JP2003280273A - Toner for developing electrostatic image, developer for developing electrostatic image, image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner having electrification stability and hardly generating weak-electrified toner and reverse-electrified toner, and not causing toner- scattering even after several ten thousands sheets of images are outputted under a high temperature and humidity environment after the toner is stored for a long period under the high temperature and humidity environment, and to provide a developer, an image forming method and an image forming apparatus. <P>SOLUTION: In the toner containing at least binding resin and coloring agent, the particle satisfying 0.04 μm≤L≤0.2 μm (L denotes the number average particle size of coloring agent particles in the toner) is set to be ≥80 number %, the particle satisfying L≥0.4 μm is set to be ≤10 number % and the particle satisfying L<0.04 μm is set to be 5 number %, and also, the toner contains the coloring agent particles of 2 to 15 wt.% to the toner of 100 wt.%, and also, the toner satisfies that a ratio a/b of the longest diameter (a) to the shortest diameter (b) of the coloring agent is 1.0 to 5.0. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner, an electrostatic charge image developing developer, an image forming method and an image forming apparatus.

[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 including a carrier and a toner and a one-component developer that does not require a carrier (magnetic toner, non-magnetic toner). )It has been known. As a full-color image forming apparatus, a 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, the non-offset property that does not adhere to the heat roller normally heated to a temperature of about 100 to 230 ° C. and the 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, there is a tendency that the transferability is deteriorated as the diameter of the toner is reduced and a poor image is formed. On the other hand, it is known that the transferability is improved by making the toner spherical (Japanese Patent Laid-Open No. 9-258474).
No. publication). 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, described in Japanese Patent Laid-Open No. 5-341617).

The "tandem system" is a system for obtaining a full-color image on a transfer paper by sequentially superposing and transferring the images formed by the image forming unit on a single transfer paper conveyed to a transfer belt. . The tandem type color image forming apparatus has a wide variety of usable transfer papers, a high quality of a full color image, and an excellent characteristic that a full color image can be obtained at a high speed. In particular, the characteristic that a full-color image can be obtained at high speed is a unique property that other types of 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.
In order to achieve higher speed in an apparatus that adopts the above method, it is necessary to shorten the time required for the paper to pass through the transfer section, and therefore, it is necessary to increase the transfer pressure in order to obtain the same transfer performance as in the past. is there. However, if the transfer pressure is increased, the toner agglomerates due to the pressure at the time of transfer, and good transfer cannot be performed, and there is a problem that hollow defects occur in a formed image.

In order to solve such problems, the circularity, particle size, specific gravity and BET specific surface area of the toner are specified to be 1 kg.
It is known that the image quality is improved by defining the adhesion stress at the time of compressing / cm ² to 6 g / cm ² or less (Japanese Patent Laid-Open No. 20-200200).
No. 00-3063). However, 1 kg / cm
² When using the adhesive stress at the time of compression, the compression pressure is too weak, so there is a problem with transferability when the transfer pressure increases, such as OHP, thick paper, and surface-coated paper, and image quality such as missing characters. It was Further, when the adhesion stress is small, there is a problem such as transfer dust.

Further, the adhesion force of one particle of toner is 3.0 dy.
It is also known that the toner discharge property is improved by defining it as ne / contact or less (Japanese Patent Laid-Open No. 2000-35284).
No. 0 publication). However, the toner adhesion force at the time of compression is not regulated, and although the discharge property is improved, it has no effect on the transfer property and the image quality improvement such as a blank image in the character portion.

It is also known that the degree of cohesion at the time of compression is regulated for the purpose of improving the developability and its stability over time (described in Japanese Patent No. 3002063). However, it is difficult to sufficiently improve the transferability and the transfer rate by defining the degree of cohesion at the time of compression, because there is still a problem in the image quality such as blank areas in the character portion.

Further, the product of the cohesion degree and the loose apparent density is defined to be 7 or less to improve the hollow portion of the character portion (Japanese Patent Application Laid-Open No. 2-9
No. 000-267422) is also known, but the behavior of physical properties at the time of toner compression is not reflected, and there is no sufficient effect in an intermediate transfer system, a strong agitation development system, or the like that stresses the toner more. .

The ratio between the loose apparent density and the solid apparent density is the loose apparent density / the solid apparent density =
A technology of 0.5 to 1.0 and a cohesion degree of 25% or less (described in JP-A-2000-352840)
It is also known, but apparent density is 5 because it was used here.
The value obtained by measuring the bulk density after tapping 0 times is close to the physical properties that reflect the fluidity, and the factor that increases the bulk density when mechanical stress is applied to the toner cannot be reflected. The intermediate transfer system and the strong agitation developing system did not have sufficient effect.

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 fluidity and charging characteristics of the toner, which is called an external additive. There is. Further, 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 coated with a specific resin. It is also proposed to do.

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 are known. In particular, silica fine particles and titanium oxide particles obtained by reacting silica or titanium oxide fine particles with an organic silicon compound such as dimethyldichlorosilane, hexamethyldisilazane, or silicone oil to replace the silanol groups on the surface of the silica fine particles with organic groups to make them hydrophobic are used. Has been.

Of these, it exhibits sufficient hydrophobicity, and
Silicone oil is preferred as the hydrophobizing agent which, when contained in the toner, exhibits excellent transferability due to its low surface energy. Japanese Examined Patent Publication No. 7-3600 and Japanese Patent No. 2568244 specify the degree of hydrophobicity of silica treated with silicone oil. Also,
JP-A-7-271087 and JP-A-8-29598
The publication describes the amount of silicone oil added and the carbon content in the additive.

In order to ensure the stability of the chargeability of the developer under high humidity by hydrophobizing the inorganic fine particles as the base material of the external additive, the silicone oil content and hydrophobization in the above-mentioned publications are required. I was satisfied with the degree. However, a member that comes into contact with a developer by utilizing low surface energy, which is an important peculiarity of silicone oil, such as a contact charging device, a developer carrier (sleeve) or a doctor blade, a carrier, an electrostatic latent image carrier ( No active attempts have been made to reduce the adhesion to the photoconductor) and the intermediate transfer member.

In particular, background stains due to strong adhesion of the developer to the photosensitive member, blemishes after transfer at the edge portion and the center portion of the character portion, line portion, dot portion in the image (developer not transferred portion) Could not be improved simply by adjusting the amount of silicone oil added 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,
Image quality deteriorates due to 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, examples in which improvement of charging property by an additive of a toner for developing electrostatic image is proposed are disclosed in JP-A-3-294864, which is a non-magnetic material containing inorganic powder treated with silicone oil. A one-component developer is disclosed in 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, according to these proposals, sufficient charging uniformity may not be obtained or the toner charge amount may not rise sufficiently, and the toner charge amount may be environmentally stable, particularly humidity. It was not always sufficient for the stability against. 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 using the liquid phase method as described in JP-A-8-202071, sufficient hydrophobicity can be obtained due to the influence of the medium-liquid substance remaining inside the particles. In some cases, the hydrophobicity did not exist, or the hydrophobicity changed with time.

On the other hand, as a binder resin, from the viewpoint of properties required for toners, 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 transfer to a vinyl chloride resin sheet as described above, in JP-A-60-263951 and JP-A-61-24025, styrene resin or polyester resin is plasticized for vinyl chloride resin. Proposals have been made to blend epoxy resins that are not plasticized with agents.

However, when such a blended resin is used especially for a color toner, the offset property, the curl of the fixed image, and the glossiness (in the case of a color toner image, there is no glossiness) due to the incompatibility between different kinds of resins. It appears as a poor image), coloring, transparency, and color developability.
These problems are caused by the conventional epoxy resin and JP-A-61-23.
Even the acetylated modified epoxy resin as proposed in Japanese Patent No. 5852 cannot solve all problems.

Therefore, it is conceivable to solve the above problems by using the epoxy resin alone, but as a new problem, the reactivity of the epoxy resin with the amine occurs. 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. A crosslinking reaction occurs during kneading,
It may not be usable as a toner. 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. Also,
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, the toner is composed of a binder resin, a colorant, a charge control agent and the like. Various dyes and pigments are known as colorants, some of which have charge controllability, and some of which have two functions of a colorant and a charge control agent. It has been widely practiced to use an epoxy resin as a binder resin 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 carried out 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 coloring is poor and the degree of coloring is low. If the charge control agent is not well dispersed, the charge distribution will be non-uniform, resulting in poor charging, scumming, scattering, and ID.
This causes various defects such as insufficient (image density), blurring, and poor cleaning.

Further, JP-A-61-219051 discloses a toner using an epoxy resin ester-modified with ε-caprolactone as a binder resin, but it has improved vinyl chloride resistance and fluidity. However, the modification amount was 15 to 90% by weight, and the softening point was too low and the gloss was too high.

Further, Japanese Patent Application Laid-Open No. 52-86334 describes 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 may be considered that the epoxy group and the amine cause a crosslinking reaction and cannot be used as a toner. Furthermore, JP-A-52-1566.
No. 32, it is described 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, etc., but the epoxy groups remain. If such is the case, problems such as reactivity with amines, toxicity, and hydrophilicity occur as described above. Further, some of the above reaction products are hydrophilic, ones that affect the charging, and some that affect the pulverizability when forming a toner, and are not always effective.

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 a monocarboxylic acid, an ester derivative thereof, or an ester with a lactone is used. However, the curl in fixing is not so much improved, although the reactivity, toxicity and hydrophilicity of the epoxy resin have been solved.

Further, in general, a solvent such as xylene is often used when synthesizing an epoxy resin or a polyol resin (for example, described in JP-A No. 11-189646). A large amount of monomers and the like was present in the resin after production, and the residual amount was large in toners using those resins, which was a problem.

On the other hand, the performance required for the electrostatic toner image developing color toner used particularly 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-57-57
There is one described in Japanese Patent Publication No. 130044. However, when a dye is used as the colorant, the resulting image has excellent transparency and good color development, and it is possible to form a clear color image. In this case, there is a problem of discoloration or fading.

On the other hand, as a colorant using a pigment, Japanese Patent Laid-Open Nos. 49-46951 and 52-1 are available.
There is one disclosed in Japanese Patent No. 7023. 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 the coloring degree (color-forming property) and the transparency are inferior.

A method for improving the dispersibility of the pigment in the binder resin is described in JP-A-62-280755.
A polyester resin (resin A) is used as a binder resin, a pigment is previously coated with a polyester resin (resin B) having a higher molecular weight than the resin A, and the coated pigment is dispersed in the resin A to obtain a color toner. JP-A-2-66561 describes that a processed pigment obtained 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 Is smaller than the weight average molecular weight of the binder resin, and the weight average molecular weight of the binder resin is 100,000 or more.
No. 101632, a mixture of a binder resin and a pigment is kneaded in advance with an organic solvent at a temperature lower than the melting temperature of the binder resin, and then the binder resin and the charge control agent are added to the mixture. JP-A-4-39671 discloses a binder resin having a weight average molecular weight of 40,000 or less, and a colorant comprising a flushing pigment using the binder resin. A toner characterized by containing a solvent is described in JP-A-4-230770, and a solvent, a first binder resin soluble in the solvent, and particles of a colorant insoluble in the solvent are mixed and added. Temperature 5 under pressure condition
After the particles of the colorant are dispersed in the binder resin while applying a shearing force at 0 to 100 ° C., the solvent is removed to obtain a colored binder resin composition in which the particles of the colorant are dispersed. Then, a binder resin and a charge control agent are further added, and the toner is obtained by heat-melting and kneading in the second stage.

However, the above-mentioned JP-A-62-2807 is used.
In either of the methods described in JP-A-55-55 and JP-A-2-66561, no sufficient pigment dispersion can be obtained.
At present, the transparency is poor. Further, the methods described in JP-A-9-101632, JP-A-4-39671, and JP-A-4-230770 improve the dispersion of the pigment, but since any method uses a solvent, Even if it is removed, a very small amount of solvent remains in the product or toner, which reduces the charge amount of toner in a special environment where it is used in a high temperature environment, and causes problems such as toner scattering in the developing section. It has become clear recently that the present inventors have studied. 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.

Further, a technique for defining the particle diameter of the colorant in the toner is known (described in Japanese Patent Nos. 2992924 and 3047310), but the degree of coloring is sufficient with these particle size distributions. However, sufficient effects were not obtained in terms of color transparency, 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, JP-A 2001-228653 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, all the raw materials are mixed at once and heated, melted and dispersed by a kneader or the like to obtain a uniform composition. After that, cool it and crush it,
A method for producing a toner having a volume average particle size of about 6 to 10 μm by classification is generally adopted. In particular,
A color toner for developing an electrostatic charge image used for forming a color image is generally constituted by dispersing and containing various chromatic dyes or pigments in a binder resin. In this case, the performance required for the toner 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, proper color development (coloring degree) and overhead projector (O
Optical transparency (transparency) when used for HP) is required. Examples of using a dye as a colorant include, for example,
JP-A-57-130043, JP-A-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.

Further, as the image forming apparatus, a plurality of visible color developed images sequentially formed on the image bearing member are sequentially superimposed and primary-transferred on an endlessly moving intermediate transfer member, and the primary transfer on the intermediate transfer member is performed. 2. Description of the Related Art There is known an intermediate transfer type image forming apparatus that collectively secondarily transfers a transfer image (toner image) onto a transfer material. In recent years, the image forming apparatus using the intermediate transfer method is advantageous in that it is downsized and there are few restrictions on the type of transfer material to which a visible image is finally transferred. It tends to be used as a device.

In such an image forming apparatus, due to a local transfer omission during the primary transfer and the secondary transfer of a toner image forming a color developed image, a transfer paper or the like which is a final image medium is caused. In the image on the transfer material, a so-called insect bite-shaped (blank character) portion may be locally generated in which no toner is locally transferred. In the case of a solid image, the insect bite-shaped image has a certain area and becomes a transfer omission. Further, in the case of a line image, transfer omission occurs so that the line is interrupted.

Such an abnormal image is likely to occur when forming a four-color full-color image. This is because the toner layer becomes thicker and the primary transfer is repeated up to four times, so that mechanical contact between the image bearing member surface and the toner and between the intermediate transfer member surface and the toner is a non-coulombic mechanical force. It is due to strong generation of force (force other than electrostatic force such as van der Waals force). Further, in the process of repeatedly performing the image forming process, a filming phenomenon occurs in which toner adheres to the surface of the intermediate transfer body in a film shape, and the adhesion between the surface of the intermediate transfer body and the toner increases. Conceivable.

Therefore, as a technique for avoiding the occurrence of such a bug-eating image, a lubricant is applied to the surfaces of the image carrier and the intermediate transfer member to reduce the adhesive force with the toner, or the adhesive force of the toner itself. Techniques such as reducing the amount with external additives have already been put to practical use in market machines. However, four-color full-color or adhesion force between toners when the transfer contact pressure generated during high-speed transfer increases, tensile rupture strength, etc. are not considered, especially for thick paper, surface-coated paper, OHP film, There was a problem with the stability of image quality during transfer.

Further, in Japanese Unexamined Patent Publication No. 8-211755, by adjusting the relative balance between the toner adhering force of the image carrier and the toner adhering force of the intermediate transfer member, the transferability is improved and the bug-like abnormality is observed. A device for preventing image generation is disclosed. However, the adhesion force of the toner at this time was a value obtained by the centrifugal force method in the powder state, and the result was different from the physical property when the transfer contact pressure was increased, which was insufficient.

In addition, the environment of high temperature and high humidity, low temperature and low humidity, etc. during storage and transportation after toner production is severe for the toner, and the toner does not aggregate even after environmental storage, and charging characteristics, fluidity, and There is no deterioration of transferability and fixing ability,
Alternatively, there is a demand for a toner having an extremely small storage stability, but no effective means for this has been found.

[0044]

SUMMARY OF THE INVENTION An object of the present invention is to stably provide the following. That is, even after storing the toner for a long time in a high temperature and high humidity environment and outputting tens of thousands of images in a high temperature and high humidity environment, there are few weakly charged and reversely charged toners excellent in charging stability, and toner scattering does not occur. To provide a toner, a developer, an image forming method, and an image forming apparatus. Moreover, not only in a normal temperature and normal humidity environment, but also in a low temperature and low humidity environment, even after outputting tens of thousands of images, the charge stability is excellent. To provide a toner, a developer, an image forming method, and an image forming apparatus, which have less charged and oppositely charged toner and which do not cause background stain (fog), and also have sufficient coloring even after outputting tens of thousands of images. To provide a toner, a developer, an image forming method, and an image forming apparatus, which have properties, light resistance, transparency, color development, sharpness, color reproducibility, saturation, and gloss. Stress in the developing machine For electrostatic charge image development that can form high-quality images that are not affected by the material of the transfer material and that have excellent cohesiveness, transferability with properly controlled adhesion between toner particles, developability, and fixability. An object is to provide an external additive, a toner, a developer, an image forming method, and an image forming apparatus, and an object is to provide an image forming apparatus and an image forming method having high durability and low maintenance as an image forming system. In addition, the present invention also provides an image forming apparatus and an image forming method that have excellent replenishment properties that have sufficient fluidity during non-compression, and excellent charge rising properties at the same time as transfer properties when toner is compressed. Image forming device and image type with excellent environmental stability as an agent, printing speed comparable to low to high speed region, no image density reduction in continuous image output, and excellent balance of fixing property and non-offset property. It is to provide a method,
Further, it is to provide an image forming apparatus and an image forming method in which a toner image is not transferred onto a sheet even when a fixed image surface is brought into close contact with a vinyl chloride resin sheet, and the fixed image is substantially curled. The present invention also provides an image forming apparatus and an image forming method that do not have the above-mentioned problem. Further, the toner image formed on the electrostatic image carrier is primarily transferred onto an intermediate transfer member, and the toner image is secondarily transferred onto a transfer material. Type image forming apparatus,
Another object of the present invention is to provide an image forming apparatus capable of high-speed output by a tandem system, which can prevent the occurrence of abnormal images such as bug-eating images, transfer dust, and poor reproducibility of fine lines.

[0045]

Means for Solving the Problems The above-mentioned problems can be solved by (1) "a toner containing at least a binder resin and a colorant, wherein the number average particle size L of the colorant particles in the toner is 0.04 μm. 80 particles% or more of ≦ L ≦ 0.2 μm and 10 particles of 0.4 μm or more
5% or less of particles of less than 0.04 μm
% Or less, the colorant particles are contained in an amount of 2% by weight to 15% by weight with respect to the toner, and the ratio of the longest diameter a to the shortest diameter b of the colorant particles and the a / b value are 1.0. To 5.0, electrostatic latent image developing toner ”, (2)“ the toner has a volume average particle diameter of 3 to 8 μm. Toner for developing an electrostatic image, (3) "the number average molecular weight (Mn) of the toner is 2
000 to 8,000, and weight average molecular weight / number average molecular weight (Mw / Mn) of 1.5 to 20, and at least 1
One peak molecular weight (Mp) is 3,000 to 13,000, the toner for developing an electrostatic image according to the above (1) or (2), (4) "the binder resin of the toner is A toner for developing an electrostatic image according to any one of the items (1) to (3), characterized in that it contains at least a polyol resin. The toner for developing an electrostatic charge image according to any one of items (1) to (4), characterized in that it contains at least a polyol resin having an epoxy resin part and a polyoxyalkylene part in the chain.
(6) "The toner for developing an electrostatic charge image according to any one of (1) to (5) above, wherein the binder resin of the toner contains at least a polyester resin", (7) "At least a wax is contained in the toner, and the dispersion average particle diameter of the wax in the toner is 3 μm.
The toner for developing an electrostatic charge image according to any one of items (1) to (6), characterized in that:
(8) “The toner has a softening point of 50 to 150 ° C., an outflow starting temperature of 60 to 130 ° C., and a glass transition temperature (Tg) of 30 to 70 ° C. The problem is solved by the electrostatic charge image developing toner according to any one of items (1) to (7).

Further, the above-mentioned problem is characterized in that (9) of the present invention includes "the toner according to at least any of the above (1) to (8) and a carrier comprising magnetic particles. It is solved by "component type developer".

Further, the above-mentioned problem is (10) of the present invention, "An image forming method characterized by using the toner or the developer according to any one of (1) to (9) above". (11) “The electrostatic charge image on the electrostatic charge image carrier is developed with a developer for developing an electrostatic charge image to form a toner image, and the transfer means is brought into contact with the surface of the electrostatic charge image carrier through a transfer material. An image forming method of electrostatically transferring the toner image onto the transfer material, wherein the developer used is a carrier composed of magnetic particles and the toner according to any one of the items (1) to (8). An image forming method characterized by being a two-component type developer composed of a toner for developing a charge image ", (12)" an electrostatic charge image divided into a plurality of colors on an electrostatic charge image carrier On the surface of the electrostatic image carrier by developing with a developer for electrostatic image development consisting of Utsushizai is brought into contact with transfer means through,
An image forming method of electrostatically transferring the toner image onto the transfer material a number of times or collectively, wherein the developer used is a carrier composed of magnetic particles and any one of the above items (1) to (8). An image forming method characterized by being a two-component type developer comprising the electrostatic image developing toner according to
(13) "An image forming method of a system in which a toner image formed on an electrostatic image carrier is primarily transferred onto an intermediate transfer member and the toner image is secondarily transferred onto a transfer material, and the toner used is An image forming method including the toner according to any one of items (1) to (8), and (14) "an intermediate transfer member for transferring a toner image formed on an electrostatic image carrier". An image forming method in which the toner image is first transferred onto the transfer material and the toner image is secondarily transferred onto a transfer material, wherein the intermediate transfer member has a static friction coefficient of 0.1 to 0.6, and the toner used is An image forming method including the toner according to any one of the items (1) to (8), and (15) “a belt driving roller and a belt driven roller. An image formed by a plurality of image forming units arranged along the transfer belt. A tandem-type color image forming method for obtaining a color image on the transfer material by sequentially superimposing and transferring the same onto a single transfer material conveyed to the transfer belt. (8) An image forming method including the toner according to any one of the items (8), (16) “Primarily transferring a toner image formed on an electrostatic charge image carrier onto an intermediate transfer member, An image forming method of secondarily transferring a toner image onto a transfer material, which is formed by a plurality of image forming units arranged along an intermediate transfer belt spanned between a belt driving roller and a belt driven roller. The color image is obtained on the intermediate transfer material by sequentially superposing and transferring the formed image on a single intermediate transfer material conveyed to the intermediate transfer belt, and then secondary transfer to the transfer material. Tandem type A color image forming method, the first (1) section, second (8) The image forming method, which comprises a toner according to any one of Items "
Will be solved by.

Further, the above-mentioned problem is characterized in that an image is obtained by loading a container filled with the toner or the developer according to any one of (17) "(1) to (9) of the present invention. Forming device ", (18)" an electrostatic charge image on the electrostatic charge image carrier is developed with a developer for developing an electrostatic charge image to form a toner image, and a transfer means is provided on the surface of the electrostatic charge image carrier via a transfer material. An image forming apparatus which electrostatically transfers the toner image onto the transfer material by bringing the toner image into contact with the carrier comprising magnetic particles and the developer according to any one of the above items (1) to (8). An image forming apparatus characterized by being a two-component developer comprising the toner for developing an electrostatic charge image described in "," (19) "a plurality of electrostatic images divided into multiple colors on an electrostatic image carrier. Electrostatic latent image is formed by developing with a developer for developing electrostatic image consisting of An image forming apparatus for electrostatically transferring the toner image to the transfer material a large number of times or collectively by bringing a transfer unit into contact with the surface of the carrier via a transfer material, wherein the developer used is a carrier composed of magnetic particles. And an image forming apparatus comprising the two-component developer comprising the toner for developing an electrostatic image according to any one of (1) to (8) above, (20) "static An image forming apparatus of the type in which a toner image formed on a charge image carrier is primarily transferred onto an intermediate transfer member, and the toner image is secondarily transferred onto a transfer material, wherein the toner used is the one described in the item (1). To (8), the image forming apparatus including the toner according to any one of (8) to (2).
1) “An image forming apparatus of a system in which a toner image formed on an electrostatic charge image carrier is primarily transferred onto an intermediate transfer member, and the toner image is secondarily transferred onto a transfer material. An image forming apparatus having a static friction coefficient of 0.1 to 0.6, and the toner to be used contains the toner according to any one of the items (1) to (8) ", (22)
“Images formed by a plurality of image forming units arranged along a transfer belt that is stretched between a belt driving roller and a belt driven roller are sequentially transferred onto a single transfer material conveyed to the transfer belt. A tandem-type color image forming apparatus for obtaining a color image on the transfer material by superposing and transferring the image, comprising the steps (1) to (8) above.
(23) "Image forming apparatus including the toner according to any one of the items 1 to 23", (23) "The toner image formed on the electrostatic image carrier is primarily transferred onto an intermediate transfer member, and the toner image is transferred. An image forming apparatus of a secondary transfer type onto a transfer material, wherein an image formed by a plurality of image forming units arranged along an intermediate transfer belt suspended between a belt driving roller and a belt driven roller. To obtain a color image on the intermediate transfer material by sequentially superposing and transferring on a single intermediate transfer material conveyed to the intermediate transfer belt,
Then, a tandem type color image forming apparatus of secondary transfer to a transfer material, characterized in that the image forming apparatus includes the toner according to any one of the items (1) to (8). Will be solved by.

The above problem is solved by (24) "the image forming method characterized by using the image forming apparatus according to any one of the items (18) to (23)" of the present invention. To be done.

As a result of intensive studies conducted by the present inventors to achieve the above object, the number average particle size L of the colorant particles in the toner is 0.04 μm ≦ in a toner containing at least a binder resin and a colorant. 80% by number or more of particles of L ≦ 0.2 μm, 10% or less of particles of 0.4 μm or more, less than 5% of particles of less than 0.04 μm, and a colorant The particles are 1% by weight to 15% by weight with respect to the toner, and the ratio of the longest diameter a to the shortest diameter b of the colorant particles, a / b, is 1.0 to 5.0. By using the toner for electrostatic image development, even after storing the toner in a high temperature and high humidity environment for a long time and outputting tens of thousands of images, there is little weak charging, less reverse charging toner, and less toner scattering. It does not occur, and it can be , Even after outputting tens of thousands of images under high temperature and high humidity environment and low temperature and low humidity environment, there are few weakly charged and reverse charging toner with excellent charge stability, no background stain (fog), and tens of thousands of images It was found that even after outputting, a high-quality image excellent in coloring property, light resistance, transparency, color forming property, vividness, color reproducibility, saturation and gloss can be formed.

Although the mechanism is currently being elucidated, the following was inferred from some analysis data. The number average particle size L of the colorant particles in the toner is 0.04.
80% by number or more of particles having μm ≦ L ≦ 0.2 μm, more preferably 90% by number or more, and further preferably 95% by number.
The presence of the above causes the wavelength of visible light (0.4 μm to 0.
7 μm) or less (0.2 μm or less) of the colorant particles to improve the colorability, color developability, color transparency, color mixability, and the like. When the number of colorant particles having a particle size of less than 0.04 μm is 5% by number or more, the crystallinity of the colorant is lowered, and particularly the light resistance is lowered, which is not preferable. In addition, the degree of coloring is also reduced. Further, the colorant particles having a size of 0.4 μm or more are 10 number% or less, more preferably 5 number% or less, so that not only the color transparency but also the toner scattering under the high temperature and high humidity environment can be prevented and the normal temperature and normal humidity environment can be prevented. In addition, it is possible to prevent the background stain (fog) under high temperature and high humidity environment and low temperature and low humidity environment. When the number of colorant particles having a particle size of 0.4 μm or more exceeds 10% by number, the aggregate of the colorant is liable to be peeled off during the generation of the toner to cause the colorant spent and the like, and the charging site of the toner is reduced, It adversely affects the charging property and image stability. In addition, the colorant is likely to be exposed on the toner surface, the surface coverage of the binder resin and the charge control agent that exerts an effect on the chargeability of the toner is lowered, and the chargeability of the total toner is adversely affected. In the environment in which the charge level is liable to be changed, such as in the environment of high temperature and high humidity, low temperature and low humidity, the effect becomes remarkable, and toner scattering and background stain occur. Further, the colorant particles are contained in the toner in an amount of 2 to 15% by weight, preferably 2 to
The content of 10% by weight, more preferably 2 to 8% by weight, in combination with the above-mentioned particle size characteristics, provides the toner with a sufficient coloring degree and an effect of preventing transfer dust, toner scattering, and background stain. ing. That is, when the amount of the colorant particles is less than 2% by weight, the degree of coloring per weight of the toner is lowered, and it is necessary to increase the thickness of the toner layer in order to have the same degree of coloring as an image. In this case, since the toner layer becomes thick, transfer dust tends to occur during toner transfer fixing. In addition, the color reproduction authenticity also decreases. On the other hand, when it exceeds 15% by weight, the coloring property is sufficient, but a problem occurs in the charging property of the toner. That is, the binder resin on the toner surface,
The amount of the charge control agent decreases, the charging ability of the toner decreases, and the above-mentioned problems occur. The colorant particles can be present in the toner in the form of primary particles, since toners which can be produced, for example, with secondary aggregation already sufficiently unraveled in the masterbatch stage, can therefore be used in toners even with small amounts of colorant. Since the binder resin can be colored to a sufficient color density and the colorant content in the toner can be reduced, the obtained toner is not so much controlled by the electrical properties of the colorant.
Since it can be controlled by the electrical properties of the other components (resin, wax), electrostatic properties and color properties (gloss, gloss,
It has the excellent content that both (including multicolor mixing) are satisfied at the same time. Further, when the ratio a / b of the longest diameter a and the shortest diameter b of the colorant particles is 1.0 to 5.0, the color development function, light resistance and transparency of the colorant are sufficiently exhibited, and the image The occurrence of unevenness can be suppressed. a
The / b value indicates the degree of circular shape of the colorant particles, and is 1 if it is a circle (sphere), and the value becomes larger as it becomes more elongated. Even if the number average particle size is the same, if the shape is different,
The dispersion state of the pigment is different, and as a result, the toner characteristics are also changed. In the present invention, it has been found that the effect is exhibited when the value is 1.0 to 5.0.

Further, the volume average particle diameter of the toner is 3-8.
By using the electrostatic image developing toner characterized by having a thickness of μm, it is possible to prevent transfer dust during toner transfer and fixing, and to exhibit sufficient colorability as a toner.
It was also effective in preventing toner scattering and background stains.

Further, the color characteristic is an important item closely related to the fixing property of the toner. The softening point of the toner is 50 to 150 ° C. and the outflow starting temperature is 60 ° C. to 130.
C., and a glass transition temperature (Tg) of 30 to 70.degree. C., which is a toner for developing an electrostatic charge image, so that toner spent is not generated and sufficient coloring property and light resistance are obtained. It has been found that transparency, color development, vividness, color reproducibility, saturation and gloss can be obtained.

Furthermore, the toner has a number average molecular weight (Mn) of 2000 to 8000, a weight average molecular weight / number average molecular weight (Mw / Mn) of 1.5 to 20, and at least one peak molecular weight (Mp). The toner for developing an electrostatic charge image having characteristics of 3000 to 13000 has sufficient fixing property, does not generate toner spent, and has sufficient coloring property, light resistance, transparency, It has been found that it is possible to obtain color developability, vividness, color reproducibility, saturation and gloss.

Further, since the binder resin of the toner contains at least the polyol resin, the dispersibility with the colorant particles is good, and sufficient tensile rupture strength, environmental stability and stable fixing characteristics are obtained. It was

Further, 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, environmental stability, stable fixing characteristics, and a vinyl chloride resin on the copy-fixed image surface are obtained. It is possible to prevent the transfer of the toner image to the sheet when it is in close contact with the resin sheet, and especially when used for color toner, it is effective in color reproducibility, stable gloss, and curl prevention of copy-fixed images. I found it.

Further, since the binder resin of the toner contains at least the polyester resin portion, not only good dispersibility with the colorant particles but also a stretchable and adhesive property is balanced, and a more stable transfer is achieved. Property, developability,
Fixing properties were obtained.

When the toner contains at least wax and is used as a release agent, the dispersed diameter of the wax in the toner is 3 μm or less, more preferably 2 μm or less, and further preferably 1 μm or less. In addition, the dispersibility of the colorant is improved, and the wax as the release agent at the time of fixing the toner prevents the hot offset due to the exudation due to heat, and the adhesive force between the toners can be reduced to improve the transferability and the transfer rate. It is possible to prevent missing images in the character area, transfer dust 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 toner is used. The development characteristics were well balanced in the adhesive force with the carrier, had a sufficient bulk density with little stress fluctuation as a developer, and had excellent charge rising properties and environmental charge stability. Further, a developing system having an excellent toner density controllability by a bulk density sensor or the like was obtained.

When the polyol resin terminal of the toner binder resin is inactive, the toner can be environmentally stable and less harmful. 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. Epoxy resin has at least two kinds of bisphenol A having different number average molecular weights in order to obtain stable fixing characteristics and gloss.
Type epoxy resin, the number average molecular weight of low molecular weight component is 36
0 to 2000, and the number average molecular weight of the high molecular weight component is 3
It is preferably from 000 to 10,000. Further, the low molecular weight component is 20 to 50 wt% and the high molecular weight component is 5 to 40 w.
It is preferably t%. 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. Further, if the amount of the high molecular weight component is too large or if the molecular weight is higher than 10,000, the gloss may be insufficient and the fixability may be deteriorated.

Examples of the compound used in the present invention include the followings as the alkylene oxide adduct of dihydric phenol. 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).

[0062]

[Chemical 1]

The alkylene oxide adduct of dihydric phenol or its glycidyl ether is preferably contained in an amount of 10 to 40 wt% with respect to the polyol resin. If the amount is too small, problems such as curling occur, and if n + m is 8 or more, or if the amount is too large, the gloss may be too high, and 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. The following are examples of monohydric phenols. Phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol and the like can be mentioned. Two
Examples of the primary 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 2
Examples thereof include polyhydric 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.

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, which is a reaction residue, can be reduced. It is possible to obtain a toner having excellent safety and resin characteristics.

Further, in the above image forming apparatus, the electrostatic charge image divided into multiple colors on the electrostatic charge image carrier is developed with an electrostatic charge image developing developer having a plurality of colors to form a toner image. An image formation method characterized by an electrostatic charge image developing method in which a transfer means is brought into contact with the surface of an electrostatic charge image carrier through a transfer material to electrostatically transfer the toner image onto the transfer material a number of times or collectively. By using the apparatus, it is possible to obtain an image forming apparatus having high image quality, which has few transfer defects at the time of transfer, and particularly has few image defects related to color color reproducibility.

Further, a multicolor developing device provided with a developing roll and a developing blade for uniformly controlling the layer thickness of the developer supplied onto the developing roll is used to form a multicolor image formed on the electrostatic image carrier. The electrostatic latent image divided into two is developed on a plurality of electrostatic charge image carriers corresponding to respective colors by developers corresponding to respective colors, and is transferred to the surface of the electrostatic charge image carriers through a transfer material to transfer means. And an electrostatic charge image forming apparatus for sequentially electrostatically transferring the toner image onto the transfer material, wherein the developer used is a one-component developer composed of the toner. A compact, high-quality image forming apparatus having few transfer defects at the time of transfer, particularly having few image defects related to color color reproducibility, was obtained.

Further, the intermediate transfer member used in the image forming apparatus of the system in which the toner image formed on the electrostatic image carrier is primarily transferred onto the intermediate transfer member and the toner image is secondarily transferred onto the transfer material is hard. Since the image forming apparatus is characterized by being an elastic intermediate belt satisfying 10 ° ≦ HS ≦ 65 ° (JIS-A), excellent transferability without worm-eating images, good fine line reproducibility, and high image quality. An image can be formed. It is necessary to adjust the optimum hardness depending on the layer thickness of the belt. Hardness 1
Those below 0 ° JIS-A are very difficult to mold with high dimensional accuracy. This is because it is susceptible to shrinkage and expansion during molding. Further, in the case of softening, it is a general method to add an oil component to the base material, but there is a disadvantage that the oil component exudes when continuously operated in a pressurized state. It was found that this contaminates the photoconductor that comes into contact with the surface of the intermediate transfer member and causes lateral stripe unevenness. Generally, a surface layer is provided to improve releasability, but in order to provide a complete exudation prevention effect, the surface layer has high required quality such as durability quality, so it is necessary to select materials and secure characteristics. It will be difficult. On the other hand, those having a hardness of 65 ° JIS-A or higher can be molded with high accuracy due to the increased hardness, and the oil content is not included or can be suppressed to a low level. Although it is possible, the effect of improving the transferability such as missing characters is not obtained, and it becomes difficult to stretch the roller.

Further, the coefficient of static friction of the intermediate transfer member is 0.
1 to 0.6, and more preferably 0.3 to 0.5, by using the image forming apparatus, the sliding condition between the toner and the intermediate transfer member becomes smooth, and the transfer property is improved, There is less background stain, less waste toner,
An image forming apparatus that consumes less toner is obtained.

In the above-mentioned image forming apparatus, a plurality of multicolor developing devices provided with a developing roll and a developing blade for uniformly controlling the layer thickness of the developer supplied onto the developing roll are mounted on the electrostatic image carrier. The electrostatic latent image divided into multicolors formed on the surface is developed on a plurality of electrostatic charge image carriers corresponding to the respective colors by using a developer corresponding to each color, and the electrostatic charge image carrier surface is developed. An image forming apparatus characterized by having an electrostatic charge image developing and recording apparatus for sequentially electrostatically transferring the toner image onto the transfer material by bringing the transfer means into contact with the transfer material via the transfer material, thereby providing excellent color reproducibility. In addition, an image forming apparatus having high image quality with few transfer defects during transfer and few image defects was obtained.

Further, in the image forming apparatus, the image formed by a plurality of image forming units arranged along the transfer belt suspended between the belt driving roller and the belt driven roller is conveyed to the transfer belt. A tandem type color image forming apparatus that obtains a color image on the transfer material by sequentially superposing and transferring the same on a single transfer material is provided, which is compatible with high-speed printing and
An image forming apparatus having high image quality, which is hardly affected by the material of the transfer material such as P, thick paper, and coated paper, has few transfer defects during the transfer, and has few image defects is obtained.

The present invention will be described in detail below. here,
As for the toner for developing an electrostatic charge image 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, known ones can be used as long as the conditions are satisfied.

(Masterbatch Colorant) In the present invention, a masterbatch colorant in which the resin and the colorant are mixed and kneaded in a ratio of about 1: 1 in advance is used for the purpose of improving the affinity between the resin and the colorant. You can also The colorant can be used as long as it is a substance that colors a pigment, a dye or the like. The ratio of the resin to the colorant is 20:80 to 80:20, more preferably
30:70 to 70:30, more preferably 40:60
˜60: 40. Further, the resin used here does not necessarily have to be the binder resin itself of the toner, and a polyol resin having a good affinity with the binder resin of the toner,
A polyester resin or the like can be more preferably used. For these, the same resins as the binder resin described later can be used. Further, by heating and kneading a resin having a low polar solvent soluble component amount and a colorant without using an organic solvent, a masterbatch colorant having excellent environmental charging stability can be obtained. Furthermore, the dispersibility can be further improved by using a dry powder pigment and water as a method for wetting the resin.
In the first place, the primary particles of the pigment are 0.001-0.1μ
Although it is very small as m, in the dry powder state of the raw material, large aggregates of several μm size are formed. The ideal dispersion of the pigment is to disintegrate this agglomerate and separate it into primary particles.
Reducing the size of primary particles of about 1 to 0.1 μm to less than that is a limit 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 aggregate to be crushed is that the surrounding resin penetrates into the voids inside the aggregate 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 the inside of 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 above the softening point, the viscosity becomes low,
A masterbatch colorant in which the pigment is dispersed in a state close to the primary particles by being able to efficiently wet the agglomerate and at the same time being replaced with water near the boiling point temperature inside the agglomerate by an effect similar to so-called flushing. Can be obtained.
Further, in the process of evaporating water, the temperature of the kneaded product is 10 because the heat of vaporization accompanying the evaporation of water is taken from the kneaded product.
Since it is maintained at a relatively low temperature and high viscosity of 0 ° C. or less, it also has an effect that shearing force is effectively applied to the pigment aggregate. As the open-type kneader for producing the masterbatch colorant, in addition to the usual two-roll, three-roll method, a method of using a Banbury mixer as an open type, a continuous two-roll kneader manufactured by Mitsui Mining Co., Ltd., etc. is used. be able to.

(Dispersion State of Colorant Particles) The number average particle diameter of the colorant according to the present invention is TEM for an ultrathin section of the toner.
It can be analyzed by observing with a (transmission electron microscope). The TEM image is loaded into a computer and the number average particle size is determined by image processing software. Hereinafter, the measurement conditions and the like will be described, but the device and method are not particularly limited as long as the same results can be obtained without being limited to these conditions.

TEM is Hitachi H-9000NAR
Was measured at an acceleration voltage of 300 kV. The magnification was increased to a level at which particles having a diameter of 0.04 μm can be identified and observed (for example, 37500 times to 100000 times). As the image processing software, an image analyzer (Luzex AP) manufactured by Nireco Corporation was used, and the TEM image was converted into binary image data. The number of colorant particles was randomly changed and measured until the number of particles became 600 or more, and the number average particle size of the colorant and the particle size distribution were obtained. The particle diameter of the present invention is a value defined by the diameter obtained by spherically approximating each colorant particle image. Similarly, the ratio of the longest diameter to the shortest diameter of the colorant can be analyzed by image analysis software. The shortest diameter is also called a minor axis, and corresponds to the length of the minor axis of an equivalent ellipse (that is, an ellipse having the same area and equal first and second moments) of an object. What is the longest diameter?
Also known as the major axis, the equivalent ellipse of an object (that is, an ellipse with the same area and equal first and second moments)
Corresponds to the length of the long axis of. The ratio of the longest diameter to the shortest diameter is
If it is a perfect circle (sphere), it will be 1.0. As the image analysis software, Image Plus Pro is also preferable. An optical microscope, a CCD camera image, a laser microscope or the like can be used as a means for observing the particle size of the colorant other than TEM, but TEM is the most excellent in terms of spatial resolution and is more preferable.

(Colorant) As the colorant of the toner of the present invention, 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 Vio Red B, Methyl Vio Red Lake, Indanthrene Blue BC, Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthragen Yellow BGL, Isoindo Linon Yellow, Bengala, Lead Tan, Lead Vermilion, Cadmium Red, Cadmium Mercury Red, Antimon Vermilion, Permanent Red 4R, Para Red, Fire Red, Parachlor Ortho Nitroaniline Red, Resor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4
RH), Fast Scarlet 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 BL, Bordeaux 1
0B, 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 rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, B
C), indigo, ultramarine, navy blue, anthraquinone blue,
Fast violet B, methyl violet rake,
Cobalt purple, manganese purple, dioxazine violet,
Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Flower, Lithopone and A mixture of them and the like. Preferably, polycondensed azo pigments, insoluble azo pigments, quinacridone pigments, carmine pigments, naphthol carmine pigments, isoindolinone pigments, perylene pigments, anthraquinone pigments, high light resistance of copper phthalocyanine pigments, etc. A pigment having high resin dispersibility is preferable.

As the magenta color pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3
7,38,39,40,41,48,48: 1,49,
50, 51, 52, 53, 53: 1, 54, 55, 5
7,57: 1,58,60,63,64,68,81,
83, 87, 88, 89, 90, 112, 114, 12
2,123,163,177,179,202,20
6,207,209,211; C.I. I. Pigment Violet 19; C.I. I. Bat red 1, 2, 10, 1
3, 15, 23, 29, 35 and the like.

As the color pigment for cyan, 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, Green 36 and the like can be mentioned.

As the color pigment for yellow, C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6,
7, 10, 11, 12, 13, 14, 15, 16, 1
7,23,55,65,73,74,83,97,11
0, 151, 154, 180; C.I. I. Butt yellow 1, 3, 20, orange 36, etc. are mentioned. The content of the colorant is 1 to 15% by weight, more preferably 2 to 10% by weight, based on the toner. 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, inorganic fine particles or hydrophobically treated inorganic fine particles can be used in combination, but the average particle diameter of the hydrophobically treated primary particles is 1 to 100 nm, more preferably 5 nm. It is more desirable to include at least two types of inorganic fine particles of 70 nm or less. 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. Moreover, the specific surface area by the BET method is 20 to 500 m.
It is preferably ² / g. Known materials can be used as long as they satisfy the conditions. For example, fine silica particles, hydrophobic silica, fatty acid metal salts (zinc stearate,
Aluminum stearate, etc.), metal oxides (titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers and the like.

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 with methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, or the like. 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, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like. Among them, silica and titanium dioxide are particularly preferable. The addition amount can be 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the toner. The average particle size of the primary particles of the inorganic fine particles is 100 nm or less, preferably 3 nm or more and 70 nm or less. 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.

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

(Resin particles) Polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, polymethacrylate ester / acrylic acid ester copolymer, polycondensation system of silicone, benzoguanamine, nylon, etc., thermosetting resin Polymer particles according to.
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 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the toner.
Can be used.

(Softening Point, Outflow Start Temperature) The softening point of the toner of the present invention is measured by a softening point measuring device (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 under the following conditions using the following differential scanning calorimeter. -Differential scanning calorimeter: SEIKO1DSC100 SEIKO1SSC5040 (Disk Station) -Measurement conditions: Temperature range: 25 to 150 ° C Temperature rising rate: 10 ° C / min Sampling time: 0.5sec Sample amount: 10mg

(Molecular weight) The number average molecular weight (Mn), weight average molecular weight (Mw) and peak molecular weight (Mp) were measured by GPC (gel permeation chromatography) as follows. 80 mg of sample is added to THF10
A sample solution is prepared by dissolving in ml, 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 + GLR40
0M + GLR400 (all manufactured by Hitachi, Ltd.)-Column temperature: 40 ° C-Mobile phase (flow rate): THF (1 ml / min) -Peak detection method: UV (254 nm)

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

(Static Friction Coefficient) The static friction coefficient of the intermediate transfer member of the present invention can be determined as follows. In this embodiment, a portable friction meter (HEIDON Tribogear Muse TYP manufactured by Shinto Kagaku Co., Ltd.) is used.
E94i200) was used. The gravure meter is used by sandwiching a pressure plate on the inner peripheral side of the belt in order to make the contact between the photosensitive belt and the intermediate transfer member and the flat indenter of the spectacle friction meter uniform. Here, instead of the photoconductor belt and the intermediate transfer member,
It is also possible to use drum-shaped ones. In this case, the contact area is slightly reduced and the data variation is slightly increased, but averaging does not pose a problem.

The static friction coefficient can be obtained by measuring the maximum frictional force acting between the flat indenter provided at the lower portion of the static friction meter and the belt, and the ratio of the forces pushing each other in the vertical direction. Further, this plane indenter is as light as about 40 gf with a metal probe of φ40 and can avoid problems such as scratches on the belt surface. Further, a cushioning material is attached between the flat indenter and the belt for measurement. In this embodiment, a thin cloth is used as the cushioning material, but
Natural fibers such as hemp, synthetic resin fibers such as rayon and polypropylene, metal fibers and non-woven fabrics can also be used. Further, a foam having an appropriate hardness, a thin film having an appropriate unevenness, etc. may also be used.

The reason for providing such a cushioning material between the flat indenter and the belt is as follows. That is,
The intermediate transfer body (or photoreceptor belt) is deformed due to the surface roughness and the softness of the material itself, and since the toner is powder, it follows the irregularities on the belt surface and also adheres to the bottom of the concave portion. Therefore, the coefficient of friction of the belt surface, which is expressed as the actual adhesive force between the belt and the toner, needs to be a measured value that includes such concave portions of the uneven surface. Therefore, the measurement is performed using a cushioning material made of a material that is compatible with the uneven surface and is soft and easy to unravel so as not to damage the mating member. This makes it possible to apply an average pressure to the belt, so that an accurate friction coefficient can be obtained. The fiber bundle of the cloth used in this embodiment has a thickness of about 0.5 mm, and the fibers have a thickness of about 5 to 30 μm. Therefore, if this is attached between the plane indenter and the belt and pressed. The fibers are moderately deformed and sometimes loosen little by little to apply an average pressure to the belt. It should be noted that what is used for the cushioning material may be selected according to the surface roughness and softness of the target surface.

By the way, in addition to the measurement by the above static friction meter, the angle θ at which the indenter begins to slide down with a gradient as described in JP-A-8-211575.
There is also a method of obtaining and calculating from μ = tan θ. In the same publication, AS of HEIDON-14DR manufactured by Shinto Kagaku Co., Ltd.
A polyethylene terephthalate (PET) sheet is wound around a plane indenter specified by TM D-1894, a vertical load of 200 gf is applied between the object to be measured and the plane indenter, and 100 mm / min. The sliding resistance of the PET sheet and the sample sheet when the sample sheet is moved at the speed of is measured. However, PE used for the indenter
As described above, the stretchable resin material such as T cannot reproduce the state in which the toner is deformed and adheres according to the irregularities of the intermediate transfer member, and the frictional force is seen only by the convex portions on the surface. Further, in such a measuring instrument, a target sheet is cut out to form a sample sheet, so that it is a half-destructive inspection, and real-time evaluation such as occasional measurement during running cannot be performed. Therefore, a portable static tribometer is desirable. However, the device is not limited to the above-mentioned device, and the device and condition may not be particularly measured as long as the device can perform measurement based on the same principle.

(Dispersion Average Particle Diameter of Wax) The dispersion average particle diameter of the wax according to the present invention is determined by measuring the ultrathin section of the toner by TE.
It can be analyzed by observing with M (transmission electron microscope). If necessary, the TEM image is taken into a computer and the dispersed average particle size is determined by image processing software. TE
As a means other than M, an optical microscope, a CCD camera image, a laser microscope, or the like can be used, and there is no particular limitation as long as it can measure the average particle diameter.

(Binder Resin) As the binder resin of the toner of the present invention, polymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene and their substitution products; 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, polyester resin and polyol resin are more preferable.

More preferably, as described in the means for solving the problem, 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, a sufficient compressive strength can be obtained. , Tensile rupture strength, environmental stability, stable fixing characteristics, it is possible to prevent transfer of the toner image to the sheet when adhered to the vinyl chloride resin sheet on the copy-fixed image surface, especially used for color toner If color reproducibility,
It is more preferable because it has effects such as stable gloss and prevention of curling 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.

Here, various types of polyester resins can be used, but in particular, at least one selected from divalent carboxylic acids and their lower alkyl esters and acid anhydrides, and the following general formula ( A diol component represented by 2);

[0101]

[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. ), At least one selected from trivalent or higher polyvalent carboxylic acids and their lower alkyl esters and acid anhydrides, and trivalent or higher polyvalent alcohols, and a polyester resin obtained by reacting the above Is preferred.

Examples of the divalent carboxylic acid, its lower alkyl ester and its acid anhydride include terephthalic acid, isophthalic acid, sebacic acid, isodecylsuccinic acid, maleic acid, fumaric acid, and their monomethyl and monoethyl groups. , Dimethyl and diethyl esters, and phthalic anhydride, maleic anhydride, etc., and terephthalic acid, isophthalic acid and these dimethyl esters are particularly 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.

An example of the diol component represented by the above general formula (2) is 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, but in particular, polyoxypropylene with 2.1 ≦ n ≦ 2.5
(N) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene- (n) -2,2-bis (4-hydroxyphenyl) propane with 2.0 ≦ n ≦ 2.5 are 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, an aliphatic diol such as ethylene glycol, diethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol or propylene glycol should be used. Is also possible.

Examples of the trivalent or higher polyvalent carboxylic acid, its lower alkyl ester and its acid anhydride are:
1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,3,5-benzenetricarboxylic acid, 1,2,
4-cyclohexanetricarboxylic acid, 2,5,7-naphthylenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,
2,5-hexatricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8-
Examples include octane tetracarboxylic acid, empol trimer acid and their monomethyl, monoethyl, dimethyl and diethyl esters.

Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, and soy sauce. Sugar, 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 total 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. ) 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. 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 4 Primary ammonium salt), alkyl amide, 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, the quaternary ammonium salt Bontron P-51, the metal-containing azo dye Bontron S-34, the oxynaphthoic acid metal complex E-82, and the salicylic acid metal complex. E-8
4, E-89 (above, manufactured by Orient Chemical Industry Co., Ltd.) of a phenol-based condensate, TP-302, TP-415 (above manufactured by Hodogaya Chemical Industry Co., Ltd.) of a quaternary ammonium salt molybdenum complex, quaternary ammonium Salt copy charge PSY
VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt N
EG VP2036, Copy Charge NX VP43
4 (above, manufactured by Hoechst), LRA-901, a boron complex LR-147 (manufactured by Nippon Carlit), copper phthalocyanine, perylene, quinacridone, azo pigments, other sulfonic acid groups, carboxyl groups, quaternary ammonium salts. Polymer compounds having functional groups such as
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.
Although not uniquely limited, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The preferred range is 2 to 5 parts by weight. If it exceeds 10 parts by weight, the chargeability of the toner is too great, the effect of the main charge control agent is diminished, the static electrostatic attraction with the developing roller is increased, the fluidity of the developer is lowered, and the image density is lowered. Cause decline.

(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. The magnetic carrier has a particle size of 20 to 2
Iron powder, ferrite powder, magnetite powder of about 00 μm,
A conventionally known carrier such as a magnetic resin carrier 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, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene, vinylidene fluoride and non-fluorine Fluoroterpolymers such as terpolymers with monomers, and silicone resins can be used. The film thickness of these coating materials is 0.01 to 3 μm, more preferably 0.1 to 0.3 μm.
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. 3μ more
When it is m 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 diameter is larger than 1 μm, it becomes difficult to control the electric resistance. Further, the toner of the present invention can be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(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 thereof include alloys that exhibit ferromagnetism, for example, alloys of the type called Heusler alloys containing manganese and copper, such as manganese copper aluminum, manganese-copper-tin, 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 substance is preferably 10 to 70 parts by weight, and particularly 20 to 100 parts by weight of the obtained toner.
It is preferably about 50 parts by weight.

(Wax) In order to provide the toner or developer with a releasing property for fixing, it is preferable to include wax in the toner or developer. In particular, when an oilless fixing device in which oil is not applied to the image fixing portion is used, it is preferable that the toner contains wax. The wax has a melting point of 40 to 120 ° C.,
It is particularly preferably 50 to 110 ° C. If the melting point of the wax is too high, the fixability at low temperatures may be insufficient, while if the melting point is too low, the offset resistance and durability may be reduced. 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 preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight.

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, aliphatic 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 dispersion diameter is 3 μm or more, the wax outflow property and the transfer material peeling property are improved, but the high temperature and high humidity durability as a toner, the charging stability and the like are deteriorated.

The oxidized rice wax is obtained by air-oxidizing rice bran wax. The acid value is preferably from 10 to 30, and when it is less than 10, the fixing lower limit temperature increases and the low temperature fixing property becomes insufficient, and when it is more than 30, the cold offset temperature increases and the low temperature fixing property also becomes insufficient. Sazol wax is Sazol wax H1, H2, A1, A2, A3, A4, A6, A7
A14, C1, C2, SPRAY30, SPRAY40
Etc. can be used, but among them, H1, H2, SPRAY3
0 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 is 1 to 1 with respect to 100 parts by weight of the binder resin.
By containing 5 parts by weight, preferably 2 to 10 parts by weight, the good results shown above can be obtained.

(Cleaning Property Improver) A cleaning property improver for removing the developer after transfer remaining 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 added to the surface. Examples of the cleaning property improver include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, and polymer fine particles produced by soap-free emulsion polymerization such as polymethylmethacrylate fine particles and polystyrene fine particles. It is preferable that the fine polymer particles have a relatively narrow particle size distribution and a volume average particle diameter of 0.01 to 1 μm. The content of the cleaning property improver is 0.
001 to 5 parts by weight is preferable, and 0.001 to 1 part by weight is particularly preferable.

(Manufacturing Method) As the manufacturing method of the present invention, a known manufacturing method can be used under certain conditions. A method for producing a toner having at least a step of mechanically mixing a developer component containing a binder resin, a main charge control agent and a pigment, 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 (by-product) other than the particles to be the product mentioned here, fine particles or coarse particles other than the components to be the product of the desired particle size obtained in the crushing step and subsequent steps are carried out. It means fine particles or coarse particles other than the components that become the product of the desired particle size generated in the classification step. 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.

After the above mixing steps are completed, 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 determined with reference to the softening point of the binder resin. If the temperature is lower than the softening point, the cutting will be severe, and if it is too high, the dispersion will not proceed. When controlling the amount of volatile components in the toner, it is more preferable to set the melt-kneading temperature, time, and atmosphere while optimal conditions are being monitored while monitoring the amount of residual volatile components at that time.

After the above melt-kneading process is completed, the kneaded product is then pulverized. In this pulverizing step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, it is preferable to use a method in which the particles are crushed by colliding with a collision plate in a jet stream, or crushed in a narrow gap between a mechanically rotating rotor and a stator.

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 5 to 20 μm. When the volume average particle diameter of the toner is 2 to 8 μm, transfer dust during toner transfer and fixing can be prevented, and sufficient colorability as a toner can be exhibited. Also,
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.

When preparing the toner, in order to improve the fluidity, storability, developability and transferability of the toner, the toner of the present invention is further added to the above-produced toner of 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 the 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 are V-type mixers, rocking mixers, Loedige mixers, Nauta mixers,
Henschel mixer etc. are mentioned.

As other manufacturing method, a polymerization method, a capsule method or the like can be used. The outline of these manufacturing methods will be described below. (Polymerization method) A polymerizable monomer, a low molecular weight polymer, and if necessary, a polymerization initiator and a colorant 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) A resin and, if necessary, a colorant and the like are kneaded by a kneader to obtain a molten toner core material. 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.

[0129]

BEST MODE FOR CARRYING OUT THE INVENTION (Intermediate Transfer Member) An embodiment of the intermediate transfer member of the transfer system of the present invention 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) as an image carrier, a charging roller (20) as a charging device, an exposure device (30), a cleaning device (60) having a cleaning blade, and a charge eliminator. A charge eliminating lamp (70) as a device, a developing device (40), and an intermediate transfer member (50) as an intermediate transfer member are provided. The intermediate transfer member (50) is suspended by a plurality of suspension rollers (51) and is configured to run endlessly in the direction of the arrow by a driving means 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 that faces the intermediate transfer member (50) and transfers a developed image to a transfer paper (100) as a final transfer material. Is supplied with a transfer bias by a power supply device (not shown). A corona charger (52) as a charge applying means is provided around the intermediate transfer body (50).

The developing device (40) includes a developing belt (41) as a developer carrying member, a black (hereinafter, referred to as Bk) developing unit (45K) and a yellow (which are provided around the developing belt (41). Hereinafter, it is composed of a Y developing unit (45Y), 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). Then, it moves at almost the same speed as the photoconductor (10).

Since the construction of each developing unit is common,
The following description will be given only for the Bk developing unit (45K), and the other developing units (45Y), (45M),
For (45C), the Bk developing unit (45
For the parts corresponding to those in K), Y, M, and C are added after the numbers given to those in the unit, and the description is omitted. The developing unit (45K) includes a developing tank (42K) containing a high-viscosity and high-concentration liquid developer containing toner particles and a carrier liquid component, and a lower part for the liquid developer in the developing tank (42K). The pumping roller (43K) arranged so as to be immersed, and the pumping roller (4K
3K) and a coating roller (44K) for thinning the developer and coating it on the developing belt (41). The coating roller (44K) has conductivity, and a predetermined bias is applied from a power source (not shown).

As a device configuration of the copying machine according to the present embodiment, in addition to the device configuration shown in FIG. 1, a developing unit (45) for each color as shown in FIG.
It may be a device configuration provided around 0).

Next, the operation of the copying machine according to this embodiment will be described. In FIG. 1, the photosensitive member (10) is uniformly charged by a charging roller (20) while being rotationally driven in the direction of an arrow, and then an exposure device (30) projects an image of reflected light from an original by an optical system (not shown). To form an electrostatic latent image on the photoconductor (10). This electrostatic latent image is transferred to the developing device (4
0) to develop a toner image as a visible image. The thin developer layer on the developing belt (41) is in a thin layer state due to contact with the photoreceptor in the developing area.
It is peeled off from 1) and moves to the portion on the photoconductor (10) where the latent image is formed. The toner image developed by the developing device (40) is transferred to the intermediate transfer member (50) at the contact portion (primary transfer region) with the photosensitive member (10) and the intermediate transfer member (50) moving at a constant speed. Is transferred to the surface of the (primary transfer). Three
When color or four colors are superimposed 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 provided with the photosensitive member (1) in the rotating direction of the intermediate transfer member (50).
0) and the intermediate transfer body (50) at the downstream side of the contact facing portion, and at the upstream side of the contact facing portion between the intermediate transfer body (50) and the transfer paper (100). Then, the corona charger (52) imparts to the toner image a true charge having the same polarity as the charging polarity of the toner particles forming the toner image, and good transfer is made to the transfer paper (100). Sufficient charge to the toner image. The toner image is charged by the corona charger (52) and then transferred onto the transfer paper (100) in the direction of the arrow from a paper supply unit (not shown) by the transfer bias from the transfer roller (80). Transferred all at once (secondary transfer). After that, the transfer paper (100) to which the toner image is transferred is separated from the photoconductor (10) by a separating device (not shown), is subjected to a fixing process by a fixing device (not shown), and is then discharged 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, as described above, preferably 0.1 to 0.6, more preferably 0.
3 to 0.5 is good. The volume resistance of the intermediate transfer member is several Ωcm.
It is preferably 10 ³ Ωcm 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 known materials 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 conventionally been 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. Color images are 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.

Further, recently, there is an increasing demand for forming a full-color image on various types of paper, for example, Japanese paper or paper with intentional unevenness. 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-based 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.

Examples of elastic rubber and elastomer include butyl rubber, fluorine rubber, acrylic rubber, EPDM and NB.
R, acrylonitrile-butadiene-styrene rubber natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-
Propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, recone rubber, fluororubber,
Polysulfide rubber, polynorbornene rubber, hydrogenated nitrile rubber, thermoplastic elastomer (for example, polystyrene type, polyolefin type, polyvinyl chloride type, polyurethane type,
One type or two or more types selected from the group consisting of polyamide type, polyurea, polyester type, fluororesin type) and the like can be used. However, it goes without saying that the material is not limited to the above materials.

The resistance adjusting conductive agent is not particularly limited,
For example, carbon black, graphite, metal powder such as aluminum and nickel, tin oxide, titanium oxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), indium oxide-tin oxide composite oxide. The conductive metal oxide such as a material (ITO) and 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 adhesion force of the toner and the cleaning property.
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. body,
One kind or two or more kinds of particles or particles having different particle diameters can be dispersed and used. Also, by heat-treating like a fluorine-based rubber material, a fluorine-rich layer is formed on the surface to reduce the surface energy. It is also possible to use the prepared one.

The method for manufacturing the belt is not limited. For example, a centrifugal molding method in which a material is poured into a rotating cylindrical mold to form a belt, a spray coating method in which a liquid coating is sprayed to form a film, and a dipping method in which a cylindrical mold is immersed in a solution of a material and pulled up. There is a casting method of injecting into the inner mold and the outer mold, and a method of winding the compound around a cylindrical mold and performing vulcanization polishing, but it is not limited to this, and a belt is manufactured by combining a plurality of manufacturing methods. It is common to

As a method of preventing the expansion of the elastic belt,
There are a method of forming a rubber layer on a core resin layer having a small elongation, a method of adding a material for preventing elongation to the core layer, and the like, but the manufacturing method is not particularly limited. The material constituting the core layer for preventing elongation is, for example, natural fibers such as cotton and silk, polyester fibers, nylon fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, Polyurethane fiber, polyacetal fiber, polyfluoroethylene fiber, synthetic fiber such as phenol fiber, carbon fiber, glass fiber,
A woven fabric or thread can be obtained by using one or more selected from the group consisting of inorganic fibers such as boron fibers, metal fibers such as iron fibers and 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 on a mold and a coating layer is provided thereon, or a woven fabric woven in a tubular shape is used as a liquid rubber. And the like, a method of providing a coating layer on one side or both sides of the core layer by immersing the thread in a die or the like in a spiral shape at an arbitrary pitch, and providing a coating layer thereon. The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the expansion and contraction of the surface becomes large and cracks are likely to occur in the surface layer. Further, 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 image becomes more stretched and fringing.

(Tandem Color Image Forming Apparatus) An embodiment of the tandem color image forming apparatus of the present invention will be described. In the tandem type electrophotographic apparatus, as shown in FIG. 3, 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 transferred directly to the intermediate transfer member (4) sequentially by the primary transfer device (2), and then the intermediate transfer member is transferred. (4) There is an indirect transfer system in which the above image is collectively transferred onto the sheet (s) by the secondary transfer device (5). The transfer device (5) shown in the figure 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 on the upstream side of the tandem type image forming apparatus (T) in which the photoconductors (1) are arranged.
Since the fixing device (7) must be arranged on the downstream side, there is a drawback that the size is increased in the sheet conveying direction. On the other hand, in the latter, the secondary transfer position can be set relatively freely. The sheet feeding device (6) and the fixing device (7) can be arranged so as to overlap with the tandem image forming apparatus (T), which is advantageous in that the size can be reduced.

In the former case, the fixing device (7) is arranged close to the tandem type image forming device (T) in order not to increase the size in the sheet conveying direction. 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 end of the sheet (s) enters the fixing device (7) (especially for a thick sheet). And 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, the fixing device (7) affects the image formation on the upstream side. There are easy drawbacks. In contrast,
In the latter case, the fixing device (7) can be arranged with a sufficient margin that allows the sheet (s) to bend.
It is possible to make the fixing device (7) hardly influence the image formation. From the above, recently, the tandem type electrophotographic apparatus, in particular, the indirect transfer type has attracted attention.

In this type of color electrophotographic apparatus, as shown in FIG. 4, the transfer residual toner remaining on the photoconductor (1) after the primary transfer is removed by the photoconductor cleaning device (8). Clean the surface of the photoconductor (1),
It was prepared for another image formation. Further, the transfer residual toner remaining on the intermediate transfer body (4) after the secondary transfer is removed by the intermediate transfer body cleaning device (9) to clean the surface of the intermediate transfer body (4) to prepare for the image formation again. Was there.

FIG. 5 shows an embodiment of the present invention, which is a tandem type indirect transfer type electrophotographic apparatus. In the figure, reference numeral (101) is a copying apparatus main body, (200) is a paper feed table on which the copying apparatus is placed, and (300) is a copying apparatus main body (10).
1) A scanner mounted on top, and (400) is an automatic document feeder (ADF) mounted on it. An endless belt-shaped intermediate transfer member (11) is provided at the center of the copying apparatus main body (101). Then, as shown in FIG. 5, in the illustrated example, three support rollers (14), (15),
It can be rotated and conveyed in the clockwise direction in the figure by being hung around (16). In this example, the second supporting roller (1
On the left of 5), an intermediate transfer member cleaning device (17) for removing the residual toner remaining on the intermediate transfer member (11) after image transfer is provided. Further, among the three, on the intermediate transfer body (11) stretched between the first support roller (14) and the second support roller (15), yellow, cyan, and magenta are provided along the transport direction. , Black four image forming means (18) are arranged side by side to form a tandem image forming apparatus (29).

An exposure device (21) is further provided on the tandem image forming device (29) as shown in FIG. On the other hand, a secondary transfer device (22) is provided on the side opposite to the tandem image forming device (29) with the intermediate transfer member (11) interposed therebetween.
Equipped with. In the illustrated example, the secondary transfer device (22) is configured by spanning a secondary transfer belt (24), which is an endless belt, between two rollers (23), and a secondary transfer device (22) is provided with an intermediate transfer member (11). It is pressed against the support roller (16) of No. 3 and arranged,
The image on the intermediate transfer body (11) is transferred to a sheet.

Next to the secondary transfer device (22), a fixing device (25) for fixing the transferred image on the sheet is provided. The fixing device (25) is a fixing belt (26) which is an endless belt.
The pressure roller (27) is pressed against the structure. The above-mentioned secondary transfer device (22) also has a sheet conveying function of conveying the sheet after the image transfer to this 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, an image is recorded on both sides of the sheet under the secondary transfer device (22) and the fixing device (25) in parallel with the tandem image forming device (29) described above. Sheet reversing device (2
8) is provided. Now, when making a copy using this color electrophotographic apparatus, the automatic document feeder (400)
Place the original on the original table (31). Alternatively, the automatic document feeder (400) is opened, a document is set on the contact glass (32) of the scanner (300), and the automatic document feeder (400) is closed and pressed by it. When a start switch (not shown) is pressed, when the original is set on the automatic document feeder (400), the original is conveyed and moved onto the contact glass (32), and then the other contact glass (32). When the original is set on the scanner, the scanner (300) is immediately driven to drive 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 to the second traveling body (3).
4), the light is reflected by the mirror of the second traveling body (34) and is inserted into the reading sensor (36) through the imaging lens (35) to read the contents of the document.

When a start switch (not shown) is pressed, the supporting rollers (14), (1
5) and (16) are rotationally driven to rotate the other two supporting rollers, and the intermediate transfer member (11) is rotatably conveyed. At the same time, the photoconductors (81) are rotated by the individual image forming means (18) to form black, yellow, magenta and cyan monochromatic images on the photoconductors (81), respectively. Then, as the intermediate transfer body (11) is conveyed, the single color images are sequentially transferred to form a composite color image on the intermediate transfer body (11). On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers (82) of the paper feed table (200) is selectively rotated to move the paper bank (83).
Sheets are fed out from one of the paper feed cassettes (84) provided in multiple stages, separated by a separation roller (85) one by one, placed in a paper feed path (86), and conveyed by a conveyance roller (87) to form a copying machine. It is guided to the paper feed path (88) in the main body (101) and abutted against the registration roller (89) to be stopped. Alternatively, the paper feed roller (59) is rotated to feed out the sheets on the manual feed tray (91), and the sheets are separated one by one by the separation roller (92) and put into the manual paper feed path (53). ) And stop. Then, the intermediate transfer member (1
1) The registration roller (89) is rotated in time with the composite color image above, and the sheet is fed between the intermediate transfer body (11) and the secondary transfer device (22), and the secondary transfer device (22). To print a color image on the sheet. The sheet after the image transfer is conveyed by the secondary transfer device (22) and sent to the fixing device (25), where the fixing device (2
After the transfer image is fixed by applying heat and pressure in 5), it is switched by the switching claw (55) and discharged by the discharge roller (56),
The sheets are stacked on the discharge tray (57). Or, switch it with the switching claw (55) and put it in the sheet reversing device (28),
Then, after reversing and guiding to the transfer position and recording an image on the back side, the discharge roller (56) is used to discharge the paper to the discharge tray (57).
Discharge on top. On the other hand, the intermediate transfer body (11) after image transfer
The intermediate transfer member cleaning device (17) removes the residual toner remaining on the intermediate transfer member (11) after the image transfer and prepares for another image formation by the tandem image forming device (29). Here, the registration roller (89) is generally grounded and used in many cases, but it is also possible to apply a bias to remove paper dust from the sheet.

By the way, the tandem image forming apparatus (2
In 9), the individual image forming means (18) is specifically, for example, as shown in FIG. 6, a drum-shaped photoconductor (8).
1) around the charging device (93), the developing device (6
1) A primary transfer device (62), a photoconductor cleaning device (63), a charge eliminating device (64), etc. are provided.

[0157]

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. The evaluation machine used, the obtained properties and the evaluation results are shown in Table 1. In the examples, evaluation was performed as follows.

(Evaluator) The images used in the evaluation were evaluated using any of the following assessors A, B, C and D. (Evaluator A) Tandem type full-color laser printer IPSIO Color 8000 having a non-magnetic two-component developing unit for four colors and a photoconductor for four colors.
The fixing unit was improved to an oilless fixing unit and tuned using an evaluation machine A. The printing speed was evaluated by high-speed printing (change from 20 to 50 sheets / min / A4).

(Evaluator B) Tandem type full color laser printer IPSIO Colo of tandem type 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 toner image was secondarily transferred to a transfer material, an intermediate transfer system was changed, and the evaluation unit B was tuned by modifying the fixing unit into an oilless fixing unit.
The printing speed was evaluated by high-speed printing (change from 20 to 50 sheets / min / A4).

(Evaluator C) The four-color developing unit develops the two-component type developer on one drum-shaped photoconductor for each color, and sequentially transfers it to the intermediate transfer member, thereby transferring the four colors at once to the transfer material. 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.

(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 evaluation was performed by using an evaluation machine D tuned in the oil coating type.

(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. The printing speed was evaluated by high-speed printing (change 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. 80 in single color 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) Under a low temperature and low humidity environment, a background stain single-color mode was used.
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. When this value is less than 1.2, it is ×, when it is 1.2 or more and less than 1.4, Δ, 1.4 or more and 1.
When it was less than 8, it was evaluated as ◯, and when it was 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.
Measured with P type. The order of good transparency is ⊚, ○, Δ, and x.

(5) Color vividness In the monochrome mode, an image chart of 50% image area is set to 100,
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 light fastness monochromatic mode,
After running output of 000 sheets, output the image to 6000 paper made by Ricoh Co., Ltd. with XENONTESTER X
The image after irradiating the image with W-150 (manufactured by Shimadzu Corporation) at 10,000 lux for 15 hours was observed, 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 An image chart of 50% image area in the monochromatic mode 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%, development was performed every 1000 sheets while running and outputting 100,000 sheets of an image chart having a 7% image area in a single color mode. A part of the agent 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.

(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 during running output of an image chart of 7% image area in a single color 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.

(13) The fixing lower limit temperature and the fixing upper limit temperature of the fixing toner are sufficiently within the fixing temperature range, hot offset and cold offset do not occur, and winding troubles, paper jams, and the like are unlikely to occur. The overall fixability was evaluated as ⊚, ∘, Δ, and × in order of good fixing.

(Evaluation of Two-Component Developer) In the case of image evaluation with a two-component developer, a ferrite carrier having an average particle size 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.

[0177] (Manufacturing of carriers) ・ Core material     Cu-Zn ferrite particles (weight average diameter: 35 μm) 5000 parts ・ Coating material     Toluene 450 parts     Silicone resin SR2400       (Toray Dow Corning Silicone, non-volatile content 50%) 450 parts     Aminosilane SH6020       (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 coated while forming a swirling flow provided with a rotary bottom plate disk and stirring blades in a fluidized bed. The coating solution was put into a coating device and applied onto the core material. The obtained coated product was baked in an electric furnace at 250 ° C. for 2 hours to obtain the above carrier.

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) <Black Toner> Water 1000 parts Phthalocyanine green water-containing cake (solid content 30%) 200 parts Carbon black (MA60 manufactured by Mitsubishi Chemical Corporation) 1000 parts Polyol resin 1 1000 parts The above raw materials were mixed with a Henschel mixer. Mixing gave a mixture with water soaked into the pigment agglomerates. This was kneaded for 45 minutes by two rolls set to a roll surface temperature of 130 ° 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 5 parts (fatty acid ester wax, melting point 83 ° C, viscosity 280 mPa · s (90 ° C))

After the above materials were mixed with a mixer, they were 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 (type I mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and a wind classification by swirling flow (DS classifier; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) were performed, and the volume average particle diameter was 6.5 μm. To obtain black colored particles. Furthermore, hydrophobic silica (H
DK H2000, Clariant Japan) 1.0w
t%, titanium oxide having a primary particle diameter of 15 nm (MT-150
(A, Takea) was added in an amount of 0.9 wt%, mixed with a Henschel mixer, and passed through a sieve having an opening of 50 μm to remove aggregates, thereby obtaining Black Toner 1. The dispersed diameter of the wax in the toner was 3 μm.

<Yellow Toner> Water 600 parts Pigment Yellow 17 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 a pigment aggregate. This was kneaded for 45 minutes by two rolls set to a roll surface temperature of 130 ° 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 5 parts (fatty acid ester wax, melting point 83 ° C, viscosity 280 mPa · s (90 ° C))

After the above materials were mixed with a mixer, they were 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 (type I mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and a wind classification by swirling flow (DS classifier; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) were performed, and the volume average particle diameter was 6.5 μm Yellow colored particles were obtained. Furthermore, hydrophobic silica (H
DK H2000, Clariant Japan) 1.0w
t%, titanium oxide having a primary particle diameter of 15 nm (MT-150
(A, Takea) was added in an amount of 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 yellow toner 1. The dispersed diameter of the wax in the toner was 1 μm.

<Magenta Toner> Water 600 parts Pigment Red 57 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 130 ° 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 5 parts (fatty acid ester wax, melting point 83 ° C, viscosity 280 mPa · s (90 ° C))

After the above materials were mixed with a mixer, they were 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 (type I mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and a wind classification by swirling flow (DS classifier; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) were performed, and the volume average particle diameter was 6.5 μm. To obtain magenta colored particles. Furthermore, a hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm was added to 1.
0 wt%, titanium oxide having a primary particle diameter of 15 nm (MT-1
Magenta Toner 1 was obtained by adding 0.9 wt% of 50A, Takea), mixing with a Henschel mixer, and passing through a sieve having an opening of 50 μm to remove agglomerates. The dispersed diameter of the wax in the toner was 2 μm.

<Cyan Toner> Water 600 parts Pigment Blue 15: 3 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 a pigment aggregate. This was kneaded for 45 minutes by two rolls set to a roll surface temperature of 130 ° 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 5 parts (fatty acid ester wax, melting point 83 ° C, viscosity 280 mPa · s (90 ° C))

After the above materials were mixed with a mixer, they were 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 (type I mill; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and a wind classification by swirling flow (DS classifier; manufactured by Nippon Pneumatic Mfg. Co., Ltd.) were performed, and the volume average particle diameter was 6.5 μm. Cyan colored particles were obtained. In addition, hydrophobic silica (H
DK H2000, Clariant Japan) 1.0w
t%, titanium oxide having a primary particle diameter of 15 nm (MT-150
Magenta Toner 1 was obtained by adding 0.9 wt% of (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 1.5 μm. The dispersion state and shape of the colorant of the obtained toner are shown in Table 2.

Example 2 In Example 1, the production conditions of the masterbatch colorant,
Toner in the same manner as in Example 1 except that the prescription amount was changed,
A developer was prepared and evaluated. As the masterbatch colorant, the crushed masterbatch colorant obtained in Example 1 was kneaded again with a two-roll for 45 minutes, rolled and cooled, and pulverized with a palperizer to obtain a masterbatch colorant. The dispersion state and weight% of the obtained colorant are shown in Table 2.

Example 3 A toner and a developer were prepared and evaluated in the same manner as in Example 1 except that the prescription amount of the masterbatch colorant was changed to 2% by weight. . The dispersion state of the obtained colorant is shown in Table 2.

Example 4 Example 1 was repeated except that the formulation amount of the masterbatch colorant was changed to 13% by weight of the colorant.
A toner and a developer were prepared and evaluated in the same manner as in. The dispersion state and weight% of the obtained colorant are shown in Table 2.

Example 5 In Example 1, the production conditions of the masterbatch colorant,
Toner in the same manner as in Example 1 except that the prescription amount was changed,
A developer was prepared and evaluated. As the masterbatch colorant, the crushed masterbatch colorant obtained in Example 1 was kneaded again with two rolls for 45 minutes, rolled and cooled, crushed, and further kneaded with two rolls for 60 minutes and rolled and cooled. Grinding gave a masterbatch colorant. The dispersion state and weight% of the obtained colorant are shown in Table 2.

Example 6 In Example 1, the volume average particle diameter of the toner is 2.8 μm.
A toner and a developer were prepared and evaluated in the same manner as in Example 1 except that the toner was classified so that The dispersion state and weight% of the colorant in the obtained toner are shown in Table 2.

Example 7 In Example 1, the volume average particle diameter of the toner is 8.5 μm.
A toner and a developer were prepared and evaluated in the same manner as in Example 1 except that the toner was classified so that The dispersion state and weight% of the colorant in the obtained toner are shown in Table 2.

Example 8 In Example 1, the kneading conditions of the toner were set stronger so that the softening point of the toner was 108 ° C., the glass transition temperature (Tg) was 61 ° C., and the outflow starting temperature was 110 ° C. Kneading conditions (kneading 6 times with a 3-roll mill, roller temperature 13
Evaluation was made in the same manner as in Example 1 except that the temperature was changed to 0 ° C. The dispersion state of the colorant in the obtained toner is shown in Table 2.

Example 9 In Example 1, the kneading conditions of the toner were weaker so that the softening point of the toner was 133 ° C., the glass transition temperature (Tg) was 92 ° C., and the outflow starting temperature was 129 ° C. Evaluation was carried out in the same manner as in Example 1 except that the kneading conditions (co-kneader manufactured by Buss Co., Ltd., feed weak kneading conditions) were changed. The dispersion state of the colorant in the obtained toner is shown in Table 2.

Example 10 In Example 1, the toner has a number average molecular weight (Mn) of 4,200 and a weight average molecular weight / number average molecular weight (Mw).
/ Mn) is 3.8, and at least one peak molecular weight (Mp) is 4800, except that the kneading conditions of the toner are changed to weaker kneading conditions (co-kneader manufactured by Buss Co., Ltd. and weak feed kneading conditions). It evaluated similarly. The dispersion state of the colorant in the obtained toner is shown in Table 2.

Example 11 In Example 1, the toner had a number average molecular weight (Mn) of 3400, and a weight average molecular weight / number average molecular weight (Mw).
/ Mn) is 2.9 and at least one peak molecular weight (Mp) is 4100, the kneading conditions of the toner are set to stronger kneading conditions (kneading 7 times with a three-roll mill, roller temperature 120 ° C.). The evaluation was performed in the same manner except that it was changed. The dispersion state of the colorant in the obtained toner is shown in Table 2.

Example 12 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 dispersion state of the colorant in the obtained toner is shown in Table 2.

Example 13 Evaluation was made in the same manner as in Example 1 except that 4 parts by weight of free fatty acid type carnauba wax (acid value 4) was newly added during the mixing and kneading. The dispersed average particle diameter of the wax in the toner was 0.8 μm. The dispersion state of the colorant in the obtained toner is shown in Table 2.

Example 14 Evaluation was made in the same manner as in Example 1 except that the evaluation machine B was used. Example 15 In Example 1, it evaluated similarly except having used the evaluation machine C. Example 16 In Example 1, it evaluated similarly except having used the evaluation machine D. Example 17 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.

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 30 minutes with a two-roll roll set at a roll surface temperature of 120 ° C. The dispersion state of the obtained colorant is shown in Table 2.

Comparative Example 2 Same as Example 1 except that the formulation amount of the masterbatch colorant was changed to 4% by weight and the production conditions of the masterbatch colorant were changed. Then, a toner and a developer were prepared and evaluated. The masterbatch colorant was obtained by kneading for 60 minutes with a three-roll roll set at a roll surface temperature of 150 ° C. The dispersion state of the obtained colorant is shown in Table 2.

Comparative Example 3 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 20 minutes with a two-roll roll set to a roll surface temperature of 100 ° C. The dispersion state of the obtained colorant is shown in Table 2.

Comparative Example 4 A toner and a developer were prepared and evaluated in the same manner as in Example 1 except that the prescription amount of the masterbatch colorant was changed to 1% by weight. . The dispersion state of the obtained colorant is shown in Table 2.

Comparative Example 5 Example 1 was repeated except that the prescription amount of the masterbatch colorant was changed to 16% by weight of the colorant.
A toner and a developer were prepared and evaluated in the same manner as in. The dispersion state of the obtained colorant is shown in Table 2.

Comparative Example 6 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 prepared under the conditions of a kneader manufactured by Buss Co., Ltd. and weak feed kneading, instead of using two rolls. The dispersion state of the obtained colorant is shown in Table 2.

[0207]

[Table 1]

[0208]

[Table 2]

[0209]

As is apparent from the above detailed and specific description, in the toner of the present invention containing at least the binder resin and the colorant, the number average particle size L of the colorant particles in the toner is 0.04 μm ≦ L ≦ 0.2
The number of particles of μm is 80% by number or more, the number of particles of 0.4 μm or more is 10% by number or less, the number of particles of less than 0.04 μm is 5% by number or less, and the colorant particles are used as a toner. On the other hand, the content of 2% to 15% by weight, the ratio of the longest diameter a to the shortest diameter b of the colorant particles, and the a / b value of 1.0 to
By using the toner for developing an electrostatic charge image, which is characterized by being 5.0, the toner has stable charge even after storing the toner for a long time in a high temperature and high humidity environment and outputting tens of thousands of images in the high temperature and high humidity environment. Toner, developer, image forming method, which does not cause toner scattering, with weakly charged and reversely charged toner with excellent properties
It is possible to provide an image forming apparatus, and not only the normal temperature and normal humidity environment, but also the low charging and reverse charging toner, which has excellent charging stability even after outputting tens of thousands of images under low temperature and low humidity environment.
It is possible to provide a toner, a developer, an image forming method, and an image forming apparatus in which background stain (fog) does not occur, and even after outputting tens of thousands of images, sufficient coloring property, light resistance, transparency, color forming property, Toner with sharpness, color reproducibility, saturation, and gloss,
A developer, an image forming method, and an image forming apparatus can be provided, and cohesiveness after toner transfer compression or after stress in a developing machine, transferability in which adhesion between toner particles is appropriately controlled,
An external additive for developing an electrostatic charge image, which has excellent developability and fixability, is less affected by the material of the transfer material, and can form a high quality image,
A toner, a developer, an image forming method, and an image forming apparatus can be provided, and an image forming apparatus and an image forming method that have high durability and low maintenance as an image forming system can be provided, and transferability at the time of toner compression. At the same time, it is possible to provide an image forming apparatus and an image forming method which are excellent in replenishment property with sufficient fluidity during non-compression and excellent in charging rise property, and are excellent in environmental electrification stability as a toner and a developer, and printing speed is high. It is possible to provide an image forming apparatus and an image forming method which have an excellent balance of fixing property and non-offset property, which is comparable to low-speed to high-speed regions and which does not cause image density reduction in continuous image output. An image forming apparatus that does not transfer a toner image to a sheet even when it is in close contact with the resin sheet,
It is possible to provide an image forming method and an image forming apparatus and an image forming method in which a fixed image does not substantially curl, and a toner image formed on an electrostatic image carrier is transferred onto an intermediate transfer body. In an image forming apparatus of a primary transfer type and a secondary transfer of the toner image to a transfer material, or an image forming apparatus capable of high-speed output by a tandem type, a bug-eating image, transfer dust, fine line reproducibility, etc. It is now possible to provide an image forming apparatus capable of preventing the occurrence of abnormal images.

[Brief description of drawings]

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

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

FIG. 3 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention.

FIG. 4 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention.

FIG. 5 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention.

FIG. 6 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention.

[Explanation of symbols]

1 photoconductor 2 Transfer device 3 Sheet conveyor belt s sheet 4 Intermediate transfer body 5 Transfer device T tandem image forming apparatus 6 Paper feeder 7 Fixing device 8 Photoconductor cleaning device 9 Intermediate transfer member cleaning device 10 photoconductor 11 Intermediate transfer body 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer member cleaning device 18 Image forming means 20 charging roller 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 29 Tandem image forming apparatus 30 exposure equipment 31 Platen 32 contact glass 33 First running body 34 Second traveling body 35 Resolution lens 36 reading sensor 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 Manual feed path 55 Switching claw 56 discharge roller 57 Output tray 59 paper feed roller 60 cleaning device 61 Developing device 62 Primary transfer device 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 80 Transfer roller 81 photoconductor 82 Paper feed roller 83 Paper Bank 84 paper feed cassette 85 Separation roller 86 paper feed path 87 Conveyor roller 88 paper feed path 89 Registration roller 90 Cleaning device 91 bypass tray 92 Separation roller 93 Charging device 100 transfer paper 101 Copying device main body 200 paper feed table 300 scanner 400 Automatic Document Feeder (ADF)

   ─────────────────────────────────────────────────── ─── 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 CA07 CA08 CA14                       EA03 EA05 EA06 EA07 EA10                       FA02

Claims (11)

[Claims] 1. A toner containing at least a binder resin and a colorant, wherein the number average particle diameter L of the colorant particles in the toner is 0.04 μm ≦ L ≦ 0.2 μm, and 80% by number or more, Further, the number of particles of 0.4 μm or more is 10 number% or less, the number of particles of less than 0.04 μm is 5 number% or less, and the colorant particles are contained in the toner in an amount of 2% by weight to 15% by weight. And the ratio of the longest diameter a and the shortest diameter b of the colorant particles, a / b value is 1.0 to 5.0.
The toner for developing an electrostatic charge image according to claim 1. 2. The volume average particle diameter of the toner is 3 to 8 μm.
The toner for developing an electrostatic charge image according to claim 1, wherein the toner is m. 3. The number average molecular weight (Mn) of the toner is 2
000 to 8,000, and weight average molecular weight / number average molecular weight (Mw / Mn) of 1.5 to 20, and at least 1
The toner for developing an electrostatic charge image according to claim 1 or 2, wherein one peak molecular weight (Mp) is 3000 to 13000. 4. The electrostatic image developing toner according to claim 1, wherein the binder resin of the toner contains at least a polyol resin. 5. The electrostatic charge image according to claim 1, wherein the binder resin of the toner contains at least a polyol resin having an epoxy resin part and a polyoxyalkylene part in the main chain. Toner for development. 6. The binder resin of the toner contains at least a polyester resin.
6. The toner for developing an electrostatic charge image according to any one of items 1 to 5. 7. The toner contains at least wax, and the dispersion average particle diameter of the wax in the toner is 3 μm.
The toner for developing an electrostatic charge image according to any one of claims 1 to 6, wherein: 8. The softening point of the toner is 50 to 150.
C., the outflow start temperature is 60.degree. C. to 130.degree. C., and the glass transition temperature (Tg) is 30 to 70.degree. C. 8. The electrostatic image development according to claim 1, wherein toner. 9. A two-component developer comprising at least the toner according to claim 1 and a carrier composed of magnetic particles. 10. An image forming method comprising using the toner or the developer according to claim 1. 11. An image forming apparatus comprising a container filled with the toner or the developer according to any one of claims 1 to 9.