JP2005099846A - Toner for developing electrostatic charge image, developer containing the toner, image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for developing electrostatic charge image and a color toner full color toner kit which has excellent charging stability, hardly produces weak charging and inversely charged toner and does not cause toner scattering and surface contamination even after outputting several ten thousands sheets of pictures in high temperature/high humidity environment and not only in normal temperature/normal humidity environment but also in low temperature/low humidity environment after long time storage in the high temperature/high humidity environment, to provide one component system toner and two component system developer containing the toner, to provide an image forming method using the developer, to provide a container filled with the developer and to provide an image forming apparatus loading the container. <P>SOLUTION: The toner for developing electrostatic charge image which contains at least binder resin and colorant has nitrogen atom of 0.05-1.3 atom% on the toner surface and has the colorant content of 2-15 wt.% per the toner, and can be used for color image formation according to the tandem system where a printing speed equivalent to A4 size is 20 sheets/min or more. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrostatic image developing toner, an electrostatic image developing full color kit, an electrostatic image developing developer containing the toner, an image forming method using the developer, a container filled with the developer, and The present invention relates to an image forming apparatus loaded with the container.

  In a typical image forming process using an electrostatic charge image developing method or an electrostatic printing method, a photoconductive insulating layer is uniformly charged, the insulating layer is exposed, and then the charge on the exposed portion is dissipated. A development process for forming an electrical latent image and making the latent image visible by attaching a finely charged toner to the latent image, and transferring the resulting visible image to a transfer material such as transfer paper It consists of a fixing step for fixing by a process, heating or pressurization (usually using a heat roller). As a developer for developing an electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner, non-magnetic toner) )It has been known. As a full-color image forming apparatus, a system is well known in which toner images of respective colors formed on a photosensitive member are sequentially transferred to an intermediate transfer member, temporarily held, and then collectively transferred again onto a sheet.

  The toner used in such an electrostatic charge image developing method or electrostatic printing method has a binder resin and a colorant as main components, and if necessary, an additive such as a charge control agent or an offset preventive agent. Various performances are required in each of the above steps. For example, in the development process, in order to attach toner to an electrical latent image, the toner and the binder resin for toner are charged appropriately for a copier or printer without being affected by the surrounding environment such as temperature and humidity. You must keep the amount. Further, in the fixing step by the heat roller fixing method, the anti-offset property that does not adhere to the heat roller that is usually heated to a temperature of about 100 to 230 ° C. and the fixing property to paper must be good. Furthermore, blocking resistance that prevents toner from blocking during storage in a copier is also required.

  In recent years, in the field of electrostatic charge image development, high image quality has been studied from various angles, and among them, the recognition that toner diameter reduction and spheroidization are extremely effective is increasing. However, as the diameter of the toner is reduced and the spheroidization is progressed, environmental charging stability and the like are lowered, and the phenomenon that the toner is scattered and adhered from the developing unit to the inner wall of the apparatus (toner scattering) has become a problem. In particular, this phenomenon occurs remarkably in a high temperature and high humidity environment.

  Under such circumstances, further speeding up of image formation is desired in the field of color copiers and color printers. The “tandem method” is effective for speeding up (for example, Patent Document 1). The “tandem method” is a method in which an image formed by an image forming unit is transferred onto a transfer sheet (transfer material) by sequentially superimposing and transferring it onto a single transfer sheet (transfer material) conveyed to a transfer belt. This is a method for obtaining a full-color image. The tandem color image forming apparatus has a wide variety of usable transfer papers (transfer materials), has high quality of full color images, and can obtain full color images at high speed. In particular, obtaining a full-color image at a high speed is a unique property not found in other types of color image forming apparatuses.

  On the other hand, attempts have been made to achieve high speed while improving image quality using spherical toner. However, since it is necessary to shorten the time required for the toner to pass through the developing portion if an attempt is made to achieve high speed in an apparatus that employs the above-described method, it is necessary to reduce the developer when attempting to obtain the same developing ability as in the past. It is necessary to stir at high speed and with high torque for charge development. As a result, weakly charged toner and reversely charged toner are likely to be generated, and toner scattering from the developing portion is a problem.

  On the other hand, a method of mixing toner particles and inorganic powders such as various metal oxides for the purpose of improving the flow characteristics and charging characteristics of the toner has been proposed and is called an external additive. If necessary, the surface of the inorganic powder may be treated with a specific silane coupling agent, titanate coupling agent, silicone oil, organic acid, etc., or a specific resin may be coated to improve the hydrophobicity or charging characteristics of the surface of the inorganic powder. A method to do this has also been proposed. As the inorganic powder, for example, silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide, tin oxide and the like are known. In particular, silica particles obtained by reacting silica or titanium oxide fine particles with an organosilicon compound such as dimethyldichlorosilane, hexamethyldisilazane, or silicone oil to replace the silanol groups on the surface of the silica fine particles with organic groups to make them hydrophobic are used.

  Of these, silicone oil is known as a hydrophobizing agent that exhibits sufficient hydrophobicity and exhibits excellent transferability due to its low surface energy when contained in the toner. Patent Document 2 and Patent Document 3 define the degree of hydrophobicity of silica treated with silicone oil. Patent Documents 4 and 5 define the amount of silicone oil added and the carbon content in the additive. In order to ensure the stability of developer chargeability under high humidity by hydrophobizing inorganic fine particles that are the base material of external additives, the silicone oil content and hydrophobization degree described in the above publication are satisfactory. did it.

  However, the low surface energy, which is an important characteristic of silicone oil, makes contact with the developer, such as contact charging devices, developer carriers (sleeves), doctor blades, carriers, electrostatic latent image carriers (photosensitive). No attempt has been made to reduce the adhesion to the intermediate transfer member or the like. Silicone oil is especially used for background stains due to strong developer adhesion to the photoconductor, and for post-transfer on the character and line portions of the image, the edge portion and the center portion of the dot portion (portions where the developer is not transferred). It could not be improved only by adjusting the amount of addition and the degree of hydrophobicity. Further, the white spots due to the inability to transfer to the recesses during transfer to a transfer member with severe irregularities have not been improved as well. Patent Document 6 discloses inorganic fine particles containing a specific amount of silicone oil as a liquid component. However, such a definition of the amount cannot satisfy the above-mentioned characteristics.

Further, the toner for developing an electrostatic image is required to be charged uniformly and stably. If these are insufficient, the image quality is deteriorated due to the occurrence of background stains, density unevenness and the like. Further, since the developing mechanism has been miniaturized with the miniaturization of the image forming apparatus, the toner charge rising has become an even more important item in order to obtain high image quality. In order to improve these, various proposals have been made so far. Among these, as an example in which an improvement in chargeability is proposed by using an additive for developing an electrostatic charge image toner, Patent Document 7 discloses a non-magnetic one-component developer containing inorganic powder treated with silicone oil. Document 8 discloses a one-component magnetic developer having a coverage of the additive of 3 to 30% with respect to the toner, and Patent Document 9 discloses a toner in which fine particles having a BET specific surface area of 5 to 100 m ² / g are fixed on the toner surface. An electrostatic charge developer externally added to the toner and containing particles having a specific surface area of 1.2 times or more of the fine particles fixed to the toner is disclosed in Patent Document 10 as a hydrophobic silica fine powder and a specific powder. A developer using a non-magnetic one-component toner containing hydrophobic titanium oxide, and Patent Document 11 discloses a developer containing an additive for toner composed of organic-inorganic composite particles containing an organic polymer skeleton and a polysiloxane skeleton. There is disclosed, respectively.

  However, even with the above method, sufficient charge uniformity cannot be obtained, the toner charge amount does not rise sufficiently, and the environmental stability of the toner charge amount, particularly the stability against humidity, is not necessarily sufficient. There wasn't. In particular, the use of additives that have been improved in hydrophobicity by surface treatment of general oxide particles, as seen in many of the proposals, shows initially desired charge stability, but the additives are used over time such as running. There is a problem that the toner is deteriorated due to the composition change. Further, for example, in composite particles synthesized using the liquid phase method as described in Patent Document 11, sufficient hydrophobicity cannot be obtained due to the influence of the liquid substance remaining inside the particles, and the hydrophobicity is deteriorated over time. Sometimes it changed.

  On the other hand, as a binder resin, polystyrene, styrene are required in terms of properties required for toner, that is, transparency, insulation, water resistance, fluidity (as powder), mechanical strength, gloss, thermoplasticity, grindability, etc. -Acrylic copolymers, polyester resins, epoxy resins and the like are generally used, and among them, styrene resins are widely used because they are excellent in grindability, water resistance and fluidity. However, in order to store a copy obtained with a styrene resin-containing toner, if placed in a vinyl chloride resin sheet document holder, the image surface of the copy is left in close contact with the sheet. That is, the plasticizer contained in the vinyl chloride resin is transferred and plasticized to the fixed toner image and welded to the sheet side. As a result, when the copy is released from the sheet, the toner image is partially or completely peeled from the copy. The sheet also had the disadvantage of getting dirty. Such a defect is also seen in the polyester resin-containing toner.

  As a measure for preventing the transition to the vinyl chloride resin sheet as described above, Patent Document 12 and Patent Document 13 propose to blend a styrene resin or a polyester resin with an epoxy resin that is not plasticized with a vinyl chloride resin plasticizer. Yes. However, when such a blend resin is used particularly for color toners, the incompatibility between different types of resins causes offset properties, fixed image curl, and glossiness (in the case of color toner images, poor images without gloss). Colorability, transparency, and color developability become problems. These problems cannot be solved by conventional epoxy resins or acetylated modified epoxy resins as proposed in Patent Document 14.

  Therefore, it is conceivable to solve the above-mentioned problems by using an epoxy resin alone, but as a new problem, there arises a problem of reactivity of the epoxy resin with an amine. Epoxy resins are generally used as curable resins having excellent mechanical strength and chemical resistance by reacting an epoxy group with a curing agent to form a crosslinked structure. Curing agents are roughly divided into amine-based and organic acid anhydride-based. Of course, an epoxy resin used as an electrostatic charge image developing toner is used as a thermoplastic resin. However, dyes and pigments kneaded together with the resin as a toner, some charge control agents are amine-based, A cross-linking reaction may occur during kneading and may not be used as a toner. In addition, the chemical activity of this epoxy group is considered to be biochemical, that is, toxic such as skin irritation, and its presence requires careful attention. In addition, since the epoxy group exhibits hydrophilicity, water absorption at a high temperature and high humidity is remarkable, which causes a decrease in charge, background contamination, poor cleaning, and the like. Furthermore, the charging stability in the epoxy resin is also a problem.

  Generally, a toner is composed of a binder resin, a colorant, a charge control agent, and the like. Various dyes and pigments are known as colorants, some of which have charge controllability, and some of which have two functions of a colorant and a charge control agent. Although various resins are used as binder resins to form toners with the above-described composition, there is a problem that there is dispersibility of dyes and pigments, charge control agents and the like. In general, the kneading of the binder resin, the dye / pigment, the charge control agent and the like is performed by a hot roll mill, and it is necessary to uniformly disperse the dye / pigment, the charge control agent and the like in the binder resin. However, it is difficult to sufficiently disperse, and if the dye / pigment as a colorant is poorly dispersed, color development is poor and the coloring degree is lowered. Further, when the dispersion of the charge control agent or the like is poor, the charge distribution becomes non-uniform, which causes various defects such as charging failure, background smearing, scattering, insufficient ID, blurring, and cleaning failure. Patent Document 15 discloses a toner using an epoxy resin ester-modified with ε-caprolactone as a binder resin, but the modified amount is 15 to 90 wt. %, The softening point was too low, and the gloss was too high.

  Further, Patent Document 16 discloses that an aliphatic primary or secondary amine and a terminal epoxy group of a ready-made epoxy resin are reacted to have positive chargeability. As described above, an epoxy group and an amine are disclosed. It can be considered that a crosslinking reaction occurs and the toner cannot be used. Furthermore, Patent Document 17 discloses that one or both of the terminal epoxy groups of the epoxy resin are reacted with alcohol, phenol, Grignard reagent, organic acid sodium acetylide, alkyl chloride, or the like. If remains, problems such as reactivity with amine, toxicity and hydrophilicity occur as described above. In addition, some of the reactants described above are hydrophilic, have an effect on charging, and have an effect on pulverizability when being made into toner, and are not necessarily all effective in the present invention.

  Patent Document 18 discloses one in which both terminal epoxy groups of an epoxy resin are reacted with a monovalent active hydrogen-containing compound and then esterified with monocarboxylic acids, their ester derivatives, or lactones. However, the reactivity, toxicity, and hydrophilicity of the epoxy resin have been solved, but curling has not been improved much in fixing. Further, in general, a solvent such as xylene is often used during the synthesis of an epoxy resin or a polyol resin (for example, Patent Document 19), but these solvents or unreacted residual monomers such as bisphenol A are present in the resin after production. There were not a few, and even in toners using these resins, the remaining amount was large, which was a problem.

  On the other hand, the performance required for a color toner for developing an electrostatic image, particularly used for forming a color image, is stricter than that for obtaining a black image. In other words, in addition to mechanical and electrical stability against external factors such as impact and humidity, as a toner, appropriate color expression (coloring degree), color reproducibility when color is superimposed, color developability, and color gradation , Clarity, light transparency (transparency) when used in an overhead projector (OHP), and high light resistance in all environments.

  As what uses dye as a coloring agent, there exist a thing of patent document 20 and patent document 21, for example. However, when a dye is used as the colorant, the resulting image is excellent in transparency and can form a clear color image with good color development, but on the other hand, it is inferior in light resistance and left under direct light. , Discoloration, fading. On the other hand, examples of using a pigment as a colorant include those described in Patent Document 22 and Patent Document 23. However, although pigment-based color toners are excellent in light resistance, there is a problem that the degree of coloring (coloring property) and transparency are inferior because the dispersibility of the pigment in the binder resin is poor.

As a method for improving the dispersibility of the pigment with respect to the binder resin, (1) Patent Document 24; a polyester resin (resin A) is used as the binder resin, and the pigment is preliminarily applied with a polyester resin (resin B) having a higher molecular weight than the resin A. A technique for coating and dispersing the coated pigment in resin A to obtain a color toner.

  (2) Patent Document 25: A processed pigment selected by melting and kneading a resin and a resin for pigment is dispersedly contained in the binder resin, and the weight average molecular weight of the pigment resin is the weight average of the binder resin. A color toner having a molecular weight smaller than that of the binder resin, wherein the binder resin has a weight average molecular weight of 100,000 or more.

  (3) Patent Document 26: Firstly kneading a mixture of a binder resin and a pigment together with an organic solvent at a temperature lower than the melting temperature of the binder resin, and further adding a binder resin and a charge control agent 2 Technology to obtain color toner by heat melting and kneading at the stage.

  (4) Patent Document 27: A toner comprising a binder resin having a weight average molecular weight of 40,000 or less and a colorant made of a flushing pigment using the binder resin.

(5) Patent Document 28: Mixing a solvent, a first binder resin soluble in the solvent, and particles of a colorant insoluble in the solvent, and applying a shearing force at a temperature of 50 to 100 ° C. under pressure. The colorant particles are dispersed in the binder resin while being applied, and then the solvent is removed to obtain a colored binder resin composition in which the colorant particles are dispersed. Technology to add toner and heat-knead in the second stage to obtain toner.
Etc. have been proposed.

  However, neither of the above methods (1) and (2) can provide a sufficient dispersion of the pigment, and the degree of coloration and transparency are currently inferior. Further, although the methods (3), (4) and (5) improve the dispersion of the pigment, since any method uses a solvent, no matter how much it is removed, it is extremely small in the product or in the toner. Recently, it has been found that the solvent remains and this causes a problem such as a decrease in toner charge amount in a special environment of use in a high-temperature environment and a problem of toner scattering in the developing unit. It became clear by examination. Toner scattering not only causes a decrease in maintainability of the apparatus, but also causes a problem that the scattered toner adheres to the non-printing portion.

  In addition, there are known examples in which the particle diameter of the colorant in the toner is defined (Patent Documents 29 and 30). However, these particle size distributions have sufficient coloration, but color transparency, color developability, A sufficient effect was not obtained in terms of light resistance. In particular, the effect of improving toner scattering under high-temperature and high-humidity environment and background stain under low-temperature and low-humidity could not be obtained. Similarly, in Patent Document 31, the particle size distribution is defined, but the small particle size side is not considered, and there is a problem in light resistance in particular.

  On the other hand, as represented by Patent Document 32, as a toner production method, all the raw materials are mixed at once and heated, melted and dispersed by a kneader or the like to obtain a uniform composition, and then cooled. A method of producing a toner having a volume average particle diameter of about 6 to 10 μm by pulverization and classification is generally employed. In particular, a color toner for developing an electrostatic image used for forming a color image is generally constituted by dispersing and containing various chromatic dyes or pigments in a binder resin. In this case, the performance required for the toner to be used is stricter than that for obtaining a black image. That is, as a toner, in addition to mechanical and electrical stability against external factors such as impact and humidity, appropriate color expression (coloring degree) and light transmission (transparency) when used in an overhead projector (OHP) )Is required. As what uses dye as a coloring agent, there exist a thing as described in patent document 33 and patent document 34, for example. However, when a dye is used as the colorant, the resulting image has excellent transparency and good color development, and a clear color image can be formed, but on the other hand, it is inferior in light resistance and left under direct light. In this case, there is a problem of discoloration or fading.

Also, high temperature and high humidity, low temperature and low humidity environment during storage and transportation after toner production are harsh conditions for the toner, and the toner does not aggregate even after storage in the environment, charging characteristics, fluidity, transferability, fixing However, an effective means for this has not been found so far.
JP-A-5-341617 Japanese Patent Publication No.7-3600 Japanese Patent No. 2568244 Japanese Patent Laid-Open No. 7-271087 JP-A-8-29598 JP 11-212299 A JP-A-3-294864 JP-A-4-204665 JP-A-4-335357 JP 7-43930 A JP-A-8-202071 JP-A-60-263951 Japanese Patent Laid-Open No. 61-24025 JP 61-235852 A JP-A-61-219051 JP-A-52-86334 JP 52-156632 A JP-A-1-267560 JP 11-189646 A JP-A-57-130043 JP 57-130044 A JP 49-46951 A JP-A 52-17023 JP-A-62-280755 JP-A-2-66561 JP-A-9-101632 Japanese Patent Laid-Open No. 4-39671 JP-A-4-230770 Japanese Patent No. 2992924 Japanese Patent No. 3047310 JP 2001-228653 A JP-A-1-304467 JP-A-57-130043 JP 57-130044 A

  An object of the present invention is to provide the following stably.

  1. The toner is stored in a high-temperature and high-humidity environment for a long time, and even after printing tens of thousands of sheets in a high-temperature and high-humidity environment, it has excellent charging stability and good chargeability. To provide a toner, a developer, an image forming method, and an image forming apparatus.

  2. Toner, developer, which does not generate background stains (fogging) with little weakly charged or reversely charged toner with excellent charging stability even after outputting tens of thousands of images in low temperature and low humidity environment, not only in normal temperature and normal humidity environment To provide an image forming method and an image forming apparatus.

  3. Even after outputting tens of thousands of images, a toner, developer, image forming method, and image forming apparatus having sufficient colorability, light resistance, transparency, color development, sharpness, color reproducibility, saturation, and gloss To provide.

  4). To provide an image forming apparatus and an image forming method having both high durability and low maintenance as an image forming system.

  5). To provide a toner, a developer, an image forming apparatus, and an image forming method exhibiting necessary and sufficient charge rising property and holding charge amount in both high temperature and high humidity and low temperature and low humidity environments.

  6). To provide an image forming apparatus and an image forming method excellent in the balance between fixing property and non-offset property, in which printing speed is not inferior from a low speed region to a high speed region, image density is not lowered by continuous image output.

  7). Even for spherical toners with small particle size and high circularity, excellent charging stability and good chargeability, little weakly charged and reversely charged toner, no toner scattering, toner, developer, image forming method, image forming Providing equipment.

  8). To provide an image forming apparatus and an image forming method in which a toner image is not transferred to a sheet even when a fixed image surface is closely attached to a vinyl chloride resin sheet.

  9. To provide an image forming apparatus and an image forming method in which a fixed image is not substantially curled.

  According to the present invention, there are provided the following electrostatic charge image developing toners (1) to (13), a developer containing the same, a container filled therewith, an image forming method, and an image forming apparatus.

  (1) In a toner containing at least a binder resin and a colorant, the nitrogen atom on the toner surface is 0.05 to 1.3 atomic%, and the content of the colorant is 2 to 15% by weight with respect to the toner. %, And is used for color image formation by a tandem method with a printing speed equivalent to A4 size and 20 sheets / min or more.

  (2) The electrostatic image developing toner according to (1), wherein the binder resin of the toner contains at least a polyol resin. In particular, the toner for developing an electrostatic charge image, wherein the binder resin of the toner contains at least a polyol resin having an epoxy resin part and a polyoxyalkylene part in the main chain.

  (3) The toner for developing an electrostatic charge image according to (1) or (2), wherein the toner has a volume average particle diameter of 1 to 6 μm.

  (4) The staticity according to any one of (1) to (3), wherein the toner has a circularity SF-1 value of 100 to 140 and a circularity SF-2 value of 100 to 130. Toner for charge image development.

  (5) The color toner for developing an electrostatic charge image according to any one of (1) to (4), wherein the colorant is black, magenta, yellow, or cyan. In particular, a full-color toner for developing electrostatic images, characterized in that it is a kit combining at least two different color toners among the color toners.

  (6) A developer containing the toner according to any one of (1) to (5). In particular, a two-component developer comprising a carrier comprising the magnetic particles.

  (7) An image forming method using the developer according to (6).

  (8) A container filled with the developer according to (6).

  (9) An image forming apparatus comprising the container according to (8).

  According to the present invention, in the toner containing at least the binder resin and the colorant, the nitrogen atom on the surface of the toner is 0.05 to 1.3 atomic%, and the colorant is 2 to 15% by weight with respect to the toner. The electrostatic charge image developing toner is characterized by the fact that the toner is contained in the toner, and the charging stability is improved even after the toner is stored for a long time in a high-temperature and high-humidity environment and after outputting tens of thousands of images in the high-temperature and high-humidity environment. Providing toner with excellent, weakly charged and reversely charged toner and no toner scattering, developer containing the toner, image forming method using the toner, container filled with the developer, and image forming apparatus loaded with the toner it can. In addition, not only in normal temperature and humidity environments, but also in low-temperature and low-humidity environments, a toner that has excellent charging stability, has few weakly charged and reversely charged toners, and does not cause background stains (fogging). , An image forming method using the developer, a container filled with the developer, and an image forming apparatus loaded with the developer. Furthermore, even after outputting tens of thousands of images, a toner having sufficient colorability, light resistance, transparency, color development, sharpness, color reproducibility, saturation, and gloss, a developer containing the same, and a developer using the same An image forming method, a container filled with the developer, and an image forming apparatus loaded with the container can be provided.

  Next, embodiments of the present invention will be described with reference to the drawings.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that, in a toner containing at least a binder resin and a colorant, the nitrogen atom on the toner surface is 0.05 to 1.3 atomic% and coloring is performed. After the toner is stored for a long time in a high-temperature and high-humidity environment by using a toner for developing an electrostatic image characterized in that the agent is contained in an amount of 2 to 15% by weight with respect to the toner, and after outputting tens of thousands of images In addition, there are few weakly charged and reversely charged toners with excellent charging stability, toner scattering does not occur, and tens of thousands of images were output not only in normal temperature and normal humidity environments but also in high temperature and high humidity environments and low temperature and low humidity environments Even after this, weakly charged with excellent charging stability, less reversely charged toner, no background stain (fogging) occurs, and even after outputting tens of thousands of images, sufficient coloring, light resistance, transparency, color development , Sharpness, color reproducibility Saturation found that can form a good quality image of the gloss.

  The mechanism is currently being elucidated, but the following were inferred from some analysis data. The surface of the toner is very important in terms of generating and maintaining charge, and the control of the surface state is essential for controlling the chargeability, fixability, color characteristics, and the like. On the other hand, it has been found that nitrogen atoms have an electrically positive chargeability, and the presence of the negatively charged toner particularly has an adverse effect on the chargeability of the toner. Nitrogen may be contained in the resin, but it is often contained in the colorant, and its dispersion state control is important. That is, if nitrogen atoms are present on the toner surface above a certain amount, the chargeability of the toner is adversely affected, and the resin skeleton other than nitrogen and the charge control agent that exert negative charge on the toner are covered, resulting in charging sites of the toner. It was found to reduce In the case of a positively charged toner, the chargeability is unnecessarily increased, causing a decrease in image density and the like. As described above, the nitrogen atom on the surface of the toner is 0.05 to 1.3 atomic%, and the colorant is contained in an amount of 2 to 15% by weight based on the toner. It has been found that a toner having sufficient charging characteristics can be obtained.

  In the present invention, XPS (X-ray photoelectron spectroscopy) is particularly preferable as a means for quantifying the toner surface nitrogen amount. The XPS method is a method of analyzing the energy of generated photoelectrons by irradiating a sample with X-rays. This is a technique that enables qualitative and quantitative analysis of the elements on the extreme surface (several nm) of the sample.

  Here, when the surface amount of nitrogen atoms is less than 0.05 atomic%, the toner surface amount of the colorant particles is too small, and the colorant is reduced or the colorant is finely dispersed in order to reduce the surface amount. Thus, the crystallinity of the colorant is lowered, and the light resistance is particularly lowered, which is not preferable. It has also been found that, if the dispersion is too high, the molecular chain of the binder resin is broken, and the fixing property such as the occurrence of hot offset is adversely affected. In the case of a pulverized toner, the pulverization property of the toner is lowered, which is undesirable because it causes a reduction in productivity and an increase in cost. On the other hand, if the surface amount of nitrogen atoms exceeds 1.3 atomic%, aggregates such as the colorant on the toner surface and the nitrogen-containing component of the resin are peeled off during toner generation, and the colorant (toner) spent is removed from the carrier surface. Or the developing sleeve surface, and the charging site of the toner is reduced, which adversely affects the chargeability and print quality stability. Further, the colorant and the nitrogen component are easily exposed on the toner surface, and the surface coverage of the binder resin and the charge control agent that exert an effect on the chargeability of the toner is lowered, which adversely affects the chargeability of the total toner. In addition, it produces weakly charged toner and reversely charged toner, especially in environments where the charge level tends to fluctuate, such as in high-temperature, high-humidity, low-temperature, low-humidity environments, and this effect is particularly significant, leading to the occurrence of toner scattering and background contamination. .

  Further, when the colorant is 2 to 15% by weight with respect to the toner, the toner has a sufficient coloring degree and an effect of preventing toner scattering, background stains, and the like. That is, when the colorant is less than 2% by weight, the degree of coloration per weight of the toner is lowered, and it is necessary to increase the thickness of the toner layer in order to give the same degree of coloration as the image. In this case, as the toner layer becomes thicker, toner development and transfer amount increase, and toner scattering, transfer toner dust and the like are more likely to occur. Further, since the layer is thick, the color reproduction accuracy is also lowered. On the other hand, if it exceeds 15% by weight, the colorability is sufficient, but a problem occurs in terms of the chargeability of the toner. That is, the colorant covers the toner surface, the amount of the binder resin and charge control agent on the toner surface is reduced, the charging ability as the toner is reduced, and problems such as toner scattering and background contamination as described above occur.

  In the present invention, it is important to control the amount of the colorant on the surface of the toner, that is, control of the dispersibility of the colorant in the resin. However, since the binder resin of the toner contains at least a polyol resin, Dispersibility was extremely good, and sufficient environmental chargeability, tensile breaking strength, environmental stability, and stable fixing characteristics were obtained. Further, the binder resin of the toner contains at least a polyol resin having an epoxy resin portion and a polyoxyalkylene portion in the main chain, so that more stable colorant dispersibility and environmental stability, stable fixing characteristics, copy fixing image The toner image can be prevented from being transferred to the sheet when it is in close contact with the vinyl chloride resin on the surface, especially when used with color toners for color reproducibility, stable gloss, curling of copy-fixed images, etc. I found it to be effective.

  Further, when an electrostatic charge image developing toner having a small particle diameter of 1 to 6 μm is used, the toner is advantageous in terms of high image quality. Due to the diameter, the chargeability of each toner particle tends to decrease from the point of contact charging probability, and weakly charged and reversely charged toner tends to increase. . As a means for making full use of this small particle size toner, it has been found that by controlling the amount of nitrogen on the surface of the toner, it is possible to maintain a sufficient degree of coloration and to prevent toner scattering, background contamination, and the like.

  Further, when a toner having a high degree of circularity with a circularity SF-1 of 100 to 140 and a circularity SF-2 of 100 to 130 is used, the toner is also advantageous in terms of high image quality. However, due to the spherical shape, the frictional resistance between the toner and the carrier (developing sleeve) decreases, making it difficult for the toner to be held with the carrier (developing sleeve), and there is a problem with a small margin for toner scattering and dirt. It was. As a means for making full use of this high-circularity toner, it has been found that by controlling the amount of nitrogen on the surface of the toner, it is possible to maintain a sufficient degree of coloring and to prevent toner scattering, background contamination, and the like.

  In addition, by using a two-component development system including at least a carrier composed of the toner and magnetic particles, stable charging characteristics can be maintained even when the highly colored and highly dispersed colorant toner is used. As a result, it was possible to obtain development characteristics excellent in charge rising property and environmental charge stability, having a sufficient bulk density with little fluctuation in stress as a developer, with a good balance of adhesion with the carrier. Further, a developing system having excellent toner density controllability using a bulk density sensor or the like was obtained.

  In addition, the electrostatic image divided into multiple colors on the electrostatic charge image carrier is developed with a plurality of multi-color electrostatic charge image developing agents to form a toner image and transferred to the surface of the electrostatic charge image carrier. In the tandem type color image forming apparatus that obtains a color image on the transfer material by sequentially superposing and transferring the toner image on a single transfer material by contacting the means, the printing speed is equivalent to A4 size and 20 sheets / Min or more, more preferably 25 sheets / min or more, and even more preferably 30 sheets / min or more, it is necessary to shorten the time required for the toner to pass through the developing section. In order to obtain the capability, it is necessary to stir the developer at a higher speed and with a higher torque to perform charging development. As a result, weakly charged toner and reversely charged toner are more likely to be generated, and toner scattering from the developing portion occurs. It was a problem . As a countermeasure, it has been found that by controlling the amount of nitrogen on the surface of the toner, it is possible to maintain a sufficient degree of coloring and to prevent toner scattering, background staining, and the like. As a result of the above, images that support high-speed printing, are less affected by the material of the transfer material such as OHP, cardboard, coated paper, etc., have few transfer defects, have few image defects, and have high image quality and excellent maintainability. A forming device was obtained.

  Hereinafter, the present invention will be described in further detail. Here, as long as the conditions regarding the electrostatic image developing toner used in the present invention, the production method and materials of the developer, and the overall system related to the electrostatic image development process are satisfied, all known ones can be used.

(Toner surface nitrogen atom weight)
In the present invention, the amount of nitrogen atoms on the toner surface can be determined by XPS (X-ray photoelectron spectroscopy) method or the like. The measurement method, apparatus type, conditions, and the like are not particularly limited as long as similar results can be obtained, but the following conditions are preferable.

Apparatus: PHI 1600S type X-ray photoelectron spectrometer X-ray source: MgKα (400 W)
Analysis area: 0.8 × 2.0mm
Pretreatment: Sample was packed in an aluminum pan and measured by adhering to a sample holder with a carbon sheet. Surface atomic concentration calculation: Relative sensitivity factor provided by PHI was used (masterbatch colorant)
In the present invention, for the purpose of improving the affinity between the resin and the colorant, a master batch colorant in which the resin and the colorant are mixed and kneaded in advance can also be used. Any colorant can be used as long as it is a substance colored by pigments, dyes and the like. The ratio (weight) of the resin to the colorant is 20:80 to 80:20, more preferably 30:70 to 70:30, and still more preferably 40:60 to 60:40. The resin used here is not necessarily the toner binder resin itself, and a polyol resin, a polyester resin, or the like having good affinity with the toner binder resin can be used more preferably. For these, the same resin as the binder resin described later can be used. Furthermore, dispersibility can be further improved by using a dry powder pigment as the colorant and using water as a method of wetting with the resin. In the first place, the primary particles of the pigment are as small as 0.001 to 0.1 μm, but in the state of the raw material dry powder, a large aggregate of several μm is formed. The ideal dispersion of the pigment is to break up the agglomerates into pieces of primary particles. However, the primary particles of about 0.001 to 0.1 μm are reduced to less than that by a normal kneading method. The reduction in size is the limit in such a normal kneading method by repeated mechanical shearing. That is, the fact that the dispersion of the pigment is bad is none other than that the aggregate cannot be crushed. The necessary condition for the aggregates to be crushed is that the surrounding resin enters the voids inside the aggregates and efficiently wets all the primary particle surfaces. Accordingly, the point of pigment dispersion is whether or not the surrounding resin can enter the voids inside the aggregate. However, since the binder resin used in normal toner has a high melt viscosity, it requires a large amount of energy to enter the aggregate, and the pigment is not yet the primary particle desired. It is.

  Organic pigments that are generally used as colorants are hydrophobic, but in the manufacturing process, they are washed with water and dried, so if some force is applied, water is soaked into the pigment aggregate. It is possible. When a mixture of a pigment in which water is soaked into the aggregate and a resin is kneaded at a set temperature of 100 ° C. or higher with an open type kneader, the water inside the aggregate instantaneously reaches the boiling point and expands in volume. Therefore, a force is applied to break up the aggregate from the inside of the aggregate. The force from the inside of the aggregate can disintegrate the aggregate very efficiently compared to the force applied from the outside. Furthermore, at this time, since the resin is heated to a temperature higher than the softening point, the viscosity is lowered and the aggregate is efficiently wetted. By substituting with the effect, a master batch colorant in which the pigment is dispersed in a state close to primary particles can be obtained. Furthermore, in the process of evaporating water, the heat of vaporization accompanying water evaporation is taken away from the kneaded product, so the temperature of the kneaded product is kept at a relatively low temperature and high viscosity of 100 ° C. or less, so the shearing force is effective. In addition, it has the effect of being added to the pigment aggregate. As an open type kneader for producing a masterbatch colorant, a method of using a Banbury mixer as an open type, a continuous two roll kneader manufactured by Mitsui Mining Co., Ltd., etc. is used in addition to the usual two rolls and three rolls. be able to. As a means for better dispersing the colorant in the resin, it is also effective to coarsely pulverize the master batch colorant once kneaded with a pulverizer or the like and then knead it again twice or three times.

(Coloring agent)
As the colorant of the toner of the present invention, all known dyes and pigments can be used. Of these, organic pigments having particularly high lipophilicity are more preferable. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, oil yellow, Hansa yellow, (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Pyrazolone Orange, Benzidine Orange G, Permanent Red 4R, Watching Red Calcium Salt, Brilliant Carmine 38, Fast Bio Red B, Methyl Bio Red Lake, Indanthrene Blue BC, Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anslagen Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Cado New Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fire Red, Parachlor Ortho Nitroaniline Red, Rissor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scalate VD, Belcan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Naphthol Carmine, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, -Damin Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigolet B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone 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, Ultraviolet, Bituminous, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, manganese purple, dioxazine violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridiane Emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof.

  Preferably high light resistance such as polycondensed azo pigments, insoluble azo pigments, quinacridone pigments, carmine pigments, naphthol carmine pigments, isoindolinone pigments, perylene pigments, anthraquinone pigments, copper phthalocyanine pigments, Highly resin dispersible pigments are preferred. Specific examples include the following. As a coloring pigment for magenta, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned. Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, green 7 and green 36, and the like. Examples of the color pigment for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant is 2 to 15% by weight, more preferably 3 to 10% by weight, based on the toner. Various dispersion improvers can also be contained for the purpose of improving the dispersibility of the colorant in the resin.

(External additive)
Any known external additive can be used. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), fluoropolymers, and the like may be contained. Particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (above Hoechst), and R972, R974, RX200, RY200, R202, R805, and R812 (above Nippon Aerosil). Further, as titania fine particles, P-25 (Nippon Aerosil), STT-30, STT-65C-S (above Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT-600B MT-150A (taker above). Particularly, the hydrophobized titanium oxide fine particles include T-805 (Nippon Aerosil), STT-30A, STT-65S-S (above Titanium Industry), TAF-500T, TAF-1500T (above Fuji Titanium Industry), MT -100S, MT-100T (above Taka), IT-S (Ishihara Sangyo), etc.

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

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

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

The amount of the external additive added is 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the toner. The average particle size of the primary particles of the inorganic fine particles is 100 nm or less, preferably 3 nm or more and 70 nm or less. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor is undesirably damaged. As the external additive, inorganic fine particles and hydrophobized inorganic particles can be used in combination, but at least 2 inorganic fine particles having an average particle size of 1 to 100 nm, more preferably 5 to 70 nm, of the primary particles subjected to the hydrophobizing treatment can be used. It is more desirable to include more than one type. Further, it is more preferable that at least two kinds of inorganic fine particles having an average particle diameter of 20 nm or less of the primary particles subjected to the hydrophobization treatment and at least one kind of inorganic fine particles of 30 nm or more are contained. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

(Surface treatment agent)
Examples of surface treatment agents for external additives containing fine oxide particles include silane coupling agents such as dialkyl dihalogenated silanes, trialkyl halogenated silanes, alkyl trihalogenated silanes, and hexaalkyldisilazanes, silylating agents, and alkyl fluorides. Examples thereof include a silane coupling agent having a group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and silicone varnish. More preferred are organosilicon compound surface treatment agents and hydrophobic treatment agents.

(Resin fine particles)
Resin fine particles can also be added as an external additive. For example, polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and polymer particles made of thermosetting resin Can be mentioned. By using in combination with such resin fine particles, the chargeability of the developer can be enhanced, the reversely charged toner particles can be reduced, and the background stain can be reduced. The added amount is usually 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the toner.

(Roundness)
The shape factors SF-1 and SF-2, which are the circularity used in the present invention, are obtained by randomly sampling 300 SEM images of toner obtained by measurement with a FE-SEM (S-4200) manufactured by Hitachi, Ltd. The image information was introduced into an image analysis apparatus (Luzex AP) manufactured by Nireco through an interface and analyzed, and the values obtained from the following equations were defined as SF-1 and SF-2. The values of SF-1 and SF-2 are preferably values obtained by the above Luzex, but are not particularly limited to the FE-SEM device and the image analysis device as long as similar analysis results can be obtained.

SF-1 = (L ² / A) × (π / 4) × 100
SF-2 = (P ² / A) × (1 / 4π) × 100
(Here, L represents the absolute maximum length of the toner, A represents the projected area of the toner, and P represents the maximum peripheral length of the toner.)
In the case of a true sphere, both SF-1 and SF-2 become 100, and the value becomes larger from 100 and becomes an indeterminate shape. In particular, SF-1 represents the shape of the whole toner (ellipse, sphere, etc.), and SF-2 is a shape factor indicating the degree of surface irregularities.

(Softening point, outflow start temperature)
The softening point of the toner of the present invention was measured using a softening point measuring device (FP90, manufactured by Mettler Co., Ltd.) at a heating rate of 1 ° C./min.

(Glass transition temperature (Tg))
The Tg of the toner of the present invention was measured under the following conditions using the following differential scanning calorimeter.

・ Differential scanning calorimeter: DSC-60A, manufactured by Shimadzu Corporation
Thermal analysis workstation: TA-60WS, manufactured by Shimadzu Corporation
·Measurement condition:
Temperature range: 25-150 ° C
Temperature increase rate: 10 ° C / min
Sample amount: 5mg
(Molecular weight)
The number average molecular weight (Mn), weight average molecular weight (Mw), and peak molecular weight Mp were measured by GPC (gel permeation chromatography) as follows. A sample solution is prepared by dissolving 80 mg of a sample in 10 ml of THF, filtered through a 5 μm filter, 100 μl of this sample solution is injected into the column, and the retention time is measured under the following conditions. Moreover, the retention time was measured using polystyrene having a known average molecular weight as a standard substance, and the number average molecular weight of the sample was determined in terms of polystyrene from a calibration curve prepared in advance.

Column: guard column + GLR400M + GLR400M + GLR400 (all manufactured by Hitachi, Ltd.)
Column temperature: 40 ° C. Mobile phase (flow rate): THF (1 ml / min)
-Peak detection method: UV (254 nm)
(Penetration, heat-resistant storage stability)
The toner was weighed 10 g at a time, placed in a 20 cc glass container and left in a thermostatic bath set at 50 ° C. for 5 hours, and the penetration was measured with a penetration meter.

(Binder resin)
Examples of the binder resin of the toner of the present invention include polymers of styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene- Vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl Ketone copolymer, styrene Styrene copolymers such as tadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, poly Butyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic Examples thereof include hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes, which can be used alone or in combination. In particular, a polyol resin and a polyester resin are more preferable. Further, when the polyol resin terminal of the binder resin is inactive, a toner having less environmental stability and harmfulness can be obtained.

1. Examples of Polyol Resin Various types of polyol resin can be used, and the polyol resin (epoxy resin) used in the present invention is preferably obtained by binding bisphenol such as bisphenol A and bisphenol F and epichlorohydrin. Is. In order to obtain stable fixing characteristics and gloss, the epoxy resin is at least two types of bisphenol A type epoxy resins having different number average molecular weights. The low molecular weight component has a number average molecular weight of 360 to 2000, and has a high molecular weight component. The number average molecular weight is preferably 3000 to 10,000. Further, the low molecular weight component is preferably 20 to 50% by weight, and the high molecular weight component is preferably 5 to 40% by weight. When the amount of the low molecular weight component is too large or the molecular weight is lower than the molecular weight 360, there is a possibility that the gloss is too high or the storage stability is deteriorated. Further, when the amount of the high molecular weight component is too large or the molecular weight is higher than 10,000, the gloss may be insufficient or the fixing property may be deteriorated.

  Moreover, the following are preferable as what is used for this invention. As a polyol resin, [1] the epoxy resin, [2] an alkylene oxide adduct of dihydric phenol or glycidyl ether thereof, and [3] a compound having one active hydrogen that reacts with an epoxy group in the molecule, [4] It is preferable to use a polyol obtained by reacting a compound having two or more active hydrogens in the molecule that react with an epoxy group. Furthermore, [1] The epoxy resin is particularly preferably at least two or more bisphenol A type epoxy resins having different number average molecular weights. This polyol resin imparts good image gloss and transparency, and has an anti-offset effect if it is roller-fixed.

  Examples of [2] dihydric phenol alkylene oxide adducts used in the present invention include the following. Examples include reaction products of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof with bisphenols such as bisphenol A and bisphenol F. The resulting adduct may be used after glycidylation with epichlorohydrin or β-methylepichlorohydrin. In particular, diglycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following general formula (1) is preferable.

また、２価フェノールのアルキレンオキサイド付加物もしくはそのグリシジルエーテルが、ポリオール樹脂に対して１０〜４０重量％含まれていることが好ましい。ここで量が少ないとカールが増すなどの不具合が生じ、またｎ＋ｍが７以上であったり量が多すぎると光沢が出すぎたり、さらには保存性の悪化の可能性がある。

Moreover, it is preferable that 10 to 40 weight% of the alkylene oxide adduct of dihydric phenol or its glycidyl ether is contained with respect to polyol resin. If the amount is small, problems such as an increase in curl occur, and if n + m is 7 or more, or if the amount is too large, the gloss may be excessively increased, and the storage stability may be deteriorated.

  [3] Compounds having one active hydrogen that reacts with an epoxy group in the molecule used in the present invention include monohydric phenols, secondary amines, and carboxylic acids. The following are illustrated as monohydric phenols. Examples include phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, and p-cumylphenol. Secondary amines include diethylamine, dipropylamine, dibutylamine, N-methyl (ethyl) piperazine, piperidine and the like. Examples of carboxylic acids include propionic acid and caproic acid.

  [4] Compounds having at least two active hydrogens that react with epoxy groups in the molecule used in the present invention include dihydric phenols, polyhydric phenols, and polycarboxylic acids. Examples of the dihydric phenol include bisphenols such as bisphenol A and bisphenol F. Examples of polyhydric phenols include orthocresol novolaks, phenol novolacs, tris (4-hydroxyphenyl) methane, and 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] benzene. Examples of the polyvalent carboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, trimellitic acid, and trimellitic anhydride. In addition, by controlling the epoxy equivalent of the binder resin to 20000 or more, the thermal characteristics of the resin can be controlled, and the amount of low-molecular epichlorohydrin, etc., which is a reaction residue can be reduced, and safety is ensured. In addition, the toner can have excellent resin characteristics.

  In order to obtain a polyol resin having an epoxy resin portion and an alkylene oxide portion in the main chain of the present invention, various raw materials can be combined. 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 dihydride, isocyanate, diamine, dithiol, polyhydric phenol, or dicarboxylic acid. Of these, the reaction with dihydric phenol is most preferable from the viewpoint 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. Here, the amount of polyphenols and polycarboxylic acids is preferably 15% by weight or less, more preferably 10% by weight or less, based on the total amount. Examples of the polyhydric phenols include tris (4-hydroxyphenyl) methane and 1- [α-methyl-α (4-hydroxyphenyl) ethyl] benzene. Examples of the polyvalent carboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, terephthalic acid, trimellitic acid, and trimellitic anhydride.

  By containing at least a polyol resin or at least a polyol resin having an epoxy resin part and a polyoxyalkylene part in the main chain, sufficient compression resistance, tensile strength at break, environmental stability, stable fixing characteristics, and chlorination of the copy fixing image surface The toner image can be prevented from transferring to the sheet when it is in close contact with the vinyl resin, especially when used for color toners, and it is effective for color reproducibility, stable gloss, curling of copy-fixed images, etc. More preferred. Further, by including at least a polyol resin portion and a polyester resin portion, a toner having a good balance between stretch resistance and adhesion as well as compression strength is obtained, and more stable transferability, developability, and fixing characteristics are obtained.

2. Examples of polyester resins Polyester resins can also be preferably used as binder resins, and various types of polyester resins can be used.
[1] 'at least one selected from any of divalent carboxylic acids and lower alkyl esters and acid anhydrides thereof;
[2] 'A diol component represented by the following general formula (2),

（式中、Ｒ^１及びＲ^２は、同一でも異なっていてもよく、炭素数２〜４のアルキレン基であり、またｘ、ｙは繰り返し単位の数であり、各々１以上であって、ｘ＋ｙ＝２〜１６である。）
［３］’ ３価以上の多価カルボン酸ならびにその低級アルキルエステル及び酸無水物、及び、３価以上の多価アルコールのいずれかから選ばれる少なくとも一種、の上記［１］［２］［３］とを反応させてなるポリエステル樹脂であることが好ましい。

(In the formula, R ¹ and R ² may be the same or different and each is an alkylene group having 2 to 4 carbon atoms, and x and y are the number of repeating units, each being 1 or more, and x + y = 2-16.)
[3] ′ The above [1] [2] [3] of at least one selected from any of trivalent or higher polyvalent carboxylic acids and lower alkyl esters and acid anhydrides thereof and trivalent or higher polyhydric alcohols. ] Is preferable.

  Here, as an example of the divalent carboxylic acid of [1] ′ and its lower alkyl ester and acid anhydride, terephthalic acid, isophthalic acid, sebacic acid, isodecyl succinic acid, maleic acid, fumaric acid and monomethyl thereof, There are monoethyl, dimethyl and diethyl esters, phthalic anhydride, maleic anhydride and the like, and terephthalic acid, isophthalic acid and these dimethyl esters are particularly preferred in terms of blocking resistance and cost. These divalent carboxylic acids and their lower alkyl esters and acid anhydrides greatly affect the fixing properties and blocking resistance of the toner. That is, although depending on the degree of condensation, if a large amount of aromatic terephthalic acid, isophthalic acid or the like is used, the blocking resistance is improved, but the fixing property is lowered. Conversely, if a large amount of sebacic acid, isodecyl succinic acid, maleic acid, fumaric acid or the like is used, the fixing property is improved, but the blocking resistance is lowered. Accordingly, these divalent carboxylic acids are appropriately selected according to the other monomer composition, ratio and degree of condensation, and used alone or in combination.

  As an example of the diol component represented by the general formula (2) of [2] ′, polyoxypropylene- (n) -polyoxyethylene- (n ′)-2,2-bis (4-hydroxyphenyl) propane , Polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (n) -2,2-bis (4-hydroxyphenyl) propane and the like, 2.1 <= n <= 2.5 polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane and 2.0 <= n <= 2.5 polyoxyethylene- (n) -2,2-bis (4-hydroxyphenyl) propane is preferred. Such a diol component has the advantage of improving the glass transition temperature and making it easier to control the reaction. In addition, it is also possible to use aliphatic diols such as ethylene glycol, diethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, propylene glycol as the diol component. is there.

  Examples of [3] ′ trivalent or higher polyvalent carboxylic acids and lower alkyl esters and acid anhydrides thereof include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,3,5-benzenetricarboxylic acid. Acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthylenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexa Tricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, emporic trimer acid and their monomethyl, Examples include monoethyl, dimethyl, and diethyl ester.

  Examples of [3] ′ trihydric or higher polyhydric alcohols include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, Sucrose, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, tri Examples include methylolpropane and 1,3,5-trihydroxymethylbenzene.

  Here, the blending ratio of the trivalent or higher polyvalent monomer is suitably about 1 to 30 mol% of the whole monomer composition. When it is 1 mol% or less, the offset resistance of the toner is lowered, and the durability is likely to deteriorate. On the other hand, when the amount is 30 mol% or more, toner fixability tends to deteriorate. Of these trivalent or higher polyvalent monomers, benzenetricarboxylic acids such as benzenetricarboxylic acid and anhydrides or esters of these acids are particularly preferable. That is, by using benzenetricarboxylic acids, both fixability and offset resistance can be achieved.

  Further, these polyester resins and polyol resins are preferably non-crosslinked or weakly crosslinked (THF insoluble content is 5% or less) because it is difficult to obtain transparency and gloss when having a high crosslinking density. It is preferable. Moreover, the manufacturing method of these binder resin is not specifically limited, Any of block polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc. can be used.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEGVP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex ( Nippon Carlit), copper phthalocyanine, perylene, quinacridone, Examples thereof include azo pigments and other polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined uniquely by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 1 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. On the other hand, when the amount is less than 0.1 part by weight, the function of the charge control agent cannot be exhibited sufficiently.

(Career)
In addition, when the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is 1 to 100 parts by weight of the carrier. 10 parts by weight is preferred. Any known carrier can be used, and conventionally known carriers such as iron powder, ferrite powder, magnetite powder, and magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used.

  Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, the film thickness of these coating materials is 0.01-3 micrometers, More preferably, it is 0.1-0.3 micrometers. When the thickness is 0.01 μm or less, film control is difficult and the function as a coat film cannot be exhibited. Further, if it is 3 μm or more, conductivity cannot be obtained, which is not preferable.

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

  The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(Magnetic material)
Furthermore, the toner of the present invention contains a magnetic material and can be used as a magnetic toner. When the magnetic toner is used, the toner particles may contain magnetic fine particles. Such magnetic materials include metals, alloys such as ferrite, magnetite and other irons, nickel, cobalt, etc., or compounds containing these elements, and those containing no ferromagnetic elements, but by applying an appropriate heat treatment. An alloy that exhibits ferromagnetism, for example, a seed alloy called Heusler alloy containing manganese and copper such as manganese copper aluminum and manganese-copper-tin, chromium dioxide, and the like. It is preferable that the magnetic material is contained in a uniformly dispersed form in the form of fine powder having an average particle size of 0.1 to 1 μm. The content of the magnetic material is preferably 10 to 70 parts by weight, particularly preferably 20 to 50 parts by weight, with respect to 100 parts by weight of the obtained toner.

(wax)
In the present invention, it is preferable to contain a wax in the toner or developer in order to give the toner or developer a fixing releasability. In particular, when an oilless fixing machine that does not apply oil to the image fixing unit is used, it is preferable that the toner contains wax. The wax has a melting point of 40 to 120 ° C., and preferably 50 to 110 ° C. When the melting point of the wax is excessive, the fixing property at a low temperature may be insufficient. On the other hand, when the melting point is excessively low, the offset resistance and durability may be decreased. The melting point of the wax can be determined by differential scanning calorimetry (DSC). That is, the melting peak value when a sample of several mg is ripened at a constant temperature increase rate, for example, (10 ° C./min) is defined as the melting point. The content of the wax is preferably 0 to 20 parts by weight, and more preferably 0 to 10 parts by weight.

  Examples of the wax that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, dead monoketone, fatty acid metal salt wax, fatty acid ester wax, and partial kenne. And fatty acid ester wax, silicone varnish, higher alcohol, carnauba wax and the like. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used. In particular, polyolefins and esters having a softening point by the ring-and-ball method of 60 to 150 ° C are preferable, and polyolefins and esters having a softening point of 70 to 120 ° C are more preferable.

  More preferably, it contains at least one kind of wax selected from de-free fatty acid type carnauba wax having an acid value of 5 or less, montan ester wax, oxidized rice wax having an acid value of 10 to 30 and sazol wax. Turned out to be. The de-free fatty acid type carnauba wax is obtained by removing free fatty acid from carnauba wax as a raw material. Therefore, the acid value is 5% or less, and it becomes finer than conventional carnauba wax, resulting in a binder resin. The dispersion average particle diameter becomes 1 μm or less, and dispersibility is improved. The montan-based ester wax is refined from a mineral, becomes microcrystalline like the carnauba wax, has a dispersion average particle size of 1 μm or less in the binder resin, and improves dispersibility. In the case of montan ester wax, the acid value is particularly preferably 5 to 14. The dispersion diameter of the wax is desirably 3 μm or less, more preferably 2 μm or less, and further preferably 1 μm or less. When the dispersion diameter is 3 μm or more, the wax outflow property and the transfer material peelability are improved, but the high-temperature and high-humidity durability as a toner, the charging stability and the like are lowered.

  Oxidized russian wax is air-oxidized rice bran wax. The acid value is preferably 10 to 30, and if it is less than 10, the minimum fixing temperature increases and the low temperature fixability becomes insufficient. If it exceeds 30, the cold offset temperature increases and the low temperature fixability becomes insufficient. As the sazol wax, Sazol wax H1, H2, A1, A2, A3, A4, A6, A7, A14, C1, C2, SPRAY30, SPRAY40, etc. can be used, among which H1, H2, SPRAY30, SPRAY40. Is preferable because of low temperature fixing and storage stability. The wax may be used alone or in combination, and is preferably contained in an amount of 1 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the binder resin.

(Cleaning improver)
It is more preferable that a cleaning property improving agent for removing the transferred developer remaining on the photoreceptor or the primary transfer medium is contained in the toner or added to the toner surface, or contained in the developer or added to the surface. Examples of the cleaning improver include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles, polystyrene fine particles, and the like. . The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm. The content of the cleaning improver is preferably 0.001 to 5 parts by weight, and more preferably 0.001 to 1 part by weight.

(Production method)
As the method for producing the toner of the present invention, all known production methods can be used as long as conditions are met. For example, a toner production method comprising a step of mechanically mixing a developer component including at least a binder resin, a main charge control agent, and a pigment (colorant), a melt-kneading step, a pulverizing step, and a classification step. Is applicable. In addition, in the mechanical mixing step and the melt-kneading step, a production method is also included in which powder other than the particles that are products obtained in the pulverization or classification step is returned and reused. The powders (sub-products) other than the particles used as the product referred to here are fine particles and coarse particles other than the components used as the product having a desired particle size obtained in the pulverization step after the melt-kneading step, and a subsequent classification step. It means fine particles or coarse particles other than the components that are produced as products having a desired particle size. It is preferable that such a by-product is mixed in the weight ratio of the other raw material 50 to the sub-product 50 from the other raw material 99 to the sub-product 1 in the mixing step and the melt-kneading step.

  The mixing step of mechanically mixing at least the binder resin, the main charge control agent and the pigment, and the developer component including the by-product may be performed under normal conditions using a normal mixer using a rotating wing. There is no limit. More preferably a resin and a colorant in advance.

  When the above mixing process is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Kay Sea Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works Co., Ltd. A kneader or the like is preferably used. It is important that this melt-kneading is performed under appropriate conditions so as not to break the molecular chain of the binder resin. Specifically, the melt-kneading temperature should be performed with reference to the softening point of the binder resin. If the temperature is too low than the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed. When controlling the amount of volatile components in the toner, it is more preferable to set optimum conditions for the melt-kneading temperature, time, and atmosphere while monitoring the amount of residual volatile components at that time.

  When the above melt-kneading process is completed, the kneaded product is then pulverized. In this pulverization step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a collision pulverization method in which the pulverization is performed by colliding with a collision plate in a jet stream, or a rotor pulverization method in which pulverization is performed with a narrow gap between a mechanically rotating rotor and a stator is preferably used. Examples of the collision pulverizer include a hammer mill, a ball mill, a tube mill, and a vibration mill. I-type and IDS type collision type crushers (manufactured by Nippon Pneumatic Industrial Co., Ltd.) can be preferably used as jet type crushers comprising compressed air and a collision plate as main components. Examples of the rotor pulverizer include a roll mill, a pin mill, and a fluidized bed jet mill. In particular, the rotor pulverizer includes a fixed container as an outer wall and a rotating piece having the same central axis as the fixed container as main components. Those are preferred. A turbo mill (manufactured by Turbo Industry Co., Ltd.), a kryptron (manufactured by Kawasaki Heavy Industries, Ltd.), a fine mill (manufactured by Nippon Pneumatic Industrial Co., Ltd.), etc. can be used as this type of rotor type pulverizer. In order to make the toner more spherical, it is preferable to use a rotor grinder.

  After the pulverization step is completed, the pulverized product is classified in an air stream by centrifugal force or the like, thereby producing a toner (matrix particle) having a predetermined particle diameter, for example, a volume average particle diameter of 1 to 20 μm. When the toner has a volume average particle diameter of 1 to 6 μm, it is possible to prevent transfer dust in toner transfer and fixing and to exhibit sufficient colorability as a toner. It was also effective in preventing toner scattering and background contamination. Further, it is more preferable from the viewpoint of image quality, production cost, coverage with external additives, and the like. The volume average particle diameter can be measured using, for example, COULTERTA-II (COULTER ELECTRONICS, INC).

  Further, when preparing the toner, in order to improve the fluidity, storage stability, developability, and transferability of the toner, the oxide fine particles of the present invention listed above in addition to the toner produced as described above, Inorganic fine particles such as hydrophobic silica fine powder may be added and mixed. For mixing these external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.

As other production methods, a polymerization method, a capsule method, or the like can be used. An outline of these production methods is described below.
(Polymerization method)
[1] Polymerizable monomer, low molecular weight polymer If necessary, a polymerization initiator, a colorant and the like are granulated in an aqueous dispersion medium.

  [2] The granulated monomer composition particles are classified to an appropriate particle size.

  [3] The monomer composition particles having a prescribed inner particle diameter obtained by the classification are polymerized.

  [4] After removing the dispersant by appropriate treatment, the polymerized product obtained above is filtered, washed with water and dried to obtain base particles.

(Capsule method)
[1] A resin and, if necessary, a colorant are kneaded with a kneader or the like to obtain a molten toner core material.

  [2] The toner core material is put in water and stirred vigorously to form a fine particle core material.

  [3] The core material fine particles are placed in a shell material solution, and a poor solvent is dropped while stirring, and the core material surface is covered with a shell material to encapsulate.

  [4] Capsules obtained above are filtered and dried to obtain base particles.

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

  The developing device 40 includes a developing belt 41 as a developer carrying member, a black (hereinafter referred to as Bk) developing unit 45Bk, a yellow (hereinafter referred to as Y) developing unit 45Y, The developing unit 45M is hereinafter referred to as magenta and the cyan (hereinafter referred to as C) developing unit 45C. Further, the developing belt 41 is stretched between a plurality of belt rollers, and is configured to run endlessly in a direction indicated by an arrow by a driving unit such as a motor (not shown). Moves at approximately the same speed as 10.

  Since the configuration of each developing unit is common, the following description will be given only for the Bk developing unit 45Bk, and the other developing units 45Y, 45M, and 45C will be shown in the portions corresponding to those in the Bk developing unit 45Bk in the figure. Y, M, and C are appended to the numbers given to those in the unit, and the description is omitted. The developing unit 45Bk is disposed so that a developing tank 42Bk containing a high-viscosity and high-concentration liquid developer containing toner particles and a carrier liquid component and a lower part are immersed in the liquid developer in the developing tank 42Bk. And a coating roller 44Bk that thins the developer pumped from the pumping roller 43Bk and applies it to the developing belt 41. The application roller 44Bk has conductivity, and a predetermined bias is applied from a power source (not shown).

  The apparatus configuration of the copying machine according to the embodiment of the present invention includes a developing unit 45 for each color as shown in FIG. 2 in addition to the apparatus configuration shown in FIG. It may be a device configuration.

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

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

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

  The material of the intermediate transfer member is not particularly limited, and all known materials can be used. An example is shown below.

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

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

(3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the width of the belt is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .
Conventionally, a fluorine-based resin, a polycarbonate resin, a polyimide resin, or the like has been used for the intermediate transfer belt, but in recent years, an elastic belt in which the entire belt layer or a part of the belt is used as an elastic member has been used. The transfer of a color image using a resin belt has the following problems. That is, a color image is usually formed with four color toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet), and the cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has a high hardness and does not deform according to the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely to occur. Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a paper with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. When the transfer pressure at the secondary transfer portion is increased to improve the adhesion, the condensing power of the toner layer is increased, and the above-described character void is generated.

  The elastic belt is used for the following purposes. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, since the elastic belt deforms following local irregularities, it is possible to obtain a good adhesion without excessively increasing the transfer pressure with respect to the toner layer, and a paper with poor flatness that has no void in characters. In contrast, a transfer image with excellent uniformity can be obtained.

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

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

  A resistance value adjusting conductive agent can be used, and the resistance value adjusting conductive agent is not particularly limited. For example, carbon black, graphite, metal powder such as aluminum and nickel, tin oxide, titanium oxide, and antimony oxide. Indium oxide, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), conductive metal oxides such as indium oxide-tin oxide composite oxide (ITO), conductive metal oxides are barium sulfate, silica It may be coated with insulating fine particles such as magnesium acid and calcium carbonate. Of course, the conductive agent is not limited thereto.

  The surface layer material and the surface layer are required to prevent contamination of the photoconductor by the elastic material, reduce the surface friction resistance to the transfer belt surface, reduce the adhesion of the toner, and improve the cleaning property and the secondary transfer property. . For example, materials that use one or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and increase lubricity, such as fluororesin, fluorine compound, fluorocarbon, titanium dioxide, silicon carbide powder One body, two or more kinds of particles, or particles having different particle diameters can be dispersed and used. Further, it is also possible to use a material such as a fluorine-based rubber material in which a surface is reduced by forming a fluorine-rich layer on the surface by heat treatment.

  Although the manufacturing method of a belt is not limited, The following method is mentioned.

Centrifugal molding method in which material is poured into a rotating cylindrical mold to form a belt Spray coating method in which a liquid paint is sprayed to form a film Dipping method in which a cylindrical mold is dipped in a solution of the material and pulled up Internal and external molds Casting method for pouring into a method Method of winding a compound around a cylindrical mold and performing vulcanization polishing In the present invention, the invention is not limited to this, and it is common to produce a belt by combining a plurality of manufacturing methods It is.

  As a method for preventing elongation by elastic belting, there are a method of forming a rubber layer in a core resin layer with little elongation, a method of putting a material for preventing elongation into a core layer, etc., but it is not particularly related to the manufacturing method. .

  Materials constituting the core layer for preventing elongation include, for example, natural fibers such as cotton and silk, polyester fibers, nylon fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, One or two selected from the group consisting of synthetic fibers such as polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers and phenol fibers, inorganic fibers such as carbon fibers, glass fibers and boron fibers, and metal fibers such as iron fibers and copper fibers A woven or thread-like material can be formed using more than one seed. Of course, the material is not limited to the above.

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

  The manufacturing method for providing the core layer is not particularly limited. For example, a method in which a woven fabric woven in a cylindrical shape is covered with a mold and a coating layer is provided thereon, a woven fabric woven in a cylindrical shape is immersed in liquid rubber or the like, and a coating layer is formed on one or both sides of the core layer. Examples thereof include a method of providing, a method of winding a thread around a metal mold or the like at an arbitrary pitch, and providing a coating layer thereon. The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur in the surface layer. Also, it is not preferable that the thickness is too large (approximately 1 mm or more) because the amount of expansion and contraction becomes large and the spread of the image increases.

(Tandem type color image forming device)
An embodiment of a tandem color image forming apparatus of the present invention will be described. As shown in FIG. 3, the tandem electrostatic image developing device includes a direct transfer system in which an image on each photoreceptor 1 is sequentially transferred onto a sheet s conveyed by a sheet conveying belt 3 by a transfer device 2. As shown in FIG. 4, the image on each photoconductor 1 is once transferred sequentially to the intermediate transfer member 4 by the primary transfer device 2, and then the image on the intermediate transfer member 4 is sheeted by the secondary transfer device 5. There is an indirect transfer system that performs batch transfer to s. The transfer device 5 is a transfer conveyance belt, but there are also roller shapes and methods.

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

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

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

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 5 shows an embodiment of the present invention, which is a tandem indirect transfer type electrostatic charge image developing apparatus. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) mounted thereon. The copying machine main body 100 is provided with an endless belt-shaped intermediate transfer member 10 at the center. Then, as shown in FIG. 5, in the illustrated example, it is wound around three support rollers 14, 15, and 16 so that it can be rotated and conveyed clockwise in the figure. In this illustrated example, an intermediate transfer body cleaning device 17 for removing residual toner remaining on the intermediate transfer body 10 after image transfer is provided on the left of the second support roller 15 among the three. Further, among the three images, four images of yellow, cyan, magenta, and black are arranged on the intermediate transfer member 10 stretched between the first support roller 14 and the second support roller 15 along the conveyance direction. The tandem image forming apparatus 20 is configured by arranging the forming units 18 side by side.

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

  A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt. The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveying function together. In the illustrated example, under such a secondary transfer device 22 and a fixing device 25, a sheet reversing device 28 for reversing the sheet so as to record images on both sides of the sheet in parallel with the tandem image forming device 20 described above. Is provided.

  Now, when making a copy using this color electrostatic image developing device, the document is set on the document table 30 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it. When a start switch (not shown) is pressed, when a document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. Immediately drives the scanner 300 and travels through the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34, and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.

  When a start switch (not shown) is pressed, one of the support rollers 14, 15, and 16 is rotationally driven by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer member 10 is rotated and conveyed. At the same time, the individual image forming means 18 rotates the photoconductor 40 to form black, yellow, magenta, and cyan monochrome images on each photoconductor 40. Then, along with the conveyance of the intermediate transfer member 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer member 10.

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

  The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge roller. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56. On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for another image formation. Here, the registration roller 49 is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.

Now, in the tandem image forming apparatus 20 described above, the individual image forming means 18 includes, for example, a charging device 60, a developing device 61, and a primary device around a drum-shaped photoconductor 40 as shown in FIG. The image forming apparatus includes a transfer device 62, a photoconductor cleaning device 63, a charge removal device 64, and the like.
<Example>
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited only to these examples. In the following examples, parts and% are based on weight unless otherwise specified.

  [Evaluation] The evaluation machine used for evaluation, the evaluation method of characteristics, and the evaluation criteria are as follows.

(Evaluation machine)
Images used in the evaluation were evaluated using any of the following evaluation machines A, B, C, D, and E.

(Evaluation machine A)
Using the tandem Ricoh full color laser printer IPSiO Color 8000 fixing unit, which has a 4-color non-magnetic two-component developing unit and a 4-color photoconductor, an oilless fixing unit, and tuned the evaluation machine A And evaluated. The printing speed was evaluated by changing the printing speed from 20 to 50 sheets / min · A4 in high-speed printing and full color.
(Evaluation machine B)
Tandem Ricoh's full-color laser printer IPSiO Color 8000, which has a four-color non-magnetic two-component developing unit and a four-color photoconductor, was modified to perform primary transfer onto an intermediate transfer member, and the toner image Evaluation was performed using an evaluation machine B that was tuned by changing to an intermediate transfer system that performs secondary transfer onto a transfer material and improving the fixing unit to an oilless fixing unit. The printing speed was evaluated by changing the printing speed from 20 to 50 sheets / min · A4 in high-speed printing and full color.

(Evaluation machine C)
RICOH's full-color laser copying machine IMAGEIO, in which the four-color development unit develops each component on a drum-shaped photoreceptor on a two-component developer, sequentially transfers it to an intermediate transfer member, and transfers all four colors onto the transfer material. The Color 2800 fixing unit was evaluated as an evaluation machine C, which was improved to an oil-less fixing unit and tuned. The printing speed was evaluated at 6 sheets / min · A4 in full color.

(Evaluation machine D)
Ricoh's full-color laser printer with a four-color developing unit that develops each non-magnetic one-component developer on a belt photoreceptor in sequence, transfers it onto an intermediate transfer member, and transfers all four colors onto a transfer material. The IPSiO Color 5000 fixing unit was improved to an oilless fixing unit, and evaluation was performed using an evaluation machine D that was improved and tuned to an oilless fixing unit. The printing speed was evaluated at 6 sheets / min · A4 in full color.

(Evaluation machine E)
Evaluation was performed using an evaluation machine E which was tuned with a tandem Ricoh full color laser printer IPSiO Color 8000 having a four-color non-magnetic two-component developing unit and a four-color photoconductor as an oil-coated fixing unit. . Evaluation was made by changing the printing speed from high-speed printing to 20 to 50 sheets / min · A4.

(Evaluation item)
1) Toner scattering property under high temperature and high humidity environment After the toner is conditioned and stored for 12 hours in a high temperature and high humidity environment at 35 ° C and 80%, an evaluation machine is installed in the same environment, and 80% image area is obtained in the monochrome mode. After running 30,000 image charts, the amount of toner scattered from the developing unit was judged visually by opening the developing unit. The rank improves in the order of ×, Δ, ○, ◎.

2) Background stains in a low-temperature, low-humidity environment After running 30,000 7% image area image charts in monochrome mode, the blank image is stopped during development, and the developer on the photoconductor after development is taped. The difference from the image density of the transferred and untransferred tape was measured with a 938 spectrodensitometer (manufactured by X-Rite). The smaller the difference in image density, the better the background dirt, and the rank improves in the order of x, Δ, ○, ◎.

3) Image density (coloring degree)
After running 200,000 image charts with 50% image area in monochrome mode, the solid image was output to 6000 paper manufactured by Ricoh, and the image density was measured by X-Rite (manufactured by X-Rite). This was performed for four colors alone, and an average was obtained. If this value is less than 1.2, x, if it is 1.2 or more and less than 1.4, Δ, if it is 1.4 or more and less than 1.8, ○, if it is 1.8 or more and less than 2.2 ◎.

4) Transparency After running 100,000 sheets of an image chart with a 50% image area in the single color mode, the image density is 1.0 mg / cm ² and the fixing temperature on a Ricoh type DX OHP sheet. And fixed at 140 ° C. and measured with a continuous haze computer model HGM-2DP manufactured by Suga Test Instruments Co., Ltd. ◎, ○, Δ, and × in order of good transparency.

5) Color vividness After running 100,000 image charts with 50% image area in the monochromatic mode, the image of the vividness of the color output on 6000 paper manufactured by Ricoh was visually evaluated. ◎, ○, Δ, and × in the order of goodness.

6) Color reproducibility After running 100,000 image charts of 50% image area in monochromatic mode, the color reproducibility was visually evaluated on the image output on 6000 paper manufactured by Ricoh. ◎, ○, Δ, and × in the order of goodness.

7) Gloss After running 100,000 image charts of 50% image area in monochrome mode, the image output to 6000 paper manufactured by Ricoh is used to measure the gloss meter (VG-1D) (manufactured by Nippon Denshoku). The light projecting angle and the light receiving angle were adjusted to 60 °, and the S and S / 10 switch SWs were adjusted to S, and the measurement was performed after 0 preparation and standard setting using a standard plate. From those having good glossiness, ◎: 13 or more, ◯: 5 or more and less than 13, Δ: 2 or more to less than 5, and x: less than 2.

8) Light resistance After running 100,000 sheets of image chart with 50% image area in monochromatic mode, the image output to 6000 paper manufactured by Ricoh is converted into 10,000 images by XENONTESTER XW-150 (manufactured by Shimadzu Corporation). The image after irradiation for 15 hours was observed, and the light resistance was evaluated according to the following criteria.

  A: Almost no change.

  ○: Slightly changes.

  Δ: Slightly changes.

  X: It changes considerably.

9) Fine line reproducibility After running 30,000 image charts with a 50% image area in monochromatic mode, a 600 dpi thin line image was output to Ricoh type 6000 paper, and the degree of fine line bleeding was compared with a step sample. . The rank improves in the order of ×, Δ, ○, ◎. This was performed by overlapping four colors.

10) Heat resistant storage 10g of each color toner is weighed, put into a 20ml glass container, tapped 100 times into a glass bottle, left in a thermostat set at 55 ° C for 24 hours, and then penetrated with a penetration meter. Was measured. From the good one, ◎: 20 mm or more, ◯: 15 mm or more and less than 20 mm, Δ: 10 mm or more to less than 15 mm, x: less than 10 mm.

11) High-temperature and high-humidity environment charging stability In an environment where the temperature is 40 ° C and the humidity is 90%, a part of the developer is used for every 1000 sheets while the image chart of 7% image area is output in 100,000 sheets in monochrome mode. The charge stability was evaluated by sampling and measuring the charge amount by the blow-off method. ◎, ○, Δ, and × were given in the order of stable and favorable charge increase and charge decrease.

12) Low-temperature, low-humidity environment charging stability In an environment where the temperature is 10 ° C and the humidity is 15%, a part of the developer is sampled every 1000 sheets while 100,000 sheets of 7% image area running output is performed in the monochrome mode. Then, the charge amount was measured by the blow-off method to evaluate the charging stability. ◎, ○, Δ, and × were given in the order of stable and favorable charge increase and charge decrease.

13) Fixability The minimum fixing temperature and the maximum fixing temperature of the toner are sufficient within the fixing temperature range, hot offset and cold offset do not occur, conveyance trouble such as winding and paper jams hardly occur, and fixing is good. Overall fixability was evaluated as ◎, ○, Δ, and × in order.

(Evaluation of two-component developer)
When evaluating an image with a two-component developer, a ferrite carrier having an average particle diameter of 50 μm coated with a silicone resin with an average thickness of 0.3 μm is used as follows, and each color toner 5 is added to 100 parts by weight of the carrier. The developer was prepared by uniformly mixing and charging the parts by weight using a tumbler mixer of the type in which the container rolls and stirs.

(Carrier production)
・ Core material: Cu—Zn ferrite particles (weight average diameter: 35 μm) 5000 parts ・ Coating material: Toluene 450 parts Silicone resin SR2400 (Toray Dow Corning: Silicone, 50% non-volatile content) 450 parts Aminosilane SH6020 (Toray Dow Corning 10 parts Carbon black 10 parts The above coating material is dispersed with a stirrer for 10 minutes to prepare a coating solution, and the coating solution and the core material are swirled with a rotating bottom plate disk and stirring blades in a fluidized bed. The coating solution was applied to the core material while being formed and applied to a coating apparatus for coating. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to obtain the carrier.

Example 1
(Polyol resin 1)
In a separable flask equipped with a stirrer, a thermometer, an N ₂ inlet, and a cooling tube, 378.4 g of a low molecular bisphenol A type epoxy resin (number average molecular weight: about 360), a high molecular bisphenol A type epoxy resin (number average molecular weight: About 2700) 86.0 g, diglycidylation product of bisphenol A type propylene oxide adduct [n + m: about 2.1 in the above general formula (1)] 191.0 g, bisphenol F 274.5 g, p-cumylphenol 70.1 g, 200 g of xylene was added. The temperature was raised to 70 to 100 ° C. in an N ₂ atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., water was added under reduced pressure, and water and xylene were volatilized by bubbling water and xylene. And the polar solvent-soluble component is removed and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours, Mn: 3800, Mw / Mn: 3.9, Mp: 5000, softening point 109 ° C., Tg 58 ° C., 1000 g of a polyol resin having an epoxy equivalent of 20000 or more was obtained (polyol resin 1). The reaction conditions were controlled so that no monomer component remained in the polymerization reaction. The polyoxyalkylene part of the main chain was confirmed by NMR.

(Manufacture of toner)
<Magenta toner>
Water 600 parts Pigment Red 122 1200 parts Polyol resin 1 1200 parts The above raw materials were mixed in a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.

Polyol resin 1 100 parts Master batch 14 parts Charge control agent (Orient Chemical Co., Bontron E-84) 2 parts Wax (fatty acid ester wax, melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) 5 parts After mixing with a mixer, the mixture was melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. Thus, magenta colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0% by weight of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9% by weight of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm were added, and a Henschel mixer was used. A magenta toner was obtained by mixing and passing through a sieve having an opening of 50 μm to remove aggregates. The dispersion diameter of the wax in the toner was 0.2 μm. The obtained toner had a colorant of 6% by weight and the amount of nitrogen on the toner surface was 0.67 atomic%.

Example 2
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner was produced as follows.

<Cyan toner>
Water 600 parts Pigment Blue 15: 3 1200 parts Polyol resin 1 1200 parts The above raw materials were mixed in a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.

Polyol resin 1 100 parts Master batch 7 parts Charge control agent (Orient Chemical Co., Bontron E-84) 2 parts Wax (fatty acid ester wax, melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) 5 parts After mixing with a mixer, the mixture was melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. Cyan colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0% by weight of hydrophobic silica (HDKH2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9% by weight of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm are added and mixed with a Henschel mixer. Then, the toner was passed through a sieve having an opening of 50 μm to remove aggregates, thereby obtaining a cyan toner. The dispersion diameter of the wax in the toner was 0.2 μm. The obtained toner was 3% by weight of the colorant and the amount of nitrogen on the toner surface was 0.66 atomic%.

Example 3
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner was produced as follows.

<Yellow toner>
Water 600 parts Pigment Yellow 180 1200 parts Polyol resin 1 1200 parts The above raw materials were mixed in a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.

Polyol resin 1 100 parts Master batch 12 parts Charge control agent (Orient Chemical Co., Ltd., Bontron E-84) 2 parts Wax (fatty acid ester wax, melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) 5 parts After mixing with a mixer, the mixture was melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. As a result, yellow colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0% by weight of hydrophobic silica (HDKH2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9% by weight of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm are added and mixed with a Henschel mixer. A yellow toner was obtained by passing through a sieve having an opening of 50 μm to remove aggregates. The dispersion diameter of the wax in the toner was 0.3 μm. The obtained toner was 5% by weight of a colorant and the amount of nitrogen on the toner surface was 0.89 atomic%.

Example 4
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner was produced as follows.

<Magenta toner>
Water 600 parts Pigment Red 57: 1 1200 parts Polyol resin 1 1200 parts The above raw materials were mixed in a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.
Polyol resin 1 100 parts Master batch 8 parts Charge control agent (Orient Chemical Co., Ltd. Bontron E-84) 2 parts Wax (fatty acid ester wax, melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) 5 parts After mixing with a mixer, the mixture was melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. Thus, magenta colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0% by weight of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9% by weight of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm were added, and a Henschel mixer was used. A magenta toner was obtained by mixing and passing through a sieve having an opening of 50 μm to remove aggregates. The dispersion diameter of the wax in the toner was 0.2 μm. The obtained toner had a colorant of 3% by weight and the amount of nitrogen on the toner surface was 0.11 atomic%.

Example 5
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner was produced as follows.

<Magenta toner>
Water 600 parts Pigment Red 185 1200 parts Polyol resin 1 1200 parts The above raw materials were mixed in a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This is kneaded for 45 minutes with two rolls set at a roll surface temperature of 126 ° C, rolled and cooled, pulverized with a pulverizer, and further kneaded for 40 minutes with two rolls set at a roll surface temperature of 125 ° C. Rolled and cooled, and a pulverized masterbatch colorant was obtained using a pulverizer.

Polyol resin 1 100 parts Master batch 8 parts Charge control agent (Orient Chemical Co., Bontron E-84) 2 parts Wax (fatty acid ester wax, melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) 5 parts After mixing with a mixer, the mixture was melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. Thus, magenta colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0% by weight of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9% by weight of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm were added, and a Henschel mixer was used. A magenta toner was obtained by mixing and passing through a sieve having an opening of 50 μm to remove aggregates. The dispersion diameter of the wax in the toner was 0.2 μm. The obtained toner was 3% by weight of the colorant and the amount of nitrogen on the toner surface was 0.46 atomic%.

Example 6
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner was produced as follows.

<Magenta toner>
Water 600 parts Pigment Red 57: 1 1200 parts Polyol resin 1 1200 parts The above raw materials were mixed in a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.

Polyol resin 1 100 parts Master batch 30 parts Charge control agent (Orient Chemical Co., Bontron E-84) 2 parts Wax (fatty acid ester wax, melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) 5 parts After mixing with a mixer, the mixture was melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. Thus, magenta colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0% by weight of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9% by weight of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm were added, and a Henschel mixer was used. A magenta toner was obtained by mixing and passing through a sieve having an opening of 50 μm to remove aggregates. The dispersion diameter of the wax in the toner was 0.2 μm. The obtained toner was 11% by weight of the colorant and the amount of nitrogen on the toner surface was 0.06 atomic%.

Example 7
A full color toner kit containing magenta toner, cyan toner, yellow toner described in Examples 1, 2, and 3 and black toner described below was prepared and evaluated in the same manner as in Example 1. Various evaluations were performed in full color mode. Since the black toner prepared here does not contain nitrogen, the amount of nitrogen was not measured.

<Black toner>
Water 1000 parts Phthalocyanine green hydrous cake (solid content 30%) 200 parts Carbon black (MA60, manufactured by Mitsubishi Chemical Corporation) 1000 parts Polyol resin 1 1000 parts The above raw materials are mixed in a Henschel mixer, and water soaks into the pigment aggregate. Got a mixture. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.

Polyol resin 1 100 parts Master batch 10 parts Charge control agent (Orient Chemical Co., Ltd. Bontron E-84) 2 parts Wax (fatty acid ester wax, melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) 5 parts After mixing with a mixer, the mixture was melt-kneaded three or more times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. Black colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0% by weight of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9% by weight of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm are added and mixed with a Henschel mixer. The black toner was obtained by passing through a sieve having an opening of 50 μm to remove aggregates. The dispersion diameter of the wax in the toner was 0.15 μm. The resulting toner was 4% by weight of colorant.

Example 8
In Example 1, the resin was a polyester resin (fumaric acid, polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.3) -2,2- Resin synthesized from bis (4-hydroxyphenyl) propane and trimellitic anhydride, acid value; 10, hydroxyl value; 30, Mn; 5000, Mw / Mn; 10, Mp; 9000, Tg; 61 ° C., softening point Evaluation was conducted in the same manner as in Example 1 except that the temperature was changed to 108 ° C. The obtained toner had a volume average particle size of 5.5 μm and a number average particle size of 4.5 μm. The obtained toner was 6% by weight of a colorant and the amount of nitrogen on the toner surface was 0.72 atomic%. .

Example 9
In Example 1, a toner and a developer are prepared in the same manner as in Example 1 except that the toner is obtained by classification so that the volume average particle diameter of the toner is 6.5 μm and the number average particle diameter is 5.4 μm. And evaluated. The obtained toner had a colorant of 6% by weight, and the amount of nitrogen on the toner surface was 0.65 atomic%.

Example 10
In Example 1, a toner and a developer were prepared in the same manner as in Example 1 except that the toner was obtained by classification so that the volume average particle diameter of the toner was 4.5 μm and the number average particle diameter was 3.6 μm. And evaluated. The obtained toner had a colorant of 6% by weight and the amount of nitrogen on the toner surface was 0.85 atomic%.

Example 11
In Example 1, a toner and a developer were prepared in the same manner as in Example 1 except that the toner was obtained by classification so that the volume average particle diameter of the toner was 2 μm and the number average particle diameter was 1.4 μm. evaluated. The obtained toner had a colorant of 6% by weight, and the amount of nitrogen on the toner surface was 1.23 atomic%.

Example 12
In Example 1, toner and developer were prepared and evaluated in the same manner as in Example 1 except that the toner was pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.) and the toner shape was spheroidized. The circularity SF-1 of the toner was 140, and SF-2 was 130. The obtained toner had a colorant of 6% by weight and the amount of nitrogen on the toner surface was 0.75 atomic%.

Example 13
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner production method was changed to the following emulsion polymerization method. First, for the production of the resin dispersion 1,
Styrene 350 parts Butyl acrylate 41 parts Acrylic acid 9 parts Dodecyl mercaptan 16 parts Carbon tetrabromide 5 parts (all are manufactured by Wako Pure Chemical Industries, Ltd.)
9 parts of a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd., Nonibol 85) and 11 parts of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) were prepared by mixing and dissolving the above raw materials. Dissolved in the part, dispersed and emulsified in the flask, and slowly mixed for 15 minutes, 50 g of ion-exchanged water in which 3.4 g of ammonium persulfate (manufactured by Tokai Denka Co., Ltd.) was dissolved was added to perform nitrogen substitution. Thereafter, the flask was heated with an oil bath while stirring the flask until the content reached 73 ° C., and emulsion polymerization was continued for 7 hours, and then cooled to room temperature to obtain a resin dispersion. The solvent was left in an oven at 80 ° C. to remove moisture from the obtained resin dispersion. A resin dispersion 1 having a central particle size of 120 nm, a glass transition point of 55 ° C., and a Mw of 22,000 was obtained.

  Pigment Pigment Red 122, 70 parts are added and mixed in 300 parts of ion-exchanged water together with 2 parts of an anionic surfactant (Sanyo Kasei Co., Ltd., Ionette D-2), and dispersed with IKA Ultra Turrax T50. A pigment dispersion 1 having a center diameter of 160 nm was obtained. 50 parts of wax (fatty acid ester wax, melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) and 2 parts of anionic surfactant (Sanyo Kasei Co., Ltd., Ionette D-2) are added and mixed in 300 parts of ion-exchanged water. Then, a dispersion treatment was performed using an Ultra-Turrax T50 manufactured by IKA to obtain a wax dispersion 1.

Next, the resin dispersion 1, the pigment dispersion 1, and the wax dispersion 1 are mixed in the following proportions:
Ion-exchanged water 300 parts Resin dispersion 1 240 parts Pigment dispersion 1 40 parts Wax dispersion 1 35 parts Cationic surfactant 2 parts (Sanisol B50, manufactured by Kao Corporation)
The above materials were mixed and dispersed in a round stainless steel flask using Ultra Turrax T50, and then heated to 48 ° C. while stirring the flask in an oil bath for heating. After maintaining at 48 ° C. for 4 hours, observation with an optical microscope confirmed that aggregated particles of about 5.5 μm were formed. Then, after adding 6 parts of neogen SC further, it heated to 93 degreeC, continuing stirring, and hold | maintained for 9 hours. Thereafter, the flask was cooled to room temperature at 10 ° C./min, further filtered, thoroughly washed with ion-exchanged water, and kept in a vacuum dryer at 50 ° C. for 12 hours. The volume average particle diameter was 5.5 μm, the number average Magenta colored particles having a particle diameter of 4.7 μm and a molecular weight Mw of 22,000 were obtained. Furthermore, 1.0% by weight of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9% by weight of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm were added, and a Henschel mixer was used. A magenta toner was obtained by mixing and passing through a sieve having an opening of 50 μm to remove aggregates. The toner circularity SF-1 was 108, and SF-2 was 105. The obtained toner had a colorant of 8% by weight and the amount of nitrogen on the toner surface was 1.21 atomic%.

Example 14
In Example 1, it evaluated similarly except having used the evaluation machine B.

Example 15
In Example 1, it evaluated similarly except having used the evaluation machine C.

Example 16
In Example 1, it evaluated similarly except having used the evaluation machine D.

Example 17
In Example 1, toner was manufactured without adding wax, and evaluation and production were performed in the same manner as in Example 1 except that the evaluation machine E was used. The obtained toner had a volume average particle size of 5.5 μm, a number average particle size of 4.6 μm, the obtained toner was 6% by weight of a colorant, and the amount of nitrogen on the toner surface was 0.57 atomic%.

Comparative Example 1
In Example 1, a toner and a developer were prepared and evaluated in the same manner as in Example 1 except that the production conditions of the master batch colorant were changed. The master batch colorant was obtained by kneading for 40 minutes with two rolls set at a roll surface temperature of 115 ° C. The obtained toner had a colorant of 6% by weight and the amount of nitrogen on the toner surface was 1.42 atomic%.

Comparative Example 2
In Example 4, the toner production conditions were changed, that is, the toner kneading was changed to a bus conifer, the kneaded product was rolled and cooled, coarsely pulverized, and then kneaded again with a kneader. A toner was prepared and evaluated in the same manner as in Example 4 except that a final kneaded product was obtained. The obtained toner was 3% by weight of the colorant and the amount of nitrogen on the toner surface was 0.04 atomic%.

Comparative Example 3
In Example 1, a toner was prepared and evaluated in the same manner as in Example 1 except that the prescription amount ratio of the master batch colorant and the binder resin was changed so that the colorant in the toner was 1.3% by weight. . The amount of nitrogen on the obtained toner surface was 0.08 atomic%.

Comparative Example 4
In Example 4, a toner was prepared and evaluated in the same manner as in Example 1 except that the prescription amount ratio of the master batch colorant and the binder resin was changed so that the colorant in the toner was 16% by weight. The amount of nitrogen on the obtained toner surface was 0.96 atomic%.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus (copier) according to the present invention. It is a schematic block diagram which shows the other example of the image forming apparatus (copier) of this invention. 1 is a schematic configuration diagram of a color image forming apparatus of a tandem type direct transfer system according to the present invention. 1 is a schematic configuration diagram of a color image forming apparatus of a tandem type indirect transfer system of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic configuration diagram of an entire tandem indirect transfer type electrostatic charge image developing apparatus according to the present invention. FIG. 6 is an enlarged schematic configuration diagram of an image forming unit portion of the electrostatic charge image developing device shown in FIG. 5.

Explanation of symbols

(FIGS. 1 and 2)
DESCRIPTION OF SYMBOLS 10 Photoconductor 20 Charging roller 30 Exposure apparatus 40 Developing apparatus 41 Developing belt 42 Developing tank 43 Pumping roller 44 Coating roller 45 Developing unit 50 Intermediate transfer body 51 Suspension roller 52 Corona charger 53 Constant current source 60 Cleaning apparatus 70 Static elimination lamp 80 Transfer Roller 90 Cleaning device 100 Transfer paper (FIGS. 3 and 4)
T tandem type image forming apparatus 1 photoconductor 2 transfer device (or primary transfer device)
3 Sheet transport belt 4 Intermediate transfer member 5 Secondary transfer device 6 Paper feed device 7 Fixing device 8 Photoconductor cleaning device 9 Intermediate transfer member cleaning device S Sheet (FIGS. 5 and 6)
DESCRIPTION OF SYMBOLS 100 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder 10 Intermediate transfer body 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer body cleaning device 18 Image forming means 20 Tandem image forming device 21 Exposure device 22 Secondary transfer Device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Document table 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Read sensor 40 Photoconductor 42 Supply Paper roller 43 Paper bank 44 Paper feed cassette 45 Separation roller 46 Paper feed path 47 Transport roller 48 Paper feed path 49 Registration roller 50 Paper feed roller 51 Manual feed tray 52 Separation roller 53 Paper feed path 55 Switching claw 56 Paper discharge roller 57 Paper discharge tray 60 Charging roller 61 Development Device 62 Primary transfer device 63 Photoconductor cleaning device 64 Static elimination device

Claims (9)

  In a toner containing at least a binder resin and a colorant, the nitrogen atom on the toner surface is 0.05 to 1.3 atomic%, and the content of the colorant is 2 to 15% by weight with respect to the toner. A toner for developing an electrostatic charge image, which is used for color image formation by a tandem method with a printing speed equivalent to A4 size and 20 sheets / min or more.   The electrostatic charge image developing toner according to claim 1, wherein the binder resin of the toner contains at least a polyol resin.   The electrostatic charge image developing toner according to claim 1, wherein the toner has a volume average particle diameter of 1 to 6 μm.   4. The electrostatic image developing toner according to claim 1, wherein the toner has a circularity SF-1 value of 100 to 140 and a circularity SF-2 value of 100 to 130.   5. The color toner for developing an electrostatic charge image according to claim 1, wherein the colorant is black, magenta, yellow, or cyan.   A developer comprising the toner according to claim 1.   An image forming method using the developer according to claim 6.   A container filled with the developer according to claim 6.   An image forming apparatus loaded with the container according to claim 8.

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