact fixing. If it is 5.0 or more, uniform melt-fixing quality cannot be obtained in non-contact heat fixing.
The glass transition point of the polyol resin used in the present invention is preferably in the range of 50 to 70 ° C, more preferably in the range of 55 to 65 ° C. When the temperature is lower than 50 ° C., the storage stability may be deteriorated. When the temperature is higher than 70 ° C., the desired gloss cannot be obtained in the non-contact heat fixing method, and further, the fixability may be deteriorated.

  In the image forming method of the present invention, the latent image carrier is cylindrical, and it is preferable to perform one-pass simultaneous double-sided image formation with an image forming apparatus arranged in a staggered manner with a continuous transfer material interposed therebetween, and with a small toner adhesion amount. It is possible to obtain a printed material on a high-quality continuous transfer material with no transfer failure on both sides in one pass.

（式中、Ｘⁿ⁺はカチオン、ｎは１又は２の整数を示す）
で表される有機ホウ素化合物であることが好ましく、前記有機ホウ素化合物を用いることにより、前記したように帯電立上り性が良く、経時での帯電変化の少ない画像形成が可能となる。 In the present invention, the charge control agent is represented by the formula (I):

(Wherein, X ^{n +} represents a cation, and n represents an integer of 1 or 2)
It is preferable that the organic boron compound is used, and by using the organic boron compound, it is possible to form an image with good charge rising property and little change in charge with time as described above.

  In the present invention, the charge control agent is preferably blended in the range of 0.5 to 5.0 parts by weight, more preferably 0.7 to 3.0 parts by weight, still more preferably 100 parts by weight of the colored particles. Is 0.9 to 2.0 parts by weight. If the amount is less than 0.5 part by weight, the chargeability of the toner is insufficient and impractical. If the amount exceeds 5.0 parts by weight, the fluidity of the toner and / or developer is affected, and the image density decreases. Invite.

  In the present invention, it is preferable that silica having a large primary particle diameter of 80 to 200 nm is externally added in the range of 0.3 to 1.5 parts by weight with respect to 100 parts by weight of the colored particles. When the average primary particle size of 80 to 200 nm of large particle size silica is less than 0.3 parts by weight, the spacer effect between the toner particles cannot be exhibited and transfer failure occurs. Although the effect can be exerted, it is likely to be detached from the toner particles and causes problems such as filming and developer deterioration. Therefore, it is preferably in the range of 0.3 to 1.5 parts by weight, more preferably The range is 0.4 to 1.0 part by weight.

  The volume average particle size (Dv) of the toner used in the present invention is preferably 5 to 7 μm. By setting the volume average particle diameter (Dv) of the toner to 5 to 7 μm, it is possible to obtain a high-quality printed matter with a small toner adhesion amount. When the volume average particle diameter (Dv) is less than 5 μm, it is not preferable because charge control of the toner becomes difficult and problems such as toner scattering occur. On the other hand, if it exceeds 7 μm, it is not desirable particularly in the formation of high-definition images such as 1200 dpi. Therefore, the preferable range is 5 to 7 μm, and more preferably 5 to 6.5 μm.

  The ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner used in the present invention is preferably 1.10 to 1.25. Dv / Dn can be made to be 1.10 to 1.25 by performing classification processing or the like so that the particle size distribution becomes sharp after pulverization. By sharpening the particle size distribution, the charge distribution can also be sharpened, and a good printed product free from image defects such as background stains can be obtained. The ratio of Dv / Dn is preferably in the range of 1.10 to 1.25, more preferably in the range of 1.10 to 1.20. In the present invention, Dv / Dn is more preferable as it approaches 1.00, but it is preferable if it is 1.10 or more from both aspects of productivity and quality, and if it exceeds 1.25, the charge amount distribution becomes broad. As a result, image defects such as background stains occur.

  Volume average particle size, number average particle size, and measurement of 4 μm or less number% are measured by Coulter Counter TAII manufactured by Coulter Electronics, USA, and output interface for number distribution and volume distribution (manufactured by Nikka) and PC9801 personal computer (manufactured by NEC). ) And used. The electrolyte was adjusted to a 1% NaCl aqueous solution using primary sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzenesulfonate is added as a dispersant to 50 to 100 ml of the electrolytic solution, and 1 to 10 mg of a sample is added. This is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser, and 100 to 200 ml of an electrolytic aqueous solution is put into another beaker, and the sample dispersion is added to a predetermined concentration therein, and the Coulter Counter TA- Measure the particle size distribution of 30000 particles of 2 to 40 μm based on the number using a 100 μm aperture as an aperture according to type II, calculate the volume distribution and number distribution of 2 to 40 μm particles, and calculate the weight from the volume distribution The standard volume average particle size was determined.

  In the present invention, the weight ratio of the wax to the colored particles is preferably in the range of 1 to 5% by weight. In the image forming method of the present invention, fixing by non-contact heating in an oven or the like is performed, which is different from the function required for wax for fixing used for general roll pressure fixing toner. In the present invention, a function for assisting in melt-bonding of toner particles at the time of low-temperature fixing is particularly necessary, and the function can be exhibited in the range of 1 to 5% by weight. Although the above functions can be exhibited even if the amount exceeds 5% by weight, it becomes a factor that deteriorates glossiness and color reproducibility. Therefore, in order to obtain a high-quality printed matter, it is important that the amount be 5% by weight or less. . If the amount is less than 1% by weight, poor fusion between toner particles tends to occur particularly during low-temperature fixing, and problems such as a decrease in glossiness and a decrease in smear quality occur. Preferably it is the range of 1 to 5 weight%, More preferably, it is the range of 1.5 to 3.0 weight%.

  Known waxes can be used, and examples thereof include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long-chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing waxes, and the like. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.

  The melting point of the wax used in the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat-resistant storage stability, and a wax having a melting point of more than 160 ° C. does not provide an effect of assisting melt-bonding between toners during low-temperature fixing. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps are poor in the effect of improving fusion bonding.

The ½ melting temperature measured with a flow tester of the toner used in the present invention is preferably 100 to 115 ° C.
According to the present invention, it is important that the ½ melting temperature of the toner measured with a flow tester is 115 ° C. or lower. When the temperature exceeds 115 ° C., fixing at a very high temperature is required for fixing by non-contact heating, and there is a possibility that paper as a transfer material is ignited.
Further, according to the present invention, when the 1/2 melt viscosity of the toner is lowered, filming on the latent image carrier, carrier, developing sleeve and the like is likely to occur. In consideration of filming, the more preferable range of the ½ melting temperature is 100 to 115 ° C, and more preferably 105 to 115 ° C.
According to the present invention, it is further important that the difference in the 1/2 melting temperature of each toner is within 10 ° C. This effect is noticeable when used in an image forming method in which two or more layers of different color toners are combined to reproduce multiple colors. This is because when there are two or more toner layers, it is necessary to consider the adhesion between the toner and the toner in addition to the fixing property between the transfer material and the toner. By setting the difference in ½ melting temperature of each toner within 10 ° C., preferably within 7 ° C., the adhesion between each toner during fixing is increased (separation between toner layers is suppressed), and as a result, the fixing property is increased. It has become clear that the deterioration of color reproducibility is suppressed.

In addition, the 1/2 melting temperature measured with the flow tester used in the present invention is the melting temperature measured by the 1/2 method of CFT-500C (manufactured by Shimadzu Corporation), and the measurement conditions are as follows. is there. The melting temperature is calculated by calculating 1/2 of the difference between the outflow end point and the minimum value in the flow curve (piston stroke-temperature) by the temperature raising method, and setting the temperature at the position where the calculated value and the minimum value are added to 1 The melting temperature was determined by the / 2 method.
Cylinder pressure: 10.0 kgf / cm ²
Die; L: 1.0 ± 0.005mm
Die; D: 0.50 ± 0.01mm
Starting temperature: 50 ° C
Temperature rising temperature: 3.0 ° C / min
1.00 ± 0.05 mg of toner is compression molded with a flow tester granulator corresponding to a piston diameter of 11.282 + 0.002 / 0 mm.
A predetermined die is attached, a sample is charged, the temperature is raised under the above conditions, and the 1/2 melting temperature is measured.

The non-contact heat fixing toner used in the image forming method of the present invention is used in the image forming method described above.
The two-component developer comprising the non-contact heat fixing toner of the present invention and a magnetic carrier is used in the image forming method described above. The content ratio of the carrier and the toner in the two-component developer of the present invention is preferably 1 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier.

  As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl chloride, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoro Ethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride Fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluoride monomers including, and silicone resins.

  Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The method for producing a non-contact heat fixing toner of the present invention comprises a step of melt-kneading a composition containing at least a polyol resin, a charge control material, a colorant, and a wax to obtain a kneaded product, and cooling the obtained kneaded product. A step of obtaining a cooled solidified product, a step of obtaining a finely pulverized product by pulverizing the cooled solidified product, and a step of performing surface treatment by adding mechanical energy and / or fluid energy to the obtained pulverized product. And a fine powder classification step of selectively removing only fine powder from the surface-treated powder, and a step of adding / mixing an external additive containing a large particle size silica having an average primary particle size of at least 80 to 200 nm. Is preferred.

  The present invention is characterized in that surface treatment is performed by applying mechanical energy and / or fluid energy to a finely pulverized product obtained by a so-called pulverization method. In the pulverization method, the wax is easily pulverized at the interface, and the wax exudes to the surface due to heat generation by applying mechanical energy and / or fluid energy to obtain the desired circularity. This makes it possible to create a state in which a large amount of wax is present on the surface of the toner particles so that the toner particles can be easily melted and bonded when fixing by non-contact heating. A large amount of wax component on the surface tends to cause problems such as spent on the carrier, but the balance can be maintained by externally adding silica having a large average particle size of 80 nm to 200 nm.

  As an example of the method for producing the toner according to the present invention, first, the polyol resin, the pigment or dye as the colorant, the charge control agent, the wax, and other additives are sufficiently mixed by a mixer such as a Henschel mixer. After that, batch type two rolls, Banbury mixer and continuous type twin screw extruder, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. Using a heat kneader such as an extruder, a PCM type twin screw extruder manufactured by Ikekai Tekko Co., Ltd., a KEX type twin screw extruder manufactured by Kurimoto Iron Works Co., Ltd., and a continuous type single screw kneader, for example, a co-kneader manufactured by Buss. The constituent materials are kneaded well.

Subsequently, after cooling, coarse pulverization is performed using a hammer mill or the like. In the case of a color toner, for the purpose of improving the dispersion of the pigment, it is common to use a master batch obtained by previously melt-kneading a part of the binder resin and the pigment as the colorant.
Further, these coarsely pulverized products are finely pulverized by using a fine pulverizer or a mechanical pulverizer using a jet airflow alone or in combination, and the airflow pulverization method is preferable for obtaining a toner having a small particle diameter.

Since the obtained finely pulverized product has an angular shape peculiar to pulverization, a step of performing surface treatment by adding mechanical energy and / or fluid energy is required to obtain the circularity of the present invention. . Examples of the surface treatment machine include a turbo mill manufactured by Turbo Industry Co., Ltd., a faculty manufactured by Hosokawa Micron Co., Ltd., and a kryptron manufactured by Kawasaki Heavy Industries, Ltd.
Subsequently, the pulverized finely pulverized product is classified by a classifier using a swirling airflow or a classifier using a Coanda effect to obtain colored particles having desired circularity and particle size.

  The surface treatment and the fine powder classification step are preferably performed simultaneously, and according to the above-mentioned Faculty of Hosokawa Micron Co., Ltd., the surface treatment and the fine powder classification can be performed at the same time.

After obtaining colored particles, an external additive is added and mixed. In the present invention, in the step of adding and mixing the external additive, it is preferable to mix and stir only the colored particles before adding the external additive, and then add the external additive and perform the mixing treatment. Since the particles tend to agglomerate as the size of the colored particles becomes smaller, only the colored particles are mixed and agitated and dispersed before the external addition treatment, and then the external additive is added to achieve a uniform external addition treatment. Is possible.
For external mixing, general powder mixers such as V-type mixers, rocking mixers, Roedige mixers, Nauter mixers, Henschel mixers, super mixers, etc. are used. It is desirable to be able to adjust.

  Conventionally known dyes and pigments can be used as the colorant used in the present invention. For example, carbon black, lamp black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthra Zan Yellow BGL, Isoindolinone Yellow, Bengala, Red Plum, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Carlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Velcan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thio Indigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B , Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green , Titanium oxide, zinc white, litbon and mixtures thereof can be used. The amount used is generally 0.1 to 50 parts by weight per 100 parts by weight of the binder resin.

  The toner of the present invention may contain inorganic fine particles in addition to large particle size silica having an average primary particle size of 80 to 200 nm as necessary. Examples of the inorganic fine particles include silica, titanium oxide, alumina, and the like. Barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, Examples thereof include antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

It is preferable that at least one of the inorganic fine particles used together with the large particle size silica having an average primary particle size of 80 to 200 nm has an average primary particle size of 30 nm or less from the viewpoint of imparting fluidity. By setting the average primary particle size to 30 nm or less, necessary fluidity is obtained, toner charging becomes uniform, and toner scattering and background contamination are improved.
Silica fine particles having an average primary particle size of 30 nm or less are preferably hydrophobized, such as HDK H 2000, HDK H 2050EP, HVK21 (above Hoechst), R972, R974, RX200, RY200, R202, R805, R812 (above). Nippon Aerosil), TS530, TS720 (Cabot).

Moreover, as titanium oxide fine particles, P-25 (Nippon Aerosil), STT-30, STT-65C-S (above Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT- Examples thereof include titania fine particles such as 600B (taken above).
Hydrophobized titanium oxide fine particles include T-805 (Nippon Aerosil), STT-30A, STT-65S-S (above Titanium Industry), TAF-500T, TAF-1500T (above Fuji Titanium Industry), MT- 100S, MT-100T (above Taka), IT-S (Ishihara Sangyo), etc.
In the present invention, silica fine particles and titanium oxide fine particles may be used in combination with large particle size silica having an average primary particle size of 80 to 200 nm.

In the present invention, it is desirable that the average primary particle diameters of the inorganic fine particles are different. These additives are known to be gradually embedded in the toner due to a load in the development process. However, when the particle diameters are different, the inorganic fine particles having the larger particle diameters are separated from the toner particle surface and the latent image. It plays a role of a spacer in contact with a carrier (typically a photoreceptor) or a carrier surface, and has a role of preventing the inorganic fine particles having a smaller particle diameter from being embedded in the toner particle surface. Therefore, the toner surface covering state of the additive in the initial state is maintained for a long time, and the filming suppressing effect in the present invention can be further maintained.
In addition, since at least one of the inorganic fine particles used in the present invention is a hydrophobic inorganic fine particle treated with an organic silane compound, it achieves high image quality with excellent environmental stability and fewer image defects such as missing characters. More preferred. Of course, both of the two inorganic fine particles used in the present invention may be hydrophobized.

  Examples of the hydrophobizing agent include dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane. P-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, p-chlorophenyltrichlorosilane, 3-chloropropyltrichlorosilane, 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinylmethoxysilane, Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinyldichlorosilane, dimethylbi Luchlorosilane, octyltrichlorosilane, decyltrichlorosilane, nonyltrichlorosilane, (4-t-propylphenyl) trichlorosilane, (4-t-butylphenyl) trichlorosilane, dipentyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane , Dinonyl dichlorosilane, didecyl dichlorosilane, didodecyl dichlorosilane, dihexadecyl dichlorosilane, (4-t-butylphenyl) octyl dichlorosilane, dioctyl dichlorosilane, didecenyl dichlorosilane, Dinonenyldichlorosilane, di-2-ethylhexyldichlorosilane, di-3,3-dimethylpentyldichlorosilane, trihexylchlorosilane, trioctylchlorosilane, tridecylchlorosilane, dioctylmethyl Lorsilane, octyldimethylchlorosilane, (4-t-propylphenyl) diethylchlorosilane, isobutyltrimethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, trimethoxy (3,3,3-trifluoropropyl) silane, hexamethyl Organic silane compounds such as disilazane, hexaethyldisilazane, diethyltetratyldisilazane, hexaphenyldisilazane, hexatolyldisilazane, dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, Alkyl modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone oil, epoxy Silicone oil such as xy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and other silylation Agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, and the like. Of these, organic silane compounds are preferred.

By treating these hydrophobizing agents with the inorganic fine particles, the hydrophobic inorganic fine particles used in the present invention are produced.
The average primary particle size of the large particle size silica used in the present invention and other inorganic fine particles is a particle size distribution measuring device using dynamic light scattering, such as DLS-700 manufactured by Otsuka Electronics Co., Ltd. It can be measured by Coulter N4 manufactured by Coulter Electronics. However, since it is difficult to dissociate the secondary agglomeration of the particles after the treatment with the organic silane compound, it is preferable to directly determine the particle diameter from a photograph obtained by a scanning electron microscope or a transmission electron microscope. In this case, at least 100 or more inorganic fine particles are observed, and the average value of the major axis is obtained.

  For measurement of circularity, a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation) is used. As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the degree of circularity is measured with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited only to these Examples. In the following examples, parts and% are based on weight unless otherwise specified.

The composition, glass transition point, number average molecular weight, and weight average molecular weight of the polyol resin A and polyol resin B used in the following toner production are as follows.

<Toner Production Example 1>: Yellow toner 1
600 parts of water
Pigment Yellow 17 Hydrous cake (solid content 50%) 1200 parts are thoroughly stirred with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.)
100 parts Master batch 10 parts Charge control agent (LR-147 manufactured by Nippon Carlit Co., Ltd.) 1.5 parts Carnauba wax (WA-05 made by Celerica Noda) 2.0 parts After mixing the above materials with a mixer, a two-roll mill The mixture was melt kneaded and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 1 minute to obtain colored particles having an average circularity of 0.94.
After adding 100 parts by weight of the colored particles to a Henschel mixer and dispersing the colored particles at a rotation speed of 1000 rpm and a mixing time of 60 seconds,
Large particle silica (average primary particle size 120 nm) 0.75 parts Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particle size 15 nm) 0.50 parts A yellow toner 1 was obtained by stirring and mixing with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles). The obtained toner had a volume average particle size of 5.8 μm, Dv / Dn of 1.18, and a 1/2 melting temperature of 109 ° C.

<Toner Production Example 2>: Magenta toner 1
600 parts of water
Pigment Red 57 hydrous cake (solid content 50%) 1200 parts are thoroughly stirred with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.)
100 parts Master batch 10 parts Charge control agent (LR-147 manufactured by Nippon Carlit Co., Ltd.) 1.5 parts Carnauba wax (WA-05 made by Celerica Noda) 2.0 parts After mixing the above materials with a mixer, a two-roll mill The mixture was melt kneaded and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 1 minute to obtain colored particles having an average circularity of 0.95.
Further, in the same manner as the yellow toner 1, additives were added and mixed with a Henschel mixer to obtain a magenta toner 1. The obtained toner had a volume average particle diameter of 5.7 μm, Dv / Dn of 1.14, and a 1/2 melting temperature of 108 ° C.

<Toner Production Example 3>: Cyan Toner 1
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 100 parts Master batch 10 parts Charge control agent (LR-147 manufactured by Nippon Carlit) 1.5 parts Carnauba wax (WA-05 Celalica Noda) Manufactured) 2.0 parts The above materials were mixed with a mixer and then melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 1 minute to obtain colored particles having an average circularity of 0.94.
Further, an additive was added in the same manner as in the yellow toner 1 and mixed with a Henschel mixer to obtain a cyan toner 1. The obtained toner had a volume average particle size of 5.9 μm, Dv / Dn of 1.16, and a 1/2 melting temperature of 109 ° C.

<Toner Production Example 4>: Black toner 1
Water 1200 parts Phthalocyanine green water-containing cake (solid content 30%) 200 parts Carbon black (MA60, manufactured by Mitsubishi Chemical Corporation) 540 parts is thoroughly stirred with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 100 parts Master batch 10 parts Charge control agent (LR-147 manufactured by Nippon Carlit) 1.5 parts Carnauba wax (WA-05 Celalica Noda) Manufactured) 2.0 parts The above materials were mixed with a mixer and then melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 1 minute to obtain colored particles having an average circularity of 0.95.
Further, as in the case of the yellow toner 1, additives were added and mixed with a Henschel mixer to obtain a black toner 1. The obtained toner had a volume average particle diameter of 5.8 μm, Dv / Dn of 1.16, and a 1/2 melting temperature of 109 ° C.

<Toner Production Example 5>: Cyan Toner 2
Into a Henschel mixer, 100 parts by weight of the colored particles obtained in Toner Production Example 3 were placed, and the colored particles were dispersed at a rotation speed of 1000 rpm and a mixing time of 60 seconds.
Large particle size silica (average primary particle size 120 nm) 0.35 parts Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particle size 15 nm) 0.50 parts Cyan toner 2 was obtained by stirring and mixing with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles).

<Toner Production Example 6>: Cyan Toner 3
Into a Henschel mixer, 100 parts by weight of the colored particles obtained in Toner Production Example 3 were placed, and the colored particles were dispersed at a rotation speed of 1000 rpm and a mixing time of 60 seconds.
Large particle size silica (average primary particle size 120 nm) 1.45 parts Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particle size 15 nm) 0.50 parts Cyan toner 3 was obtained by stirring and mixing with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles).

<Toner Production Example 7>: Cyan Toner 4
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 100 parts Master batch 10 parts Charge control agent (LR-147 manufactured by Nippon Carlit) 0.5 parts Carnauba wax (WA-05 Celalica Noda) Manufactured) 2.0 parts The above materials were mixed with a mixer and then melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (4000 rpm) and classification (7000 rpm) were performed for 30 seconds to obtain colored particles having an average circularity of 0.93.
After adding 100 parts by weight of the colored particles to a Henschel mixer and dispersing the colored particles at a rotation speed of 1000 rpm and a mixing time of 60 seconds,
Large particle silica (average primary particle size 80 nm) 0.75 parts Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particle size 15 nm) 0.50 parts Cyan toner 4 was obtained by stirring and mixing with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles). The obtained toner had a volume average particle size of 6.1 μm and Dv / Dn of 1.15.

<Toner Production Example 8>: Cyan toner 5
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 100 parts Master batch 10 parts Charge control agent (LR-147 manufactured by Nippon Carlit) 0.5 parts Carnauba wax (WA-05 Celalica Noda) Manufactured) 2.0 parts The above materials were mixed with a mixer and then melt kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (6000 rpm) and classification treatment (7000 rpm) were performed for 90 seconds to obtain colored particles having an average circularity of 0.96.
Further, an additive was added in the same manner as in the cyan toner 4 and mixed with a Henschel mixer to obtain a cyan toner 5. The obtained toner had a volume average particle diameter of 5.8 μm and Dv / Dn of 1.18.

<Toner Production Example 9>: Cyan toner 6
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 100 parts Master batch 10 parts Charge control agent (LR-147 manufactured by Nippon Carlit) 1.5 parts Carnauba wax (WA-05 Celalica Noda) Manufactured) 2.0 parts The above materials were mixed with a mixer and then melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 7 μm with a counter jet pulverizer, and spheronization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 1 minute to obtain colored particles having an average circularity of 0.95.
After adding 100 parts by weight of the colored particles to a Henschel mixer and dispersing the colored particles at a rotation speed of 1000 rpm and a mixing time of 60 seconds,
Large particle silica (average primary particle size 120 nm) 0.50 parts Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particle size 15 nm) 0.50 parts Cyan toner 6 was obtained by stirring and mixing with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles). The obtained toner had a volume average particle diameter of 6.8 μm and Dv / Dn of 1.15.

<Toner Production Example 10>: Cyan Toner 7
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 100 parts Master batch 10 parts Charge control agent (LR-147 manufactured by Nippon Carlit) 1.5 parts Carnauba wax (WA-05 Celalica Noda) Manufactured) 2.0 parts The above materials were mixed with a mixer and then melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 5 μm with a counter jet pulverizer, and spheronization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 1 minute to obtain colored particles having an average circularity of 0.96.
After adding 100 parts by weight of the colored particles to a Henschel mixer and dispersing the colored particles at a rotation speed of 1000 rpm and a mixing time of 60 seconds,
Large particle size silica (average primary particle size 120 nm) 1.00 parts Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particle size 15 nm) 0.50 parts Cyan toner 7 was obtained by stirring and mixing with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles). The obtained toner had a volume average particle diameter of 5.2 μm and Dv / Dn of 1.18.

<Toner Production Example 11>: Cyan toner 8
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 100 parts Master batch 10 parts Charge control agent (LR-147 manufactured by Nippon Carlit) 1.5 parts Carnauba wax (WA-05 Celalica Noda) 5.8 parts The above materials were mixed with a mixer and then melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 1 minute to obtain colored particles having an average circularity of 0.95.
After adding 100 parts by weight of the colored particles to a Henschel mixer and dispersing the colored particles at a rotation speed of 1000 rpm and a mixing time of 60 seconds,
Large particle silica (average primary particle size 180 nm) 1.00 parts Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particle size 15 nm) 0.50 parts Cyan toner 8 was obtained by stirring and mixing with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles). The obtained toner had a volume average particle diameter of 6.0 μm and Dv / Dn of 1.18.

<Toner Production Example 12>: Cyan toner 9
Cyan toner 9 was obtained in the same manner as in Toner Production Example 11 except that the prescription amount of carnauba wax (WA-05 made by Celalica Noda) was 1.2 parts. The obtained toner had a ½ melting temperature of 112 ° C.

<Toner Production Example 13>: Cyan toner 10
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 50 parts Polyol resin B (Mn; 2000, Mw; 4500, Tg; 58 ° C.) 50 parts The master batch 10 parts Charge control agent (LR-147 1.5 parts Carnauba wax (WA-05 made by Celerica Noda) 2.0 parts The above materials were mixed with a mixer, melted and kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 1 minute to obtain colored particles having an average circularity of 0.96.
After adding 100 parts by weight of the colored particles to a Henschel mixer and dispersing the colored particles at a rotation speed of 1000 rpm and a mixing time of 60 seconds,
Large particle silica (average primary particle size 120 nm) 0.75 parts Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particle size 15 nm) 0.50 parts Cyan toner 10 was obtained by stirring and mixing with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles). The obtained toner had a volume average particle size of 5.9 μm, Dv / Dn of 1.13, and a 1/2 melting temperature of 106 ° C.

<Toner Production Example 14>: Cyan toner 11
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin B (Mn; 2000, Mw; 4500, Tg; 58 ° C.) 100 parts Master batch 10 parts Charge control agent (LR-147 manufactured by Nippon Carlit) 1.5 parts Carnauba wax (WA-05 Celalica Noda) Manufactured) 2.0 parts The above materials were mixed with a mixer and then melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 1 minute to obtain colored particles having an average circularity of 0.96.
After adding 100 parts by weight of the colored particles to a Henschel mixer and dispersing the colored particles at a rotation speed of 1000 rpm and a mixing time of 60 seconds,
Large particle silica (average primary particle size 180 nm) 1.00 parts Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particle size 15 nm) 0.50 parts Cyan toner 11 was obtained by stirring and mixing with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles). The obtained toner had a volume average particle size of 6.0 μm, Dv / Dn of 1.15, and a 1/2 melting temperature of 102 ° C.

<Toner Production Example 15>: Cyan toner 12
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, water was removed by kneading at 150 ° C. for 30 minutes, rolling and cooling, pulverization with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 100 parts Master batch 10 parts Charge control agent (LR-147 manufactured by Nippon Carlit Co., Ltd.) 1.5 parts 2 roll mills after mixing the above materials with a mixer The kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 7 μm with a counter jet pulverizer, and spheronization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 60 seconds to obtain colored particles having an average circularity of 0.94.
100 parts by weight of the colored particles in a Henschel mixer,
Large particle size silica (average primary particle size 120 nm) 2.00 parts Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particle size 15 nm) Cyan toner 12 was obtained by stirring and mixing at a rotational speed of 1890 rpm, mixing time of 30 seconds, rest time of 60 seconds, and 5 cycles. The obtained toner had a volume average particle diameter of 7.5 μm, Dv / Dn of 1.19, and a 1/2 melting temperature of 114 ° C.

<Toner Production Example 16>: Cyan Toner 13
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 100 parts Master batch 10 parts Charge control agent (E-84 manufactured by Orient Chemical Co., Ltd.) 2.0 parts Carnauba wax (WA-05 Celalica Noda) 2.0 parts The above materials were mixed with a mixer and then melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (2000 rpm) and classification treatment (5000 rpm) were performed for 15 seconds to obtain colored particles having an average circularity of 0.91.
100 parts by weight of the above colored particles are put into a Henschel mixer, and further, large particle size silica (average primary particle size 120 nm) 0.75 part hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts titanium oxide fine particles (average primary particles) 0.50 part was added, and the mixture was stirred and mixed with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles) to obtain cyan toner 13. The obtained toner had a volume average particle size of 5.9 μm, Dv / Dn of 1.37, and a 1/2 melting temperature of 110 ° C.

<Toner Production Example 17>: Cyan toner 14
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 100 parts Master batch 10 parts Charge control agent (E-84 manufactured by Orient Chemical Co., Ltd.) 2.0 parts The mixture was melt-kneaded with a roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 60 seconds to obtain colored particles having an average circularity of 0.95.
100 parts by weight of the above colored particles are put into a Henschel mixer, and further, a large particle size silica (average primary particle size 300 nm) 1.00 parts Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particles) 0.50 part was added, and the mixture was stirred and mixed with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles) to obtain cyan toner 14. The obtained toner had a volume average particle size of 6.1 μm, Dv / Dn of 1.17, and a 1/2 melting temperature of 115 ° C.

<Toner Production Example 18>: Cyan toner 15
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further 2 with 3 rolls. Passed to obtain a masterbatch pigment.
Polyol resin A (Mn; 3000, Mw; 7000, Tg; 60 ° C.) 100 parts Master batch 10 parts Charge control agent (E-84 manufactured by Orient Chemical Co., Ltd.) 0.5 parts Carnauba wax (WA-05 Celalica Noda) 2.0 parts The above materials were mixed with a mixer and then melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification treatment (7000 rpm) were performed to obtain colored particles having an average circularity of 0.95.
Add 100 parts by weight of the above colored particles to a Henschel mixer, and further add 1.00 parts of hydrophobic silica fine particles (average primary particle size 20 nm) 1.00 parts of titanium oxide fine particles (average primary particle size 15 nm). The cyan toner 15 was obtained by stirring and mixing at several 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, and 5 cycles). The obtained toner had a volume average particle size of 5.9 μm, Dv / Dn of 1.16, and a 1/2 melting temperature of 109 ° C.

<Toner Production Example 19>: Cyan toner 16
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) Stir well 1200 parts with a flasher. To this, 1200 parts of a polyester resin (Mn; 8000, Mw; 17000, Tg; 61 ° C.) was added, kneaded at 150 ° C. for 30 minutes, water was removed, rolled and cooled, pulverized with a pulverizer, and further passed with three rolls. To obtain a master batch pigment.
Polyester resin (Mn; 8000, Mw; 17000, Tg; 61 ° C.) 100 parts Master batch 10 parts The above materials were mixed with a mixer, melt-kneaded with a two-roll mill, and the kneaded product was rolled and cooled. After that, pulverization is performed while adjusting the feed amount and pulverization air pressure so that the particle size after classification is about 6 μm with a counter jet pulverizer, and spheroidization is performed with the surface treatment machine Faculty F400 (manufactured by Hosokawa Micron). (5000 rpm) and classification (7000 rpm) were performed for 60 seconds to obtain colored particles having an average circularity of 0.95.
100 parts by weight of the above colored particles are put into a Henschel mixer, and further, a large particle size silica (average primary particle size 50 nm) 1.00 part Hydrophobic silica fine particles (average primary particle size 20 nm) 0.50 parts Titanium oxide fine particles (average primary particles) The diameter was 15 nm) 1.50 parts were added, and the mixture was stirred and mixed with a Henschel mixer (rotation speed 1890 rpm, mixing time 30 seconds, stationary time 60 seconds, 5 cycles) to obtain cyan toner 16. The obtained toner had a volume average particle size of 6.1 μm, Dv / Dn of 1.17, and a 1/2 melting temperature of 120 ° C.

<Carrier Production Example 1>: Carrier A
Silicone resin solution (manufactured by Shin-Etsu Chemical Co., Ltd., KR50) 100 parts γ- (2-aminoethyl) aminopropyltrimethoxysilane 3 parts Toluene 100 parts The above formulation was dispersed with a homomixer for 30 minutes to prepare a coating layer forming solution. This coating layer forming solution was used to obtain carrier A having a coating layer formed on the surface of 1000 parts of spherical ferrite having an average particle size of 35 μm using a fluidized bed coating apparatus.

Example 1
1615 g of carrier A and 85 g of yellow toner 1 were mixed by a tumbler mixer to obtain a two-component developer having a toner concentration of 5%. This developer was set in the developing station 5 in the printing stations A and A ′ of the image forming apparatus shown in FIG. Yellow toner 1 was set in the toner supply section.
1615 g of carrier A and 85 g of magenta toner 1 were mixed by a tumbler mixer to obtain a two-component developer having a toner concentration of 5%. This developer was set in the developing station 5 in the printing stations C and C ′ of the image forming apparatus shown in FIG. Magenta toner 1 was set in the toner supply unit.
1615 g of carrier A and 85 g of cyan toner 1 were mixed by a tumbler mixer to obtain a two-component developer having a toner concentration of 5%. This developer was set in the developing station 5 in the printing stations B and B ′ of the image forming apparatus shown in FIG. Cyan toner 1 was set in the toner supply unit.
1615 g of carrier A and 85 g of black toner 1 were mixed by a tumbler mixer to obtain a two-component developer having a toner concentration of 5%. This developer was set in the developing station 5 in the printing stations D and D ′ of the image forming apparatus shown in FIG. Black toner 1 was set in the toner supply section.
A continuous paper of 190 g / m ² is set on the continuous paper web shown in FIG. 1, and at the conveyance speed of 120 mm / sec and the set temperature of the image fixing station 18 at 130 ° C., one pass at a time using an evaluation image adapted to the evaluation. Double-sided printing was performed and evaluated as follows. Table 1 shows the results relating to the evaluation toner formulation and toner characteristics, and Table 2 shows the other evaluation results. In addition, an evaluation result shows the average value of each color front surface and back surface.

<<< Evaluation method >>>
For image evaluation, a DCP320D machine manufactured by XEIKON is used, and development conditions (Bias setting, LDA setting) are set so that the solid image portion of each color has an arbitrary image density (1.40: measured by GRETAG D19C, filter 47B). ) Was printed while printing 10K sheets. The test was carried out after leaving overnight in a predetermined temperature and humidity environment (23 ° C., 50% RH), and continuous paper (190 g / m ² ) was used as the transfer material. Unless otherwise noted, each evaluation was tested after 10K running prints. In addition, each evaluation was performed by obtaining an average value of the front and back surfaces of the toner of each color.

1) Toner adhesion amount An image having a solid of 20 × 100 mm was developed on a latent image carrier, transferred to a transfer material, and the apparatus was stopped without performing a fixing process to create an unfixed image. After measuring the weight of the unfixed image, suck the toner from the transfer material with a suction pump equipped with a filter, measure the weight of the transfer material again, and calculate the toner adhesion amount (g / m ² ) from the weight difference. .

2) Transfer defect An image of a solid image of an isosceles triangle having a base of 12 mm and a height of 38 mm was taken out, and a visual evaluation was performed regarding the image blurring state of the tip edge portion.
Rank 5: Excellent (no image blurring)
Rank 4: Good (very slight image blur is observed)
Rank 3: acceptable (there is an image blur but acceptable level)
Rank 2: Inferior (the level is unacceptable due to image blurring)
Rank 1: Very inferior (image blurring is terrible)

3) Fixability A mending tape (manufactured by 3M) was applied to the solid image portion, and after applying a certain pressure, it was slowly peeled off, and the image was evaluated as a fixing evaluation image.
Rank 5: Excellent (no toner adheres to the tape and there is no change in the image)
Rank 4: Good (slight toner adheres to the tape, but there is no problem on the image)
Rank 3: acceptable (image is thinned in some places but acceptable level)
Rank 2: Inferior (the image is unacceptably low in some places)
Rank 1: considerably inferior (the whole image becomes unacceptable because the image becomes thinner)

4) Glossiness Using a sample glossiness meter (VG-1D: manufactured by Nippon Denshoku Co., Ltd.), the light projection angle and the light reception angle are set to 60 °, S and S / 10 switch SW are set to S, zero adjustment and A standard plate was used, and after standard setting, a solid image part was placed on the sample stage and measured. A glossiness of 8% or more was evaluated as ◎, a glossiness of 6% or more and less than 8% was evaluated as ◯, a glossiness of 4% or more and less than 6% as Δ, and a glossiness of 4% or less as ×.

5) Dot reproducibility A halftone image consisting of halftone dots with a printing rate of 50% and 600 dpi was printed and visually evaluated.
Rank 5: Excellent (no missing dots)
Rank 4: Good (level at which there are few missing dots and is not noticeable at all)
Rank 3: acceptable (dot missing but acceptable level)
Rank 2: Inferior (the level is unacceptable due to missing dots)
Rank 1: Very inferior (level with a lot of missing dots and an unacceptable level)

6) Toner scattering The toner contamination state around each development station after printing 10K sheets was visually evaluated.
○ indicates that the toner is not observed at all and is in a good condition, Δ indicates that the toner is slightly observed, and x indicates that the toner is very dirty outside the allowable range.

8) Durability The following evaluation was comprehensively evaluated as the durability by comparing the charge amount (-μC / g) and image quality (transfer defect, dot reproducibility) after printing 10K sheets with the initial state.
As for the charge amount, the toner and carrier were frictionally charged in an environment of 23 ° C. and 55% RH to obtain a developer, and the charge amount (−μC / g) was measured by a blow-off method.
Rank 5: Almost no change in Q / M Rank 4: Q / M changes but no change in image quality Rank 3: Acceptable level although Q / M changes and image quality also changes Rank 2 : Q / M changes and image quality deteriorates.
Rank 1: Q / M changes and image quality is significantly deteriorated.

Example 2
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 2 prepared in Toner Production Example 5. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.
Example 3
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 3 produced in Toner Production Example 6. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.
Example 4
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 4 produced in Toner Production Example 7. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.

Example 5
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 5 prepared in Toner Production Example 8. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.
Example 6
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 6 prepared in Toner Production Example 9. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.
Example 7
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 7 prepared in Toner Production Example 10. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.

Example 8
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 8 produced in Toner Production Example 11. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.
Example 9
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 9 prepared in Toner Production Example 12. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.
Example 10
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 10 prepared in Toner Production Example 13. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.
Example 11
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 11 prepared in Toner Production Example 14. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.

Comparative Example 1
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to the cyan toner 12 produced in Toner Production Example 15. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.
Comparative Example 2
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 13 produced in Toner Production Example 16. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.
Comparative Example 3
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 14 prepared in Toner Production Example 17. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.

Comparative Example 4
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 15 prepared in Toner Production Example 18. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.
Comparative Example 5
Evaluation was performed in the same manner as in Example 1 except that the cyan toner was changed to cyan toner 16 produced in Toner Production Example 19. Table 1 shows the results relating to the toner formulation and toner characteristics, and Table 2 shows the other evaluation results.

It is the schematic which shows the typical image forming method of this invention. FIG. 2 is an enlarged view of an image forming unit in FIG. 1.

Explanation of symbols

1. Continuous paper2. Drum 3. 3. Photosensitive drum surface 4. Development drum Development station 6. 6. Cleaning brush Cleaning unit8. 8. exposure station Pre-charging device 10. Charging device 11. Discharge device 12. Transfer device 13. Guide roller 14. Continuous raw paper15. Brake 16a. Drive roller 16b. Drive roller 17. Reverse roller 18. Image fixing station 19. Cooling unit 20. Cutting station 21. Stackers A, B, C, D. Surface printing stations A ′, B ′, C ′, D ′. Back side printing station

Claims (9)

  An image forming method for forming an image on a transfer material while driving a latent image carrier by contact of a continuous transfer material, wherein the toner used is an average comprising at least a polyol resin, a charge control agent, a colorant and a wax The colored particles having a circularity of 0.93 to 0.97 are externally added with a large particle size silica having an average primary particle size of 80 to 200 nm, and the fixing is performed by a non-contact heat fixing method. An image forming method.   2. The image forming method according to claim 1, wherein the latent image carrier has a cylindrical shape, and one-pass simultaneous double-sided image formation is performed by an image forming apparatus arranged in a staggered manner with a continuous transfer material interposed therebetween. 3. The image forming method according to claim 1, wherein the charge control agent is an organoboron compound represented by the following formula (I).

(Wherein, X ^{n +} represents a cation, and n represents an integer of 1 or 2)   The image forming method according to claim 1, wherein the charge control agent is blended in the range of 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the colored particles.   The large primary silica having an average primary particle size of 80 to 200 nm is externally added in the range of 0.3 to 1.5 parts by weight with respect to 100 parts by weight of the colored particles. An image forming method according to claim 1.   The image forming method according to claim 1, wherein the toner used has a volume average particle diameter (Dv) of 5 to 7 μm.   The ratio Dv / Dn of the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner used is 1.10 to 1.25. The image forming method described.   The image forming method according to claim 1, wherein the weight ratio of the wax to the colored particles is in the range of 1 to 5% by weight.   The image forming method according to any one of claims 1 to 8, wherein a ½ melting temperature measured by a flow tester of the toner used is 100 to 115 ° C.

Images