JP2000347464A - Toner and image forming method - Google Patents

Abstract

(57) [Abstract] (with correction) [Problem] To be highly applicable to an electrophotographic process without having an adverse effect on a photoreceptor and an intermediate transfer member, having excellent chargeability, less image deterioration such as transfer omission, and the like. To provide a toner. (A) a charging step of charging an image carrier for carrying an electrostatic latent image; (b) an exposure step of forming an electrostatic latent image on the charged image carrier by image exposure; A) a developing step of forming a toner image by developing the electrostatic latent image by bringing a toner layer uniformly supported on the surface of the toner carrier into contact with the surface of the image carrier; Transferring a toner image formed on the surface of the carrier to a transfer material via an intermediate transfer member or without the intermediate transfer member;
(E) a toner used in an image forming method using a developing and cleaning method in which the developing device also serves in a developing step to collect toner remaining on the surface of the image carrier after the transfer step; A melt index (at 125 ° C./5 kg load) of the toner, which contains at least a binder resin, a colorant, a wax component, and a compound represented by the following general formula <A>, and is measured according to “JIS K7210”; MI) is 0.5 to 80 g / 10 min.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method utilizing an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet recording method and the like, and an image forming method. Specifically, the present invention forms a toner image on an electrostatic latent image carrier by a non-magnetic one-component contact developing method,
It is used for electrophotography, electrostatic recording, electrostatic printing of full color copiers, printers, faxes, etc., which has a mechanism to form an image by transferring it to a transfer material and collect the residual toner in the developing device at the same time as developing. And / or a full-color toner and an image forming method.

[0002]

2. Description of the Related Art Conventionally, many methods have been known as electrophotography. In general, a photoconductive substance is used to form an electric latent image on an image carrier (photoreceptor) by various means. After forming the latent image, the latent image is developed with a toner to make it a visible image, and if necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat / pressure. To obtain a copy.

[0003] Methods for visualizing an electric latent image include a magnetic two-component developing method comprising a magnetic toner and a carrier, a non-magnetic two-component developing method comprising a non-magnetic toner and a carrier, and a non-magnetic toner to which externally added particles are externally added. Generally, a non-magnetic one-component developing method using only a magnetic material and a magnetic one-component developing method using a magnetic toner are widely used.

On the other hand, in the electrophotographic industry, the resolution of an image of a printer device or the like has been increased to 1200 or 2400 dpi. Accordingly, a higher definition has also been required for the developing method of the printer device. In addition, the functions and digitalization of copiers have been advanced, and high resolution and high definition have been demanded similarly to printer devices.

To meet these demands, development systems have been improved, and among various development systems, a non-magnetic one-component contact development system, which can easily attain high resolution and high definition requirements, is preferable. Used.

In order to meet such demands, various improvements have been made to toner properties.

For example, it has been proposed to use various charge control agents in the toner so as to obtain an appropriate charge amount. If the charge amount of the toner deviates from an appropriate region, for example, if the charge amount is too high, the adhesion of the toner to the photoreceptor becomes strong, the transferability is reduced, and the characters or images are undesirably lost. On the other hand, if the charge amount of the toner is too low, the image density is reduced due to a decrease in the developing property, and a high-definition image cannot be obtained.

The charge control agents known in the art today include, as negative triboelectrification, a metal complex salt of a monoazo dye, a metal complex salt of hydroxycarboxylic acid, dicarboxylic acid, aromatic diol and the like, and a resin containing an acid component. Etc. Nigrosine dyes, azine dyes, triphenylmethane dyes and pigments, quaternary ammonium salts, and polymers having quaternary ammonium salts in the side chain are known as positive triboelectrification.

[0009] Japanese Patent Application Laid-Open Nos. 2-221967 and 3
JP-A-39973 and JP-A-5-72812 propose a toner containing a boron benzylate compound.

Japanese Patent Application Laid-Open No. 5-61257 proposes a toner in which a boron compound is embedded in a toner precursor. However, these methods are still insufficient for the above-mentioned problems, and further improvements are required.

In a full-color image forming apparatus, in particular, an electrostatic latent image is generally developed using a magenta toner, a cyan toner, a yellow toner and a black toner, and a multi-color image is formed by superimposing toner images of respective colors. The image is being reproduced. For this reason, full-color toners are required to have more appropriate charging properties than monochrome toners.

Further, in order to obtain a stable full-color image, the toner is required to have a characteristic that quickly rises to an appropriate charge amount. If the charge amount of the toner does not quickly rise to an appropriate charge amount, it is not preferable because remarkable image defects such as image fogging and a decrease in density occur at the time of initial use or reuse after being left for several days without using the apparatus.

In recent years, miniaturization of a full-color image forming apparatus has been studied, but for that purpose, it is necessary to reduce the size of a developing device. In order to reduce the size of the developing device, for example, a non-magnetic one-component developing system is preferably used. In the non-magnetic one-component developing system, the toner on the elastic toner carrier is regulated by a regulating member, and the toner is charged by rubbing the toner surface to give the toner a chargeability. Therefore, the toner used in the non-magnetic one-component developing method includes:
It is necessary to have an appropriate charging property and a rising speed for quickly rising to an appropriate charging amount.

Further, the toner needs to have physical strength enough to withstand rubbing during development. If the physical strength is insufficient, the toner is deformed or crushed flat by the rubbing for imparting charge to the toner particles, and as the number of printed sheets increases, the toner adheres to the toner regulating member surface to form a fused mass. This may cause the fused mass to disproportionate the coat on the toner carrier. In such a case, uneven coating of the toner on the toner carrier, which contributes to the development, undesirably causes a coating streak in the image developing direction. In particular, this coat unevenness is most conspicuous as an image defect when an image having a high print density is output. In addition, during full-color printing, a secondary color in which a plurality of developed colors are superimposed is used. However, in this case, the coating unevenness is not preferable because it becomes very noticeable as an image defect.

JP-A-5-165257 describes a color developer used in a non-magnetic one-component contact or non-contact developing method containing a boron complex.
JP-A-250442 discloses a non-magnetic one-component developing method using a toner containing a boron complex salt and having a limited glass transition temperature of a resin. However, there is no description suggesting the physical strength of the toner itself such as the viscoelasticity and the melt index of the toner itself, and the above-mentioned problems have not been solved.

Further, with a demand for a higher printing speed of a printer or the like, a demand for a higher developing and fixing speed is increasing.

In order to increase the speed of development, it is necessary to give the toner particles an arbitrary chargeability instantaneously. Therefore, by using an appropriate charge control agent and increasing the linear pressure of the toner regulating member,
It is necessary to increase the friction force. Also in this case, a high physical strength of the toner is required from the viewpoint of fusing lines.

On the other hand, unnecessarily increasing the physical strength is not preferable because a large amount of heat energy is required at the time of fixing. Further, in a high-speed machine that requires high-speed fixing, it is necessary to instantaneously apply a large amount of fixing energy to the recording material.In this case, the fixing energy consumption of the main body is high, and the fixing device is heated when the printer main body is started. Undesirable situations such as a long waiting time are required. Therefore, such toner is required to be fixed at a low temperature, and is required to have an appropriate range of physical strength.

[0019]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner and an image forming method which solve the above-mentioned problems of the prior art.

That is, an object of the present invention is to provide an excellent chargeability,
An object of the present invention is to provide a toner and an image forming method with less image deterioration such as transfer omission.

Another object of the present invention is to provide a toner and an image forming method in which the amount of untransferred toner is small and the collectability of untransferred toner during development is improved.

Another object of the present invention is to provide a toner and an image forming method which do not adversely affect a photoreceptor or an intermediate transfer member and which can be highly applied to an electrophotographic process.

[0023]

Means for Solving the Problems The inventors of the present invention have made intensive studies to overcome such a problem, and as a result, have limited the melt index of the toner and combined the toner with the specified charge control agent with a specific developing method. The inventors have found that the above problems can be overcome by using the same, and have led to the present invention.

That is, the present invention provides (a) a charging step of charging an image carrier for carrying an electrostatic latent image; and (b) an exposure for forming an electrostatic latent image on the charged image carrier by image exposure. (C) a developing step of forming the toner image by developing the electrostatic latent image by bringing the toner layer uniformly carried on the surface of the toner carrier into contact with the surface of the image carrier; (d) transferring the toner image formed on the surface of the image carrier to a transfer material with or without an intermediate transfer member; and (e) the image carrier after the transfer process. A toner used in an image forming method using a developing and cleaning system in which the developing device also collects toner remaining on the surface in a developing step, and the toner includes a binder resin, a colorant, and a wax component. And represented by the following general formula <A>"JISK7210" containing at least the compound
A toner having a melt index (MI) of 0.5 to 80 g / 10 min.

[0025]

Embedded image(Where R₁And R_FourIs a substituted or unsubstituted aromatic (fused ring)
And R)_TwoAnd R_ThreeRepresents a hydrogen atom, an alkyl group,
Represents a substituted or unsubstituted aromatic (including a condensed ring), and M is
B, T i, Fe, Co, Cr, Al and Ni
X represents the element selected from the loop^{n +}Indicates a cation
You. Further, the present invention relates to an image forming method using the toner.
You.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the general formula <A> will be described in detail below.

Examples of R ₁ and R ₄ include condensed aromatic rings such as an aromatic ring having a benzene skeleton and a naphthalene ring. Derivatives having the following substituents on the aromatic ring are also preferable. Specific substituents include an alkyl group, an aralkyl group, an alkoxy group, an alkenyl group, an aryl group, a halogen atom, a nitro group, a cyan group, an amino group, a hydroxyl group and the like. R ₂ and R ₃ are the same groups as R ₁ and R ₄ , or
The substituents shown below are preferred. In particular,
Hydrogen atom, methyl group, ethyl group, n-butyl group, t
-Butyl group, iso-propyl group, iso-amyl group,
and alkyl groups such as n-dodecyl group, n-octadecyl group and cyclohexyl group.

In the formula, M is B, T i, Fe, Co,
Element selected from the group consisting of Cr, Al and Ni
Is shown.

As X ^{n +} , various inorganic cations and organic cations are used. Examples of the inorganic cation include a hydrogen ion and a metal ion. A monovalent alkali metal such as Li ⁺ , Na ⁺ , K ⁺ , or Mg ²⁺ , Ca ²⁺ , Z
and divalent alkaline earth metals such as n ²⁺ and Ba ²⁺ . Particularly preferred as these inorganic cations are
It is a monovalent alkali metal such as Li ⁺ , Na ⁺ , and K ⁺ .
These alkali metals form salts with the boron complex. As organic cations, ammonium ions,
Examples include iminium ions and phosphonium ions.

Preferred among the above organic cations are those represented by the following general formulas <B>, <C>, <D> or <E>.

[0031]

Embedded image

Where R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ ,
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Z ₁ and Z ₂ represent A non-metallic atomic group that forms a 5- or 6-membered ring by bonding to a nitrogen atom is shown.

Examples of the alkyl group include methyl, ethyl, n-butyl, t-butyl, iso-propyl, iso-amyl, n-dodecyl, n-octadecyl, cyclohexyl and the like. . Examples of the aryl group include a phenyl group and an α-naphthyl group.
These alkyl or aryl groups are an alkyl group,
Aralkyl groups, halogen atoms, alkoxy groups, hydroxyl groups,
It may be substituted with various substituents such as a cyano group and an aryl group. Examples of Z ₁ and Z ₂ include a group of non-metallic atoms necessary for forming various heterocycles such as a pyridine ring, an isoquinoline ring, a pyrrole ring, an imidazole ring, a piperidine ring and a pyrrolidine ring.

Table 1 shows specific examples of the compound represented by the general formula <A>. The compound No. Is commonly used in the embodiments.

[0035]

[Table 1]

The compound represented by the general formula <A> added to the toner component is used in an amount of generally 0.1 to 10 parts by weight, preferably 0.6 to 5 parts by weight, based on 100 parts by weight of the binder resin. is there.

When the amount of the compound represented by the general formula <A> added to the toner component is less than 0.1 part by weight, charging of the toner particles is insufficient, and the image density is extremely low. It is not preferable because fogging occurs. When the amount of the compound represented by the general formula <A> exceeds 10 parts by weight, the charge amount of the toner becomes unstable, and the toner on the toner carrier is not developed by the applied bias at the time of development. It is not preferable because the concentration is low. Moreover, it is not economically preferable.

The toner of the present invention preferably has a melt index (MI) in the range of 0.5 to 80 g / 10 minutes, more preferably 3 to 25 g / 10 minutes. When the melt index exceeds 80 g / 10 minutes, there is a risk that toner fusion may occur during storage in a developing container.
When used in a non-magnetic one-component developing system, toner particles are remarkably fused to the upper surface of the developing blade when the toner carrier and the developing blade are rubbed, and the fused material causes uneven coating on the toner coat layer on the carrier. This is not preferable because it causes uneven development and causes streaks on the image. If the melt index is less than 0.5 g / 10 minutes, the fixing temperature becomes too high, so that the temperature inside the apparatus becomes too high due to an increase in the power consumption of the fixing apparatus and an increase in the temperature inside the apparatus. Is not preferable because the toner is deteriorated. 0.5 to maintain these balances well
範 囲 80 g / 10 min, preferably 3-25 g / 10 min.
Minutes are more preferred. Therefore, when the melt index is within the range of the present invention, the fusion of the developing blade is reduced, and good matching with the image forming apparatus as shown in the embodiment of the present invention is exhibited.

The melt index is measured by a manual cutting method under the following measurement conditions in accordance with the apparatus described in "JIS K7210", a flow test method for thermoplastics according to Japanese Industrial Standards. At this time, the measured value is converted into a 10-minute value.

Measurement temperature: 125 ° C. Load: 5 kg Sample filling amount: 5 to 10 g

As the toner shape suitable for the present invention, the average number equivalent diameter of circles in the particle size frequency distribution based on the number of toners is 2 to 10 μm, and the average circularity in the circularity frequency distribution is 0.920 to 0.2 μm. At 995, the circularity standard deviation is preferably less than 0.040. By precisely controlling the toner particle shape to these shapes, transferability and developability can be improved in a well-balanced manner.

By reducing the average particle diameter of the circle equivalent number in the particle size frequency distribution based on the number of toners to 2 to 10 μm, the reproducibility of the contour portion of the image, particularly, the development of a character image or a line pattern is excellent. It will be. However, in general, when the particle size of the toner particle is reduced, the existence ratio of the toner having a small particle size necessarily increases, so that it becomes difficult to uniformly charge the toner, and not only image fogging occurs, but also the electrostatic latent image carrying Adhesion to the body surface is increased, resulting in an increase in transfer residual toner.

However, when the circularity standard deviation of the circularity frequency distribution is less than 0.035, the toner of the present invention has good stability against development and transferability due to environmental fluctuations, and further has good durability. , Phenomena such as "image fog" and "transfer missing" can be reduced. This is because, in particular, an intermediate transfer member is used to superimpose and develop multiple colors, and furthermore, the transfer step is performed in two steps.
It is very effective in a full-color developing method that requires multiple times, and an excellent full-color image can be obtained by using the toner of the present invention.

The average circularity in the circularity frequency distribution is 0.970 to 0.995, preferably 0.980 to 0.980.
By setting the ratio to 0.995, the transferability of the toner having a small particle diameter, which has been difficult in the related art, is greatly improved, and the developing ability for a low-potential latent image is significantly improved. It is particularly effective when developing a digital minute spot latent image.

When the average circularity is less than 0.970, not only the transferability is reduced but also the developability is reduced. On the other hand, when the average circularity exceeds 0.995, the surface of the toner deteriorates remarkably, causing problems in durability and the like. In particular, it becomes apparent when a full-color copying machine that develops / transfers a plurality of toner images as described above is used. That is, in the generation of a full-color image, it is difficult to uniformly transfer the toner images of four colors, and when an intermediate transfer member is used, problems in color unevenness and color balance are likely to occur. It is difficult to output stably.

In the present invention, the circle equivalent diameter and circularity of the toner and the frequency distribution thereof are used as a simple method for quantitatively expressing the shape of the toner. In the present invention, a flow type particle image measuring apparatus is used. The measurement was performed using “FPIA-1000 type” (manufactured by Toa Medical Electronics Co., Ltd.) and calculated using the following equation.

[0047]

(Equation 1)

Here, the “particle projection area” is the area of the binarized particle image, and the “perimeter of the particle projection image” is the length of the contour obtained by connecting the edge points of the particle image. Is defined.

The circularity in the present invention is an index indicating the degree of unevenness of the toner. The circularity is 1.000 when the toner is perfectly spherical, and the circularity becomes smaller as the surface shape becomes more complicated.

In the present invention, the circle-equivalent number average diameter D ₁ (μ
m) and the particle size standard deviation SDd are calculated from the following equation, where di is the particle size (center value) at the dividing point i of the particle size distribution, and f _i is the frequency.

[0051]

(Equation 2)

[0052]

[0053]

(Equation 3)

As a specific measuring method, 10 ml of ion-exchanged water from which impurity solids and the like have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersing agent thereto. Further, 0.02 g of the measurement sample is added and uniformly dispersed. As a means for dispersing, using a ultrasonic dispersing machine “UH-50” (manufactured by SMT Corporation) with a titanium alloy chip of 5φ attached as a vibrator, a dispersion treatment for 1 to 5 minutes, and a dispersion for measurement Liquid. At this time, the dispersion is appropriately cooled so that the temperature of the dispersion does not become 40 ° C. or higher.

For the measurement of the shape of the toner, the above-mentioned flow type particle image measuring device was used.
The concentration of the dispersion is readjusted so as to be about 10,000 / μl, and 1,000 or more toner particles are measured. After the measurement, using this data, the equivalent circle diameter and circularity frequency distribution of the toner are obtained.

The toner of the present invention preferably contains a wax component for improving the releasability at the time of fixing.

Specific examples of the wax component include the following compounds.

For example, silicone resins, polyesters, polyurethanes, polyamides, epoxy resins, polyvinyl butyral, rosin, modified rosin, terpene resins, phenolic resins, aliphatic or alicyclic hydrocarbon resins such as low molecular weight polyethylene or low molecular weight polypropylene, and aromatics Group petroleum resin, chlorinated paraffin, paraffin wax and the like.

Of these, waxes preferably used are low molecular weight polypropylene and its by-products, low molecular weight polyester and ester waxes, and aliphatic derivatives.

From these waxes, waxes obtained by fractionating the wax by molecular weight by various methods are also preferably used in the present invention. After the fractionation, oxidation, block copolymer, or graft modification may be performed.

The wax component according to the present invention can be used for observation of a tomographic surface of a toner using a transmission electron microscope (TEM).
It is preferable that the wax component be substantially spherical and / or spindle-shaped and dispersed in an island shape without being compatible with the binder resin.

In the present invention, the dispersion state of the wax component as described above is defined as follows. In other words, the circle-equivalent weight average diameter D means the average value of the weight-based particle size frequency distribution of the toner measured by the above-mentioned flow type particle image measuring apparatus.
₄ (μm), D ₄ × 0.9 or more, and D ₄ × 1.
20 tomographic planes of toner having a major axis of 1 or less are selected. Then, the major axis R of the tomographic plane of each selected toner,
Among the phase separation structures caused by the wax component existing in the tomographic plane of the toner having the major diameter R, the largest major axis r is measured, and the arithmetic mean value of r / R (r / R) _st is _calculated . Ask. The arithmetic mean value (r / R) _{st of the} obtained r / R is 0.0
When the wax component is in a dispersion state satisfying 5 ≦ (r / R) _st ≦ 0.95, the wax component has a substantially spherical and / or spindle-shaped island dispersion state in a state in which the wax component is not compatible with the binder resin. It is assumed that

By dispersing the wax component as described above and including the wax component in the toner, it is possible to prevent the deterioration of the toner and the contamination of the image forming apparatus. In particular, r /
The arithmetic mean value of R (r / R) _st is 0.25 ≦ (r / R)
_The dispersion state satisfying _st ≦ 0.90 is preferable because good chargeability is maintained and a toner image excellent in dot reproduction can be formed for a long period of time. Also, since the wax component works efficiently during heating,
The low-temperature fixability and the offset resistance are also good.

In the present invention, a specific method for observing the tomographic plane of the toner is as follows. After sufficiently dispersing the toner particles in an epoxy resin curable at normal temperature, the toner is dispersed in an atmosphere at a temperature of 40 ° C.
The cured product obtained after curing for a day is dyed using ruthenium tetroxide, osmium tetroxide, if necessary.
A flaky sample is cut out using a microtome provided with diamond teeth, and the tomographic morphology of the toner is observed using a transmission electron microscope (TEM). In the present invention, it is preferable to use a ruthenium tetroxide dyeing method in order to provide a contrast between materials by utilizing a slight difference in crystallinity between the low softening point substance used and the resin constituting the outer shell.

In the toner particles obtained in Examples described later, it was observed that the wax component was encapsulated in the outer shell resin.

The wax component according to the present invention showed a 5% increase in temperature according to a DSC curve measured by a differential scanning calorimeter.
A maximum endothermic peak is shown in the range of 0 to 100 ° C., and the onset temperature of the starting point of the endothermic peak including the maximum endothermic peak is 4
0 ° C. or more, and particularly, a temperature difference between the peak temperature of the maximum endothermic peak and the onset temperature is 7 to 50 ° C.
Is preferably within the range.

In the DSC curve at the time of temperature rise, by using a wax component that melts in the above temperature range, the dispersibility of other additives can be improved, and
The wax component itself can be easily controlled to the dispersed state as described above.

As a result, in addition to the good fixability of the toner, the releasing effect of the wax component is effectively exhibited, a sufficient fixing area is secured, and the developing property and the anti-blocking property of the conventionally known wax component are ensured. These characteristics are significantly improved because the adverse effects on the performance and the image forming apparatus are eliminated. In particular, since the specific surface area of the toner decreases as the particle shape becomes spherical, it is very effective to control the dispersion state of the wax component.

In the present invention, in the DSC measurement, the exchange of heat of the wax is measured and its behavior is observed. Therefore, from the measurement principle, it is preferable that the measurement is performed with a high-precision internal heating type input compensation type differential scanning calorimeter. . For example, DSC-7 manufactured by PerkinElmer can be used.

The measurement method is described in “ASTM D3418-8.
2). The DSC curve used in the present invention is:
When only the wax component is measured, a DSC curve measured when the temperature is raised at a temperature rate of 10 ° C./min after the temperature is raised and lowered once to obtain a pre-history is used. When the measurement is performed in a state where the toner is included in the toner, a DSC curve that is measured as it is without using a previous history is used.

The binder resin used in the present invention is not particularly limited as long as it is used for producing a toner. As the binder resin used in the present invention, for example, the following polymerizable monomers alone, or a copolymerization product of two or more polymerizable monomers is used. More specifically, a styrene-acrylic acid copolymer or a styrene-methacrylic acid copolymer is preferred.

Examples of the styrene polymerizable monomer include styrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert And styrene such as -butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, and derivatives thereof.

Examples of the (meth) acrylate-based polymerizable monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate. Α-methylene aliphatic monocarboxylic esters such as 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-acrylate Butyl, isobutyl acrylate,
Examples include acrylates such as propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate, and derivatives thereof.

The binder resin used in the present invention preferably contains the following crosslinkable polymerizable monomers in order to adjust the fixing temperature of the toner.

As the crosslinkable polymerizable monomer, a polymerizable monomer having two or more polymerizable double bonds is mainly used. Specific examples include bifunctional crosslinking agents such as divinylbenzene, divinylnaphthalene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butane. Diol diacrylate, 1,5-pentanediol diacrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester type diacrylate (trade name: MANDA (Nippon Kayaku)), and those obtained by replacing the above acrylate with methacrylate.

Examples of polyfunctional crosslinking agents include pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy, Polyethoxyphenyl) propane, diallyl phthalate, triallyl cyanurate,
Triallyl asocyanurate, triallyl isocyanurate, triallyl trimellitate, diarylchlorendate and the like.

Among these crosslinkable polymerizable monomers, aromatic divinyl compounds (particularly divinylbenzene) and diacrylate compounds linked by a chain containing an aromatic group and an ether bond are preferably used. And the other polymerizable monomer component in an amount of 0.01 to 5 parts by weight based on 100 parts by weight.
It is preferable to use about parts by weight (further, about 0.03 to 3 parts by weight). By adding an appropriate amount of these crosslinkable polymerizable monomers, the melt index of the toner can be controlled, and blade fusion can be reduced in a non-magnetic one-component developing system. Further, the storage stability and environmental stability of the toner are improved.

In order to obtain the binder resin used in the present invention, it is preferable to use a polymerization initiator as exemplified below.

Specifically, examples of the peroxide-based initiator include t-butylperoxy-2-ethylhexanoate, cumin perpivalate, t-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide Oxide, octanoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide,
1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, n-butyl 4,4-bis (t
-Butylperoxy) valerate, dicumyl peroxide and the like and derivatives thereof.

Examples of the azo and diazo initiators include 2,2′-azobisisobutyronitrile, 2,2 ′
-Azobis (2-methylbutyronitrile), 2,2'-
Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like and derivatives thereof.

These polymerization initiators may be used alone or in combination of two or more. The used amount is 0.05 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymerizable monomer.

On the other hand, in the toner of the present invention, the residual amount of the polymerizable monomer in the toner is preferably 200 ppm or less, more preferably 150 ppm or less, and further preferably 50 ppm or less. If the amount of the polymerizable monomer remaining in the toner exceeds 200 ppm, problems arise in the chargeability and blocking resistance of the toner.

In the present invention, the polymerizable monomer remaining in the toner and the unreacted monomer in the production of a binder resin described later or the production of a toner by a direct polymerization method.

As a method for reducing the residual monomer in the toner, a known method can be applied. For example, when a binder resin is produced or a toner is produced by a direct polymerization method, a method of adding an initiator or a reaction may be used. The residual monomer can be suppressed by controlling the temperature, or the residual monomer can be removed by performing distillation after the polymerization. In addition, when producing a toner by a pulverization method, the raw materials are removed under reduced pressure when heating and kneading with a kneader or the like, and when a toner is produced by a polymerization method, spray drying or the like is used to relatively efficiently. Residual monomers can be removed. In particular, when producing a toner by a suspension polymerization method,
The toner particles can be removed even when heated and dried, and the treatment is performed using a conical mixer (dryer) with stirring under heating and reduced pressure. In this case, in general, not only the removal of the residual monomer but also the sphering treatment of the toner particles can be performed at the same time by adjusting the stirring conditions and the processing time, although the moisture in the toner remains dry. The shape of the toner can be made preferable. In the conventional toner, it is difficult to remove the residual monomer under such processing conditions, and aggregation or coalescence of the toner particles has occurred. By specifying the characteristics as described later, it becomes easy to remove the residual monomer from the inside of the toner, and the influence of the coarsening of the toner and the wax component on the sphering process of the toner particles as described above is minimized. This is very effective.

In the present invention, the residual monomer in the toner can be determined by a method using thermogravimetry (TG), which is measured as a weight loss during heating using a thermobalance or the like, or using gas chromatography (GC). A known method such as a method can be applied. Among these, the method using GC is a particularly effective method.

In the present invention, when the residual monomer in the toner is quantified by TG, the residual monomer can be determined from the weight loss observed when the sample is heated to 200 ° C. Specific examples are described below.

<Measurement conditions of TG> Apparatus: TGA-7, PE7700 (manufactured by PerkinElmer) Temperature rising rate: 10 ° C./min Measurement environment: under N ₂ atmosphere Further, the residual monomer in the toner is determined by GC. A specific example of such a case is shown below.

<GC measurement conditions> Apparatus: GC-14A (manufactured by Shimadzu Corporation) Column: fused silica capillary column (J & W SC)
Manufactured by IENTIFC; size: 30m x 0.249m
m, liquid phase: DBWAX, film thickness: 0.25 μm) Sample: 2.55 mg of DMF as an internal standard
Add 0 ml of acetone to make a solvent containing the internal standard. Next, 400 mg of the toner is made into a 10 ml solution with the above solvent. After 30 minutes on an ultrasonic shaker, leave for 1 hour. Next, the mixture is filtered with a 0.5 μm filter. The volume of the implanted sample is 4 μl. Detector: FID (split ratio: 1:20) Carrier gas: N ₂ gas Oven temperature: 70 ° C. → 220 ° C. (After waiting at 70 ° C. for 2 minutes, the temperature is raised at a rate of 5 ° C./min.) Inlet temperature: 200 ° C. Detector temperature: 200 ° C. Preparation of calibration curve: DMF in the same manner as the sample solution, and gas chromatographic measurement of a standard sample obtained by adding the target polymerizable vinyl monomer to an acetone solution, and the polymerizable vinyl monomer The weight ratio / area ratio between the body and the internal standard DMF is determined.

The glass transition point of the toner is determined by the polymerizable monomer,
The glass transition point Tg of the toner of the present invention is determined by a combination of a crosslinking agent, an initiator, polymerization conditions, and the like.
C. to 75.degree. C. is preferable, and 50.degree. When the glass transition point Tg is lower than 40 ° C., the storage stability is deteriorated and blocking occurs during storage, which is not preferable. When the glass transition point Tg exceeds 75 ° C.,
It is necessary to increase the energy consumption of the fixing device in order to obtain a fixed matter having a certain gloss, so that the power consumption is large, and the fixing heat energy needs to be sufficiently supplied to the toner. Must be. Therefore, a problem that an image cannot be formed at a general speed occurs, which is not preferable.

The glass transition point Tg of the toner according to the present invention
For example, a Perkin Elmer DSC-
The measurement is performed using a high-precision internal heating type input compensation type differential scanning calorimeter such as 7. The measurement method is “ASTM D3418-
82 ". In the present invention, the sample is heated once to obtain a pre-history, then rapidly cooled, and then cooled again at a temperature
A DSC curve measured when the temperature is raised in the range of 0 ° C / min and a temperature of 0 to 200 ° C is used.

The colorant that can be used in the toner of the present invention includes any appropriate pigment or dye. Toner colorants are well known and include, for example, black pigments such as carbon black, magnetic material, aniline black, acetylene black, lamp black, graphite, or mixtures thereof, or the following yellow colorants / magenta colorants / cyan colorants. What is mixed and toned to black is used.

As the yellow colorant, a condensed azo compound, an isoindolinone compound, an anthraquinone compound,
An azo metal complex, a methine compound, a compound represented by an allylamide compound, or the like is used. Specifically, C.I. I.
Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 109, 110,
111, 128, 129, 147, 168, 180 and the like are preferably used.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
44, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254 are particularly preferred.

Although such a pigment may be used alone, it is more preferable to use the pigment in combination with a dye to improve the sharpness from the viewpoint of the image quality of a full-color image.

Specific examples of the dye include, for example, C.I. I. Direct Red 1, C.I. I. Direct Blue 1, C.I. I.
Direct Green 6 and the like.

These are used in an amount necessary to maintain the optical density of the fixed image, and are usually 0.1 to 60 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the binder resin.
Used by weight.

The toner of the present invention can be used as a magnetic toner by incorporating a magnetic material into the toner particles. in this case,
Magnetic materials can also serve as colorants. Examples of the magnetic material used in the magnetic toner include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, and antimony. , Beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, alloys with metals such as vanadium and mixtures thereof. These may be appropriately subjected to a surface treatment such as a hydrophobic treatment.

These magnetic materials preferably have an average particle diameter of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount contained in the toner is preferably 20 to 200 parts by weight, more preferably 40 to 15 parts by weight, based on 100 parts by weight of the binder resin.

For producing the toner according to the present invention, known methods such as a melt pulverization method and a polymerization method are used.

As an example of the melt pulverization method, a compound represented by the general formula <A>, a binder resin, a wax, a pigment or a dye as a colorant, a magnetic material as required, and other additives are mixed with Henschel. After sufficiently mixing with a mixer such as a mixer or a ball mill, the resins, resins, and the like are melt-kneaded using a heat kneader such as a heating roll, a kneader, or an extruder so that the resins are mutually compatible. Is dispersed or dissolved, and after cooling and solidifying, pulverization and classification are performed to obtain the toner according to the present invention. In the classification step, it is preferable to use a multi-division classifier in terms of production efficiency.

As an example of the polymerization method, a compound represented by the general formula <A>
And a polymerizable monomer, a cross-linking agent, a polymerization initiator, a wax, a pigment as a coloring agent, a dye, or a magnetic substance, and other additives are mixed and dispersed, and a suspension dispersion stabilizer Polymerizable colorant resin particles are synthesized by suspension polymerization in an aqueous system in the presence, and solid-liquid separation, drying, and classification are performed to obtain the toner according to the present invention.

Specific examples of the suspension stabilizer include, for example, inorganic oxides such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, and the like. Examples include magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina, a magnetic material, and ferrite. As the organic compound, for example, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, starch and the like are used by being dispersed in an aqueous phase. It is preferable to use 0.2 to 10 parts by weight of these dispersants based on 100 parts by weight of the polymerizable monomer.

In the toner of the present invention, charging stability,
It is preferable to externally add an external additive to toner particles in order to improve developability, fluidity, and durability. Specific examples of the external additive include silica fine powder, hydrophobized silica fine powder, various resin particles, fatty acid metal salts, and the like, and these are preferably used alone or in combination.

The silica fine powder suitably used in the present invention has a specific surface area by nitrogen adsorption of 20 as measured by the BET method.
m ² / g or more and (especially 30 to 400 m ² / g) within the scope of. The amount of the silica fine powder is preferably 0.01 to 8 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner particles.

The silica fine powder is preferably treated with a surface treating agent, if necessary, for the purpose of hydrophobization and charge control. Specific examples of the surface treatment agent include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having a functional group, and other organosilicon compounds. These treating agents may be used alone or in combination.

Further, a lubricant powder may be added to the toner.
Examples of the lubricant powder include fluorine resins such as Teflon and polyvinylidene fluoride; fluorine compounds such as carbon fluoride; fatty acid metal salts such as zinc stearate; fatty acid derivatives such as fatty acids and fatty acid esters; and molybdenum sulfide.

It is also preferable to add the following inorganic powder in order to improve the developability and durability of the toner. Magnesium, zinc, aluminum, cerium, cobalt, iron,
Zirconium, chromium, manganese, strontium,
Oxides of metals such as tin and antimony; composite metal oxides such as calcium titanate, magnesium titanate and strontium titanate; metal salts such as calcium carbonate, magnesium carbonate and aluminum carbonate; clay minerals such as kaolin; Phosphoric acid compound; silicon carbide,
Silicon compounds such as silicon nitride; and carbon powders such as carbon black and graphite.

Among them, zinc oxide, aluminum oxide,
Fine powders of cobalt oxide, manganese dioxide, strontium titanate, and magnesium titanate are preferred.

In the image forming method of the present invention, various charging methods are used, and the direct charging method in which the charging member is brought into contact with the photosensitive member as described above is also preferably used. In this case, when a general toner is used, if residual toner after cleaning adheres directly to a charging member in a later process, charging failure is caused, and charging unevenness occurs on an image. Therefore, the amount of residual toner needs to be smaller and less likely to adhere as compared with corona discharge or the like in which the charging means does not contact the photoconductor. Therefore, in the direct charging method, it is necessary to use a toner whose average circularity and circularity standard deviation are strictly defined.

The condition of the developing step in the image forming method of the present invention is that it is essential that the toner carrier and the surface of the photoreceptor are in contact with each other, and more preferably, the reversal developing method is used. Further, by using the developing and cleaning system together, the size of the apparatus can be significantly reduced. At this time, at the time of development or at the time of blank before and after development, a bias of DC or AC component is applied to control the potential so that the development and the remaining toner on the photoreceptor can be collected. At this time, the DC component is located between the light portion potential and the dark portion potential.

As the toner carrier, a method of using an elastic roller, coating the surface of the elastic roller with a developer, and bringing the developer into contact with the surface of the photoreceptor is also used. In this case, development is performed by an electric field acting between the photoconductor and the elastic roller facing the photoconductor surface via the developer. Therefore, it is necessary to have an electric potential on the surface of the elastic roller or in the vicinity of the surface, and to have an electric field on the surface of the photoreceptor at a narrow gap between the toner carrying surface. For this reason, it is also possible to use a method in which the elastic rubber of the elastic roller is resistance-controlled in the medium resistance region to keep the electric field while preventing conduction with the photoreceptor surface, or to provide a thin insulating layer on the surface layer of the conductive roller. . Further, it is also possible to adopt a configuration in which a conductive layer is provided on a conductive roller on a conductive roller on which the side facing the photoreceptor surface is covered with an insulating material, or on a side not facing the photoreceptor with an insulating sleeve. It is also possible to employ a configuration in which a rigid roller is used as the toner carrier and the photosensitive member is made flexible such as a belt. The resistance of the developing roller as a toner carrier is 1
0 range of ^{2 ~l0 9 Ω} · cm is preferable.

When the surface shape of the toner carrier is set so that the surface roughness Ra (μm) is 0.2 to 3.0, both high image quality and high durability can be achieved. The surface roughness Ra correlates with the toner carrying ability and the developer charging ability.
When the surface roughness Ra of the toner carrier exceeds 3.0, it is not only difficult to reduce the thickness of the toner layer on the toner carrier, but also the chargeability of the toner is not improved, so that an improvement in image quality cannot be expected. . By setting the ratio to 3.0 or less, the toner carrying capacity on the surface of the toner carrier is suppressed, the toner layer on the toner carrier is made thinner, and the number of times of contact between the toner carrier and the toner increases. Since the chargeability of the toner is also improved, the image quality is synergistically improved. On the other hand, when the surface roughness Ra is 0.2
If it is smaller, it becomes difficult to control the amount of toner coating.

In the present invention, the surface roughness Ra of the toner carrier is measured using a surface roughness measuring device (Surfcoder SE-30H, manufactured by Kosaka Laboratory Co., Ltd.) based on JIS surface roughness "JISB 0601". Corresponds to the center line average roughness measured. Specifically, a 2.5 mm portion is extracted from the roughness curve in the direction of the center line as the measurement length a,
The center line of the extracted portion is the X axis, and the direction of the vertical magnification is Y.
When an axis and a roughness curve are represented by y = f (x), a value obtained by the following equation is represented by a micrometer (μm).

[0114]

(Equation 4)

In the image forming method according to the present invention, the toner carrier may rotate in the same direction as the peripheral speed of the photosensitive member.
It may be rotating in the opposite direction. When the rotation is in the same direction, the peripheral speed of the toner carrier is set at 1.0 to the peripheral speed of the photoconductor.
It is preferable to set so as to be 5 to 3.0 times.

If the peripheral speed of the toner carrier is less than 1.05 times the peripheral speed of the photoconductor, the effect of stirring the toner on the photoconductor becomes insufficient, and good image quality cannot be expected.
Also, when developing an image that requires a large amount of toner over a large area, such as a solid black image, the amount of toner supplied to the electrostatic latent image is insufficient and the image density is reduced. The higher the peripheral speed ratio, the greater the amount of toner supplied to the development site, the more frequently the toner is attached to and detached from the latent image, and unnecessary parts are collected and added to necessary parts. Thus, an image faithful to the latent image can be obtained. From the viewpoint of development and cleaning according to the present invention, when there is residual transfer toner adhered to the photoreceptor, the surface of the photoreceptor and the portion where the toner adheres are frictionally charged by the peripheral speed difference, and the toner is positively charged. Since the effect of collecting by the electric field is important, the higher the peripheral speed ratio is, the more convenient the collecting of the residual toner is. However, if the peripheral speed ratio exceeds 3.0, on the other hand, in addition to the various problems caused by the excessive charging of the toner as described above (image density reduction due to excessive toner charge-up, etc.), mechanical The deterioration of the toner due to the stress and the adhesion of the toner to the toner carrier are generated and accelerated, which is not preferable.

As the photosensitive member, a-Se, CdS, Zn
A photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as O ₂ , OPC or a-Si is preferably used.

The binder resin of the organic photosensitive layer in the OPC photosensitive member is not particularly limited. Among them, polycarbonate resin, polyester resin, and acrylic resin are particularly preferable because they are excellent in transferability and are less likely to cause fusion of a toner to a photoreceptor and filming of an external additive.

Next, the image forming method of the present invention will be described below with reference to the accompanying drawings.

In FIG. 1, reference numeral 140 denotes a developing device;
, A photosensitive member (image carrier); 127, a transfer material such as paper;
Reference numeral 4 denotes a transfer member, 126 denotes a pressure roller for fixing, 128 denotes a heating roller for fixing, and 117 denotes a primary charging member for directly charging the photosensitive member 100 by contacting the same.

A bias power supply 131 is connected to the primary charging member 117 so as to uniformly charge the surface of the photosensitive member 100.

The developing device 140 contains the toner 142, and includes the toner carrier 104 which rotates in the direction of the arrow in contact with the photosensitive member 100. Further, a developing blade 143 for regulating the amount of toner and applying a charge, and an application roller 141 that rotates in the direction of the arrow to attach the toner 142 to the toner carrier 100 and apply the charge to the toner by friction with the toner 100 are also provided. ing. A developing bias power supply 133 is connected to the toner carrier 104. A bias power supply 132 is also connected to the application roller 141, and the voltage is set to a negative side of the developing bias when using a negatively charged toner, and to a positive side than the developing bias when using a positively charged toner. Is done.

The transfer member 114 is connected to a transfer bias power supply 134 having a polarity opposite to that of the photosensitive member 100.

Here, the photosensitive member 100 and the toner carrier 10
The length of the contact portion 4 in the rotational direction, that is, the so-called development nip width is preferably 0.2 mm or more and 8.0 mm or less.
If the thickness is less than 0.2 mm, a sufficient image density cannot be obtained due to an insufficient development amount, and the transfer residual toner cannot be sufficiently recovered. 8.0
mm, the toner supply becomes excessive,
Fog suppression is apt to worsen, and also adversely affects wear of the photoreceptor.

As the toner carrier, a so-called elastic roller having an elastic layer on its surface is preferably used.

The hardness of the material of the elastic layer used is as follows.
Those having a temperature of 20 to 65 degrees (JIS A) are preferably used.

Further, the resistance of the toner carrier is preferably in the range of about 10 ² to 10 ⁹ Ω · cm in terms of volume resistance.
If it is lower than 10 ² Ω · cm, for example, if there is a pinhole on the surface of the photoconductor 100, an overcurrent may flow. On the other hand, when it is higher than 10 ⁹ Ω · cm, the toner is liable to be charged up due to frictional charging, and the image density is liable to be reduced.

The toner coat amount on the toner carrier is 0.1
1-1.5 mg / cm < ² > is preferable. 0.1 mg / cm ²
If the amount is less than 1.5 mg, it is difficult to obtain a sufficient image density.
/ Cm ^2, it becomes difficult to uniformly triboelectrically charge all the individual toner particles, which causes deterioration of fog suppression. Furthermore, 0.2 to 0.9 mg / cm ² is more preferable.

The toner coating amount is controlled by the developing blade 143. The developing blade 143 is in contact with the toner carrier 104 via the toner layer. The contact pressure at this time is preferably in the range of 5 to 50 g / cm. 5g
If it is less than / cm, it becomes difficult to control the amount of toner coat and uniform triboelectric charging, causing fog density and the like.
On the other hand, if it is larger than 50 g / cm, the toner particles are subjected to an excessive load, so that deformation of the particles and fusion of the toner to the developing blade or the toner carrier are liable to occur, which is not preferable.

As the toner coating amount regulating member, a metal blade, a roller, or the like may be used in addition to the elastic blade for press-applying the toner.

For the elastic regulating member, it is preferable to select a material of a triboelectric series suitable for charging the toner to a desired polarity. Silicone rubber, urethane rubber, NB
Rubber elastic bodies such as R; synthetic resin elastic bodies such as polyethylene terephthalate; metal elastic bodies such as stainless steel, steel and phosphor bronze can be used. Further, a composite thereof may be used.

When durability is required for the elastic regulating member and the toner carrier, it is preferable to apply a resin or rubber to the metal elastic body so as to contact the sleeve contact portion or apply a coating. .

Further, an organic substance or an inorganic substance may be added to the elastic regulating member, may be melted and mixed, or may be dispersed. For example, metal oxides, metal powders, ceramics, carbon allotropes, whiskers, inorganic fibers, dyes, pigments,
The chargeability of the toner can be controlled by adding a surfactant or the like. Particularly, when the elastic body is a molded body such as rubber or resin, fine particles of metal oxides such as silica, alumina, titania, tin oxide, zirconium oxide, and zinc oxide, carbon black, a charge control agent generally used for toner And the like.

Further, by applying a DC electric field and / or an AC electric field to the regulating member, the uniform thin layer coating property and the uniform charging property are further improved due to the loosening action on the toner, and the sufficient image density can be obtained. Achieved and good quality images can be obtained.

In FIG. 1, the primary charging member 117 uniformly charges the photosensitive member 100 rotating in the direction of the arrow.

The primary charging member used here is a core 117b at the center and a conductive elastic layer 117 forming the outer periphery thereof.
a is a charging roller having a basic configuration. Charging roller 1
Reference numeral 17 is abutted on the entire surface of the photoconductor with a pressing force, and is rotated by the rotation of the photoconductor 100.

A preferable process condition when the charging roller is used is that the contact pressure of the roller is 5 to 500 g / cm.
As the applied voltage, a DC voltage or a voltage obtained by superimposing an AC voltage on a DC voltage or the like is used, and is not particularly limited. However, in the present invention, an applied voltage of only a DC voltage is suitably used, and in this case, a voltage value is used. ± 0.2 to ± 5
Used in the range of kV.

Other charging methods include a method using a charging blade and a method using a conductive brush. These contact charging means, compared to non-contact corona charging,
There are effects that a high voltage becomes unnecessary and generation of ozone is reduced. The material of the charging roller and the charging blade as the contact charging means is preferably a conductive rubber, and a release coating may be provided on the surface thereof. As the release coating, a nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride) or the like can be applied.

After the primary charging step, an electrostatic latent image corresponding to the information signal is formed on the photoreceptor 100 by exposure 123 from the light emitting element 121, and the electrostatic latent image is Is developed into a visible image. Furthermore, in the image forming method of the present invention, especially in combination with a developing system in which a digital latent image is formed on a photoreceptor, it becomes possible to faithfully develop a dot latent image without disturbing the latent image. . Next, the visible image is transferred onto the transfer material 127 by the transfer member 114, and the transfer toner 129 is transferred to the heating roller 128 together with the transfer target 127.
, And is fixed by passing between the pressure roller 126 and a permanent image. As the heating and pressing fixing means, a heating roller having a built-in heating element such as a halogen heater and an elastic pressing roller pressed against the pressing roller with a pressing force are used in addition to the heating roller system having a basic configuration. A method of fixing by heating with a heater via a film is also used.

On the other hand, the untransferred toner 124 remaining on the photoreceptor 100 without being transferred is transferred to the developing bias 1 at the same time as the development.
At 33, the toner is collected from the photoconductor 100 into the developing container 142 via the toner carrier 104.

Next, a full-color image forming method of a contact developing method using an intermediate transfer member will be described.

In the apparatus system shown in FIG. 2, the developing devices 4-1, 4-2, 4-3, and 4-4 respectively include a developer having a cyan toner and a developer having a magenta toner.
A developer having a yellow toner and a developer having a black toner are introduced, and the electrostatic latent image formed on the photoconductor 1 is developed by the above-described developing method or the like, and a toner image of each color is formed on the photoconductor 1. .

As the developing means, development can be performed using, for example, a developing means having a developing device 140 as shown in FIG. Specifically, the developer 142 b supplied from the application roller 141 and having its coating amount regulated by the developing blade 103 comes into contact with the photoconductor 100 while applying a direct current or an alternating electric field to the developer carrier 104 by a power supply. Development is performed in the state. When an alternating electric field is used, various waveforms such as a triangular wave, a rectangular wave, a sine wave, a waveform in which the duty ratio is changed, and a waveform in which the alternation is periodically turned off can be selected and used. A DC electric field with a small voltage load on the body is preferably used, and the applied voltage is set to an appropriate value between a dark potential (potential immediately after the charging step) and a light potential (potential after the exposure step) on the photoreceptor. Is done.

In any case, it is more preferable to set the peripheral speed of the developer carrying member to be 1.05 to 3.0 times the peripheral speed of the photosensitive member.

The visualized toner image on the photosensitive member is applied to a voltage (for example, ±
(0.1 to 5 kV) is primarily transferred to the intermediate transfer member 5 to which a voltage of 0.1 to 5 kV is applied. At this time, the transfer residual toner on the photoreceptor that has not been transferred passes through the charging and exposure unit, and is collected in the developing container during development by the developer carrier 104 in contact with the photoreceptor.

The intermediate transfer member 5 is provided in parallel with the photosensitive member 1 so as to be in contact with the lower surface of the photosensitive member 1, and is rotated at the same peripheral speed as the photosensitive member 1 in the counterclockwise direction indicated by the arrow. I do.

The first color toner image formed and carried on the surface of the photoreceptor 1 passes through the transfer nip where the photoreceptor 1 and the intermediate transfer member 5 are in contact with each other, and is successively applied to the outer surface of the intermediate transfer member 5. The intermediate transfer is performed. After the transfer of the toner image to the transfer material, the surface of the intermediate transfer body 5 is cleaned by the detachable cleaning means 10.

The transfer means 7 is disposed in parallel with the intermediate transfer body 5 and is brought into contact with the lower surface of the intermediate transfer body 5. The transfer means 7 is, for example, a transfer roller or a transfer belt. 5 rotates in the clockwise direction of the arrow at the same peripheral speed. The transfer unit 7 may be disposed so as to directly contact the intermediate transfer member 5, or a belt or the like may be disposed so as to contact between the intermediate transfer member 5 and the transfer unit 7.

In the case of the transfer roller, the basic configuration is a core metal 7b at the center and a conductive elastic layer 7a formed on the outer periphery thereof.

The intermediate transfer member 5 includes a pipe-shaped conductive core 5b and a medium-resistance elastic layer 5 formed on the outer peripheral surface thereof.
a. The cored bar 5b may be formed by applying a conductive plating to a plastic pipe.

The medium resistance elastic layer 5a is made of an elastic material such as silicone rubber, Teflon (registered trademark) rubber, chloroprene rubber, urethane rubber, ethylene-propylene-diene terpolymer (EPDM), or carbon black. , Zinc oxide, tin oxide, silicon carbide and the like, and an electric resistance (volume resistivity) of 10 ⁵ to 10
^{This is} a solid or foamed layer adjusted to medium resistance of ¹¹ Ω · cm.

By setting the volume resistivity of the elastic layer of the intermediate transfer member to be smaller, the voltage applied to the transfer roller can be reduced, a good toner image can be formed on the transfer material, and the transfer material can be transferred to the intermediate transfer member. Winding can be prevented. In particular, it is preferable that the volume resistivity of the elastic layer of the intermediate transfer member is 10 times or more the volume resistivity of the elastic layer of the transfer roller.

For example, the conductive elastic layer 7b of the transfer roller 7
Is a polyurethane, ethylene-propylene-diene-based terpolymer (EPD) in which a conductive material such as carbon is dispersed.
M) and the like are made of an elastic body having a volume resistance of about 10 ⁶ to 10 ¹⁰ Ω · cm. A bias is applied to the core metal 7a from a low voltage power supply. The bias conditions are ±
0.2 to 10 kV is preferred.

Since the toner of the present invention contains a wax in a special dispersion state in addition to controlling the surface shape, it does not adversely affect the charging of the toner. Since the residual toner is small, the charging device is hardly affected. Further, the transfer residual toner that has passed through the charging device is satisfactorily collected in the developing container at the same time as the development in the developing section, so that the image after development is less likely to be adversely affected.

Furthermore, even when a multi-sheet durability test is performed, the amount of toner fusion to the developing blade, which tends to occur when a conventional toner is used, is very small, so that a good image without development unevenness is maintained for a long time. I can do it.

Next, the toner image on the transfer material 6 is fixed by a heat and pressure fixing means to obtain a permanent image.

[0157]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Production Examples and Examples, but this does not limit the present invention in any way. All parts in the following formulations are parts by weight.

Production Example (1) An aqueous solution of Na ₃ PO ₄ was added to a two-liter four-necked flask equipped with a high-speed stirrer TK-Homomixer, the rotation speed was adjusted to 9000 rpm, and the mixture was heated to 63 ° C. Was.
An aqueous solution of CaCl ₂ was gradually added thereto to prepare an aqueous dispersion medium containing a minute hardly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ .

On the other hand, styrene monomer 80 parts by weight 2-ethylhexyl acrylate monomer 20 parts by weight divinylbenzene monomer 0.2 parts by weight Saturated polyester resin 10 parts by weight (terephthalic acid-propylene oxide-modified bisphenol A, acid value 15 mgKOH / g) 8 parts by weight of carbon black (primary particle diameter 40 nm) 10 parts by weight of wax component (ester wax) 2.0 parts by weight of compound (1) The above materials were dispersed for 3 hours using a ball mill. After that, the contents were isolated from a ball mill. A polymerizable monomer composition to which 3 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added to the content was charged into the aqueous dispersion medium. 9000 rpm
granulated while maintaining m. Thereafter, the mixture was reacted at 65 ° C. for 4 hours while being stirred by a paddle stirring blade, and further polymerized at 80 ° C. for 5 hours, and then 13.3 kPa (100 Torr) at 85 ° C.
r) The polymerizable monomer remaining in the toner was reduced by distillation under reduced pressure to the following pressure.

After the completion of the reaction, the suspension was cooled, hydrochloric acid was added to dissolve the poorly water-soluble dispersant Ca ₃ (PO ₄ ) _2, and the mixture was filtered, washed with water and dried, and then classified into a desired particle size by air classification. Thus, colored particles (1) were obtained.

With respect to 100 parts by weight of the above colored particles (1)
Treated with hexamethyldisilazane as flow improver
Hydrophobic silica fine powder (BET specific surface area: 300m^Two /
g) 1.5 parts by weight are dry-mixed with a Henschel mixer.
Thus, the toner (1) of the present invention was obtained.

The toner (1) has a melt index of 10
g / 10 minutes, the circle-equivalent average particle diameter D ₁ was 6.7 μm, the average circularity was 0.973, the circularity standard deviation was 0.029, and the toner with a circularity less than 0.950 was 9%. Further T
As a result of observation of a cross section in the toner by EM, the wax dispersion state in the toner particles was spherical, and the value of (r / R) _st was 0.55. The residual amount of the polymerizable monomer in the toner was 50 ppm.

Production Examples (2) to (8) Colored particles (2) to ( 8) were prepared in the same manner as in Production Example (1) except that the formulation in Production Example (1) was changed only in the portions shown in Table 2. 8) and Toners (2) to (8) were prepared.

Comparative Production Example (1) In Production Example (1), 1 part by weight of the following compound <F> was used in place of compound (1), and the particle size of the colored particles was changed by changing the air classification conditions. A comparative colored particle (1) and a comparative toner (1) were prepared in the same manner as in Production Example (1) except for the change.

[0165]

Embedded image

Comparative Production Example (2) In the production example (1), 1 part by weight of the compound (8) was used instead of the compound (1), a toner was synthesized without performing a distillation operation, and styrene and acrylic components were used. Comparative Colored Particles (2) and Comparative Toner (2) were prepared in the same manner as in Production Example (1) except that the ratio was changed as shown in Table 2.

Table 2 summarizes the formulations and various properties of the obtained toners.

[0168]

[Table 2]

Production Example (9) 100 parts by weight of styrene / 2-ethylhexyl acrylate copolymer resin (glass transition temperature 65 ° C., crosslinked content 5%) 10 parts by weight of carbon black (primary particle diameter 35 nm) 10 parts by weight Compound (1) 2.0 parts by weight • 10 parts by weight of a wax component (ester wax; mp = 80 ° C.) were mixed and melt-kneaded with a twin-screw extruder. After cooling, the kneaded material was roughly pulverized by a hammer mill and finely pulverized by a jet mill. Further, the particles were sprayed in a hot air, heated to be spherical, and then classified to obtain colored particles (9).

Hydrophobic silica fine powder treated with hexamethyldisilazane as a flow improver (BET specific surface area: 300 m ² /
g) 1.5 parts by weight were dry-mixed with a Henschel mixer to obtain Toner (9).

The toner (9) had a melt index of 18 g / 10 min and a circle-equivalent average particle diameter D ₁ of 8.2 μm.
m, average circularity is 0.950, circularity standard deviation is 0.0
36, the toner having a circularity of less than 0.950 was 14%. Further, as a result of observation of a cross section in the toner by TEM, the wax dispersion state in the toner particles was finely dispersed.
The residual amount of the polymerizable monomer in the toner was 130 ppm.
Met.

Production Examples (10) to (12) Toner (1) was prepared in the same manner as in Production Example (9) except that the formulation in Production Example (9) was changed only in the portion shown in Table 3.
0) to (12) were prepared.

Comparative Production Example (3) In Production Example (9), 1 part by weight of the compound (F) was used in place of the compound (1), and the binder resin was a styrene / 2-ethylhexyl acrylate copolymer resin (glass transition Comparative Colored Particles (3), Comparative Toner (3), and Comparative Developer (3) were prepared in the same manner as in Production Example (9) except that the temperature was changed to 80 ° C. and the cross-linking amount was 25%.

Comparative Production Example (4) In Production Example (9), 1 part by weight of the compound (8) was used instead of the compound (1), and the binder resin was styrene.
Coloring for comparison was carried out in the same manner as in Production Example (9) except that the process was changed to a 2-ethylhexyl acrylate copolymer resin (glass transition temperature: 50 ° C, no cross-linking component), and the step of spraying in hot air and heating was omitted. Particles (4), Comparative toner (4)
Was prepared.

Comparative Production Example (5) Comparative Production Particles (5) and Comparative Colored Particles (5) were prepared in the same manner as in Production Example (9) except that Compound (1) was not used. Toner (5) was prepared.

Table 3 summarizes the formulations and properties of the toner particles obtained in Production Examples (9) to (12) and Comparative Production Examples (3) to (5).

[0177]

[Table 3]

<Examples 1 to 12 and Comparative Examples 1 to 5> The image forming apparatus used in this example will be described below.

FIG. 3 is a schematic diagram of a modified machine of a 600 dpi laser beam printer (manufactured by Canon: LBP-860) using an electrophotographic process of a non-magnetic one-component contact developing system. In this embodiment, an apparatus modified from the following parts (a) to (h) was used. (A) The process speed was changed to 65 mm / s. (B) The charging method of the apparatus was direct charging performed by abutting a rubber roller, and the applied voltage was a DC component (-1200 V). (C) A medium-resistance rubber roller (16φ, hardness: silicone rubber containing carbon black dispersed in a toner carrier)
(ASKER C 45 °, volume resistance: 10 ⁵ Ω · cm) and contacted the photosensitive member. (D) The rotational peripheral speed of the toner carrier is in the same direction at the portion in contact with the photoreceptor, and is 14 relative to the rotational speed of the photoreceptor.
It was driven to be 0%. (E) The photoconductor was changed to the following.

The photosensitive member used here is 30φ, 2
A 54 mm Al cylinder was used as a substrate, and layers having the following constitutions were sequentially laminated by dip coating on the substrate to prepare a photoreceptor. -Conductive coating layer: mainly composed of tin oxide and titanium oxide powder dispersed in a phenol resin (film thickness: 15 μm).
m). -Undercoat layer: mainly composed of modified nylon and copolymerized nylon (film thickness 0.6 μm). -Charge generation layer: mainly composed of a butyral resin in which a titanyl phthalocyanine pigment having absorption in a long wavelength region is dispersed (film thickness: 0.6 μm). Charge transport layer: Mainly composed of a hole transporting triphenylamine compound dissolved in a polycarbonate resin (molecular weight 20,000 according to Ostwald viscosity method) at a weight ratio of 8:10 (film thickness: 20 μm). (F) As a means for applying the toner to the toner carrier, an application roller made of urethane foam rubber is provided in the developing device,
It was brought into contact with the toner carrier. About -5 for the application roller
A voltage of 50 V is applied. (G) A stainless steel blade coated with a resin for controlling the toner coat layer on the toner carrier was attached such that the contact pressure with the toner carrier was about 20 g / cm. (H) The applied voltage at the time of development was only the DC component (−450 V).

The electrophotographic apparatus was remodeled and the process conditions were set as follows so as to conform to the remodeling of these process cartridges.

The modified device uniformly charges the image carrier using a roller charger (only DC is applied). After charging, an electrostatic latent image is formed by exposing an image portion with a laser beam, a visible image is formed with toner, and then the toner image is transferred to a transfer material by a roller to which a voltage of +700 V is applied. An outline is shown in FIG.

Further, the charging potential of the photosensitive member is set to -5
80 V, and the bright portion potential was -150 V.

With the image forming apparatus, toners (1) to
(12) and comparative toners (1) to (5),
The durability test was performed under the conditions of a temperature of 23 ° C. and a humidity of 55%.

The durability test was conducted by using a horizontal line pattern image having a print area ratio of 6% using a CLC paper manufactured by Canon. Table 4 summarizes the above image evaluation results. Table 5 shows the matching with the image forming apparatus.

[0186]

[Table 4]

[0187]

[Table 5]

In Examples 1 to 12, the matching with the image forming apparatus was good. This is because the developer containing the exemplified compound has good chargeability and charging speed, and the toner has a spherical shape. It is considered that the fact that the transfer was good and no omission occurred during the transfer due to good transfer, and that the simultaneous recovery with development was good is the result of the synergistic effect.

The evaluation criteria shown in this example are shown below.

Printout Image Evaluation (1) Image Density The image density was evaluated based on the image density at the end of printing 100 sheets. The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth) with respect to the printout image of a white background portion having a document density of 0.00. A: 1.35 or more B: 1.25 or more, less than 1.35 C: 1.00 or more, less than 1.25 D: less than 1.00

(2) Image fog The fog density (%) was calculated from the difference between the whiteness of the white portion of the printout image measured by the “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper. Image fog was evaluated. A: less than 1.5% B: 1.5% or more, less than 2.5% C: 2.5% or more, less than 4.0% D: 4.0% or more

(3) Missing During Transfer The “surprise” character pattern shown in FIG.
g / m ² ) (Figure 4)
(State (b)) was visually evaluated. A: Almost no occurrence B: Slight hollowing out C: Some hollowing out D: Remarkable hollowing out

(4) Recoverability of Residual Toner The transfer residual toner on the developing drum, which is generated when a solid image of 15 mm square is printed on thick paper (128 g / m ² ), is collected simultaneously with development immediately after passing through the developing unit. From the difference between the measured value of Macbeth density (“Macbeth reflection densitometer” (manufactured by Macbeth)) obtained by taping the toner image remaining on the developing drum and the measured value of the Macbeth density of the non-image portion of the taping. The toner recoverability was evaluated. A: below the detection limit B: less than 0.20 C: 0.20 or more, less than 0.50 D: 0.50 or more

Matching with Image Forming Apparatus (5) Developing Streaks The state of the coating streaks on the developing sleeve after developing 100 sheets was visually evaluated. A: Not generated B: Slight scratches are seen, but there is no effect on the image C: Clear streak, but little effect on image D: Clear streak, vertical streak image Cause defects

(6) Fusion of Drums A single color halftone image was continuously printed out on 1,000 sheets, and the drum was visually evaluated. A: Level at which no deposits on the drum can be confirmed B: Some deposits on the drum can be confirmed C: Deposits on the drum can be confirmed D: Deposits on the drum are remarkable, and traces can be confirmed on the image

(7) Back Stain by Offset Paying attention to the stain on the back of the printing paper due to the offset at the time of fixing, the back stain in 100 printouts was visually observed and evaluated based on the following evaluation criteria. A: Not recognized at all B: 1-2 out of 100 C: 3-5 out of 100 D: 6 or more out of 100

<Example 13> Under the following experimental conditions,
A durability evaluation was performed on a full-color image.

FIG. 2 is a schematic sectional view of an image forming apparatus applied to the thirteenth embodiment, and FIG. 3 is a view of a developing device of the image forming apparatus.

The photosensitive drum 1 has a photosensitive layer 1b having an organic optical semiconductor on a substrate 1a. The charging roller 2 (conductive elastic layer 2a, core metal 2b, ) To charge the photosensitive drum 1 to a surface potential of about -600 V. In the exposure, a polygon mirror is turned on / off on the photoreceptor in accordance with digital image information, so that an exposure portion potential is -100 V and a dark portion potential is -600.
An electrostatic charge image of V is formed. Developing units 4-1, 4-2, 4
-3 and 4-4, the toner (1), the toner (3), the toner (5) and the toner (7) are respectively introduced, and the electrostatic latent image formed on the photoconductor 1 by the non-magnetic one-component system is formed. Reverse development is performed, and a toner image of each color is formed on the photoconductor 1. The toner images are sequentially transferred onto the intermediate transfer body 5 after the development for each color, and finally are collectively transferred onto the transfer body 6. At this time, the toner remaining on the photoreceptor 1 without being transferred is collected at the same time as the development at the time of development by the sleeve in contact with the photoreceptor 1, so that the toner is collected in the developing device.

The intermediate transfer member 5 is obtained by coating a pipe-shaped core 5b with an elastic layer 5a in which a carbon black conductive material is sufficiently dispersed in nitrile-butadiene rubber (NBR). The hardness of 5a is "J
SK-6301 "and a volume resistivity of 10 ⁹ Ω · cm. In this experiment, the transfer from the photoconductor 1 to the intermediate transfer body 5 was performed at +700 V from the power supply.
Was applied on the cored bar 5b.

The transfer roller 7 has an outer diameter of 20 mm. The transfer roller 7 is made of an ethylene-propylene-diene terpolymer (EPDM) on a core bar 7 b having a diameter of 10 mm. Elastic layer 7 formed by coating a substance sufficiently dispersed in a foam.
a, and the volume resistivity of the elastic layer 7a is 10 ⁶ Ω · c
For m, the standard hardness of “Jls K-6301” having a value of 35 degrees was used. A voltage was applied to the transfer roller, and a transfer current of 11 μA was passed.

As the heat fixing device H, a heat roll type fixing device having no oil application function was used.

Under the above set conditions, a temperature of 25 ° C./humidity of 55
%, An image having a print area of 4% was evaluated for durability by continuous printing at a sheet passing speed of 8 sheets / min (A4 size).

As a result, no image defect due to a poor recovery of the transfer residual toner is observed, and an image having excellent image density, transferability and resolution and less fogging can be stably obtained up to 1000 printed sheets. In addition, no streaks were generated during development, and no fusion of toner was confirmed on the drum or the intermediate transfer member.

[0205]

As described above, according to the image forming method of the present invention, by combining a toner containing a specific compound and exhibiting a melt index value within a certain range with an appropriate contact developing system, By simultaneous recovery with development, it becomes possible to efficiently collect transfer residual toner in the developing device. In addition, stable image density and low image fog can be realized, and excellent image characteristics in which occurrence of omission during transfer is suppressed can be obtained. Further, it is possible to obtain a toner and an image forming method that are highly matched to the electrophotographic process by suppressing the occurrence of development streaks and drum fusion.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a one-component image forming apparatus suitable for the present invention.

FIG. 2 is a schematic diagram of a full-color image forming apparatus using an intermediate transfer member suitable for the present invention.

FIG. 3 is a schematic explanatory view of a developing device suitable for the present invention.

FIG. 4 is a schematic explanatory diagram of the evaluation of transfer omission used in the present invention.

DESCRIPTION OF SYMBOLS 100 Photoconductor (image carrier) 104 Toner carrier 117 Charging means 123 Exposure 127 Transfer material 140 Developing device 142 Toner 143 Developing blade

Continued on the front page F term (reference) 2H005 AA01 AA06 AA15 AB06 CA04 CA14 CA25 DA02 EA03 EA05 2H077 AA37 AD06 AD31 BA03 CA19 EA14 EA15

Claims (17)

[Claims] 1. An image carrier for carrying an electrostatic latent image.
(B) forming an electrostatic latent image on the charged image carrier by image exposure
An exposing step for forming; (c) a toner uniformly carried on the surface of the toner carrier
The layer contacts the surface of the image carrier to form the electrostatic latent image.
(D) intermediately rotating the toner image formed on the surface of the image carrier;
A transfer process that transfers to a transfer material with or without a photoreceptor
And (e) toner remaining on the surface of the image carrier after the transfer step.
In the developing process, the developer is also used in the developing process.
Image forming method using image and cleaning method
Wherein the toner comprises a binder resin, a colorant, a wax component,
At least a compound represented by the general formula <A>,
And measured according to “JIS K7210” of the toner.
Melt index at 125 ° C / 5 kg load (M
I) is 0.5 to 80 g / 10 min.
toner. Embedded image(Where R₁And R_FourIs a substituted or unsubstituted aromatic (fused ring)
And R)_TwoAnd R_ThreeRepresents a hydrogen atom, an alkyl group,
Represents a substituted or unsubstituted aromatic (including a condensed ring), and M is
B, T i, Fe, Co, Cr, Al and Ni
X represents the element selected from the loop^{n +}Indicates a cation
You. ) 2. A melt index (MI) of 3 to 25.
The toner according to claim 1, wherein g / 10 minutes. 3. In a scattergram of circle-based circularity-circularity based on the number of toners measured by a flow-type particle image measuring apparatus, the circle-equivalent number average diameter D ₁ (μm) of the toner is 2
And the average circularity of the toner is 0.1 to 10 μm.
The toner according to claim 1, wherein the circularity standard deviation is 920 to 0.995 and less than 0.040. 4. The toner has an average circularity of 0.950 or more.
4. The toner of claim 3 wherein the circularity standard deviation is less than 0.035 at 0.995. 5. The toner has an average circularity of 0.970 or more.
0.990, circularity standard deviation is 0.015 or more and 0.0
The toner according to claim 3, wherein the ratio is less than 35. 6. In a scattergram of a circle equivalent diameter-circularity based on the number of toners measured by a flow-type particle image measuring device, toner particles having a circularity of less than 0.950 are 15% by number or less. The toner according to any one of claims 1 to 5, wherein 7. Observation of a tomographic plane of toner particles using a transmission electron microscope (TEM): (1) A circle-equivalent weight average diameter D ₄ (μm ) To 0.9
Twenty tomographic planes of toner particles exhibiting a long diameter R (μm) satisfying the relationship of ≦ R / D ₄ ≦ 1.1 are selected. (2) A phase caused by a wax component present in the tomographic planes of the selected toner particles. Among the separation structures, the longest diameter r of the largest one is measured. (3) The arithmetic mean value (r / R) _{st of the obtained} r / R is 0.05 ≦ (r / R) _st ≦ 0. The toner according to any one of claims 1 to 6, wherein the wax component is dispersed in the binder resin in a spherical and / or spindle-shaped island shape so as to satisfy 95. 8. The arithmetic mean value of the r / R (r / R)
_The wax component is dispersed in the binder resin into spherical and / or spindle-shaped islands so that _st satisfies 0.25 ≦ (r / R) _st ≦ 0.90. 7. The toner according to 7. 9. The residual amount of the polymerizable monomer in the toner is 20.
The toner according to any one of claims 1 to 8, wherein the content is 0 ppm or less. 10. An image carrier for carrying an electrostatic latent image.
Charging step of charging the carrier; (b) charging the image carrier
An exposure step of forming an electrostatic latent image by image exposure;
The toner layer uniformly supported on the surface of the toner carrier
The electrostatic latent image is developed by contacting the surface of the carrier.
A developing step which is accomplished to form a toner image;
The toner image formed on the surface of the image carrier is transferred via an intermediate transfer member.
A transfer step of transferring to a transfer material with or without
And (e) on the surface of the image carrier after the transfer step.
The recovery of the remaining toner is performed in the developing
Image type using the development and cleaning method that is also used by the device
A toner for use in a method of forming
Fat, colorant, wax component, and represented by the following general formula <A>
Containing at least a compound represented by the formula
125 ° C / 5k measured according to “IS K7210”
Melt index (MI) under g load of 0.5 to 80
g / 10 minutes. Embedded image(Where R₁And R_FourIs a substituted or unsubstituted aromatic (fused ring)
And R)_TwoAnd R_ThreeRepresents a hydrogen atom, an alkyl group,
Represents a substituted or unsubstituted aromatic (including a condensed ring), and M is
B, T i, Fe, Co, Cr, Al and Ni
X represents the element selected from the loop^{n +}Indicates a cation
You. ) 11. The melt index (MI) is 3 to 2.
The image forming method according to claim 10, wherein the amount is 5 g / 10 minutes. 12. In a scattergram of circle-based circularity-circularity based on the number of toners measured by a flow-type particle image measuring apparatus, the circle-equivalent number average diameter D ₁ (μm) of the toner is 2 to 10 μm, In addition, the average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0.04.
The image forming method according to claim 10, wherein the value is less than zero. 13. The toner has an average circularity of 0.950 or more.
The image forming method according to claim 12, wherein the circularity standard deviation is less than 0.035 at 0.995. 14. The toner according to claim 1, wherein the toner has an average circularity of 0.970 or more.
0.990, circularity standard deviation is 0.015 or more and 0.0
The image forming method according to claim 12, wherein the number is less than 35. 15. In a scattergram of circularity-circularity based on the number of toners measured by a flow-type particle image measuring device, toner particles having a circularity of less than 0.950 are not more than 15% by number. The image forming method according to claim 10. 16. In a tomographic observation of toner particles using a transmission electron microscope (TEM), (1) a weight-based circle-equivalent weight average diameter D ₄ (μm) of the toner measured by a flow type particle image measuring device. ) To 0.9
Twenty tomographic planes of toner particles exhibiting a long diameter R (μm) satisfying the relationship of ≦ R / D ₄ ≦ 1.1 are selected. (2) A phase caused by a wax component present in the tomographic planes of the selected toner particles. Among the separation structures, the longest diameter r of the largest one is measured. (3) The arithmetic mean value (r / R) _{st of the obtained} r / R is 0.05 ≦ (r / R) _st ≦ 0. The image forming method according to any one of claims 10 to 15, wherein the wax component is dispersed in the binder resin into spherical and / or spindle-shaped islands so as to satisfy 95. 17. An arithmetic mean value of the r / R (r / R) _st
The wax component is dispersed in the binder resin into spherical and / or spindle-shaped islands so as to satisfy 0.25 ≦ (r / R) _st ≦ 0.90. 2. The image forming method according to 1.,