JP2003295493A - Electrostatic charge image developing toner, developer comprising the same, and method for forming image and image forming device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner, a full-color toner kit of color toners, a single component and two-component developer containing the above toners, a method for forming an image by using the developer, a container filled with the developer and an image forming device mounting the container, all having features of excellent electrification stability, little toner with weak charges or inverted charges and no scattering of the toner or contamination of the image base in a high temperature and high humidity environment after stored for a long time in a high temperature and high humidity environment, or not only in a normal temperature and normal humidity environment but in a low temperature and low humidity environment, or even after output of images on several ten thousands of sheets. <P>SOLUTION: The electrostatic charge image developing toner comprising at least a binder resin and a colorant features that nitrogen atoms are present by 0.05 to 1.3 at.% on the toner surface and that the content of the colorant is 2 to 15 wt.% with respect to the toner. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art A typical image forming process using an electrostatic image development method or electrostatic printing method is to uniformly charge a photoconductive insulating layer, expose the insulating layer, and then expose the exposed portion. Development process to form an electric latent image by dissipating the electric charge of the toner, and to visualize the latent image by adhering the charged fine powder toner to the latent image. Transfer the obtained visible image to a transfer paper or the like. It comprises a transfer step of transferring to a material and a fixing step of fixing by heating or pressurization (usually using a heat roller). As a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer consisting of a carrier and a toner, and a one-component developer not requiring a carrier (magnetic toner, non-magnetic toner) )It has been known. As a full-color image forming apparatus, a method is well known in which toner images of respective colors formed on a photoconductor are sequentially transferred to an intermediate transfer body, temporarily held, and then collectively transferred again onto paper.

The toner used in such an electrostatic image development method or electrostatic printing method contains a binder resin and a colorant as main components, and if necessary, additives such as a charge control agent and an offset preventive agent. It is contained, and various performances are required in each of the above steps. For example, in the developing process, the toner and the binder resin for the toner are not affected by the surrounding environment such as temperature and humidity in order to attach the toner to the electric latent image, so that the toner and the binder resin for the toner are suitable for the copying machine or the printer. You have to hold a quantity. Further, in the fixing step by the heat roller fixing method, offset resistance that does not adhere to the heat roller normally heated to a temperature of about 100 to 230 ° C. and fixability on paper must be good. Further, blocking resistance that toner does not block during storage in a copying machine is also required.

Further, in recent years, in the field of electrostatic image development, high image quality has been studied from various angles, and in particular, it has been recognized that reducing the diameter and spheroidizing of toner is extremely effective. However, as the diameter of the toner is reduced and the toner is made into a spherical shape, environmental charging stability and the like are deteriorated, and a phenomenon in which toner is scattered and attached from the developing unit to the inner wall of the apparatus (toner scattering) becomes more significant, which is a problem. This phenomenon occurs remarkably under high temperature and high humidity environment.

Under these circumstances, in the fields of color copying machines and color printers, further speeding up of image formation is desired. The "tandem system" is effective for speeding up (for example, Japanese Patent Laid-Open No. 5-341617). The “tandem system” is a method in which the images formed by the image forming unit are sequentially superimposed and transferred onto a single transfer paper (transfer material) that is conveyed to the transfer belt, and transferred onto the transfer paper (transfer material). This is a method for obtaining a full-color image. The tandem type color image forming apparatus has a wide variety of transfer papers (transfer materials) that can be used, the quality of the full-color image is high, and the full-color image can be obtained at high speed.
In particular, obtaining a full-color image at high speed is a unique property that other color image forming apparatuses do not have.

On the other hand, attempts have been made to achieve high speed while achieving high image quality by using spherical toner.
However, in order to achieve higher speed in an apparatus adopting the above method, it is necessary to shorten the time required for the toner to pass through the developing section. It is necessary to agitate at high speed and with high torque to carry out electrostatic charge development. As a result, weakly charged toner and reversely charged toner are likely to be generated, and toner scattering from the developing section is a problem.

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

Of these, it exhibits sufficient hydrophobicity, and
Silicone oil is known as a hydrophobizing agent which, when contained in a toner, exhibits excellent transferability due to its low surface energy. JP-B-7-3600 and Japanese Patent No. 2568244 specify the degree of hydrophobicity of silica treated with silicone oil. In addition, JP-A-7-271087 and JP-A-8-29598 specify the amount of silicone oil added and the carbon content in the additive. In order to ensure the stability of the electrostatic properties of the developer under high humidity by hydrophobizing the inorganic fine particles that are the base material of the external additive, the silicone oil content and the degree of hydrophobicity in the publications listed above are sufficient. did it.

However, a member that comes into contact with a developer by utilizing the low surface energy which is an important peculiarity of silicone oil, for example, a contact charging device, a developer carrier (sleeve)
No active attempts have been made to reduce the adhesiveness to a doctor blade, a carrier, an electrostatic latent image bearing member (photosensitive member), an intermediate transfer member, or the like. In particular, the background oil stains due to the strong adhesion of the developer to the photoconductor, the characters and lines in the image, the edges of the dots and the central part after transfer (the part where the developer is not transferred) are silicone oil. It could not be improved only by adjusting the addition amount and the degree of hydrophobicity. Further, the white voids due to the failure to transfer to the recesses at the time of transfer to the transfer member having the severe unevenness could not be similarly improved. Japanese Unexamined Patent Publication No. 11-212299 discloses inorganic fine particles containing a specific amount of silicone oil as a liquid component. However, the above-mentioned characteristics could not be satisfied by the definition of such an amount.

Further, the toner for developing an electrostatic charge image is required to be uniformly and stably charged, and when these are insufficient, the image quality is deteriorated due to the occurrence of background stains, uneven density and the like. Further, since the developing mechanism has become smaller along with the downsizing of the image forming apparatus, the rise of toner charging has become a more important item in order to obtain high image quality. In order to improve these, various proposals have been made so far. Among these, an example in which the chargeability is improved by the additive of the toner for developing an electrostatic image is disclosed in JP-A-3-294864, which is a non-magnetic one-component developing containing an inorganic powder treated with silicone oil. The agent is JP-A-4-
No. 204665 discloses a one-component magnetic developer having a toner coverage of 3 to 30%.
No. 5357 discloses a BET specific surface area of 5 to 100 m ² /
of the fine particles fixed on the surface of the toner and the fine particles fixed to the toner.
An electrostatic charge developer containing particles having a specific surface area not less than twice is disclosed in Japanese Patent Laid-Open No. 7-43930, using a non-magnetic one-component toner containing a hydrophobic silica fine powder and a specific hydrophobic titanium oxide. JP-A-8-202071 discloses a developing agent containing an additive for toner comprising organic-inorganic composite particles containing an organic polymer skeleton and a polysiloxane skeleton.

However, even with the above method, sufficient charging uniformity cannot be obtained, the toner charge amount does not rise sufficiently, and further, the toner charge amount is not necessarily sufficient in environmental stability, particularly in humidity stability. I couldn't say that. In particular, in many of the proposals, in the case of using an additive whose hydrophobicity is increased by the surface treatment of general oxide particles, although the desired charge stability is initially shown, the additive is added depending on the time such as running. However, there is a problem that the toner is deteriorated due to the change in the composition. Further, for example, in the composite particles synthesized by using the liquid phase method as disclosed in JP-A-8-202071, sufficient hydrophobicity cannot be obtained due to the influence of the liquid medium substance remaining inside the particles, and There was a case where the hydrophobicity was changed by.

On the other hand, as the binder resin, from the viewpoint of the properties required for toner, that is, transparency, insulation, water resistance, fluidity (as powder), mechanical strength, gloss, thermoplasticity, pulverizability, etc. Polystyrene, styrene-acrylic copolymer, polyester resin, epoxy resin and the like are generally used, and among them, styrene resin is widely used because it has excellent pulverizability, water resistance and fluidity. However, when the copy obtained with the styrene resin-containing toner is stored in a document holder made of a vinyl chloride resin sheet to store the copy, the image surface of the copy is left in close contact with the sheet, so that the sheet, That is, the plasticizer contained in the vinyl chloride resin transfers and plasticizes to the fixed toner image and fuses it 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,
In addition, the sheet also has the drawback of becoming dirty. Such a defect is also found in the polyester resin-containing toner.

As a measure for preventing the transfer to the vinyl chloride resin sheet as described above, JP-A-60-263951 and 61-61
No. 24025 proposes blending a styrene resin or a polyester resin with an epoxy resin that is not plasticized with a plasticizer for a vinyl chloride resin. However, when such a blended resin is used for color toners in particular, offset properties due to incompatibility between different resins, curl of a fixed image, and glossiness (in the case of a color toner image, a glossy image is poor ,), And colorability, transparency, and color development become problems. All of these problems cannot be solved by the conventional epoxy resin or the acetylation-modified epoxy resin as proposed in JP-A-61-235852.

Therefore, it is conceivable to solve the above-mentioned problems by using the epoxy resin alone, but as a new problem, there arises a problem of the reactivity of the epoxy resin with the amine. Epoxy resin is generally used as a curable resin having excellent mechanical strength and chemical resistance by reacting an epoxy group with a curing agent to form a crosslinked structure. Hardeners are roughly classified into amine type and organic acid anhydride type.
Of course, the epoxy resin used as a toner for developing an electrostatic image is used as a thermoplastic resin, but there are amine-based dyes and pigments and charge control agents that are kneaded together with the resin as a toner. In some cases, a crosslinking reaction occurs during kneading, and the toner cannot be used. Further, the chemical activity of this epoxy group is considered to be biochemical, that is, toxicity such as skin irritation, and its presence requires careful attention. Further, since the epoxy group exhibits hydrophilicity, water absorption under high temperature and high humidity is remarkable, which causes reduction of electrostatic charge, scumming and poor cleaning. Furthermore, the charging stability of the epoxy resin is also a problem.

Generally, a toner contains a binder resin, a colorant,
It is composed of 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. It is widely practiced to use various resins as binder resins to form a toner with the above composition, but the problem is dispersibility of dyes and pigments, charge control agents and the like. Generally, the kneading of the binder resin with 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 the pigment, and if the dye / pigment as a colorant is poorly dispersed, the color development is poor and the degree of coloring is low. Further, if the charge control agent or the like is not well dispersed, the charge distribution becomes non-uniform, which causes various defects such as poor charging, scumming, scattering, ID shortage, blurring, and poor cleaning. Further, JP-A-61-219051 discloses a toner in which an epoxy resin ester-modified with ε-caprolactone is used as a binder resin. However, although the vinyl chloride resistance and fluidity are improved, the amount of modification is 15-90% by weight
However, the softening point was too low and the gloss was too high.

Further, Japanese Patent Laid-Open No. 52-86334 discloses a compound having a positive charging property by reacting an aliphatic primary or secondary amine with a terminal epoxy group of a ready-made epoxy resin. As described above, it is considered that the epoxy group and the amine cause a cross-linking reaction and cannot be used as a toner. Further, JP-A No. 52-156632 discloses that either 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. However, when the epoxy group remains, problems such as reactivity with amine, toxicity and hydrophilicity occur as described above. In addition, some of the above reaction products are hydrophilic, one that affects charging, and one that affects pulverizability when forming a toner, and are not always effective in the present invention.

Further, in JP-A-1-267560, both terminal epoxy groups of an epoxy resin are reacted with a monovalent active hydrogen-containing compound and then esterified with a monocarboxylic acid or an ester derivative thereof or a lactone. However, although the reactivity, toxicity and hydrophilicity of the epoxy resin have been solved, the curl in fixing is not so much improved. Further, generally, a solvent such as xylene is often used during the synthesis of an epoxy resin or a polyol resin (for example, JP-A No. 11-189646), but these solvents or unreacted residual monomers such as bisphenol A are resins after production. There is a considerable amount of them in the toner, and the residual amount is large even in the toner using these resins, which is a problem.

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

When a dye is used as a colorant,
For example, JP-A-57-130043 and JP-A-57-1
There is one described in Japanese Patent No. 30044. However,
When a dye is used as a colorant, the resulting image is excellent in transparency, and it is possible to form a clear color image with good color development, but on the other hand, it is inferior in light resistance and discolors when left in direct light. , There is a problem of fading. On the other hand, examples of using a pigment as a colorant include those described in JP-A-49-46951 and JP-A-52-17023. However, although the pigment-based color toner has excellent light resistance, on the other hand, the dispersibility of the pigment in the binder resin is poor, so that there is a problem that the coloring degree (coloring property) and the transparency are poor.

As a method for improving the dispersibility of the pigment in the binder resin, (1) JP-A-62-280755, a polyester resin (resin A) is used as the binder resin, and a polyester resin having a higher molecular weight than the resin A is used. A technique in which a pigment is previously coated with (Resin B) and the coated pigment is dispersed in Resin A to obtain a color toner. (2) JP-A-2-66561: A processed pigment selected by melt-kneading a resin and a pigment resin is dispersedly contained in a binder resin, and the weight average molecular weight of the pigment resin is the binder. A color toner characterized in that it is smaller than the weight average molecular weight of the resin, and the weight average molecular weight of the binder resin is 100,000 or more. (3) Japanese Patent Application Laid-Open No. 9-101632; A mixture of a binder resin and a pigment is kneaded with an organic solvent in advance at a temperature lower than the melting temperature of the binder resin in the first stage, and further, the binder resin and the charge control agent. A technique to obtain color toners by adding the above and heating and melting and kneading the second step. (4) JP-A-4-39671; weight average molecular weight 4
A toner comprising: 10,000 or less binder resin; and a colorant comprising a flushing pigment using the binder resin. (5) JP-A-4-230770: A solvent, a first binder resin soluble in the solvent, and particles of a colorant insoluble in the solvent are mixed and the temperature is 50 to 100 ° C. under pressure. After the particles of the colorant are dispersed in the binder resin while applying a shearing force, the solvent is removed to obtain a colored binder resin composition in which the particles of the colorant are dispersed. A technology to obtain a toner by adding a resin and a charge control agent and heating and melting and kneading in the second stage. Etc. have been proposed.

However, neither of the above methods (1) and (2) can obtain sufficient pigment dispersion, and the coloring degree,
At present, the transparency is poor. Further, although the methods (3), (4), and (5) improve the dispersion of the pigment, since any method uses a solvent, no matter how much is removed, the amount is extremely small in the product or the toner. Recently, the inventors of the present invention have found that the solvent remains, which reduces the charge amount of the toner in a special environment such as use in a high temperature environment and causes a problem such as toner scattering in the developing section. It became clear by the examination of.
The toner scattering not only causes deterioration of the maintainability of the apparatus, but also causes a problem that the scattered toner adheres to the non-printing portion.

There are also known examples in which the particle size of the colorant in the toner is regulated (Japanese Patent No. 2992924 and Japanese Patent No. 3047310). The sufficient effect was not obtained from the standpoints of color, color development and light resistance. Further, the effect of improving toner scattering under high temperature and high humidity environment and background stain under low temperature and low humidity was not obtained. Similarly, Japanese Patent Laid-Open No. 2001-2
28653 also defines the particle size distribution, but the small particle size side is not taken into consideration, and there is a problem in light resistance.

On the other hand, as a method for producing a toner, as typified by JP-A-1-304467, after mixing all the raw materials at once and heating, melting and dispersing with a kneader or the like, a uniform composition is obtained. Generally, a method of manufacturing a toner having a volume average particle size of about 6 to 10 μm by cooling this, pulverizing and classifying is adopted. In particular, a color toner for developing an electrostatic charge image used for forming a color image is generally formed by dispersing and containing various chromatic dyes or pigments in a binder resin. In this case, the performance required for the toner used is more severe than that for obtaining a black image. That is, as the 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. Examples of dyes used as colorants include, for example, JP-A-57-130043 and 57-130.
There is one described in Japanese Patent Publication No. 044. However, when a dye is used as the colorant, the resulting image has excellent transparency,
Although it is possible to form a clear color image with good color development, on the other hand, there is a problem that the light resistance is poor, and when left under direct light, discoloration or fading occurs.

In addition, the high temperature and high humidity and low temperature and low humidity environments during storage and transportation after toner production are harsh conditions for the toner, and the toners do not aggregate even after storage in the environment, resulting in charging characteristics, fluidity, and transfer. Properties and fixability are not deteriorated,
Alternatively, there is a demand for a toner having an extremely small storage stability, but no effective means for this has been found.

[0025]

An object of the present invention is to stably provide the following. 1. After storing the toner in a high temperature and high humidity environment for a long time, even after printing tens of thousands of sheets in a high temperature and high humidity environment, the charge stability is excellent, the chargeability is good, the amount of weakly charged and reversely charged toner is small, and toner scattering does not occur. To provide a toner, a developer, an image forming method, and an image forming apparatus. 2. Not only in normal temperature and normal humidity environment but also in low temperature and low humidity environment, even after outputting tens of thousands of images, there are few weakly charged and reversely charged toners with excellent charge stability, toner that does not cause background stain (fog), developer, To provide an image forming method and an image forming apparatus. 3. Even after outputting tens of thousands of images, a toner, a developer, an image forming method, and an image forming apparatus having sufficient coloring property, light resistance, transparency, color forming property, vividness, color reproducibility, saturation and gloss can be provided. To provide. 4. To provide an image forming apparatus and an image forming method having 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 which exhibit a necessary and sufficient charge rising property and a retained charge amount under any environment of high temperature and high humidity and low temperature and low humidity. 6. (EN) Provided are an image forming apparatus and an image forming method which are comparable in printing speed from a low speed area to a high speed area, have no deterioration in image density in continuous image output, and have an excellent balance of fixing property and non-offset property. 7. Even for spherical toner with small particle size and high circularity, it has excellent charging stability, good charging property, little weakly charged and oppositely charged toner, and toner scattering does not occur, toner, developer, image forming method, image forming Providing equipment. 8. An image forming apparatus in which the toner image does not transfer to the sheet even when the fixed image surface is brought into close contact with the vinyl chloride resin sheet,
To provide an image forming method. 9. To provide an image forming apparatus and an image forming method in which a fixed image does not substantially curl.

[0026]

According to the present invention, a toner for developing an electrostatic image as described in (1) to (13) below, a developer containing the toner, a container filled with the toner, and an image forming method, An image forming apparatus is provided. (1) In a toner containing at least a binder resin and a colorant, the nitrogen atom on the toner surface is 0.05 to
A toner for developing an electrostatic charge image, which comprises 1.3 atom% and a colorant content of 2 to 15% by weight based on the toner. (2) The toner for developing an electrostatic image 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 at least a main chain. (3) The toner for developing an electrostatic image according to (1) or (2), wherein the toner has a volume average particle diameter of 1 to 6 μm. (4) Circularity SF-1 value of the toner is 100 to 14
0, and the circularity SF-2 value is 100 to 130, The toner for developing an electrostatic image according to any one of the above (1) to (3), wherein (5) The electrostatic toner image developing color toner according to any one of (1) to (4), wherein the colorant is black, magenta, yellow or cyan. Particularly, a full-color toner for developing an electrostatic charge image, which is a kit in which at least two different color toners among the color toners are combined. (6) A developer containing the toner according to any one of (1) to (5). In particular, a two-component developer containing a carrier composed of the magnetic particles. (7) An image forming method comprising using the developer described in (6) above. (8) The image forming method as described in (7) above, wherein a color image is formed by a tandem system in which the printing speed is equivalent to A4 size and 20 sheets / minute or more. (9) A container filled with the developer according to (6). (10) An image forming apparatus including the container described in (9) above.

As a result of intensive studies conducted by the present inventors in order to achieve the above object, in a toner containing at least a binder resin and a colorant, the nitrogen atom on the surface of the toner has a nitrogen content of 0.
The toner for developing an electrostatic image is characterized in that the content of the toner is from 0.5 to 1.3 atomic% and the colorant is contained from 2% to 15% by weight based on the toner. Even after outputting tens of thousands of images after long-term storage, there are few weakly charged and reversely charged toners with excellent charge stability, no toner scattering, and not only normal temperature and normal humidity environment, but also high temperature and high humidity environment and Even after outputting tens of thousands of images in a low temperature and low humidity environment, even after outputting tens of thousands of images, weak charging, which has excellent charging stability, little reverse charging toner, no background stain (fog), It has been found that a high-quality image having excellent colorability, light resistance, transparency, color development, sharpness, color reproducibility, saturation, and gloss can be formed.

The mechanism is currently being clarified, but the following was inferred from some analysis data. The surface of the toner is very important in terms of generating and retaining electric charge, and its surface condition control is essential for controlling charging property, fixing property, color property and others. On the other hand, it has been found that nitrogen atoms electrically show positive chargeability, and the presence of nitrogen atoms negatively affects toner chargeability. Nitrogen may be contained in the resin, but it is often contained in the colorant, and it is important to control the dispersed state thereof. That is, if more than a certain amount of nitrogen atoms are present on the toner surface, it adversely affects the chargeability of the toner and masks the resin skeleton other than nitrogen and the charge control agent that exert the negative charge of the toner, and as a result, the toner charge site Was found to reduce. Further, in the case of a positively charged toner, the charging property is unnecessarily increased and the image density is lowered, which is not preferable. As described above, the nitrogen atom on the toner surface is 0.05 to 1.3 atom%, and the colorant is contained in the toner in an amount of 2 wt% to 15 wt%, whereby the above problem can be solved, and It has been found that a toner having sufficient charging characteristics can be obtained.

In the present invention, the XPS (X-ray photoelectron spectroscopy) method is particularly preferable as a means for quantifying the nitrogen amount on the toner surface. The XPS method is a method of irradiating a sample with X-rays and analyzing the energy of photoelectrons generated. Extreme surface of sample (several n
This is a method capable of qualitatively and quantitatively determining the element m).

Here, the surface amount of nitrogen atoms is 0.05 atom%.
If it is less than, the toner surface amount of the colorant particles is too small,
The coloring degree is lowered, or the colorant is finely dispersed in order to reduce the surface amount, so that the crystallinity of the colorant is lowered, and particularly the light resistance is lowered, which is not preferable. It has also been found that when the dispersion is too high, the molecular chain of the binder resin is broken, which adversely affects the fixability such as the occurrence of hot offset. Further, in the case of a pulverized toner, the pulverizability of the toner is lowered, the productivity is lowered and the cost is increased, which is not desirable. On the other hand, when the surface amount of nitrogen atoms exceeds 1.3 atom%, aggregates such as the coloring agent on the toner surface and the nitrogen-containing component of the resin are peeled off at the time of toner production to remove the coloring agent (toner) spent on the carrier surface. And the surface of the developing sleeve are easily caused, and the charging sites of the toner are reduced, which adversely affects the charging property and the print quality stability. In addition, colorant on the toner surface,
The nitrogen component is easily exposed, and the surface coverage of the binder resin and the charge control agent that exerts an effect on the charging property of the toner is reduced, which adversely affects the total charging property of the toner. In addition, it produces weakly charged toner and reversely charged toner, especially in environments where the charging level is likely to fluctuate, such as in high-temperature high-humidity, low-temperature low-humidity environments, and the effect becomes particularly noticeable, which causes toner scattering and background stains, which is undesirable. .

Further, since the colorant is contained in the toner in an amount of 2 to 15% by weight, the toner has a sufficient coloring degree and an effect of preventing toner scattering and background stains. That is, when the amount of the colorant is less than 2% by weight, the degree of coloring per weight of toner is lowered, and it is necessary to make the thickness of the toner layer thicker in order to have the same degree of coloring as an image. In this case, since the toner layer becomes thick, the amount of toner developed and the amount of transfer increase, and toner scattering, transfer toner dust, and the like are more likely to occur. In addition, since the layer is thick, the color reproduction accuracy is also reduced. On the other hand, when it exceeds 15% by weight, the coloring property is sufficient,
Problems occur in terms of toner chargeability. That is, the colorant covers the toner surface, and the amounts of the binder resin and the charge control agent on the toner surface decrease, the charging ability of the toner decreases, and the problems such as the toner scattering and the background stain occur.

In the present invention, it is important to control the toner surface amount of the colorant, that is, to control the dispersibility of the colorant in the resin. When the binder resin of the toner contains at least a polyol resin, coloring The dispersibility with the agent was extremely good, and sufficient environmental charging property, tensile breaking strength, environmental stability, and stable fixing property were obtained. Furthermore, since 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, more stable colorant dispersibility and environmental stability, stable fixing characteristics, and copy-fixed image The transfer of the toner image to the sheet when it is in close contact with the vinyl chloride resin on the surface can be prevented, especially when used for color toner, for color reproducibility, stable gloss, curl prevention of copy-fixed images, etc. I found it to be effective.

The volume average particle diameter of the toner is 1 to 6 μm.
When a toner for developing an electrostatic image having a small particle size of m is used,
Although it is advantageous from the viewpoint of high image quality, the conventional colorant dispersibility tends to decrease the chargeability of each toner particle from the point of contact charging probability due to the small particle size and increase weak charging and reverse charging Toga. However, there is a small margin for toner scattering, background stains, etc., which is more problematic. It has been found that by controlling the amount of nitrogen on the surface of the toner as a means for making full use of this small particle diameter toner, it is possible to maintain a sufficient degree of coloring and prevent toner scattering, scumming and the like.

Further, the circularity SF-1 of the toner is 100.
.About.140 and a circularity SF-2 of 100 to 130, a toner with a high circularity and a more spherical shape is used, which is also advantageous in terms of high image quality. The frictional resistance with the sleeve decreases, and it becomes difficult to hold the toner with the carrier (developing sleeve), and there is a small margin for toner scattering and scumming, which is a problem. As a means for mastering this high circularity toner, it has been found that controlling the amount of nitrogen on the toner surface makes it possible to maintain a sufficient degree of coloration and prevent toner scattering, scumming and the like.

By using a two-component developing system characterized by containing at least the above-mentioned toner and a carrier composed of magnetic particles, stable charging characteristics can be maintained even when the highly colored and highly dispersed colorant toner is used. It was possible to obtain the developing characteristics which are well balanced in the adhesive force with the carrier, have a sufficient bulk density with little stress fluctuation as a developer, and have excellent charge rising property and environmental charging stability. Further, a developing system having an excellent toner density controllability by a bulk density sensor or the like was obtained.

The electrostatic image divided into multiple colors on the electrostatic image carrier is developed with a developer for developing an electrostatic image composed of a plurality of colors to form a toner image. In a tandem type color image forming apparatus for obtaining a color image on the transfer material by sequentially transferring the toner images onto a single transfer material by bringing the transfer means into contact with the surface,
In the case of high-speed printing at a printing speed equivalent to A4 size of 20 sheets / min or more, more preferably 25 sheets / min or more, further preferably 30 sheets / min or more, it is necessary to shorten the time required for the toner to pass through the developing unit. Therefore, in order to obtain the same developing ability as the conventional one, it is necessary to stir the developer at a higher speed with a high torque to perform the charge development, and as a result, the weakly charged toner and the reversely charged toner are more likely to be generated. However, there is a problem that toner is scattered from the developing section. For this measure,
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 prevent toner scattering, scumming and the like. As a result of the above, an image that is compatible with high-speed printing, is less affected by the material of the transfer material such as OHP, thick paper, and coated paper, has few transfer defects at the time of transfer, has few image defects, and has high image quality and excellent maintainability A forming device is obtained.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. Here, if the conditions for the electrostatic charge image developing toner used in the present invention, the manufacturing method and material of the developer, and the overall system relating to the electrostatic charge image developing process are satisfied,
All known materials can be used.

(Amount of Nitrogen Atoms on Toner Surface) In the present invention, the amount of nitrogen atoms on the toner surface can be determined by the XPS (X-ray photoelectron spectroscopy) method or the like. The measuring method, device type, conditions, etc. 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 (400W) analysis area; 0.8 × 2.0 mm pretreatment; Sample is packed in an aluminum dish and bonded to a sample holder with a carbon sheet Calculation of measured surface atomic concentration; Relative sensitivity factor provided by PHI was used

(Masterbatch Colorant) In the present invention, a masterbatch colorant prepared by mixing and kneading the resin and the colorant in advance can be used for the purpose of improving the affinity between the resin and the colorant. Any colorant can be used as long as it is a substance that pigments, dyes or the like can color. The ratio (weight) of the resin and the colorant is 20:80 to 80:20, more preferably 30:70 to 70:30, and further preferably 40:60.
˜60: 40. Further, the resin used here is not necessarily the binder resin itself of the toner, and a polyol resin, a polyester resin or the like having a good affinity with the binder resin of the toner can be more preferably used. For these, the same resins as the binder resin described later can be used. Furthermore, the dispersibility can be further improved by using a dry powder pigment as the colorant and water as the method of wetting the resin. In the first place, the pigment is 0.00
Although it is a very small value of 1 to 0.1 μm, large agglomerates of several μm size are formed in the dry powder state of the raw material. The ideal dispersion of the pigment is to disintegrate this agglomerate and separate it into primary particles. Reducing the size is a limitation in such a conventional kneading method by mechanical repeated shearing. That is, the poor dispersion of the pigment is nothing but the crushing of the aggregate. The necessary condition for the aggregates to be crushed is that the surrounding resin penetrates into the voids inside the aggregates and efficiently wets all the primary particle surfaces.
Therefore, the point of pigment dispersion lies in whether or not the surrounding resin can enter the voids inside the aggregate. However, since the binder resin used for ordinary toner has a high melt viscosity, a large amount of energy is required to get it into the inside of the agglomerate, and yet the pigment is not the intended primary particle. Is.

Generally, an organic pigment used as a colorant is hydrophobic, but since its manufacturing process involves steps of washing with water and drying, if a certain amount of force is applied, the water will reach inside the pigment aggregate. It is possible to soak. When a mixture of a pigment and a resin in which water has penetrated into the agglomerate is kneaded with an open-type kneader at a set temperature of 100 ° C. or higher, the water inside the agglomerate instantly reaches the boiling point,
Since the volume expands, a force to break the aggregate is applied from the inside of the aggregate. The force from the inside of the agglomerate can break the agglomerate much more efficiently than the force applied from the outside. Furthermore, at this time, since the resin is heated to a temperature equal to or higher than the softening point, the viscosity becomes low, and the agglomerates are efficiently wetted. By substituting with the effect, a masterbatch colorant in which the pigment is dispersed in a state close to the primary particles can be obtained. Further, in the process of evaporating water, the heat of vaporization accompanying the evaporation of water is taken from the kneaded product, so the temperature of the kneaded product is 100%.
Since it is maintained at a relatively low temperature and high viscosity of ℃ or less, it also has the effect that shearing force is effectively applied to the pigment aggregate.
As an open-type kneading machine for producing a masterbatch colorant, in addition to a normal two-roll, three-roll method, a method of using a Banbury mixer as an open type, a continuous type 2 manufactured by Mitsui Mining Co., Ltd.
This roll kneader or the like can be used. Further, as a means for better dispersing the colorant in the resin, it is also effective to roughly crush the masterbatch colorant once kneaded with a pulverizer or the like, and then knead it again twice or three times.

(Colorant) As the colorant of the toner of the present invention, all known dyes and pigments can be used. Among them, 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. Rake, Indanthrene Blue BC, Vulcan Fast Yellow (5G, R), Tartrazine Rake, Quinoline Yellow Rake, Anthragen Yellow B
GL, isoindolinone yellow, red iron oxide, red lead, red lead, cadmium red, cadmium mercury red, antimon red, permanent red 4R, para red, fire red, parachlor ortho nitroaniline red, resole fast scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin B
S, Permanent Red (F2R, F4R, FRL, F
RLL, F4RH), Fast Scallet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Naphthol Carmine, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux B.
L, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigolet B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Chrome Vermillion, Benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), Indigo, ultramarine, navy blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxazine violet, a Traquinone violet, chrome green, zinc green, chromium oxide, pyridian emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc flower, lithopone. And mixtures thereof.

Highly preferred are polycondensed azo pigments, insoluble azo pigments, quinacridone pigments, carmine pigments, naphthol carmine pigments, isoindolinone pigments, perylene pigments, anthraquinone pigments and copper phthalocyanine pigments. Lightfast and 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, 3
0, 31, 32, 37, 38, 39, 40, 41, 4
8, 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, 1
12, 114, 122, 123, 163, 177, 17
9, 202, 206, 207, 209, 211; C.I.
I. Pigment Violet 19; C.I. I. Butred 1, 2, 10, 13, 15, 23, 29, 35 and the like. Cyan color pigments include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 1
5: 3, 15: 4, 15: 6, 16, 17, 60; C.I.
I. Bat Blue 6; C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted in the phthalocyanine skeleton, green 7 and green 3
6 and the like. As a coloring pigment for yellow,
C. I. Pigment Yellow 0-16, 1, 2, 3,
4, 5, 6, 7, 10, 11, 12, 13, 14, 1
5, 16, 17, 23, 55, 65, 73, 74, 8
3, 97, 110, 151, 154, 180; C.I. I.
Butt yellow 1, 3, 20, orange 36, etc. are mentioned.

The content of the colorant is 2 to 15 with respect to the toner.
%, More preferably 3 to 10% by weight. Further, various dispersion improvers may be contained for the purpose of improving the dispersibility of the colorant in the resin.

(External Additive) As the external additive, all known additives can be used. For example, silica fine particles, hydrophobic silica,
Fatty acid metal salts (zinc stearate, aluminum stearate, etc.), metal oxides (titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers, etc. may be contained. Particularly preferable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. As silica fine particles, HDK H 200
0, HDK H 2000/4, HDK H 2050
EP, HVK21, HDK H1303 (above Hoechst), R972, R974, RX200, RY200,
R202, R805, R812 (above Nippon Aerosil)
There is. Further, as titania fine particles, P-25 (Japan Aerosil), STT-30, STT-65C-S
(Above Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT-600
B, MT-150A (above Takeya), etc. Particularly, as the titanium oxide fine particles subjected to the hydrophobic treatment, T-805
(Japan Aerosil), STT-30A, STT-65S
-S (above titanium industry), TAF-500T, TAF-
1500T (Fuji Titanium Industry Co., Ltd.), MT-100S,
MT-100T (Take above), IT-S (Ishihara Sangyo)
and so on.

To obtain hydrophobized oxide fine particles, silica fine particles, titania fine particles, and alumina fine particles, hydrophilic fine particles are subjected to silane coupling such as methyltrimethoxysilane, methyltriethoxysilane, and octyltrimethoxysilane. It can be obtained by treating with an agent. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with inorganic oil by heating, if necessary, are also suitable.

Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methylhydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, 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, acryl, 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, silica sand, clay and mica. , Wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengulas, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like. Among them, silica and titanium dioxide are particularly preferable.

The amount of the external additive added is 0.1 to 5 with respect to the toner.
%, Preferably 0.3-3% by weight can be used. The average particle diameter of the primary particles of the inorganic fine particles is 100 nm
It is preferably 3 nm or more and 70 nm or less. When it is smaller than this range, the inorganic fine particles are buried in the toner, and the function thereof is difficult to be effectively exhibited. On the other hand, if it exceeds this range, the surface of the photoconductor is unevenly scratched, which is not preferable. As the external additive, inorganic fine particles or hydrophobically treated inorganic fine particles can be used in combination, but the average particle size of the hydrophobically treated primary particles is 1 to 100 nm, more preferably 5 nm to 70 n.
It is more desirable to contain at least two kinds of inorganic fine particles of m. Furthermore, it is more preferable that the hydrophobically treated primary particles contain at least two kinds of inorganic fine particles having an average particle diameter of 20 nm or less and at least one kind of inorganic fine particles having an average particle diameter of 30 nm or more. Further, the specific surface area by the BET method is preferably 20 to 500 m ² / g.

(Surface treatment agent) As a surface treatment agent for an external additive containing fine oxide particles, for example, a silane coupling agent such as dialkyldihalogenated silane, trialkylhalogenated silane, alkyltrihalogenated silane, and hexaalkyldisilazane. Examples include silylating agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and silicone varnishes. More preferred are organosilicon compound surface-treating agents and hydrophobizing agents.

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

(Circularity) The shape factors SF-1 and SF-2, which are the circularity used in the present invention, are FE- manufactured by Hitachi Ltd.
300 SEM images of the toner obtained by measurement with SEM (S-4200) were randomly sampled, and the image information was introduced into an image analysis device (Luzex AP) manufactured by Nireco Co. through an interface for analysis. The values calculated by the following equation were defined as SF-1 and SF-2.
The values of SF-1 and SF-2 are preferably values obtained by Luzex, but are not particularly limited to the FE-SEM device and the image analysis device as long as similar analysis results can be obtained. ^{SF-1 = (L 2 /} A) × (π / 4) × 100 SF-2 = (P 2 / A) × (1 / 4π) × 100 ( wherein, L is an absolute maximum length of toner, A is The projected area of the toner, P represents the maximum perimeter of the toner.) If it is a true sphere, both SF-1 and SF-2 are 100, and as the value becomes larger than 100, the sphere becomes indefinite. Further, in particular, SF-1 represents the shape of the entire toner (ellipse, sphere, etc.), and SF-2 is a shape factor indicating the degree of surface irregularity.

(Softening Point, Outflow Start Temperature) The softening point of the toner of the present invention is measured by a softening point measuring apparatus (FP9 manufactured by METTLER CORPORATION).
0) is used at a temperature rising rate of 1 ° C./min for the softening temperature,
The outflow starting temperature was measured.

(Glass Transition Temperature (Tg)) The Tg of the toner of the present invention was measured using the following differential scanning calorimeter under the following conditions. -Differential scanning calorimeter: Shimadzu DSC-60A Thermal analysis workstation: Shimadzu TA-60
WS-Measurement conditions: Temperature range: 25 to 150 ° C Temperature rising rate: 10 ° C / min Sample amount: 5 mg

(Molecular Weight) The number average molecular weight (Mn), the weight average molecular weight (Mw) and the peak molecular weight Mp were measured by GPC (gel permeation chromatography) as follows. 80 mg sample to 10 m THF
A sample solution is prepared by dissolving in 1 l, 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. Further, 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 calculated in terms of polystyrene from a calibration curve prepared in advance.・ Column: Guard column + GLR400M + G
LR400M + GLR400 (all Hitachi Ltd.)
Column temperature: 40 ° C. mobile phase (flow rate): THF (1 ml / min) peak detection method: UV (254 nm)

(Penetration, heat-resistant storability) 10 g of each toner was weighed, put in a 20 cc glass container, left in a constant temperature bath set at 50 ° C. for 5 hours, and then the penetration was measured with a penetrometer. did.

(Binder Resin) As the binder resin of the toner of the present invention, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, or a substitute thereof; styrene-p-chlorostyrene copolymer, styrene- Propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-
Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer,
Styrene-methylmethacrylate copolymer, styrene-ethylmethacrylate copolymer, styrene-butylmethacrylate copolymer, styrene-α-chloromethylmethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl Styrene-based copolymers such as ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers Combined; polymethylmethacrylate, polybutylmethacrylate, 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 hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin Examples thereof include wax, which can be used alone or in combination. In particular, polyol resin,
Polyester resins are more preferred. Further, when the polyol resin end of the binder resin is inactive, the toner can be environmentally stable and less harmful.

1. Examples of Polyol Resin Various types of polyol resins can be used, and the polyol resin (epoxy resin) used in the present invention is preferably obtained by binding bisphenol such as bisphenol A or bisphenol F and epichlorohydrin. It is a thing. In order to obtain stable fixing properties and gloss, the epoxy resin is at least two kinds of bisphenol A type epoxy resins having different number average molecular weights, and the low molecular weight component has a number average molecular weight of 360 to 2000 and a high molecular weight component. The number average molecular weight is preferably 3,000 to 10,000. Further, it is preferable that the low molecular weight component is 20 to 50% by weight and the high molecular weight component is 5 to 40% by weight. When the amount of the low molecular weight component is too large or the molecular weight is lower than 360, the gloss may be excessive and the storage stability may be deteriorated. Also, there are too many high molecular weight components or a molecular weight of 100
If the polymer is higher than 00, the gloss may be insufficient or the fixability may be deteriorated.

Further, the followings are preferable as those used in the present invention. As the polyol resin, the epoxy resin, an alkylene oxide adduct of a dihydric phenol or its glycidyl ether, and a compound having one active hydrogen in the molecule which reacts with an epoxy group,
It is preferable to use a polyol obtained by reacting a compound having two or more active hydrogens in the molecule, which reacts with an epoxy group. Furthermore, it is particularly preferable that the epoxy resin is at least two kinds of 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 in the case of roller fixing.

Examples of the alkylene oxide adduct of dihydric phenol 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 obtained adduct may be glycidylated with epichlorohydrin or β-methylepichlorohydrin before use. Particularly preferred is diglycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following general formula (1).

[0060]

[Chemical 1]

The alkylene oxide adduct of dihydric phenol or its glycidyl ether is preferably contained in an amount of 10 to 40% by weight based on the polyol resin. If the amount is too small, problems such as curling may occur, and if n + m is 7 or more, or if the amount is too large, the gloss may be excessive, or the storage stability may be deteriorated.

The compounds having one active hydrogen in the molecule which reacts with the epoxy group used in the present invention include monohydric phenols, secondary amines and carboxylic acids. 1
Examples of the hydric phenols include the following. Phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol,
Examples include xylenol and p-cumylphenol.
Examples of secondary amines include diethylamine, dipropylamine, dibutylamine, N-methyl (ethyl) piperazine, piperidine and the like. Examples of carboxylic acids include propionic acid and caproic acid.

The compound having two or more active hydrogens in the molecule which reacts with the epoxy group used in the present invention is
Examples thereof include dihydric phenols, polyhydric phenols and polyhydric carboxylic acids. Examples of the dihydric phenol include bisphenols such as bisphenol A and bisphenol F. Further, as polyhydric phenols, orthocresol novolacs, phenol novolacs, tris (4-
Hydroxyphenyl) methane, 1- [α-methyl-α-
An example is (4-hydroxyphenyl) ethyl] benzene. As the polycarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid,
Examples thereof include phthalic acid, terephthalic acid, trimellitic acid and trimellitic anhydride. Further, 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 weight epichlorohydrin or the like that is a reaction residue can be reduced, which is safe. The toner can have excellent resin characteristics.

In order to obtain the polyol resin having an epoxy resin part and an alkylene oxide part in the main chain of the present invention, various raw materials can be combined. For example, epoxy resin with glycidyl groups at both ends and 2 with glycidyl groups at both ends
It can be obtained by reacting an alkylene oxide adduct of a polyhydric phenol with dihydride, isocyanate, diamine, dithiol, polyhydric phenol or dicarboxylic acid. Of these, it is most preferable to react a dihydric phenol from the viewpoint of reaction stability. Further, it is also preferable to use polyhydric phenols and polyhydric carboxylic acids in combination with dihydric phenols within the range where gelation does not occur. Here, the amount of polyhydric phenols and polycarboxylic acids is preferably 15% by weight or less, and more preferably 10% by weight or less, based on the total amount. Examples of polyhydric phenols include tris (4-hydroxyphenyl) methane and 1- [α-methyl-α (4-hydroxyphenyl) ethyl] benzene. Examples of polycarboxylic acids are malonic acid, succinic acid, glutaric acid,
Examples are 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 strength, tensile rupture strength, environmental stability, stable fixing characteristics, copy fixing image It is possible to prevent transfer of the toner image to the sheet when the sheet is in close contact with the vinyl chloride resin,
In particular, when it is used for color toner, it is more preferable because it has an effect on color reproducibility, stable gloss, and prevention of curl of a copy-fixed image. Further, it is more preferable that the toner contains at least a polyol resin portion and a polyester resin portion, and the toner has a balance between compression resistance and stretchability and adhesiveness, and further stable transferability, developability and fixing characteristics are obtained.

2. Examples of polyester resin Polyester resin can also be preferably used as the binder resin, and various types of polyester resins can be used, but in particular, it is selected from any one of the divalent carboxylic acid and its lower alkyl ester and acid anhydride. At least one of the diol components represented by the following general formula (2),

[Chemical 2] (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 to 16. ) 'A polyester resin obtained by reacting a polyvalent carboxylic acid having a valence of 3 or more, a lower alkyl ester thereof and an acid anhydride, and at least one selected from a polyhydric alcohol having a valence of 3 or more with the above. It is preferable.

Here, as an example of the divalent carboxylic acid of ', its lower alkyl ester and its acid anhydride,
There are terephthalic acid, isophthalic acid, sebacic acid, isodecylsuccinic acid, maleic acid, fumaric acid and their monomethyl, monoethyl, dimethyl and diethyl esters, and phthalic anhydride, maleic anhydride, etc., especially terephthalic acid, isophthalic acid and These dimethyl esters are preferable in terms of blocking resistance and cost. These two
The carboxylic acid, its lower alkyl ester and its acid anhydride greatly affect the fixing property and blocking resistance of the toner. That is, although depending on the degree of condensation, a large amount of aromatic terephthalic acid, isophthalic acid, or the like improves the blocking resistance but decreases the fixability. On the contrary, if sebacic acid, isodecylsuccinic acid, maleic acid, fumaric acid and the like are used in a large amount, the fixing property is improved, but the blocking resistance is lowered. Therefore, these divalent carboxylic acids are appropriately selected according to other monomer composition, ratio, and degree of condensation, and used alone or in combination.

As an example of the diol component represented by the above general formula (2) of ', 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 can be mentioned. Is, in particular, polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane with 2.1 ≦ n ≦ 2.5 and polyoxyethylene with 2.0 ≦ n ≦ 2.5. -(N) -2,2-bis (4-hydroxyphenyl) propane is preferred. Such a diol component has the advantages of improving the glass transition temperature and facilitating the control of the reaction. As the diol component, 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 and propylene glycol. is there.

Examples of the trivalent or higher valent polycarboxylic acid, its lower alkyl ester and acid anhydride include 1,2,4-benzenetricarboxylic acid (trimellitic acid) and 1,3,5-benzenetricarboxylic acid. Acid, 1,
2,4-cyclohexanetricarboxylic acid, 2,5,7-
Naphthrene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,2,4-butane tricarboxylic acid,
1,2,5-hexatricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,
Examples include 7,8-octane tetracarboxylic acid, empol trimer acid and their monomethyl, monoethyl, dimethyl and diethyl esters.

Examples of the polyhydric alcohol having 3 or more valences 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, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like can be mentioned.

Here, the compounding ratio of the trivalent or higher polyvalent monomer is appropriately about 1 to 30 mol% of the entire monomer composition. When it is 1 mol% or less, the offset resistance of the toner is lowered and the durability is apt to be deteriorated. On the other hand, when it is 30 mol% or more, the fixability of the toner tends to deteriorate. Among these trivalent or higher polyvalent monomers, benzene tricarboxylic acids, and benzene tricarboxylic acids such as anhydrides or esters of these acids are particularly preferable. That is, by using benzenetricarboxylic acids, both fixing property and offset resistance can be achieved.

If these polyester resins and polyol resins have a high crosslink density, it becomes difficult to obtain transparency and glossiness. Therefore, it is preferable to use noncrosslinking or weak crosslinking (THF insoluble content is 5% or less. ) Is preferable. Further, the production method of these binder resins is not particularly limited, bulk polymerization, solution polymerization, emulsion polymerization,
Any of suspension polymerization and the like can be used.

(Charge Control Agent) The toner of the present invention may contain a charge control agent, if necessary. All known charge control agents can be used, and examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdic acid chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine modified). Four
Primary ammonium salt), alkylamide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, salicylic acid derivative metal salt, and the like. Specifically, the Nigrosine dye Bontron 03 and the quaternary ammonium salt Bontron P-
51, Bontron S-34 as a metal-containing azo dye, E-82 as an oxynaphthoic acid-based metal complex, E-84 as a salicylic acid-based metal complex, and E-89 as a phenol-based condensate (all manufactured by Orient Chemical Industry Co., Ltd.), Quaternary ammonium salt molybdenum complex TP-302, TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt. Copy charge of salt NEGVP2036, copy charge NX V
P434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (manufactured by Nippon Carlit),
Examples thereof include copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymeric compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

The amount of the charge control agent used in the present invention is determined 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 0.1 to 100 parts by weight of the binder resin.
Used in the range of 10 parts by weight. Preferably, the range is 1 to 5 parts by weight. If it exceeds 10 parts by weight, the chargeability of the toner is too large, and the effect of the main charge control agent is diminished.
The static electric attraction with the developing roller is increased, resulting in a decrease in the fluidity of the developer and a decrease in the image density. If the amount is less than 0.1 parts by weight, the function of the charge control agent cannot be fully exhibited.

(Carrier) When the toner of the present invention is used in a two-component developer, it may be used by mixing it with a magnetic carrier. The content ratio of the carrier to the toner in the developer is 100 parts by weight of the carrier. On the other hand, 1 to 10 parts by weight of toner is preferable. As the carrier, all known carriers 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. Further, polyvinyl and polyvinylidene resins such as acrylic resins, polymethylmethacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and polystyrene resins such as styrene-acrylic copolymer resins, polychlorinated resins. Halogenated olefin resin such as vinyl, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, 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. The film thickness of these coating materials is 0.01 to 3 μm, more preferably 0.1 to
It is 0.3 μm. When it is 0.01 μm or less, it is difficult to control the film 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.

If necessary, conductive powder or the like may be contained in the coating resin. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. It is preferable that these conductive powders have an average particle diameter of 1 μm or less. When the average particle size is larger than 1 μm,
It becomes difficult to control the electric resistance.

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

(Magnetic Material) Further, the toner of the present invention may contain a magnetic material and be used as a magnetic toner. When the magnetic toner is used, the toner particles may contain fine particles of a magnetic material. As such a magnetic material, ferrite, magnetite and other iron, nickel, cobalt or other metals or alloys exhibiting ferromagnetism or compounds containing these elements, but not containing ferromagnetic elements, but by appropriate heat treatment Examples include alloys that exhibit ferromagnetism, for example, manganese-copper aluminum, manganese-copper-tin, and other alloys called Heusler alloys containing manganese and copper, chromium dioxide, and the like.
It is preferable that the magnetic substance is uniformly dispersed and contained in the form of fine powder having an average particle diameter of 0.1 to 1 μm. The content ratio of the magnetic material is preferably 10 to 70 parts by weight, and particularly 2 to 100 parts by weight of the obtained toner.
It is preferably from 0 to 50 parts by weight.

(Wax) In the present invention, it is preferable to add a wax to the toner or the developer in order to impart a releasing property to the toner or the developer.
In particular, when using an oilless fixing device in which oil is not applied to the image fixing portion, it is preferable that the toner contains wax. The wax has a melting point of 40 to 120 ° C., particularly preferably 50 to 110 ° C. When the melting point of the wax is too high, the fixability at low temperatures may be insufficient, while when the melting point is too low, the offset resistance and durability may deteriorate. The melting point of the wax can be determined by the differential scanning calorimetry (DSC). That is, the melting peak value when a few mg of sample is aged at a constant temperature rising rate, for example (10 ° C./min), is taken as the melting point. The wax content is 0
20 parts by weight is preferable, and 0 to 10 parts by weight is particularly preferable.

Examples of the wax that can be used in the present invention include solid paraffin wax, microwax, rice wax, fatty acid amide wax, fatty acid wax, mortal monoketones, fatty acid metal salt wax, fatty acid ester wax. , Partially saponified fatty acid ester wax, silicone varnish, higher alcohol, carnauba wax and the like. Further, polyolefins such as low molecular weight polyethylene and polypropylene can also 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, at least one wax selected from 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 is contained. Proved to be effective. The free fatty acid-type carnauba wax is obtained by removing free fatty acids from carnauba wax as a raw material. Therefore, the acid value is 5% or less, and the carnauba wax becomes finer crystals than the conventional carnauba wax. The average dispersed particle diameter is 1 μm or less, and the dispersibility is improved. The montan ester wax is refined from minerals, becomes fine crystals like the carnauba wax, and has a dispersion average particle diameter of 1 μm or less in the binder resin, thus improving the dispersibility. In the case of montan ester wax, the acid value is preferably 5 to 14. The dispersed diameter of the wax is preferably 3 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less. When the dispersed diameter is 3 μm or more, the wax outflow property and the transfer material peeling property are improved,
The high temperature and high humidity durability and charge stability of the toner decrease.

Oxidized waxy wax is obtained by air-oxidizing rice bran wax. The acid value is preferably 10 to 30, and when it is less than 10, the lower limit fixing temperature is increased and the low temperature fixing property is insufficient, and when it is more than 30, the cold offset temperature is increased and the low temperature fixing property is also insufficient. Sazol wax is Sazol wax H1, H2, A1, A2, A3, A4, A6, A
7, A14, C1, C2, SPRAY30, SPRAY
40 etc. can be used, but among them, H1, H2, SPRAY
30 and SPRAY40 are preferable because they are excellent in low-temperature fixing and storage stability. The above waxes may be used alone or in combination, and the amount of the wax may be 1 per 100 parts by weight of the binder resin.
˜15 parts by weight, preferably 2 to 10 parts by weight.

(Cleaning property improver) A cleaning property improver for removing the developer remaining after transfer on the photoconductor or the primary transfer medium is contained in the toner or added to the toner surface or contained in the developer or More preferably, it is added to the surface. Examples of the cleaning property improver include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, for example, polymer fine particles produced by soap-free emulsion polymerization of polymethylmethacrylate fine particles, polystyrene fine particles, and the like. . The fine polymer particles have a relatively narrow particle size distribution and a volume average particle diameter of 0.01 to 1 μm.
Are preferred. The content of the cleaning property improver is preferably 0.001 to 5 parts by weight, and particularly 0.001-1
More preferably, it is parts by weight.

(Manufacturing Method) As the method for manufacturing the toner of the present invention, all known manufacturing methods can be used under certain conditions.
For example, a method for producing a toner having a step of mechanically mixing a developer component containing at least a binder resin, a main charge control agent and a pigment (colorant), a step of melt-kneading, a step of pulverizing, and a step of classifying Can be applied. Further, in the mechanical mixing step and the melt-kneading step, a manufacturing method of returning powders other than particles to be the product obtained in the pulverizing or classifying step and reusing them is also included. After the step of melting and kneading with the powder other than the particles to be the product here (by-product), the fine particles and coarse particles other than the components to be the product of the desired particle size obtained in the crushing step and the classification step to be performed subsequently. It refers to fine particles or coarse particles other than the components that generate the product having a desired particle size. In the mixing step or the melt-kneading step of such by-products, it is preferable to mix the raw materials, preferably the other raw material 99 with respect to the by-product 1, and the other raw material 50 with respect to the by-product 50 in a weight ratio.

The mixing step of mechanically mixing the developer components including at least the binder resin, the main charge control agent and the pigment, and the by-products may be carried out under ordinary conditions using an ordinary mixer having rotating blades. Well, there is no particular limitation. More preferably a resin and a colorant in advance.

Upon completion of the above mixing steps, the mixture is then placed in a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch type 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 KCK, PCM twin screw extruder manufactured by Ikegai Iron Works, Buss manufactured by Bus Co. A co-kneader or the like is preferably used. It is important to carry out this melt-kneading 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, and if the temperature is lower than the softening point, the cutting is severe, and if it is too high, the dispersion does not proceed. Further, when controlling the amount of volatile components in the toner, it is more preferable to set the melt-kneading temperature, time, and atmosphere while optimally monitoring the amount of residual volatile components at that time.

When the above melt-kneading step is completed, the kneaded material is then pulverized. In this pulverizing step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a collision-type crushing method of crushing by colliding with a collision plate in a jet stream or a rotor crushing method of crushing in a narrow gap between a mechanically rotating rotor and a stator is preferably used. Examples of the collision type crusher 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 Mfg. Co., Ltd.) can be preferably used as jet type crushers equipped with compressed air and collision plates as main constituent elements. Also, as the rotor crusher, a roll mill,
A pin mill, a fluidized bed jet mill and the like can be exemplified, but it is particularly preferable to have a fixed container as an outer wall and a rotating piece having the same central axis as the fixed container as main constituent elements. A turbo mill (manufactured by Turbo Kogyo Co., Ltd.), a kryptron (manufactured by Kawasaki Heavy Industries Co., Ltd.), a fine mill (manufactured by Nippon Pneumatic Kogyo Co., Ltd.) or the like can be used as the rotor type crusher of this type. When it is desired to make the toner more spherical, it is preferable to use a rotor pulverizer.

After the completion of this pulverizing step, the pulverized product is classified in an air stream by centrifugal force or the like to produce a toner (base particles) having a predetermined particle diameter, for example, a volume average particle diameter of 1 to 20 μm. When the volume average particle diameter of the toner is 1 to 6 μm, transfer dust during toner transfer and fixing can be prevented, and sufficient colorability as the toner can be exhibited. It was also effective in preventing toner scattering and background stains. Further, it is more preferable in terms of image quality, manufacturing cost, coverage with external additives, and the like. The volume average particle size is, for example, COULTERTA-II.
(COULTER ELECTRONICS, INC)
Etc. can be used for measurement.

Further, when the toner is prepared, in order to improve the fluidity, storability, developability and transferability of the toner, the toner produced as described above is further oxidized according to the present invention. Fine particles, inorganic fine particles such as hydrophobic silica fine powder may be added and mixed. A general powder mixer is used for mixing these external additives, but it is preferable to equip a jacket or the like to control the internal temperature. To change the history of the load applied to the external additive, the external additive may be added midway or gradually. Of course, the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. A strong load may be applied first, and then a relatively weak load may be applied, or vice versa. Examples of mixing equipment that can be used include V-type mixers,
A rocking mixer, a Loedige mixer, a Nauta mixer, a Henschel mixer, etc. are mentioned.

As other manufacturing method, it is also possible to use a polymerization method, a capsule method or the like. The outline of these manufacturing methods will be described below. (Polymerization method) Polymerizable monomer, low molecular weight polymer If necessary, a polymerization initiator, a colorant and the like are granulated in an aqueous dispersion medium. The granulated monomer composition particles are classified into an appropriate particle size. The monomer composition particles having a specified inner diameter obtained by the above classification are polymerized. After appropriate treatment to remove the dispersant, the polymerization product obtained above is filtered, washed with water, and dried to obtain base particles.

(Capsule method) The resin and, if necessary, the colorant and the like are kneaded by a kneader or the like,
A toner core material in a molten state is obtained. The toner core material is put in water and stirred vigorously to form a particulate core material. The above-mentioned core material fine particles are put into a shell material solution, a poor solvent is dropped while stirring, and the core material surface is covered with a shell material to be encapsulated. The capsules obtained as described above are filtered and dried to obtain base particles.

(Intermediate Transfer Member) In the present invention, an intermediate transfer member may be used in the transfer system. Intermediate transfer body 1
An embodiment will be described. FIG. 1 is a schematic configuration diagram of a copying machine according to this embodiment. Around the photoconductor drum (hereinafter referred to as a photoconductor) 10 serving as an image carrier, a charging roller 20 serving as a charging device, an exposure device 30, a cleaning device 60 having a cleaning blade, a discharging lamp 70 serving as a discharging device, and a developing device. An apparatus 40 and an intermediate transfer body 50 as an intermediate transfer body are arranged. The intermediate transfer member 50
Is configured to be suspended by a plurality of suspension rollers 51 and to run endlessly in the arrow direction by a driving unit such as a motor (not shown). A part of the suspension roller 51 also serves as a transfer bias roller that supplies 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 unit for facing the intermediate transfer member 50 and transferring a developed image to a transfer paper 100 as a final transfer material. The transfer roller 80 is a transfer bias by a power supply device (not shown). Is supplied. A corona charger 52 as a charge applying unit is provided around the intermediate transfer member 50.

The developing device 40 includes a developing belt 41 as a developer carrying member, a black (hereinafter Bk) developing unit 45Bk and a yellow (hereinafter Y) developing unit 45Y provided around the developing belt 41. , A magenta (hereinafter, magenta) developing unit 45M and a cyan (hereinafter, C) developing unit 45C. Further, the developing belt 41 is stretched over a plurality of belt rollers and is configured to run endlessly in the direction of the arrow by a driving means such as a motor (not shown). It moves at about the same speed as 10.

Since the construction of each developing unit is common,
The following description will be given only for the Bk developing unit 45Bk, and for the other developing units 45Y, 45M, 45C, a portion corresponding to that in the Bk developing unit 45Bk in the drawing will be denoted by Y after the number assigned to that unit. , M, and C, but the description is omitted. The developing unit 45Bk is provided with a developing tank 42Bk containing a high-viscosity and high-concentration liquid developer containing toner particles and a carrier liquid component, and a lower portion thereof soaked in the liquid developer in the developing tank 42Bk. Pumping roller 43Bk
And a coating roller 4 for applying a thin layer of the developer drawn from the drawing roller 43Bk to the developing belt 41.
4Bk. The coating roller 44Bk
Has conductivity, and a predetermined bias is applied from a power source (not shown).

As the device configuration of the copying machine according to the embodiment of the present invention, in addition to the device configuration shown in FIG.
As shown in FIG. 2, the developing unit 45 for each color is attached to the photoreceptor 1.
It may be a device configuration provided around 0.

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 rotationally driven in the direction of the arrow, and then the exposure device 30 image-projects the reflected light from the original by an optical system (not shown). An electrostatic latent image is formed on. This electrostatic latent image is developed by the developing device 40 to form a toner image as a visible image. Development belt 4
The thin layer of developer on 1 is peeled off from the belt 41 in the state of a thin layer by contact with the photoconductor in the developing area.
0 moves to the part where the latent image is formed. The toner image developed by the developing device 40 is transferred to the surface of the intermediate transfer body 50 at the contact portion (primary transfer area) between the photoreceptor 10 and the intermediate transfer body 50 moving at a constant speed (primary transfer area). Transcription). When three or four colors are superposed and transferred, 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 superposed toner image on the intermediate transfer member is contacted with the photoreceptor 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. The intermediate transfer member 50 and the transfer paper 100 are placed on the downstream side of the facing part and on the upstream side of the facing part. The corona charger 52 applies a true charge having the same polarity as the charging polarity of the toner particles forming the toner image to the toner image, and is sufficient for good transfer to the transfer paper 100. Provides an electric charge to the toner image. The toner image is charged by the corona charger 52, and then is transferred by the transfer bias from the transfer roller 80 to the transfer paper 100 conveyed in the direction of the arrow from a paper supply unit (not shown).
It is collectively transferred onto the top (secondary transfer). After that, the transfer paper 100 on which the toner image is transferred is separated from the photoconductor 10 by a separation device (not shown), is subjected to a fixing process by a fixing device (not shown), and is then ejected from the device. On the other hand, the untransferred toner is collected and removed by the cleaning device 60 from the photoconductor 10 after the transfer, and the residual charge is removed by the charge removal lamp 70 in preparation for the next charging.

The coefficient of static friction 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 several Ωcm or more and 10 ³ Ωc.
It is preferably m or less. When the volume resistance is set to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer body itself is prevented from being charged, and the charge imparted by the charge imparting means is less likely to remain on the intermediate transfer body. Can prevent uneven transfer. Further, it is possible to easily apply the transfer bias during the secondary transfer.

The material of the intermediate transfer member is not particularly limited, and any known material can be used. An example is shown below. (1) A material having a high Young's modulus (tensile elastic modulus) is used as a single-layer belt, and 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 dispersion thermosetting polyimide and the like. These single-layer belts having a high Young's modulus have an advantage that the amount of deformation with respect to the stress at the time of image formation is small and, in particular, misregistration does not easily occur at the time of color image formation. (2) A belt having a two- to three-layer structure in which the above-mentioned 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 circumference thereof. It has the ability to prevent the omission of the line image caused by this. (3) It is a belt having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line defects in line images hardly occur due to their softness. Further, the belt width is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ears protruding from the roll is used to prevent the meandering, so that ribs and meandering preventive devices are not required, and low cost can be realized. .

The intermediate transfer belt has been conventionally made of a fluorine resin,
Polycarbonate resin, polyimide resin, and the like have been used, but in recent years, elastic belts in which all layers of the belt or a part of the belt are elastic members have 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.
One to four toner layers are formed on one color image. The toner layer receives pressure by passing through the primary transfer (transfer from the photoconductor 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 becomes high. If the cohesive force between the toners becomes high, the phenomenon of hollow characters or missing edges of solid images is likely to occur. Since the resin belt has a high hardness and is not deformed according to the toner layer, the toner layer is likely to be compressed and the hollow character of the character is likely to occur. In addition, recently, there is an increasing demand for forming full-color images on various types of paper, for example, Japanese paper or intentionally providing unevenness to form an image on the paper. However, paper with poor smoothness is likely to cause voids with the toner during transfer, which easily causes transfer omission. If the transfer pressure of the secondary transfer portion is increased in order to improve the adhesiveness, the condensing force of the toner layer is increased, which causes the hollow character as described above.

The elastic belt is used for the following purposes. The elastic belt deforms at the transfer portion in response to the toner layer and the paper having poor smoothness. In other words, the elastic belt is deformed following local unevenness, so that good adhesiveness can be obtained without excessively increasing the transfer pressure to the toner layer, and there is no void in characters, and the paper has poor flatness. It is possible to obtain a transferred image with excellent uniformity.

The resin of the elastic belt is polycarbonate,
Fluorine resin (ETFE, PVDF), polystyrene,
Chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer ( Styrene-methyl acrylate copolymer, styrene-
Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer (styrene-methyl methacrylate) Copolymers, styrene-ethyl methacrylate copolymers, styrene-phenyl methacrylate copolymers, etc.), styrene-α-chloromethyl acrylate copolymers, styrene-acrylonitrile-acrylic acid ester copolymers, etc. Resin (styrene or styrene-substituted homopolymer or copolymer), methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (silicone modified acrylic resin, vinyl chloride resin) Modified acrylic resin, acrylic resin Tan resin), vinyl chloride resin, styrene - vinyl acetate copolymer, vinyl chloride - vinyl acetate copolymer, rosin-modified maleic acid resins, phenol resins, epoxy resins, polyester resins, polyester polyurethane resins, polyethylene, polypropylene,
Polybutadiene, polyvinylidene chloride, ionomer resin, polyurethane resin, silicone resin, ketone resin,
One kind or two or more kinds selected from the group consisting of ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, polyamide resin, modified polyphenylene oxide resin and the like can be used.
However, it goes without saying that the material is not limited to the above materials.

As the elastic rubber and elastomer,
Butyl rubber, fluorinated 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 Tic 1,2-polybutadiene, epichlorohydrin rubber, recone rubber, fluororubber, polysulfide rubber, polynorbornene rubber, hydrogenated nitrile rubber, thermoplastic elastomers (eg polystyrene, polyolefin, polyvinyl chloride, polyurethane) , Polyamide-based, polyurea-based, polyester-based, fluororesin-based) and the like. However, it goes without saying 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, but examples thereof include carbon black, graphite, metal powders such as aluminum and nickel, tin oxide and titanium oxide. , Antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), indium oxide-tin oxide composite oxide (ITO) and other conductive metal oxides,
The conductive metal oxide may be coated with insulating fine particles such as barium sulfate, magnesium silicate and calcium carbonate. Of course, the conductive agent is not limited to the above.

The surface layer material and the surface layer prevent the contamination of the photosensitive member by the elastic material and reduce the surface friction resistance to the surface of the transfer belt to reduce the adhesive force of the toner, and the cleaning property is 2.
A material that enhances the secondary transfer property is required. For example, one or more kinds of polyurethane, polyester, epoxy resin, etc. are used to reduce surface energy and improve lubricity, for example, powder of fluororesin, fluorine compound, fluorocarbon, titanium dioxide, silicon carbide, etc. One kind or two or more kinds of bodies and particles, or those having different particle diameters can be dispersed and used. It is also possible to use a material such as a fluorine-based rubber material having a fluorine-rich layer formed on the surface by heat treatment to reduce the surface energy.

The method for manufacturing the belt is not limited, but the following methods can be mentioned. Centrifugal molding method in which a 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 immersed in a solution of a material and pulled up Internal mold, external mold Casting method of injecting into a method winding a compound around a cylindrical mold, vulcanization polishing method in the present invention is not limited to this, it is common to produce a belt by combining a plurality of manufacturing methods Is.

As a method for preventing elongation by elastic belting, a method of forming a rubber layer on a core resin layer having little elongation,
There is a method of adding a material that prevents elongation to the core layer,
It is not particularly related to the manufacturing method.

The material constituting the core layer for preventing elongation is
For example, natural fibers such as cotton and silk, polyester fibers,
Nylon fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, polyurethane fiber, polyacetal fiber, polyfluoroethylene fiber, synthetic fiber such as phenol fiber, carbon fiber, glass fiber, boron fiber, etc. A woven fabric or a thread can be obtained by using one kind or two or more kinds selected from the group consisting of inorganic fibers, iron fibers, metal fibers such as copper fibers. Of course, the material is not limited to the above.

The yarn may be any twisted yarn such as a twisted yarn of one or a plurality of filaments, a single twisted yarn, a plied yarn and a twin yarn. Further, for example, fibers of a material selected from the above material group may be mixed and spun. Of course, the thread may be used after being subjected to an appropriate conductive treatment. On the other hand, as the woven fabric, any woven fabric such as a knitted fabric can be used, and of course, a mixed woven fabric can also be used and naturally a conductive treatment can also 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 tubular shape is covered with a mold or the like and a coating layer is provided thereon, or a woven fabric woven in a tubular shape is dipped in liquid rubber or the like to form a coating layer on one or both sides of the core layer. Examples thereof include a method of providing the thread, a method of spirally winding the thread around a mold or the like at an arbitrary pitch, and providing a coating layer on the thread. The thickness of the elastic layer depends on the hardness of the elastic layer,
If it is too thick, the expansion and contraction of the surface will increase and cracks will easily occur in the surface layer. In addition, it is not preferable that the thickness is too thick (about 1 mm or more) because the amount of expansion and contraction becomes large and the spread and bleeding in the image becomes large.

(Tandem Color Image Forming Apparatus) An embodiment of the tandem color image forming apparatus of the present invention will be described. As shown in FIG. 3, the tandem type electrostatic image developing device is of a direct transfer type in which an image on each photoconductor 1 is sequentially transferred to 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 sequentially transferred to the intermediate transfer body 4 by the primary transfer device 2 and then the image on the intermediate transfer body 4 is transferred to the sheet by the secondary transfer device 5. There is an indirect transfer method in which the image is collectively transferred to s. The transfer device 5 is a transfer / transport belt, but there are also roller shapes and systems.

Comparing the direct transfer type and the indirect transfer type, the former shows that the paper feeding device 6 is provided upstream of the tandem type image forming apparatus T in which the photoconductors 1 are arranged, and the fixing device is provided downstream thereof. 7 has to be arranged, and there is a drawback that the size becomes large in the sheet conveying direction. On the other hand, in the latter, the secondary transfer position can be set relatively freely. Paper feeding device 6,
Further, the fixing device 7 can be arranged so as to overlap the tandem-type image forming apparatus T, and there is an advantage that the size can be reduced.

Further, in the former case, in order to prevent the size from increasing in the sheet conveying direction, the fixing device 7 is replaced by the tandem type image forming apparatus T.
Will be placed close to. Therefore, the fixing device 7 cannot be arranged with a sufficient margin to allow the sheet s to bend, and the impact when the leading edge of the sheet s enters the fixing device 7 (especially noticeable for a thick sheet),
There is a drawback that the fixing device 7 tends to affect the image formation on the upstream side due to the speed difference between the sheet conveying speed when passing through the fixing device 7 and the sheet conveying speed by the transfer conveying belt. On the other hand, in the latter case, since the fixing device 7 can be arranged with a sufficient margin that the sheet s can be bent, the fixing device 7 can be made to have almost no influence on image formation. From the above, recently, the tandem type electrostatic image developing device, in particular, the indirect transfer type has attracted attention.

In this type of color electrostatic image developing device, the transfer residual toner remaining on the photoconductor 1 after the primary transfer is removed by the photoconductor cleaning device 8 as shown in FIG. 1 Surface is cleaned to prepare for image formation again. 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 the image formation again.

Embodiments of the present invention will be described below with reference to the drawings. FIG. 5 shows an embodiment of the present invention, which is a tandem type indirect transfer type electrostatic charge image developing device. Reference numeral 100 in the drawing denotes a copying apparatus main body, 200
Is a paper feed table on which it is placed, and 300 is the copying apparatus main body 1
Reference numeral 400 denotes a scanner mounted on the printer 00, and reference numeral 400 denotes an automatic document feeder (ADF) mounted on the scanner 400. An endless belt-shaped intermediate transfer member 10 is provided in the center of the copying apparatus main body 100. Then, as shown in FIG. 5, in the illustrated example, the three support rollers 14, 15 and 16 are wound around and can be rotated and conveyed clockwise in the drawing. In this illustrated example, an intermediate transfer member cleaning device 17 that removes residual toner remaining on the intermediate transfer member 10 after image transfer is provided to the left of the second support roller 15 among the three. Further, on the intermediate transfer body 10 stretched between the first support roller 14 and the second support roller 15 among the three, along the carrying direction,
A tandem image forming apparatus 20 is configured by horizontally arranging four image forming units 18 for yellow, cyan, magenta, and black.

On the tandem image forming apparatus 20,
As shown in FIG. 5, an exposure device 21 is further provided. On the other hand, the tandem image forming apparatus 20 with the intermediate transfer member 10 interposed therebetween.
A secondary transfer device 22 is provided on the opposite side. In the illustrated example, the secondary transfer device 22 is configured by arranging a secondary transfer belt 24, which is an endless belt, between two rollers 23,
The image on the intermediate transfer body 10 is transferred onto a sheet by arranging it by pressing it against the third supporting roller 16 via the intermediate transfer body 10.

Next to the secondary transfer device 22, a fixing device 25 for fixing the transferred image on the sheet is provided. Fixing device 25
Is a fixing belt 26, which is an endless belt, and a pressure roller 27.
Press to configure. The secondary transfer device 22 described above is also provided with a sheet carrying function for carrying the sheet after the image transfer 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 the secondary transfer device 22 and the fixing device 25,
In parallel with the tandem image forming apparatus 20 described above, a sheet reversing device 28 for reversing the sheet to record images on both sides of the sheet is provided.

Now, when making a copy using this color electrostatic image developing device, a document is set on the document table 30 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened and the contact glass 3 of the scanner 300 is opened.
The original is set on the sheet 2, and the automatic document feeder 400 is closed and pressed by it. When a start switch (not shown) is pressed, when the original is set on the automatic document feeder 400, the original is conveyed and moved onto the contact glass 32, and then the original is set on the other contact glass 32. Immediately drives the scanner 300 to travel on the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source, and the light reflected from the document surface is further reflected and directed toward the second traveling body 34, reflected by the mirror of the second traveling body 34, and passed through the imaging lens 35. It is put in the reading sensor 36 to read the contents of the document.

When a start switch (not shown) is pressed, the supporting rollers 14 ・ 15 ・ 1 are driven by a drive motor (not shown).
One of the rollers 6 is driven to rotate and the other two support rollers are driven to rotate, and the intermediate transfer member 10 is rotatably conveyed. At the same time, the individual image forming means 18 rotates the photoconductor 40 to form black, yellow, magenta, and cyan single-color images on the photoconductor 40, respectively. Then, as the intermediate transfer body 10 is conveyed, the single color images are sequentially transferred to form a composite color image on the intermediate transfer body 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 sheets are fed out from one of the paper feed cassettes 44 provided in the paper bank 43 in multiple stages and separated. The rollers 45 separate the sheets one by one and put them in a paper feed path 46, which is conveyed by a conveyance roller 47 to be guided to a paper feed path 48 in the copying machine main body 100 and abutted against a registration roller 49 to be stopped. Alternatively, the paper feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, and the separation roller 52 separates the sheets one by one to manually feed the paper.
Then, it is put in 3 and similarly hits the registration roller 49 to stop. Then, the registration roller 49 is rotated in time with the composite color image on the intermediate transfer body 10, the sheet is fed between the intermediate transfer body 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. Record a color image on the sheet.

The sheet after the image transfer is the secondary transfer device 22.
After that, the fixing device 25 applies heat and pressure to fix the transferred image, and then the switching claw 55
And the paper is discharged by the discharge roller 56, and the discharge tray 57
Stack on top. Alternatively, the sheet is switched to the sheet reversing device 28 by switching with the switching claw 55, reversed there and guided to the transfer position again, and after the image is recorded on the back surface, the discharge roller 56.
The sheet is discharged onto the sheet discharge tray 57. On the other hand, the intermediate transfer body 10 after the image transfer is processed by the intermediate transfer body cleaning device 17,
After the image transfer, the residual toner remaining on the intermediate transfer body 10 is removed, and the tandem image forming apparatus 20 prepares for another image formation. Here, the registration roller 49 is generally grounded and used in many cases, but it is also possible to apply a bias for removing paper dust from the sheet.

Now, the tandem image forming apparatus 20 described above.
In detail, each of the image forming means 18 includes, in detail, for example, as shown in FIG.
A photoconductor cleaning device 63, a charge removing device 64, etc. are provided.

[0124]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Further, in the following examples, parts and% are based on weight unless otherwise specified.

[Evaluation] The evaluation machine used for the evaluation, the method for evaluating the characteristics, and the evaluation criteria are as follows. (Evaluation machine) The images used in the evaluation are the following evaluation machines A, B,
It evaluated using either C, D, or E.

(Evaluator A) Tandem type full-color laser printer IPSiO Colo manufactured by Ricoh Co., Ltd. having a non-magnetic two-component developing unit for four colors and a photoconductor for four colors.
The fixing unit of r 8000 was improved to an oilless fixing unit and tuned using an evaluation machine A.
Printing speed is high speed printing, full color 20 to 50 sheets / m
The evaluation was performed by changing to in A4.

(Evaluator B) Tandem type full color laser printer IPSiO Colo manufactured by Ricoh Co., Ltd. having a non-magnetic two-component developing unit for four colors and a photoconductor for four colors
By improving the r 8000, primary transfer is performed on the intermediate transfer member,
The evaluation was performed using an evaluation machine B in which the toner image was secondarily transferred to a transfer material, the intermediate transfer system was changed, and the fixing unit was improved to an oilless fixing unit and tuned. Printing speed is high-speed printing, 20-50 sheets / mi in full color
The evaluation was performed by changing up to n · A4.

(Evaluator C) The four-color developing unit develops the two-component type developer on one drum-shaped photoconductor for each color, transfers the intermediate developer to the intermediate transfer member one by one, and transfers the four colors to the transfer material all at once. Ricoh's full-color laser copier IMAGIO Col
or 2800 fixing unit was changed to an oilless fixing unit and tuned using an evaluation machine C. The printing speed was evaluated at 6 sheets / min · A4 in full color.

(Evaluator D) The four-color developing section sequentially develops the non-magnetic one-component type developer on one belt photosensitive member for each color, sequentially transfers it to the intermediate transfer member, and transfers the four colors to the transfer material all at once. System Ricoh full color laser printer IPSi
The fixing unit of O Color 5000 was improved to an oilless fixing unit, and the evaluation was performed using an evaluation machine D which was improved to an oilless fixing unit and tuned. The printing speed was evaluated at 6 sheets / min · A4 in full color.

(Evaluator E) Full color laser printer IPSiO Colo manufactured by Ricoh Co., Ltd. in a tandem system having a non-magnetic two-component developing unit for four colors and a photoconductor for four colors.
The evaluation was performed using an evaluation machine E in which r 8000 was tuned as it was in the oil coating type fixing section. High speed printing,
Evaluation was performed by changing from 20 to 50 sheets / min.A4.

(Evaluation items) 1) Toner scattering property under high temperature and high humidity environment After storing the toner for 12 hours in a high temperature and high humidity environment of 35 ° C. and 80%, an evaluation machine was installed in the same environment to obtain a single color toner. 80 in mode
After running out 30,000 sheets of the image chart of% image area, the amount of toner scattered from the developing section was visually determined by opening the developing unit. The rank is improved in the order of ×, Δ, ○, ◎.

2) An image chart of 7% image area in a background stain single color mode in a low temperature and low humidity environment was set at 30,000.
After running output of 0 sheets, the blank image is stopped during development, the developer on the photoconductor after development is tape-transferred, and the difference from the image density of the untransferred tape is measured by the 938 spectrodensitometer (X-Rite). (Made by the company). The smaller the difference in image density is, the better the background stain is, and the rank is improved in the order of ×, Δ, ○, and ⊚.

3) Image density (coloring degree) An image chart of 50% image area in the monochromatic mode is 200,
After running output of 000 sheets, the solid image was output on Ricoh's 6000 paper, and the image density was changed to X-Rit.
e (manufactured by X-Rite). This was performed for each of the four colors and the average was obtained. If this value is less than 1.2, x,
When 1.2 or more and less than 1.4, it was evaluated as Δ, when 1.4 or more and less than 1.8, it was evaluated as ◯, and when 1.8 or more and less than 2.2, it was evaluated as ⊚.

4) 100% image chart of 50% image area in the transparent monochromatic mode,
After running output of 000 sheets, Ricoh type DX
Image density on each OHP sheet in single color; 1.0
mg / cm ² , fixing temperature; 140 ° C. fixing was performed, and the continuous haze computer HGM-2D manufactured by Suga Test Instruments Co., Ltd.
It was measured by P type. In order of good transparency, ◎, ○, △,
It was set to x.

5) Color vividness 100% image chart of 50% image area in monochromatic mode,
After 000 sheets were run and output, the vividness of the color was visually evaluated on the image output to 6000 paper manufactured by Ricoh. The order of goodness was ◎, ○, △, ×.

6) Color reproducibility 100% image chart of 50% image area in monochromatic mode,
After running and outputting 000 sheets, the color reproducibility was visually evaluated for the image output to 6000 paper manufactured by Ricoh.
The order of goodness was ◎, ○, △, ×.

7) 100% image chart of 50% image area in glossy monochrome mode,
After running output of 000 sheets, the image output to 6000 paper manufactured by Ricoh Co., Ltd. was measured using a gloss meter (VG-1D) (manufactured by Nippon Denshoku Co., Ltd.) to set the projection angle and the reception angle to 6 respectively.
It was adjusted to 0 °, S and S / 10 switching SW were adjusted to S, and measurement was performed after 0 preparation and standard setting using a standard plate. From excellent glossiness, ⊚: 13 or more, ∘: 5 or more and less than 13, Δ: 2 or more and less than 5, and x: less than 2.

8) 100% image chart of 50% image area in lightfast monochromatic mode,
After running output of 000 sheets, output the image to 6000 paper made by Ricoh Co., Ltd.
The image was observed with XW-150 (manufactured by Shimadzu Corporation) after irradiating the image at 10,000 lux for 15 hours, and the light resistance was evaluated according to the following criteria. A: Almost no change. ◯: Slightly changed. Δ: slightly changed X: It changes considerably.

9) Fine line reproducibility In the monochromatic mode, an image chart of 50% image area is set to 30,0.
After running output of 00 sheets, a fine line image of 600 dpi was output on a Ricoh type 6000 paper, and the degree of fine line bleeding was compared with a step sample. ×, △, ○, ◎
The rank improves in the order of. This was repeated four colors.

10) Heat-resistant storability 10 g of each color toner is weighed and put in a 20 ml glass container, and the glass bottle is tapped 100 times, and then 55 ° C.
After leaving it in the constant temperature bath set for 24 hours, the penetration was measured with a penetration meter. From the good ones, ⊚: 20 mm or more, ∘: 15 mm or more and less than 20 mm, Δ: 10 mm or more and less than 15 mm, and x: less than 10 mm.

11) High-temperature and high-humidity environment Charge stability In an environment of a temperature of 40 ° C. and a humidity of 90%, a developer is printed every 1000 sheets while running and outputting 100,000 sheets of an image chart having a 7% image area in a monochromatic mode. Was partially sampled and the charge amount was measured by the blow-off method to evaluate the charge stability. The order of ⊚, ◯, Δ, and × was stable and good, with little increase in charge and decrease in charge.

12) Low-temperature and low-humidity environment Charging stability In an environment of a temperature of 10 ° C. and a humidity of 15%, a developer is printed every 1000 sheets while running and outputting 100,000 sheets of an image chart having a 7% image area in a monochromatic mode. A part of the sample was sampled and the charge amount was measured by the blow-off method to evaluate the charge stability. The order of ⊚, ◯, Δ, and × was stable and good, with little increase in charge and decrease in charge.

13) Fixing Toner The fixing lower limit temperature and fixing upper limit temperature are sufficiently within the fixing temperature range, hot offset and cold offset do not occur, and winding troubles, paper jams, and other conveyance problems do not easily occur. The overall fixability was evaluated as ⊚, ∘, Δ, and × in order of goodness.

(Evaluation of Two-Component Developer) In the case of image evaluation with a two-component developer, a ferrite carrier having an average particle diameter of 50 μm coated with a silicone resin in an average thickness of 0.3 μm is used as follows. , Carrier 100
A developer was prepared by uniformly mixing 5 parts by weight of each color toner with 5 parts by weight of each color toner using a turbuler mixer of a type in which a container rolls and is stirred, and charged.

(Manufacture of Carrier) Core Material Cu—Zn Ferrite Particles (Weight Average Diameter: 35 μm) 5000 Parts Coat Material Toluene 450 Parts Silicone Resin SR2400 (Toray Dow Corning Silicone, Nonvolatile Content 50%) 450 Parts Aminosilane SH6020 (manufactured by Toray Dow Corning Silicone) 10 parts Carbon black 10 parts The above coating material is dispersed with a stirrer for 10 minutes to prepare a coating liquid, and the coating liquid and the core material are put into a fluidized bed to form a rotary bottom plate disk. The coating liquid was applied to the core material by being placed in a coating device for coating while forming a swirling flow provided with stirring blades. The obtained coated product is heated in an electric furnace to 250.
The carrier was obtained by firing at ℃ for 2 hours.

Example 1 (Polyol resin 1) Stirrer, thermometer, N ₂ inlet,
In a separable flask with a cooling tube, a low molecular weight bisphenol A type epoxy resin (number average molecular weight: about 360) 378.
4 g, high molecular weight bisphenol A type epoxy resin (number average molecular weight: about 2700) 86.0 g, bisphenol A type propylene oxide adduct diglycidyl compound [n + m in the general formula (1): about 2.1] 191.0
g, bisphenol F 274.5 g, p-cumylphenol 70.1 g, and xylene 200 g were added. Under a N ₂ atmosphere, the temperature was raised to 70 to 100 ° C., and lithium chloride was added to 0.
183 g was added, the temperature was further raised to 160 ° C., water was added under reduced pressure, and water and xylene were bubbled to remove water, xylene, other volatile components, and polar solvent-soluble components.
Polymerization was carried out at a reaction temperature of ° C for 6 to 9 hours, and Mn; 380
0, Mw / Mn; 3.9, Mp; 5000, softening point 10
1000 g of polyol resin having 9 ° C., Tg of 58 ° C. and epoxy equivalent of 20000 or more was obtained (polyol resin 1). The reaction conditions were controlled so that the monomer components did not remain in the polymerization reaction. The polyoxyalkylene part of the main chain was confirmed by NMR.

(Production of Toner) <Magenta Toner> Water 600 parts Pigment Red 122 1200 parts Polyol Resin 1 1200 parts The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was impregnated in the pigment aggregate. This was kneaded for 45 minutes by two rolls set to a roll surface temperature of 128 ° C, rolled and cooled, and pulverized by a palpelizer to obtain a masterbatch colorant. Polyol resin 1 100 parts Master batch 14 parts Charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) 2 parts Wax (fatty acid ester wax, melting point 83 ° C, viscosity 280 mPa · s (90 ° C)) 5 parts The above materials After mixing with a mixer, the mixture was melt-kneaded 5 times with a two-roll mill, and the kneaded product was rolled and cooled. After that, a collision plate type crusher by a jet mill (I type mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and a wind force classification by a swirling flow (DS classifier;
(Manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain magenta colored particles having a volume average particle diameter of 5.5 μm and a number average particle diameter of 4.5 μm. Furthermore, 1.0% by weight of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and titanium oxide (MT having a primary particle diameter of 15 nm)
-150A, Takea) was added by 0.9% by weight, mixed with a Henschel mixer, and passed through a sieve having openings of 50 μm to remove agglomerates, thereby obtaining a magenta toner. The dispersed diameter of the wax in the toner was 0.2 μm. The obtained toner had a coloring agent of 6% by weight, and the amount of nitrogen on the surface of the toner was 0.
It was 67 atomic%.

Example 2 Evaluation was made in the same manner as in Example 1 except that the toner was manufactured as follows. <Cyan Toner> Water 600 parts Pigment Blue 15: 3 1200 parts Polyol Resin 1 1200 parts The above raw materials were mixed by a Henschel mixer to obtain a mixture in which water permeated the pigment aggregate. This was kneaded for 45 minutes by two rolls set to a roll surface temperature of 128 ° C, rolled and cooled, and pulverized by a palpelizer to obtain a masterbatch colorant. Polyol resin 1 100 parts Master batch 7 parts Charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) 2 parts Wax (fatty acid ester wax, melting point 83 ° C, viscosity 280 mPa · s (90 ° C)) 5 parts The above materials After mixing with a mixer, the mixture was melt-kneaded 5 times with a two-roll mill, and the kneaded product was rolled and cooled. After that, a collision plate type crusher by a jet mill (I type mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and a wind force classification by a swirling flow (DS classifier;
(Produced by Nippon Pneumatic Mfg. Co., Ltd.) to obtain cyan colored particles having a volume average particle diameter of 5.5 μm and a number average particle diameter of 4.5 μm. Further, a hydrophobic silica (HDKH2000, Clariant Japan) having a primary particle diameter of 10 nm was added to 1.
0% by weight, titanium oxide having a primary particle diameter of 15 nm (MT-1
Cyan toner was obtained by adding 0.9% by weight of 50 A, Takea), mixing with a Henschel mixer, and passing through a sieve having openings of 50 μm to remove agglomerates. The dispersed diameter of the wax in the toner was 0.2 μm. The obtained toner had a coloring agent of 3% by weight, and the amount of nitrogen on the toner surface was 0.66 atom%.

Example 3 Evaluation was made in the same manner as in Example 1 except that the toner was manufactured as follows. <Yellow Toner> Water 600 parts Pigment Yellow 180 1200 parts Polyol Resin 1 1200 parts The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water permeated the pigment aggregate. This was kneaded for 45 minutes by two rolls set to a roll surface temperature of 128 ° C, rolled and cooled, and pulverized by a palpelizer to obtain a masterbatch colorant. Polyol resin 1 100 parts Master batch 12 parts Charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) 2 parts Wax (fatty acid ester wax, melting point 83 ° C, viscosity 280 mPa · s (90 ° C)) 5 parts The above materials After mixing with a mixer, the mixture was melt-kneaded 5 times with a two-roll mill, and the kneaded product was rolled and cooled. After that, a collision plate type crusher by a jet mill (I type mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and a wind force classification by a swirling flow (DS classifier;
(Produced by Nippon Pneumatic Mfg. Co., Ltd.) to obtain yellow colored particles having a volume average particle diameter of 5.5 μm and a number average particle diameter of 4.5 μm. Further, a hydrophobic silica (HDKH2000, Clariant Japan) having a primary particle diameter of 10 nm was added to 1.
0% by weight, titanium oxide having a primary particle diameter of 15 nm (MT-1
50A, Takea) was added thereto, mixed with a Henschel mixer, and passed through a sieve having openings of 50 μm to remove agglomerates to obtain a yellow toner. The dispersed diameter of the wax in the toner was 0.3 μm. The obtained toner had a coloring agent of 5% by weight, and the amount of nitrogen on the toner surface was 0.89.
It was atomic%.

Example 4 Evaluation was made in the same manner as in Example 1 except that the toner was manufactured as follows. <Magenta Toner> Water 600 parts Pigment Red 57: 1 1200 parts Polyol resin 1 1200 parts The above raw materials were mixed by a Henschel mixer to obtain a mixture in which water was impregnated in the pigment aggregate. This was kneaded for 45 minutes by two rolls set to a roll surface temperature of 128 ° C, rolled and cooled, and pulverized by a palpelizer to obtain a masterbatch colorant. Polyol resin 1 100 parts Master batch 8 parts Charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) 2 parts Wax (fatty acid ester wax, melting point 83 ° C, viscosity 280 mPa · s (90 ° C)) 5 parts The above materials After mixing with a mixer, the mixture was melt-kneaded 5 times with a two-roll mill, and the kneaded product was rolled and cooled. After that, a collision plate type crusher by a jet mill (I type mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and a wind force classification by a swirling flow (DS classifier;
(Manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain magenta colored particles having a volume average particle diameter of 5.5 μm and a number average particle diameter of 4.5 μm. Furthermore, 1.0% by weight of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and titanium oxide (MT having a primary particle diameter of 15 nm)
-150A, Takea) was added by 0.9% by weight, mixed with a Henschel mixer, and passed through a sieve having openings of 50 μm to remove agglomerates, thereby obtaining a magenta toner. The dispersed diameter of the wax in the toner was 0.2 μm. The obtained toner had a coloring agent of 3% by weight, and the amount of nitrogen on the toner surface was 0.1.
It was 11 atomic%.

Example 5 Evaluation was made in the same manner as in Example 1 except that the toner was manufactured as follows. <Magenta Toner> Water 600 parts Pigment Red 185 1200 parts Polyol resin 1 1200 parts The above raw materials were mixed by a Henschel mixer to obtain a mixture in which water was impregnated in the pigment aggregate. This was kneaded for 45 minutes by two rolls set to a roll surface temperature of 126 ° C., rolled and cooled, and pulverized by a pulperizer.
4 by 2 rolls with roll surface temperature set at 125 ° C
Kneading was carried out for 0 minutes, followed by rolling and cooling to obtain a ground masterbatch colorant using a palpelizer. Polyol resin 1 100 parts Master batch 8 parts Charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) 2 parts Wax (fatty acid ester wax, melting point 83 ° C, viscosity 280 mPa · s (90 ° C)) 5 parts The above materials After mixing with a mixer, the mixture was melt-kneaded 5 times with a two-roll mill, and the kneaded product was rolled and cooled. After that, a collision plate type crusher by a jet mill (I type mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and a wind force classification by a swirling flow (DS classifier;
(Manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain magenta colored particles having a volume average particle diameter of 5.5 μm and a number average particle diameter of 4.5 μm. Furthermore, 1.0% by weight of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and titanium oxide (MT having a primary particle diameter of 15 nm)
-150A, Takea) was added by 0.9% by weight, mixed with a Henschel mixer, and passed through a sieve having openings of 50 μm to remove agglomerates, thereby obtaining a magenta toner. The dispersed diameter of the wax in the toner was 0.2 μm. The obtained toner had a coloring agent of 3% by weight, and the amount of nitrogen on the toner surface was 0.1.
It was 46 atomic%.

Example 6 Evaluation was made in the same manner as in Example 1 except that the toner was manufactured as follows. <Magenta Toner> Water 600 parts Pigment Red 57: 1 1200 parts Polyol resin 1 1200 parts The above raw materials were mixed by a Henschel mixer to obtain a mixture in which water was impregnated in the pigment aggregate. This was kneaded for 45 minutes by two rolls set to a roll surface temperature of 128 ° C, rolled and cooled, and pulverized by a palpelizer to obtain a masterbatch colorant. Polyol resin 1 100 parts Master batch 30 parts Charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) 2 parts Wax (fatty acid ester wax, melting point 83 ° C, viscosity 280 mPa · s (90 ° C)) 5 parts The above materials After mixing with a mixer, the mixture was melt-kneaded 5 times with a two-roll mill, and the kneaded product was rolled and cooled. After that, a collision plate type crusher by a jet mill (I type mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and a wind force classification by a swirling flow (DS classifier;
(Manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain magenta colored particles having a volume average particle diameter of 5.5 μm and a number average particle diameter of 4.5 μm. Furthermore, 1.0% by weight of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and titanium oxide (MT having a primary particle diameter of 15 nm)
-150A, Takea) was added by 0.9% by weight, mixed with a Henschel mixer, and passed through a sieve having openings of 50 μm to remove agglomerates, thereby obtaining a magenta toner. The dispersed diameter of the wax in the toner was 0.2 μm. The obtained toner had a coloring agent of 11% by weight and the amount of nitrogen on the toner surface was 0.06 atom%.

Example 7 A full color toner kit containing the magenta toner, cyan toner, yellow toner described in Examples 1, 2 and 3 and the 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 water-containing cake (solid content 30%) 200 parts Carbon black (MA60, Mitsubishi Chemical Co., Ltd.) 1000 parts Polyol resin 1 1000 parts The above raw materials are mixed with a Henschel mixer to form a pigment aggregate. A mixture soaked with water was obtained. This was kneaded for 45 minutes by two rolls set to a roll surface temperature of 128 ° C, rolled and cooled, and pulverized by a palpelizer to obtain a masterbatch colorant. Polyol resin 1 100 parts Master batch 10 parts Charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) 2 parts Wax (fatty acid ester wax, melting point 83 ° C, viscosity 280 mPa · s (90 ° C)) 5 parts The above materials After mixing with a mixer, the mixture was melt-kneaded with a two-roll mill three times or more, and the kneaded product was rolled and cooled. After that, a collision plate type crusher with a jet mill (I type mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and a wind classification by a swirling flow (DS classifier; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) were performed, and the volume average particle diameter was 5.5 μm. Thus, black colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0 wt% of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and titanium oxide (MT having a primary particle diameter of 15 nm)
-150A, Takea) was added in an amount of 0.9% by weight, mixed with a Henschel mixer, and passed through a sieve having an opening of 50 μm to remove agglomerates to obtain a black toner. The dispersed diameter of the wax in the toner was 0.15 μm. The toner obtained 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-Bis (4-hydroxyphenyl) propane, resin synthesized from trimellitic anhydride, acid value; 10, hydroxyl value; 30, Mn; 5000, M
w / Mn: 10, Mp: 9000, Tg: 61 ° C., softening point: 108 ° C.), and evaluation was performed in the same manner as in Example 1. The volume average particle diameter of the obtained toner is 5.5 μm,
The number average particle diameter was 4.5 μm, the obtained toner was 6% by weight of colorant, and the amount of nitrogen on the toner surface was 0.72 atomic%.

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

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

Example 11 A toner was prepared in the same manner as in Example 1 except that the toner was classified so as to have a volume average particle diameter of 2 μm and a number average particle diameter of 1.4 μm. A developer was prepared and evaluated. The obtained toner contained 6% by weight of the colorant, and the amount of nitrogen on the surface of the toner was 1.23 atom%.

Example 12 A toner and a 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. did. The toner circularity SF-1 is 140 and SF-2 is 13
It was 0. The obtained toner contained 6% by weight of the colorant, and the amount of nitrogen on the toner surface was 0.75 atom%.

Example 13 Evaluations were made 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 liquid 1, styrene 350 parts, butyl acrylate 41 parts, acrylic acid 9 parts, dodecyl mercaptan 16 parts, carbon tetrabromide 5 parts (all of which are manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and dissolved. A non-ionic surfactant (manufactured by Sanyo Kasei Co., Nonibol 85) (9 parts) and an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) (11 parts) were dissolved in 582 parts of ion-exchanged water. Distributed by,
50 g of ion-exchanged water in which 3.4 g of ammonium persulfate (manufactured by Tokai Denka Co., Ltd.) was dissolved was added while emulsifying and mixing slowly for 15 minutes, and nitrogen substitution was performed. After that, the content of the flask was heated in an oil bath while stirring until the content reached 73 ° C., emulsion polymerization was continued for 7 hours, and then cooled to room temperature to obtain a resin dispersion. The solvent was left in the oven at 80 ° C. to remove water from the obtained resin dispersion liquid. Central particle diameter 120 nm, glass transition point 55 ° C., Mw 22,000
A resin dispersion 1 of 0 was obtained.

Pigments Pigment Red 122, 7
0 part was added to 300 parts of ion-exchanged water together with 2 parts of an anionic surfactant (manufactured by Sanyo Kasei Co., Ltd., Ionet D-2), dispersed and treated with IKA Ultra Turrax T50, and a pigment having a center diameter of 160 nm. Dispersion liquid 1 was obtained. Wax (fatty acid ester wax, melting point 83 ° C., viscosity 280 m
50 parts of Pa · s (90 ° C.) together with 2 parts of anionic surfactant (Sanyo Kasei Co., Ltd., Ionette D-2) are added and mixed in 300 parts of ion-exchanged water, and dispersed by IKA Ultra Turrax T50. This was treated to obtain Wax Dispersion Liquid 1.

Next, the above resin dispersion 1, pigment dispersion 1,
Wax dispersion 1 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 (Kao Corporation, Sanizol B50) The above materials Was mixed and dispersed in a round stainless steel flask with Ultra Turrax T50, and then heated to 48 ° C. while stirring the flask in a heating oil bath. 4 at 48 ° C
After keeping for a while, it is about 5.5μ when observed with an optical microscope.
It was confirmed that aggregated particles of m were generated. Then, after 6 parts of Neogen SC was additionally added, the mixture was heated to 93 ° C. while continuing stirring and kept for 9 hours. After this time the flask was cooled to room temperature at 10 ° C./min and filtered,
After thoroughly washing with ion-exchanged water, in a vacuum dryer at 50 ° C, 1
After holding for 2 hours, magenta colored particles having a volume average particle diameter of 5.5 μm, a number average particle diameter of 4.7 μm and a molecular weight Mw of 22,000 were obtained. Furthermore, 1.0 wt% of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9 wt% of titanium oxide (MT-150A, Teika) having a primary particle diameter of 15 nm were added, and the mixture was mixed with a Henschel mixer. 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 coloring agent of 8% by weight, and the amount of nitrogen on the toner surface was 1.21 atom%.

Example 14 Evaluation was made in the same manner as in Example 1 except that the evaluation machine B was used.

Example 15 Evaluations were made in the same manner as in Example 1 except that the evaluation machine C was used.

Example 16 Evaluations were made in the same manner as in Example 1 except that the evaluation machine D was used.

Example 17 A toner was manufactured in the same manner as in Example 1 except that the wax was not added, and the evaluation machine E was used. The volume average particle diameter of the obtained toner is 5.5.
μm, the number average particle diameter was 4.6 μm, the obtained toner was 6% by weight of the colorant, and the amount of nitrogen on the toner surface was 0.57 atom%.

Comparative 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 masterbatch colorant were changed. The masterbatch colorant was obtained by kneading for 40 minutes with a two-roll roller set at a roll surface temperature of 115 ° C. The obtained toner contained 6% by weight of the colorant, and the amount of nitrogen on the toner surface was 1.42 atomic%.

Comparative Example 2 In Example 4, the toner manufacturing conditions were changed, that is,
Example 4 was repeated except that the kneading of the toner was changed to a Buss Co-kneader, the kneaded product was rolled and cooled, coarsely crushed and kneaded again in the co-kneader to obtain a final kneaded product. Similarly, a toner was prepared and evaluated. The obtained toner had a coloring agent of 3% by weight, and the amount of nitrogen on the toner surface was 0.04 atom%.

Comparative Example 3 Toner was prepared in the same manner as in Example 1 except that the ratio of the masterbatch colorant to the binder resin was changed so that the colorant in the toner was 1.3% by weight. Was created and evaluated. The amount of nitrogen on the obtained toner surface was 0.
It was 08 atomic%.

Comparative Example 4 A toner was prepared in the same manner as in Example 1 except that the prescription ratio of the master batch colorant and the binder resin was changed so that the colorant in the toner was 16% by weight. And evaluated. The amount of nitrogen on the surface of the obtained toner is 0.9.
It was 6 atomic%.

[0170]

[Table 1]

[0171]

According to the present invention, in a toner containing at least a binder resin and a colorant, the nitrogen atom on the surface of the toner is 0.05 to 1.3 atom%, and the colorant is contained in the toner. The toner for developing an electrostatic image is characterized by containing 2 to 15% by weight, so that after storing the toner for a long time in a high temperature and high humidity environment, after outputting tens of thousands of images in the high temperature and high humidity environment. Also has excellent charge stability, there is little weakly charged or reversely charged toner, and toner scattering does not occur,
It is possible to provide a toner, a developer containing the toner, an image forming method using the toner, a container filled with the developer, and an image forming apparatus loaded with the container. In addition to normal temperature and humidity environment,
A toner that has excellent charge stability even after outputting tens of thousands of images in a low temperature and low humidity environment, has a small amount of weakly charged and reversely charged toner, and does not cause background stain (fog), a developer containing the toner, and an image using the toner. A forming method, a container filled with the developer, and an image forming apparatus loaded with the container can be provided. 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 toner, and using it An image forming method, a container filled with the developer, and an image forming apparatus loaded with the container can be provided.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing an example of an image forming apparatus (copier) of the present invention.

FIG. 2 is a schematic configuration diagram showing another example of the image forming apparatus (copier) of the present invention.

FIG. 3 is a schematic configuration diagram of a tandem type direct transfer type color image forming apparatus of the present invention.

FIG. 4 is a schematic configuration diagram of a tandem indirect transfer type color image forming apparatus of the present invention.

FIG. 5 is an overall schematic configuration diagram of a tandem type indirect transfer type electrostatic charge image developing device of the present invention.

6 is an enlarged schematic configuration diagram of an image forming means portion of the electrostatic charge image developing device shown in FIG.

[Explanation of symbols]

(Figs. 1 and 2) 10 photoconductor 20 charging roller 30 exposure equipment 40 Developing device 41 Development Belt 42 Development tank 43 Pumping roller 44 Application roller 45 Development unit 50 Intermediate transfer body 51 suspension roller 52 Corona charger 53 constant current source 60 cleaning device 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 100 transfer paper (Figs. 3 and 4) T tandem image forming apparatus 1 photoconductor 2 Transfer device (or primary transfer device) 3 Sheet conveyor belt 4 Intermediate transfer body 5 Secondary transfer device 6 Paper feeder 7 Fixing device 8 Photoconductor cleaning device 9 Intermediate transfer member cleaning device S sheet (Figs. 5 and 6) 100 Copying machine 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 member cleaning device 18 Image forming means 20 Tandem image forming device 21 Exposure equipment 22 Secondary transfer device 23 Laura 24 Secondary transfer belt 25 Fixing device 26 fixing belt 27 Pressure roller 28 Sheet reversing device 30 platen 32 contact glass 33 First running body 34 Second traveling body 35 Imaging lens 36 reading sensor 40 photoconductor 42 paper feed roller 43 Paper Bank 44 paper feed cassette 45 Separation roller 46 paper feed path 47 Conveyor roller 48 paper feed path 49 Registration roller 50 paper feed rollers 51 bypass tray 52 Separation roller 53 paper feed path 55 Switching claw 56 discharge roller 57 Output tray 60 charging roller 61 Developing device 62 Primary transfer device 63 Photoconductor cleaning device 64 Static eliminator

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasuo Asahina             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Kazuhiko Umemura             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Minoru Masuda             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Tomomi Tamura             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh F-term (reference) 2H005 AA01 AA06 AA15 AA21 CA07                       CA15 EA05 EA07 EA10

Claims (10)

[Claims] 1. In a toner containing at least a binder resin and a colorant, the nitrogen atom on the surface of the toner is 0.05 to 1.3 atom%, and the content of the colorant is 2 to the toner. A toner for developing an electrostatic charge image, which comprises 15% by weight. 2. The toner for developing an electrostatic charge image according to claim 1, wherein the binder resin of the toner contains at least a polyol resin. 3. The volume average particle diameter of the toner is 1 to 6 μm.
The toner for developing an electrostatic charge image according to claim 1 or 2, wherein the toner is m. 4. The circularity SF-1 value of the toner is 100.
4. The toner for developing an electrostatic charge image according to claim 1, wherein the toner has a circularity SF-2 value of 100 to 130. 5. The colorant according to claim 1, wherein the colorant is black, magenta, yellow or cyan.
The color toner for developing an electrostatic image according to any one of 1. 6. A developer containing the toner according to claim 1. 7. An image forming method using the developer according to claim 6. 8. The image forming method according to claim 7, wherein a color image is formed by a tandem system at a printing speed corresponding to A4 size of 20 sheets / minute or more. 9. A container filled with the developer according to claim 6. 10. An image forming apparatus in which the container according to claim 9 is loaded.