JP2000305320A - Dry toner and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dry toner excellent in environmental stability, having no adverse effect on a photoreceptor and an interim transfer body, less liable to cause image deterioration such as fogging and highly applicable to an electrophotographic process. SOLUTION: The dry toner contains at least a bonding resin, a colorant, a wax component and a polyester resin. This polyester resin comprises polycarboxylic acids and polyols, at least one of the polycarboxylic acids and/or the polyols has an alicyclic structure and the polyester resin is contained in the dry toner by 0.1-50 wt.% of the amount of the toner. In the equivalent circular diameter-circularity scattergram of the toner on number basis measured with a flow type particle image measuring device, the equivalent circular number average diameter D1 of the dry toner is 2-10 μm, the average circularity of the toner is 0.950-0.995 and the standard deviation of circularity is <0.040.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry toner (hereinafter referred to as "toner") used in a recording method utilizing an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet method, and the like. The present invention relates to an image forming method used. More specifically, the present invention relates to a toner used in an image recording apparatus that can be used in a copying machine, a printer, a facsimile, a plotter, and the like, and an image forming method using the toner. In particular, the higher the image density, the less the fog or transfer residue, the better the image quality, as well as the good stability of the image quality due to the good chargeability, the excellent environmental stability, and the developer The present invention relates to a toner and an image forming method that cause less contamination of a carrier member, a photoconductor, a transfer roller, a fixing device, and the like.

[0002]

2. Description of the Related Art US Pat.
Numerous methods are known as described in JP-B-97,691, JP-B-42-23910 and JP-B-43-24748. Generally, a photoconductive substance is used to form an electrostatic latent image on a photoreceptor by various means, and then the electrostatic latent image is developed using toner, and if necessary, transferred to paper or film. After the toner image is transferred to the material, the toner image is fixed by heating, pressure, heating and pressurizing, or solvent vapor to obtain a toner image.

As a method for visualizing an electrostatic latent image, a cascade developing method, a magnetic brush developing method, a pressure developing method and the like are known. Further, a method is also used in which a magnetic toner is used and a rotating sleeve having a magnetic pole disposed at the center is used to fly between the photosensitive member and the sleeve by an electric field.

[0004] Unlike the two-component system, the one-component system does not require carrier particles such as glass beads and iron powder, so that the developing device itself can be reduced in size and weight. Further, in the two-component developing system, since it is necessary to keep the toner concentration in the carrier constant, a device for detecting the toner concentration and supplying a necessary amount of toner is required. Therefore, the developing device also becomes large and heavy here. In the one-component developing system, such a device is not required, so that the device can be made smaller and lighter, which is preferable.

[0005] The printer device is an LBP or LED.
2. Description of the Related Art Printers have become the mainstream in the market these days, and the direction of technology is higher resolution, that is, 300 or 600 dpi.
What has been about 1200 and 2400 dpi has been achieved. Accordingly, higher definition has been required for the developing system. In addition, the functions of the copying machine have been advanced, and the digital copying machine is moving toward digitalization. In this direction, a method of forming an electrostatic charge image with a laser is mainly used, so that the direction is also moving toward a higher resolution, and a high-resolution and high-definition developing method is required similarly to a printer. .

In order to achieve high resolution and high definition, it is required to reduce the particle size of the toner. However, when the particle size of the toner is reduced, the chargeability of the toner particles increases, and in order to achieve the above object, control of the toner particle becomes important.

For example, Japanese Patent No. 2632251 proposes a toner in which a specific carbon black is adhered to the surface of toner particles having an average particle diameter of 3 to 8 μm produced by a polymerization method. When an image is output using a toner in which a material for controlling chargeability is disposed on the surface of such particles, when the number of sheets passed exceeds approximately 5,000, carbon black adhering to the particle surface drops off. As a result, the chargeability of the toner greatly changes, and the charge stability becomes insufficient.

Japanese Patent Application Laid-Open No. 5-94042 discloses a proposal for controlling the environmental stability of charging properties from the viewpoint of materials.
And JP-A-6-19197. However, these are still insufficient levels in fog and transfer residue when image evaluation is actually performed.

As described above, in reality, there is no toner that satisfies high resolution, high definition, and environmental stability of chargeability.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which provides a high-resolution and high-definition image and satisfies the environmental stability of chargeability, and an image forming method using the toner. is there.

[0011]

Means for Solving the Problems The present inventors have examined the effects of the particle size frequency distribution and the circularity frequency distribution on the developability and transferability of the toner particles, and found that they have a very deep relationship. This has led to the present invention.

That is, the present invention relates to a dry toner containing at least a binder resin, a colorant, a wax component, and a polyester resin, wherein the polyester resin comprises a polycarboxylic acid and a polyhydric alcohol, Further, at least one of the polyhydric carboxylic acid and / or the polyhydric alcohol has an alicyclic structure, and the polyester resin is contained in the dry toner in an amount of 0.1 to 50 based on the toner.
% Of the dry toner, the circle-equivalent number average diameter D of the dry toner in the scattergram of circle-based circularity based on the number of toners measured by a flow-type particle image measuring device of the toner.
1 (μm) is 2 to 10 μm, the average circularity of the toner is 0.950 to 0.995, and the circularity standard deviation is less than 0.040.

The present invention also provides at least a charging step of applying a voltage to a charging member from the outside to charge an electrostatic latent image carrier, and forming an electrostatic latent image on the charged electrostatic latent image carrier. Forming a latent image, developing the electrostatic charge image with toner to form a toner image on the electrostatic latent image carrier, and transferring the toner image on the electrostatic latent image carrier to a transfer material The present invention relates to an image forming method including a transfer step and a fixing step of heating and fixing a toner image on a transfer material, wherein the toner having the above configuration is used as the toner.

Further, the present invention provides at least a charging step of applying a voltage to a charging member from the outside to charge the electrostatic latent image carrier, and forming an electrostatic latent image on the charged electrostatic latent image carrier. A latent image forming step of forming, and a developing step of developing the electrostatic charge image with toner to form a toner image on the electrostatic latent image carrier,
A first transfer step of transferring a toner image on an electrostatic latent image carrier to an intermediate transfer body, a second transfer step of transferring a toner image on the intermediate transfer body to a transfer material, A fixing step of heating and fixing an image, wherein the toner having the above configuration is used as the toner.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The toner of the present invention comprises a binder resin,
It is essential that a coloring agent, a wax component and a polyester resin are contained, and at least one of the polycarboxylic acids and / or polyhydric alcohols constituting the polyester resin must contain an alicyclic structure. Must.

The reason is considered to be that the water absorption of the toner is reduced by having the alicyclic structure, and as a result, the rise of the charge of the toner is accelerated, and the environmental stability of the chargeability is improved. .

The alicyclic structure, for example, in the case of a six-membered ring, a chair-shaped conformation or a twisted boat-shaped conformation is stable in terms of potential energy, and a similar structure is usually adopted in other membered rings. It is. On the other hand, an aromatic ring structure has a planar structure.

The structural difference between the two also appears as a phenomenon that water molecules are easily adsorbed to an ester group portion forming a main chain bond. In the alicyclic structure, the carbon atoms that make up the ring are relatively crowded around the ester groups, so the ring skeleton functions as a steric hindrance to water molecules, and the adsorption of water molecules is relatively inhibited. On the other hand, in the aromatic ring structure, the ring skeleton hardly functions as steric hindrance, and has no significant effect on the inhibition of water molecule adsorption.

Among the monomers constituting the polyester resin, polyvalent carboxylic acids having an alicyclic structure include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Examples include cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and / or lower alkyl esters thereof.

Examples of the polyhydric alcohol component having the same alicyclic structure include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and derivatives thereof, Cyclohexanedimethanol, spiroglycol, tricyclodecanediol, tricyclodecanedimethanol,
Examples thereof include 1,3,5-cyclohexanetrimethanol, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, and propylene oxide adduct.

These polycarboxylic acids, polyhydric alcohols and derivatives thereof may be used alone or in a mixed state.

Among the comonomers having no alicyclic structure constituting the polyester resin, polyvalent carboxylic acid components include naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and maleic acid. Dicarboxylic acids such as fumaric acid, citraconic acid, itaconic acid, succinic acid, adipic acid, sebacic acid and azelaic acid; dicarboxylic anhydrides such as phthalic anhydride and maleic anhydride; dimethyl terephthalate, dimethyl maleate and adipic acid Examples thereof include lower alkyl esters of dicarboxylic acids such as dimethyl. In particular, the main component is preferably an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, and terephthalic acid, or a derivative thereof. It should be noted that the polyester used in the present invention has a 1,2,4,
-A small amount of benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid or its anhydride, or a lower alkyl ester thereof may be used.

These polycarboxylic acids and derivatives thereof may be used alone or in a mixed state.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol,
Triethylene glycol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
2,2,4-trimethylpentane-1,3-diol,
2,2-di (4-hydroxyethoxyphenyl) propane, 2,2-di (4-hydroxypropoxyphenyl)
Examples thereof include diol compounds such as propane. These polyhydric alcohols may be used alone or in a mixed state.

The method for producing the polyester resin of the present invention is not particularly limited, and various conventionally known methods can be employed.
Usually, a monomer is charged into a reaction vessel and heated to raise the temperature to carry out an esterification reaction or a transesterification reaction. Preferably, the following production method is used. A monomer other than a polyfunctional compound is charged into a polymerization tube, and under an inert atmosphere,
At 220 ° C., an esterification reaction or a transesterification reaction is performed, and water or alcohol generated in the reaction is removed. Thereafter, the pressure was reduced to 0.1 to 100 mmHg,
Obtain a prepolymer. This prepolymer is mixed with a polyfunctional compound at 180 to 28 ° C. in a usual manner at 0.1 to
Polycondensation is carried out by reducing the pressure to 100 mmHg, and when the viscosity reaches a predetermined value, it is extracted. The molar ratio of the total amount of the total reaction of all the acid components and all the alcohol components is preferably 1: 1.1 to 1: 1.8. As a catalyst for accelerating the reaction, sulfuric acid, dibutyltin oxide, zinc oxide, dibutyltin diurarate,
Titanium butoxide, magnesium acetate, manganese acetate, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide, etc. Can be used. The polymerization temperature and the amount of the catalyst are not particularly limited, and may be arbitrarily set as needed.

The content of the alicyclic skeleton contained in the polyester resin is 0.1 to 1 with respect to the total weight of the toner.
It is preferably 0% by weight. The reason is the same as described above. If the amount is less than 0.1% by weight, environmental stability of charging property of the toner is impaired, and
If the weight percentage is exceeded, the possibility of occurrence of problems such as increased fog on the output image increases. A more preferred range is from 0.5 to 5% by weight.

The alicyclic skeleton may be contained in either the carboxylic acid component or the alcohol component, or may be contained in both. Specific examples of the alicyclic skeleton preferably include a cycloalkyl group such as cyclohexyl and cyclodecyl, and a cycloalkenyl group, and these rings are substituted with a substituent that does not inhibit the electrophotographic characteristics of the toner. If they exist, they may be combined.

If the polyester-based resin does not contain an oxyethylene chain and / or an oxypropylene chain, sites for adsorbing moisture contained in the toner are reduced and environmental stability is improved. It is preferable if other characteristics are not adversely affected.

The polyester resin of the present invention is preferable because it does not contain an aromatic ring, so that the charging characteristics are improved and the transferability is improved.

The acid value of the polyester resin is 0.0
Preferably, it is 1 to 20 mgKOH / g of resin.
If it is less than 0.01, the toner tends to charge up under low humidity conditions when it is used as a toner. On the other hand, if it exceeds 20, the charge of the toner tends to leak under high humidity conditions, which is not preferable.

The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of a sample (JIS).
K676), examples of the measurement method include titration using an indicator such as phenolphthalein, and measurement by potentiometric titration. Furthermore, when the value is small, a method is used in which a heavy metal salt such as silver nitrate is reacted with the resin solution to wash the excess salt, and then the amount of the heavy metal salt contained is determined by a fluorescent X-ray spectrum, an atomic absorption spectrum, or the like. You may ask.

The structure of the polyester resin does not need to be a linear resin, and it can be used as a branched polyester resin by copolymerizing trifunctional or higher functional monomers.

The method of controlling the molecular weight of the polyester resin is generally controlled by the ratio between the total acid component and the total alcohol component, but is not particularly limited thereto.

Further, in the present invention, as the polyester resin, the above-mentioned polyester resin and polystyrene, styrene- (meth) acrylic copolymer, general polyester, polyurethane, epoxy resin, polyolefin, polyamide, polysulfone, polycyano Block copolymers with aryl ethers, polyarylene sulfides, etc., alkyl (meth) acrylates, (meth)
It is also possible to use a graft-modified copolymer obtained by grafting acrylic acid, maleic acid, a styrene-based monomer, or the like.

The molecular weight of the polyester resin is determined to have a peak molecular weight of 1,000 to 5 in a molecular weight distribution determined by gel permeation chromatography (GPC) described later.
It is preferably within the range of 00000. When it is less than 1000, the possibility that the blocking resistance of the toner is deteriorated or the chargeability is adversely affected is extremely increased.
If it exceeds 000, the melt viscosity of the toner becomes high, which may cause a problem in fixability. Further, when the peak molecular weight is 20
00-100,000 is mentioned as a more preferable range.

The polyester resin must be contained in an amount of 0.1 to 50 parts by weight, preferably 0.1 to 30% by weight, based on the total weight of the toner. If the amount is less than 0.1% by weight, the environmental stability of the charging property of the toner is impaired. If the amount is more than 50% by weight, the possibility of occurrence of problems such as increased fog on an output image increases. I do. A more preferable range is 0.1.
2 to 20% by weight.

Other resins used in combination with the above polyester resin in the present invention include various resins generally used such as styrene-acrylic resin, polyester resin, epoxy resin, and particularly, styrene resin.
Acrylic resins can be obtained by polymerizing monomers for forming them. Specifically, styrene, o (m-, p-)-methylstyrene, m (p-)
Styrene monomers such as ethylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Propyl acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylate monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, and ene monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile, and acrylamide are preferred. Used. These may be used alone or generally in the published Polymer Handbook
Edition III-pl39-192 (John Wiley &
Sons), the theoretical glass transition temperature (Tg)
However, it is used by appropriately mixing monomers so as to show a temperature of 40 to 75 ° C. If the theoretical glass transition temperature is lower than 40 ° C., problems tend to occur in terms of storage stability and durability stability of the toner, while if it exceeds 75 ° C., the fixing point of the toner increases. In particular, in the case of a color toner for forming a full-color image, it is not preferable because the color mixing property of each color toner at the time of fixing is reduced and color reproducibility is poor, and the transparency of the OHP image is further reduced.

The measuring method of "molecular weight distribution by GPC" in the present invention is as follows.

(Measurement of Molecular Weight Distribution by GPC) In the present invention, the molecular weight of the resin in the toner was determined from the molecular weight distribution by gel permeation chromatography (GPC) as a polystyrene equivalent molecular weight.

First, as a preparation of a sample, the toner is dissolved in tetrahydrofuran (THF) at room temperature so that the resin component in the sample becomes 0.4 to 0.6 mg / ml. The solution is filtered through a 0.2 μm solvent-resistant membrane filter.

Next, the column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (T
HF) is flowed at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected for measurement. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. The standard polystyrene sample for preparing the calibration curve is TSK Standard manufactured by Tosoh Corporation.
Polystyrene F-850, F450, F-288, F
-128, F-80, F-40, F-20, F10, F
-4, F-2, F-1, A-5000, A-2500,
A calibration curve was prepared using A-1000 and A-500.
The detector used was an RI (refractive index) detector and a UV (ultraviolet) detector arranged in series. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. In the present invention, Showa Denko shode
xGPC KF-801, 802, 803, 804, 8
It measured with the combination of 05,806,807,800P. The equipment is a high-speed GPC HLC8120 GPC
(Manufactured by Tosoh Corporation) was used.

In the present invention, the content of a compound having a GPC molecular weight of 1000 or less having a repeating unit of a polyester resin in the structure is 10.0% by weight based on the toner.
The following is preferred. Compounds that adversely affect various performances and characteristics of the toner also apply to monomers of the polyester-based resin and the like.
If the content of the compound having a GPC molecular weight of 1000 or less is set to 10.0% by weight or less with respect to the toner, the above problems will not occur. Has been found through various studies by the present inventors. In order to further enhance the performance and characteristics of the toner, the content of the compound having a GPC molecular weight of 1,000 or less is more preferably 5.0% by weight or less. Needless to say, it is desirable to use a polyester resin having a dispersion ratio so small that a compound having a GPC molecular weight of 1000 or less having a repeating unit of the polyester resin in the structure is not detected at all even when various analyzes of the toner are performed. No.

In the present invention, the qualitative and quantitative analysis of a compound having a GPC molecular weight of 1,000 or less having a repeating unit of a polyester resin in the structure can be carried out by various methods. For example, the toner is subjected to spectral analysis such as nuclear magnetic resonance spectrum ( ¹ H-NMR, ¹³ C-NMR), infrared absorption spectrum (IR), Raman spectrum, ultraviolet absorption spectrum (UV), mass spectrum (MS), and elemental analysis. , GPC, gas chromatography (G
It may be analyzed by various methods such as C), liquid chromatography (HPLC), and other chemical analysis. Also,
If analysis is difficult with the toner itself, the toner is soxhlet-extracted with a solvent that dissolves the binder resin such as tetrahydrofuran and toluene, and the filtrate is concentrated with an evaporator.
The above analysis may be performed. Further, various analysis means can be employed, such as a sample obtained by fractionating a component having a molecular weight of 1000 or less by liquid chromatography or GPC or a sample extracted with a single or mixed solvent, and the above-mentioned analysis. Further, these analysis means can be used alone or in combination as needed.

The shape of the toner of the present invention is indispensable in the following shapes in order to improve transferability and developability in a well-balanced manner. That is, the number average 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 0.950 to 0.99.
5, preferably 0.970 to 0.995, more preferably 0.975 to 0.995, and a circularity standard deviation of 0.0
By precisely controlling the particle shape of the toner so as to be less than 40, preferably less than 0.035, 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 outline portion of the image, particularly, the development of a character image or a line pattern is improved. It becomes something. 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, by controlling the circularity standard deviation of the circularity frequency distribution as described above, the toner of the present invention has good stability with respect to environmental changes in developability and transferability, and furthermore has good durability. Become. The reason is that when forming a thin layer of toner on the toner carrier in the developing step, the present inventors have to maintain a sufficient amount of toner coating even if the regulating force of the toner layer regulating member is made stronger than usual. Therefore, it is considered that the toner charge amount on the toner carrier can be made higher than usual without damaging the toner carrier.

Further, by controlling the average circularity of the circularity frequency distribution as described above, the transferability of toner having a small particle diameter, which has been difficult in the past, is greatly improved, and the development of a low potential latent image is improved. The ability is also greatly improved. It is particularly effective when developing a digital minute spot latent image.

When the average circularity is less than 0.920, not only the transfer quality is deteriorated, but also the developability may be lowered.
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.

The circle equivalent diameter, circularity and frequency distribution of the toner used in the present invention are used as a simple method for quantitatively expressing the shape of the toner particles. The measurement was performed using an apparatus FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.), and calculated using the following equation.

[0050]

(Equation 1)

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

The circularity in the present invention is an index indicating the degree of unevenness of the toner particles. The circularity is 1.00 when the toner particles are perfectly spherical, and the circularity decreases as the surface shape becomes more complicated. Become.

[0053]

(Equation 2)

[0054]

[0055]

(Equation 3)

As a specific measuring method, 10 ml of ion-exchanged water from which impure 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 dispersant thereto. Further, 0.02 g of the measurement sample is added and uniformly dispersed. As a means for dispersing, an ultrasonic disperser UH-50 type (manufactured by SMT Co., Ltd.) equipped with a titanium alloy chip of 5φ as a vibrator is used for a dispersion treatment for 5 minutes to prepare a dispersion for measurement. At this time, the dispersion is appropriately cooled so that the temperature of the dispersion does not become 40 ° C. or higher.

The shape of the toner particles was measured using the above-mentioned flow type particle image measuring apparatus.
The concentration of the dispersion liquid is readjusted so as to be 100 to 10,000 particles / 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.

In the present invention, an intermediate transfer member can be provided to correspond to various types of transfer materials. In this case, since the transfer step is performed substantially twice, a decrease in the transfer efficiency causes a problem that the use efficiency of the toner is significantly reduced.
In digital full-color copiers and printers, after a color image original is color-separated using a B (blue) filter, a G (green) filter, and an R (red) filter in advance, a 20 to 70 μm dot latent image is formed on the photoreceptor. Formed, Y (yellow) toner, M (magenta) toner, C
It is necessary to reproduce a multicolor image faithful to the original by utilizing the primary color mixing action using each color toner of (cyan) toner and B (black) toner. At this time, since a large amount of Y toner, M toner, C toner, and B toner is applied on the photoreceptor or the intermediate transfer member in accordance with the color information of the document or the CRT, each color used in the present invention is used. The toner is required to have extremely high transferability, and in order to realize the transferability, the average circularity is 0.920 to 0.995, preferably 0.970 to 0.995, and the circularity standard deviation is 0. .
Preferred are toner particles having a particle size of less than 040, preferably less than 0.035.

In the present invention, in order to improve the releasability at the time of fixing with a hot roll, waxes used as a releasing agent such as hydrocarbon compounds, higher fatty acids, higher alcohols and derivatives thereof in the toner are used. It is preferable to mix them. Specific examples of such waxes include paraffin wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, alcohol, fatty acid, acid amide, Esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes,
Derivatives include oxides, block copolymers with vinyl monomers, and graft-modified products. These release agents may be used alone or in combination of two or more.

In the DSC curve measured by a differential scanning calorimeter, these wax components were 40 to 40
It has a maximum endothermic peak in the region of 130 ° C. By having the maximum endothermic peak in the above temperature range, it greatly contributes to low-temperature fixing, and also effectively expresses the releasability. When the maximum endothermic peak is less than 40 ° C., the self-cohesive force of the wax component becomes weak, and as a result, the high-temperature offset resistance deteriorates and the gloss becomes too high. On the other hand, if the maximum endothermic peak exceeds 130 ° C., the fixing temperature becomes high, and it becomes difficult to appropriately smooth the fixed image surface. Not preferred. Further, when granulation / polymerization is performed in an aqueous medium to directly obtain a toner by a polymerization method,
If the maximum endothermic peak temperature is high, problems such as precipitation of a wax component mainly during granulation are not preferred.

The maximum endothermic peak temperature of the wax component is measured according to “ASTM D 3418-8”. For the measurement, for example, DSC-7 manufactured by PerkinElmer is used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. An aluminum pan is used as a measurement sample, an empty pan is set as a control, and the measurement is performed at a heating rate of 10 ° C./min.

In the present invention, the addition amount of these wax components is not particularly limited, but may be 0.5 to toner.
The range is preferably from 30 to 30% by weight.

As the coloring agent used in the present invention, conventionally known inorganic and organic dyes and pigments can be used.
Examples include the following yellow colorants, magenta colorants, and cyan colorants. As black colorants, carbon black, aniline black, acetylene black, magnetic materials, fired pigments, or the following yellow colorants / magenta colorants / cyan coloration A mixture obtained by mixing an agent with a black color is used.

Further, the toner of the present invention uses a magnetic material as a black colorant, and can also be used as a magnetic toner.
Magnetic materials that can be used at this time include magnetite, hematite, iron oxides such as ferrite, metals such as iron, cobalt, and nickel, or aluminum, cobalt, copper, lead, magnesium, tin, and the like of these metals.
Alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof.

The magnetic material used in the present invention is more preferably a surface-modified magnetic material. When the magnetic material is used in a polymerization toner, it is hydrophobized by a surface modifier which is a substance having no polymerization inhibition. Those that have been treated are preferred. Examples of such a surface modifier include a silane coupling agent and a titanium coupling agent.

These magnetic materials have an average particle size of 2 μm or less,
Preferably, it is about 0.1 to 0.5 μm. The amount of the magnetic substance to be contained in the toner particles may be as follows:
20 to 200 parts by weight, particularly preferably 40 parts by weight, per part by weight
１５０150 parts by weight. Further, a magnetic material having a coercive force (Hc) of 20 to 300 Oersted, a saturation magnetization (σs) of 50 to 200 emu / g, and a residual magnetization (σr) of 2 to 20 emu / g when a 10 k Oersted is applied is preferable.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
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.

As the magenta coloring agent, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds and the like are used. 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.

As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used. Specifically, C.I. I.
Pigment Blue 1, 7, 15, 15: 1, 15: 2,
15: 3, 15: 4, 60, 62, 66, etc. can be particularly preferably used.

These colorants can be used alone or as a mixture or in the form of a solid solution. The colorant is selected from the points of hue, saturation, lightness, weather resistance, OHP transparency, and dispersibility. The colorant is preferably used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the resin component.

As the charge control agent used in the toner of the present invention, a known charge control agent can be used. In particular, a charge control agent which has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and having substantially no solubilized substance in an aqueous dispersion medium is particularly preferable. As specific compounds, salicylic acid, a naphthoic acid, a metal compound of an aromatic carboxylic acid such as dicarboxylic acid, a metal salt or metal complex of an azo dye or an azo pigment, a sulfonic acid or a carboxylic acid group as a negative charge control agent. Examples include a polymer type compound having a side chain, a boron compound, a urea compound, a silicon compound, and calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in a side chain, a guanidine compound, an imidazole compound and the like. The charge control agent is preferably used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the resin. However, in the present invention, the addition of a charge control agent is not essential, and in the case of using a two-component developing method, utilizing triboelectric charging with a carrier, in the case of using a non-magnetic one-component blade coating developing method, By positively utilizing frictional charging with the blade member and the sleeve member, it is not always necessary to include a charge control agent in the toner particles.

In the present invention, among the above charge control agents, compounds represented by the following general formula (I) are more preferable.

[0073]

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Typical examples of the charge control agent include the following compounds.

[0075]

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[0076]

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There are various methods for producing the toner according to the present invention. For example, when the toner is produced by a pulverization method, a binder resin comprising a polyester resin and another resin, a wax component, a colorant and / or Alternatively, a magnetic substance, a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, melt-kneaded using a heat kneader such as a pressure kneader or an extruder, and solidified after cooling and solidification. Is impinged on the target mechanically or under a jet stream to pulverize to a desired toner particle size. Thereafter, smoothing and sphering of the toner particles are performed as necessary. Next, the particle size distribution is sharpened through a classification process. Furthermore, the toner of the present invention can be obtained by sufficiently mixing the toner particles with a fluidizing agent such as fine-particle silica using a mixer such as a Henschel mixer. Further, as another method for producing a toner, there is a method in which a polyester-based resin which is micronized together with a fluidizing agent or separately is added to the toner particles and mixed sufficiently to fix the polyester-based resin on the surface of the toner particles. In this case, the binder resin in the toner particles may contain a polyester resin or may not contain the polyester resin at all. After the fixing, the toner particles may be subjected to smoothing and spheroidizing treatment.

Further, when the toner of the present invention is produced by a polymerization method, a polyester resin is dissolved in a monomer composition, and JP-B-36-10231 and JP-A-59-231 are disclosed.
No. 53856, JP-A-59-61842, a method of directly producing a toner using a suspension polymerization method, a method of dissolving a monomer and dissolving an obtained polymer in an aqueous organic solvent. The toner of the present invention can be obtained by a dispersion polymerization method for directly producing a toner using a solvent or an emulsion polymerization method typified by a soap-free polymerization method for producing a toner by directly polymerizing in the presence of a water-soluble polymerization initiator. Further, a polymer particle containing no polyester resin is produced by a polymerization method, and then a fine particle polyester resin is adhered to the surface of the polymer particle, and the particles are subjected to smoothing and spheroidizing treatment as necessary. A method and a method of seed-polymerizing a monomer (composition) containing a polyester resin can also be adopted. Further, as another method, a method described in JP-B-56-13945 or the like, in which a molten mixture containing a polyester-based resin is atomized in air using a disk or a multi-fluid nozzle to obtain a spherical toner, is exemplified.

Among the toner production methods described above, the melt spray method tends to have a broad particle size distribution of the obtained toner. On the other hand, in the dispersion polymerization method, the obtained toner shows an extremely sharp particle size distribution, but the production equipment is complicated from the viewpoint of narrow selection of materials to be used and the use of organic solvents in terms of waste solvent treatment and solvent flammability. It is easy to be complicated. Also,
The emulsion polymerization method has the advantage that the particle size distribution of the toner is relatively uniform, but generally the particle size of the generated particles is very fine, and it is difficult to use the toner as it is.
Furthermore, the terminal of the used water-soluble polymerization initiator and the emulsifier may be present on the surface of the toner particles, and may deteriorate the environmental characteristics.

On the other hand, the production method based on the smoothing and sphering treatment of the toner particles and the production method based on the polymerization method make it easy to keep the circularity and the standard deviation of the circularity of the toner within a desired range. It can be said that. Also,
The method for producing the toner of the present invention by the polymerization method is particularly easy to control the shape of the toner particles, and can be used by dissolving the polyester resin in the monomer composition.
There are many types of resins that can be used, and this is a particularly preferred production method.

The polyester resin contained in the toner of the present invention may be contained in any shape and state in the toner, and may be in a state of being compatible with other binder resins.
The phase may be separated. For example, when melt-kneading a polyester-based resin and other binder resin by the above-described pulverization method, it is not necessary that the polyester-based resin is necessarily melted in the melt-kneading step, and the melted other binder resin is used. It may be in a dispersed state. In such a case, the polyester resin in the toner is dispersed in another binder resin used in combination. When the polyester resin and the other binder resin are previously uniformly dissolved and mixed using a solvent such as xylene, there is no problem because the polyester resin is finely dispersed in the other resin, or in some cases, is compatibilized. However, without performing such a homogenizing operation, kneading the polyester resin powder and other binder resin, and,
When the kneading is performed at a temperature lower than the melting temperature of the polyester resin, the polyester resin powder is dispersed in the toner.
It is preferable to use a polyester resin finely pulverized to a size of not more than μm.

When a polymerization method is used as a method for producing a toner, the particle size distribution and the particle size of the toner particles are controlled by changing the type and amount of a poorly water-soluble inorganic salt or a dispersant that acts as a protective colloid. Predetermined toner particles can be obtained by controlling the mechanical conditions (e.g., the peripheral speed of the rotor, the number of passes, the stirring conditions such as the shape of the stirring blades and the shape of the container), or the solid content concentration in the aqueous solution. .

When a toner is produced by the direct polymerization method, for example, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, Azo or diazo polymerization initiators such as 1,1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; Peroxide polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide are used. The amount of the polymerization initiator varies depending on the desired degree of polymerization, but is generally used in an amount of 0.5 to 20% by weight based on the polymerizable monomer. The type of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature. Further, in order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like may be further added and used.

When a suspension polymerization method using a dispersion stabilizer is used as a method for producing a toner, the dispersion stabilizer to be used includes inorganic compounds such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and the like. Calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite,
Examples include silica and alumina. Examples of the organic compound include polyvinyl alcohol, gelatin, hydroxyethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose and its sodium salt, polyacrylic acid and its salt, starch and the like. These dispersion stabilizers are 0.2 to 100 parts by weight of the polymerizable monomer.
It is preferred to use 20 parts by weight.

When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but fine particles of the inorganic compound may be produced in a dispersion medium in order to obtain fine particles. For example, in the case of tricalcium phosphate,
It is preferable to mix an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring.

For fine dispersion of these dispersion stabilizers,
0.001 to 0.1 part by weight of a surfactant may be used in combination. This is to promote the action of the dispersion stabilizer, for example, sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate,
Examples include sodium laurate, potassium stearate, calcium oleate and the like.

When the direct polymerization method is used as the method for producing the toner of the present invention, the following production method is possible.

A monomer composition obtained by adding a wax component, a colorant, a charge control agent, a polymerization initiator, and other additives to a polymerizable monomer and uniformly dissolving or dispersing the mixture using a homogenizer, an ultrasonic disperser, or the like. Is dispersed in an aqueous phase containing a dispersion stabilizer using a conventional stirrer, homomixer, homogenizer, or the like. Preferably, the granulation is performed by adjusting the stirring speed and the stirring time so that the droplets of the monomer composition have a desired size of the toner particles. Thereafter, by the action of the dispersion stabilizer, the stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented. The polymerization temperature is 40 ° C or higher,
Generally, the polymerization is preferably performed at a temperature of 50 to 90 ° C. The temperature may be raised in the latter half of the polymerization reaction, and in the image forming method of the present invention, for the purpose of improving durability,
The aqueous medium may be partially distilled off from the reaction system in the latter half of the reaction for removing unreacted polymerizable monomers, by-products and the like, or after the completion of the reaction. After the completion of the reaction, the generated toner particles are collected by washing, filtration, and dried. In the suspension polymerization method, usually, 100 parts by weight of the monomer composition is mixed with 300 parts of water.
It is preferred to use 重量 3000 parts by weight as the dispersion medium.

On the other hand, if the reaction time is less than 2 hours, the desired conversion of the polymerizable monomer will not be attained, the amount of unreacted polymerizable monomer will be large and the removal step will be complicated, and the reaction time will exceed 24 hours. And the reaction time is too long, resulting in low productivity.
Four hours is preferred.

The particle size distribution may be measured by the above-mentioned flow type particle image measuring apparatus, or may be measured using a Coulter counter multisizer.

That is, the latter uses a Coulter Counter TA-II (manufactured by Coulter) as a measuring device, and is connected to an interface (manufactured by Nikkaki) for outputting the number distribution and volume distribution and a personal computer. About 1% NaC using high-grade sodium chloride
Prepare an aqueous solution. For example, ISOTON II (manufactured by Coulter Scientific Japan) can be used. The measuring method is 100 to 150 m of the electrolytic aqueous solution.
0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) is added as a dispersing agent in 1 l, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and the volume and number of the toner were measured using the Coulter Counter TA-II, for example, using a 100 μm aperture as an aperture. The volume distribution and number distribution were calculated. Then, the weight-based weight average diameter according to the present invention is determined from the volume distribution.

It is essential that the toner of the present invention contains at least a polyester resin having an alicyclic structure as a part of the binder resin. The qualitative and quantitative analysis of the polyester resin is various. The method can be implemented. For example, the toner is treated with a nuclear magnetic resonance spectrum ( ¹ H).
-NMR, ¹³ C-NMR), infrared absorption spectrum (I
R), Raman spectrum, ultraviolet absorption spectrum (U
V), spectral analysis such as mass spectrum (MS), elemental analysis, GPC, gas chromatography (GC), liquid chromatography (HPLC), and other chemical analysis. If the analysis is difficult with the toner itself, the toner may be subjected to Soxhlet extraction with a solvent that dissolves the binder resin such as tetrahydrofuran or toluene, the filtrate may be concentrated with an evaporator, and the above analysis may be performed. Furthermore, liquid chromatography and G
Various analysis means can be adopted, such as performing the above-described analysis on a sample obtained by fractionating a component having a GPC molecular weight of 1,000 or more by PC or a sample extracted with a single or mixed solvent. These analysis means can be used alone or in combination as needed.

In the toner of the present invention, charging stability,
In order to improve developability, fluidity and durability, it is preferable to use an inorganic fine powder mixed with toner particles as an additive.

The inorganic fine powder used in the present invention includes:
Examples include silica fine powder, titanium oxide, and alumina fine powder. Among them, the specific surface area by nitrogen adsorption measured by the BET method is 30 m ² / g or more (particularly 50 to 400 m ² / g).
Those within the range give good results. It is preferable to use 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight of the inorganic fine powder with respect to 100 parts by weight of the toner.

The specific surface area was determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) according to the BET method, and calculating the specific surface area using the BET multipoint method.

The inorganic fine powder used in the present invention may contain a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, a silane coupling agent, and a functional group for the purpose of hydrophobicity and charge control as required. It is also preferable to be treated with a treating agent such as a silane coupling agent having the above or another organosilicon compound.

Other additives include lubricants such as Teflon, zinc stearate and polyvinylidene fluoride (preferably polyvinylidene fluoride); abrasives such as cerium oxide, silicon carbide and strontium titanate (strontium titanate among them). A caking inhibitor; a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, and tin oxide; and a developability improver such as white fine particles and black fine particles having a polarity opposite to that of the toner particles.

In the present invention, in the case of a toner produced by stirring and mixing the inorganic fine particles and other additives with the toner particles, various physical properties of the toner particles are measured by measuring the values of these inorganic fine particles and other additives. This can be performed using the toner particles after removing the additives. The method for removing these inorganic fine particles and other additives is not particularly limited. For example, the method can be carried out by washing the toner with water as follows.

First, the toner is added to water to which a surfactant such as sodium dodecylbenzenesulfonate is added, and the mixture is sufficiently stirred and mixed. By this operation, inorganic fine particles having a relatively large particle size and other additives are released from the toner, and the toner particles and the inorganic fine particles and other additives are separately dispersed in water. Next, the toner particles are isolated from the mixed dispersion.
As an isolation method, for example, by performing a filtration operation using a filter paper having an appropriate opening, separation can be performed as a toner particle on the filter paper and an aqueous solution containing inorganic fine particles and other additives in the filtrate. Further, as another isolation method, a method of isolating toner particles by wet classification of the mixed dispersion can be employed.

Next, an image forming method to which the toner of the present invention is applied will be described below with reference to the accompanying drawings.

FIG. 1 shows a color image forming apparatus (copier or laser beam printer) using an electrophotographic process, which uses an intermediate transfer belt.

Reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member (hereinafter, referred to as a photosensitive drum) as a first image carrier, which is rotated at a predetermined peripheral speed (process speed) in the direction of an arrow.

The photosensitive drum 1 rotates in the primary charging device 2 during the rotation process.
, And is uniformly charged to a predetermined polarity and potential, and then subjected to exposure 3 by image exposure means 3 (not shown). In this way, an electrostatic latent image corresponding to the first color component image (for example, a yellow color component image) of the target color image is formed.

Next, the electrostatic latent image is developed into a yellow component image of the first color by a first developing device (yellow developing device 41). At this time, since the second to fourth developing devices, namely, the magenta developing device 42, the cyan developing device 43, and the black developing device 44 are not operating and do not act on the photosensitive drum 1, the first developing device is not used. The color yellow component image is not affected by the second to fourth developing units.

During development, it is preferable that the moving speed of the toner carrier surface in the developing area is 1.05 to 3.0 times the moving speed of the electrostatic latent image carrier surface.
By setting the moving speed to be 1.05 to 3.0 times, the toner layer on the toner carrier receives an appropriate stirring effect, so that the faithful reproduction of the electrostatic latent image is further improved. It will be.

In the present invention, the surface roughness Ra (μm) of the toner carrier is preferably 1.5 or less.
By controlling the surface roughness Ra to 1.5 or less, the toner carrying capacity 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 is increased. Therefore, the chargeability of the toner is also improved, so that the image quality is synergistically improved.

The thickness of the toner layer on the toner carrier is regulated by a regulating member.

The toner thinning regulating member is a doctor blade such as a metal blade or a magnetic blade which is arranged at a fixed distance from the toner carrier. Alternatively, instead of the doctor blade, a rigid roller or a sleeve made of metal, resin, ceramic, or the like may be used, and a magnet generating means may be provided inside the roller or the sleeve.

An elastic member such as an elastic blade or an elastic roller for press-contacting the toner may be used as a regulating member for thinning the toner. For example, the base on the upper side of the elastic blade is fixed to the developer container, and the variable part is bent in the forward or reverse direction of the toner carrier against the elasticity of the blade so that the inner surface of the blade (reverse) (In the case of the direction, the outer surface side) is brought into contact with the surface of the toner carrier with an appropriate elastic pressure. According to such an apparatus, a dense toner layer that is stable against environmental changes can be obtained. Although the reason is not clear, it is presumed that the elastic body is forcibly rubbed with the surface of the toner carrier, so that charging is always performed in the same state regardless of a change in behavior due to a change in toner environment. .

It is preferable to select a material of a triboelectric series suitable for charging the toner to a desired polarity for the elastic body. Rubber elastic bodies such as silicone rubber, urethane rubber, and NBR; synthetic materials such as polyethylene terephthalate Resin elastic body: Metal elastic bodies such as stainless steel, copper, and phosphor bronze can be used. Further, a composite thereof may be used.

When the elastic body and the toner carrier are required to have durability, it is preferable that the elastic body and the resin or rubber are adhered to the sleeve contact portion so as to contact the sleeve contact portion, or the metal elastic body is coated.

Further, an organic substance or an inorganic substance may be added to the elastic body, may be melt-mixed, or may be dispersed. For example, the chargeability of the toner can be controlled by adding a metal oxide, metal powder, ceramics, carbon allotrope, whisker, inorganic fiber, dye, pigment, surfactant, and the like. In particular, when the elastic body is a molded body such as rubber or resin, fine particles of metal oxide such as silica, alumina, titania, tin oxide, zirconia, 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 developing blade as the regulating member, the supply roller as the supply member, and the brush member,
Due to the loosening action on the toner, the uniform thin layer coating property and the uniform charging property are further improved in the regulated area on the toner carrier, and in the supply area, toner supply / stripping is more smoothly performed, and a sufficient image is obtained. Achieving density and good quality images can be obtained.

The intermediate transfer belt 20 is driven to rotate at the same peripheral speed as the photosensitive drum 1 in the direction of the arrow.

The yellow component image of the first color formed on the photosensitive drum 1 is transferred to the photosensitive drum 1 and the intermediate transfer belt 20.
In the process of passing through the nip portion of the intermediate transfer belt 20, the image is sequentially transferred to the outer peripheral surface of the intermediate transfer belt 20 by the electric field generated by the primary transfer bias applied to the intermediate transfer belt 20 from the bias power source 29 via the primary transfer roller 62 ( Primary transfer).

After the transfer of the first color yellow toner image corresponding to the intermediate transfer belt 20, the surface of the photosensitive drum 1 is cleaned by the cleaning device 13.

Hereinafter, similarly, the magenta toner image of the second color, the cyan toner image of the third color, and the black toner image of the fourth color are sequentially superimposed on the intermediate transfer belt 20 and transferred to correspond to the target color image. Thus, a combined color toner image is formed.

Reference numeral 63 denotes a secondary transfer roller, which corresponds to the secondary transfer opposing roller 64 and is supported in parallel with the intermediate transfer belt 20.
Are disposed on the lower surface of the device so as to be separated therefrom.

A primary transfer bias for transferring a toner image from the photosensitive drum 1 to the intermediate transfer belt 20 is applied from a bias power supply 29 with a polarity opposite to that of the toner. The applied voltage is in a range of, for example, +100 V to +2 kV.

In the primary transfer step of the first to third color toner images from the photosensitive drum 1 to the intermediate transfer belt 20, the secondary transfer roller 63 and the transfer residual toner charging member 52 may be separated from the intermediate transfer belt 40. It is possible.

The full-color image transferred onto the intermediate transfer belt 20 is
The transfer material P, which is the second image carrier, is fed from the paper feed roller 11 to the contact portion between the intermediate transfer belt 20 and the secondary transfer roller 63 at a predetermined timing, and the secondary transfer bias is applied. Is applied to the secondary transfer roller 63 from the bias power supply 28, so that the secondary transfer is performed on the transfer material P. The transfer material P to which the toner image has been transferred is introduced into the fixing device 15 and is fixed by heating.

After the image transfer to the transfer material P is completed, the transfer residual toner cleaning device 50 is brought into contact with the intermediate transfer belt 20, and the surface of the intermediate transfer belt 20 is cleaned.

Next, the toner image on the transfer material is fixed by a heat and pressure fixing means. As a heating and pressing fixing means, a heating roller system having a heating roller having a built-in heating element such as a halogen heater and a pressure roller of an elastic body pressed against the pressing roller with a pressing force, or a heater through a film. A method of fixing by heating (FIGS. 2 and 3) can be mentioned, but the toner of the present invention shows good matching with the above-mentioned heating and pressing fixing means.

Although the image forming method using an image forming apparatus having an intermediate transfer belt has been described above, the toner of the present invention is preferably used in an image forming apparatus having no intermediate transfer member. Can be. Further, the untransferred residual toner on the electrostatic latent image carrier after the transfer is cleaned and collected, and the collected toner is supplied to the developing unit and held by the developing unit again. It can also be suitably used in an image forming apparatus having a toner reuse mechanism for developing an electrostatic latent image.

[0125]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Production Example 1 of Polyester Resin Polyhydric carboxylic acid component and polyhydric alcohol component were adjusted so as to have the composition shown in Table 1, and as a catalyst, 0.1% of the total monomer weight was used.
Put in a glass 2 liter separable flask together with 05 parts by weight of dibutyltin oxide, attach a thermometer, a stainless steel stirrer, a falling condenser, and a nitrogen inlet tube, and carry out the esterification reaction in a mantle heater under a nitrogen stream. Performed at 200 ° C.

The reaction temperature was further raised to 230 ° C.
The polycondensation reaction was continued while maintaining a high vacuum of less than 00 Pascal (1.5 mmHg) to obtain the polyester resin (1) of the present invention.

Table 2 shows the characteristic values.

Polyester Resin Production Examples 2 to 5 The polyester resin (2) was prepared in the same manner as in the polyester resin production example 1 except that the polycarboxylic acid component and the polyhydric alcohol component used were changed as shown in Table 1. ~ (5)
I got Table 2 summarizes the characteristic values.

Comparative Preparation Example 1 of Polyester Resin Polyester resin (6) was prepared in the same manner as in Preparation Example 1 of polyester resin except that the polycarboxylic acid component and the polyhydric alcohol component used were changed as shown in Table 1. Obtained.
Table 2 summarizes the characteristic values.

[0131]

[Table 1]

[0132]

[Table 2]

Production Example 1 of Binder Resin 200 parts by weight of xylene was placed in a glass separable flask equipped with a thermometer, a stainless steel stirring rod, a falling condenser and a nitrogen inlet tube, and the temperature was raised to the reflux temperature. 80 parts by weight of styrene and n-butyl acrylate 20
After dropping a mixed solution of 2.3 parts by weight of di-tert-butyl peroxide and 2.3 parts by weight of di-tert-butyl peroxide, solution polymerization was completed in 7 hours under reflux of xylene to obtain a low molecular weight resin solution.

On the other hand, 65 parts by weight of styrene, 25 parts by weight of butyl acrylate, 10 parts by weight of monobutyl maleate, 0.2 parts by weight of polyvinyl alcohol, 200 parts by weight of degassed water, and 0.5 part by weight of benzoyl peroxide were mixed and suspended. It was turbidly dispersed. The suspension was heated and maintained at 85 ° C. for 24 hours under a nitrogen atmosphere to complete the polymerization, thereby obtaining a high molecular weight resin.

30 parts by weight of the high-molecular-weight resin is put into a solution containing 70 parts by weight of the low-molecular-weight resin at the end of the solution polymerization, completely dissolved in the solvent and mixed, and then the solvent is distilled off. Thus, a binder resin (1) was obtained.

When the binder resin (1) was analyzed, the peak molecular weight on the low molecular weight side was 10,000, the peak molecular weight on the high molecular weight side was 550,000, the weight average molecular weight (Mw) was 300,000, and the number average molecular weight (Mn) was It was 550,000. The glass transition temperature was 55 ° C.

Production Example 2 of Binder Resin 200 parts by weight of xylene was placed in a glass separable flask equipped with a thermometer, a stainless steel stirring rod, a falling condenser and a nitrogen inlet tube, and the temperature was raised to the reflux temperature. 80 parts by weight of styrene and n-butyl acrylate 20
After dropping a mixed solution of 2.3 parts by weight of di-tert-butyl peroxide and 2.3 parts by weight of di-tert-butyl peroxide, solution polymerization was completed in 7 hours under reflux of xylene to obtain a low molecular weight resin solution.

On the other hand, 75 parts by weight of styrene, 25 parts by weight of butyl acrylate, 0.2 parts by weight of polyvinyl alcohol,
200 parts by weight of degassed water and 0.5 part by weight of benzoyl peroxide were mixed and dispersed. The suspension was heated and maintained at 85 ° C. for 24 hours under a nitrogen atmosphere to complete the polymerization, thereby obtaining a high molecular weight resin.

30 parts by weight of the high-molecular-weight resin is put into a solution containing 70 parts by weight of the low-molecular-weight resin at the time of completion of the solution polymerization, completely dissolved in the solvent and mixed, and then the solvent is distilled off. Thus, a binder resin (2) was obtained.

When the binder resin (2) was analyzed, the peak molecular weight on the low molecular weight side was 12,000, the peak molecular weight on the high molecular weight side was 580,000, the weight average molecular weight (Mw) was 300,000, and the number average molecular weight (Mn). ) Was 550,000. The glass transition temperature was 55 ° C.

[Production Example of Toner ] Production Example 1 of Toner 100 parts by weight of binder resin (1) 45 parts by weight of polyester resin (1) (peak molecular weight = 4000) 45 parts by weight of carbon black (BET specific surface area = 62 m ² / g) 10 parts by weight ・ 2 parts by weight of negative charge controlling agent (compound (I) -1) ・ 5 parts by weight of low molecular weight polyethylene having a maximum endothermic peak of 115 ° C.

The above materials were mixed in a blender, melted and kneaded with a biaxial extruder heated to 160 ° C., and the cooled kneaded material was coarsely pulverized by a hammer mill, and the coarsely pulverized material was finely pulverized by a jet mill. did.

Next, a surface modification treatment was carried out using a device for applying a mechanical impact by rotating a rotor, and the obtained particles were classified to obtain a classified powder (A). The classified powder (A) 1
00 parts by weight and hydrophobic silica fine powder (BET specific surface area: 2
20 m ² / g) of 1.5 parts by weight was dry-mixed with a Henschel mixer to obtain toner (A) of the present invention.

The average circularity of the toner (A) is 0.967,
Circularity standard deviation is 0.040, circle equivalent number average particle diameter D
1 was 4.9 μm, the peak molecular weight on the high molecular weight side was 580,000, and the peak molecular weight on the low molecular weight side was 11,000.

Further, a component having a GPC molecular weight of 1,000 or less in the toner is separated by GPC, and this is separated by GPC / IR,
Analysis by ¹ H-NMR, ¹³ C-NMR, and GC / MS revealed that the content of a component having a repeating unit of a polyester resin in the structure and having a GPC molecular weight of 1,000 or less was 9.7 with respect to the toner. % By weight.

Toner Production Examples 2 to 5 Toners (B) to (E) were obtained in the same manner as in Toner Production Example 1, except that the type of the binder resin, the type of the polyester resin, and the amount added were changed. Table 3 shows the types and amounts of the materials used together with the toner (A), and Table 5 shows the analysis results of the toner.

Production Example 6 Toner High-speed stirrer TK homomixer ( manufactured by Tokushu Kika Kogyo Co., Ltd.)
And 650 parts by weight of ion-exchanged water in a two-liter four-necked flask equipped with lmol / liter -Na ₃ PO ₄
500 parts by weight of the aqueous solution is charged, and the rotation speed is 12,000 rpm.
m and heated to 70 ° C. Here, 1.0m
ol / liter-80 parts by weight of an aqueous solution of CaCl _2, and a fine, slightly water-insoluble dispersion stabilizer [calcium phosphate]
The aqueous dispersion medium containing was prepared.

On the other hand, as dispersoids: 82 parts by weight of styrene 18 parts by weight of 2-ethylhexyl acrylate 10 parts by weight of carbon black (BET specific surface area = 62 m ² / g) Polyester resin (1) (peak molecular weight = 4000) 3 7 parts by weight Wax (ester wax, mp = 76 ° C.) 7 parts by weight Negative charge control agent (Compound (I) -1) 2 parts by weight The above mixture was mixed with an attritor (manufactured by Mitsui Kinzoku) 3
After dispersion for a time, 3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to prepare a polymerizable monomer composition.

Next, the polymerizable monomer composition was charged into the aqueous dispersion medium, and the mixture was stirred at a temperature of 12,000 rpm under a nitrogen atmosphere at an internal temperature of 70 ° C. while maintaining the rotation speed at 12,000 rpm.
After stirring for minutes, the polymerizable monomer composition was granulated. Thereafter, the stirring was changed to a propeller stirring blade, and the mixture was maintained at the same temperature for 10 hours while stirring at 50 rpm to complete the polymerization. After completion of the polymerization, the suspension was cooled, and then diluted hydrochloric acid was added to remove the dispersion stabilizer. Furthermore, after repeating water washing several times, it was dried to obtain polymer particles (F). The polymer particles (F) had a weight average diameter of 6.6 μm.

100 parts by weight of the polymer particles (F) and 1.8 parts by weight of hydrophobic silica fine powder (BET; 220 m ² / g) were dry-mixed with a Henschel mixer to obtain a toner (F) of the present invention.

The average circularity of the toner (F) is 0.988,
The circularity standard deviation was 0.025, the circle-equivalent number average diameter D1 was 5.2 μm, and the peak molecular weight was 27,000.

Further, a component having a GPC molecular weight of 1000 or less in the toner is separated by GPC, and this is separated by GPC / IR,
Analysis by ¹ H-NMR, ¹³ C-NMR, and GC / MS revealed that the content of a component having a repeating unit of a polyester resin in the structure and having a GPC molecular weight of 1,000 or less was 0.4% based on the toner. % By weight.

Toner Production Examples 7 to 13 Toners (G) to (M) were obtained in the same manner as in Toner Production Example 6, except that the type of the binder resin, the type of the polyester resin, and the amount of addition were changed. Table 4 shows the types and amounts of the materials used together with the toner (F), and Table 5 shows the analysis results of the toner.

Toner Comparative Production Example 1 Toner (N) was obtained in the same manner as in Toner Production Example 1, except that the types and amounts of the raw materials were the same, and only the surface modification treatment was not performed. Table 3 shows the types and amounts of materials used.
Table 5 shows the analysis results of the toner.

Toner Comparative Production Examples 2 to 4 Toners (O) to (Q) were obtained in the same manner as in Toner Production Example 6, except that the type of the binder resin, the type of the polyester resin, and the amount of addition were changed. Table 4 shows the types and amounts of materials used.
Table 5 shows the analysis results of the toner.

[0156]

[Table 3]

[0157]

[Table 4]

[0158]

[Table 5]

[Examples 1 to 13 and Comparative Examples 1 to 4] The toners (A) to (Q) were evaluated as follows.

First, in the image forming apparatus shown in FIG.
The moving speed of the toner carrier surface was set to be 150% of the moving speed of the electrostatic latent image carrier surface.

Next, each of the toners (A) to (Q) is filled in the developing device, and the peripheral speed of the toner carrying surface of the developing device is set to 18
The developing device was mounted on the driving device of the developing device having no electrostatic latent image carrier set to be 0 mm / sec and was rotated at room temperature and normal humidity for 25 minutes without passing paper. Later the image was printed out.

Room temperature and normal humidity (25 ° C., 60% RH), high temperature and high humidity (30 ° C., 80% RH), and low temperature and low humidity (15 ° C., 1%)
In a 0% RH environment, the toners (A) to (Q) can be used in a single-color continuous mode at a printout speed of 20 sheets / min (A4 size) (that is, toner consumption can be promoted without stopping the developing device). Mode), a 20,000 printout test was performed. Then, the obtained printout image was evaluated for items described below.

In the fixing device, the heater set temperature of the fixing device 15 was 170 ° C., and the nip between the rollers was 9 mm.

Further, the matching between the used image forming apparatus and the toner was evaluated after the completion of the printout test.

The surface roughness of the toner carrier used here is 1.5, and the material of the toner regulating blade is stainless steel.

[Evaluation of Printout Image] (1) Image Density Evaluation was carried out by maintaining the image density at the end of printing out 20,000 sheets of ordinary paper for copying machines (75 g / m ² ). still,
The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth) with respect to the printout image of the white background portion where the original density was 0.00. A (excellent): 1.40 or more B (good): 1.35 or more and less than 1.40 C (acceptable): 1.00 or more and less than 1.35 D (impossible): less than 1.00

(2) Deletion of Characters When the “surprise” character pattern shown in FIG. 4 (a) is printed on thick paper (135 g / m ² ), the deletion of characters (the state shown in FIG. 4 (b)) is visually observed. evaluated. A: very good (almost no occurrence) B: good (slight) C: practical D: practical (notable)

(3) Image fog The fog density (%) was calculated from the difference between the whiteness of the white background 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: very good (less than 1.5%) B: good (1.5% or more and less than 2.5%) C: practical (2.5% or more and less than 4.0%) D: impractical ( 4% or more)

[Evaluation of Matching of Image Forming Apparatus] <1> Matching with Developing Sleeve After the printout test, the state of fixation of the residual toner on the surface of the developing sleeve was visually evaluated. A: not generated B: hardly generated C: some sticking D: many sticking

<2> Matching with Photosensitive Drum After the completion of the printout test, the occurrence of scratches on the surface of the photosensitive drum and adhesion of residual toner was visually evaluated. A: not generated B: slightly scratched C: sticking or scratching D: much sticking

<3> Matching with Intermediate Transfer Belt After the completion of the printout test, the surface of the intermediate transfer member was visually evaluated for scratches and the state of fixation of residual toner. A: not generated B: presence of residual toner on the surface is observed C: sticking or flaw D: sticking too much

<4> Matching with Fixing Device After the completion of the printout test, the surface of the fixing film and the state of fixation of the residual toner were visually evaluated. A: Not generated B: Slightly adhered C: Adhered or flawed D: Excessive adhering The evaluation results are summarized in Tables 6 and 7.

[0173]

[Table 6]

[0174]

[Table 7]

An image forming apparatus used in this embodiment will be described. In this example, a commercially available laser beam printer LBP-PX (manufactured by Canon) was modified and used for non-magnetic one-component development.

In this embodiment, an example of a reversal developing apparatus for developing a negative (negative) latent image on a photoreceptor using a negative (negative) toner will be described.

FIG. 5 is a schematic explanatory view of a cross section of a laser beam printer applied to the present invention.

OPC photosensitive drum 110 (24 m in diameter)
m) rotates in the direction of the arrow, and is uniformly charged by the charging roll 111 so that the dark portion potential (Vd) becomes −600 V. Next, the image portion is exposed by the exposure device 114 to form an electrostatic latent image having a bright portion potential (Vl) of -150V. Photoconductor drum 110 and toner application roller 11
The gap (300 μm) is set in a non-contact manner with the developer layer on the toner carrier 117 having an AC bias (f = 18).
While applying 00 Hz, Vpp = 1400 V) and a DC bias (Vdc = −400 V) to the toner carrier 117 by the bias applying means V, the image portion was developed with negative toner to form a toner image on the photosensitive drum. . The obtained toner image is transferred onto a recording material by a transfer roll 119, and the toner remaining on the surface of the photoconductor is cleaned by a cleaner 113. On the other hand, the recording material P separated from the photosensitive drum 110 is subjected to a heat fixing process by the heat fixing device H in order to fix a toner image on the recording material P. Image formation is performed by repeating the above steps. At this time, the surface temperature of the temperature measuring element 31d of the heating element 31 of the heating and fixing device H is 190 ° C., the total pressure between the heating element 31 and the pressure roller 33 is 6 kg, the nip between the pressure roller and the film is 3 mm, and the fixing film is fixed. For No. 32, a heat-resistant polyimide film having a thickness of 50 μm and having a low-resistance release layer in which a conductive material is dispersed in PTFE on a contact surface with a recording material was used.

Under the above conditions, room temperature and normal humidity (25 ° C., 60%
RH), high-temperature and high-humidity (30 ° C., 80% RH), and low-temperature and low-humidity (15 ° C., 10% RH) at a printout speed of 6 sheets / min (A4 size), and the toner according to the present invention. A printout test was continuously performed on 5000 sheets while supplying the comparative toner, and the obtained images were evaluated for the following items.

The surface roughness Ra of the toner carrier used here is 1.5, and the material of the toner regulating blade is stainless steel.

The image evaluation and the matching with the image forming apparatus were evaluated based on the evaluation items and evaluation criteria described above.

Tables 8 and 9 summarize the evaluation results.

[0183]

[Table 8]

[0184]

[Table 9]

[0185]

As described above, according to the present invention, in any environment, the electrophotographic characteristics are excellent, a high-definition image is provided, the environment stability is excellent, the developer holding member, the photosensitive member, and the fixing device. It is possible to provide a toner and an image forming method which cause less contamination of the toner and the like.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of an image forming apparatus suitable for the present invention.

FIG. 2 is an exploded perspective view of a main part of the fixing device used in the embodiment of the present invention.

FIG. 3 is an enlarged cross-sectional view of a main part showing a film state when the fixing device used in the embodiment of the present invention is not driven.

FIG. 4 is a schematic diagram showing a state where a character image is hollow;

FIG. 5 is a schematic explanatory view of an image forming apparatus used in an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photoconductor (electrostatic latent image carrier) 2 Charging roller (primary charger) 3 Exposure 20 Intermediate transfer body 28 Bias power supply 29 Bias power supply 30 Stay 31 Heating body 31a Heater substrate 31b Heating body 31c Surface protection layer 31d Temperature sensing element 32 Fixing film 33 Pressure roller 34 Coil spring 35 Film end regulating flange 36 Power supply connector 37 Disconnecting member 38 Inlet guide 39 Outlet guide (separation guide) 41 Yellow developing device 42 Magenta developing device 43 Cyan developing device 44 Black color Developing device 50 Intermediate transfer member cleaning device 62 Primary transfer roller 63 Secondary transfer roller 64 Secondary transfer opposing roller 65 Intermediate transfer belt support roller 66 Intermediate transfer belt support roller P Transfer material 110 Electrostatic latent image carrier (photosensitive drum) 111 Conductive means (charging roller) 112 cartridge 113 cleaning means 114 exposure unit 115 developer container 116 the toner application roller 117 the toner carrying member (developing sleeve) 118 elastic layer thickness regulating member 119 transfer means (transfer roller)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/20 101 G03G 9/08 346 21/10 21/00 326 (72) Inventor Akira Hashimoto Ota, Tokyo 3-30-2 Shimomaruko-ku Canon Inc. (72) Inventor Satoshi Handa 3-30-2 Shimomaruko 3-chome, Ota-ku, Tokyo Inside Canon Inc. (72) Motoki Hisagi Tsukimaruko 3 in Ota-ku, Tokyo No. 30-2 F term in Canon Inc. (reference) 2H003 BB11 CC04 2H005 AA01 AA06 AA15 CA08 CA13 CA14 CA22 DA02 DA06 DA07 EA05 EA06 EA07 EA10 FB01 2H033 BA58 BE03 2H034 BF00 CB00 2H011 AA37 EA13 AE13

Claims (54)

[Claims] 1. A dry toner containing at least a binder resin, a colorant, a wax component, and a polyester resin, wherein the polyester resin is composed of a polycarboxylic acid and a polyhydric alcohol. Polycarboxylic acids and / or
Alternatively, at least one of the polyhydric alcohols has an alicyclic structure, and the polyester resin is contained in the dry toner in an amount of 0.1 to 50% by weight based on the toner. In the scattergram of the circle equivalent diameter-circularity based on the number of toners measured by the apparatus, the circle equivalent number average diameter D1 (μm) of the dry toner is 2
And the average circularity of the toner is 0.1 to 10 μm.
A dry toner characterized by having a circularity standard deviation of from 950 to 0.995 and less than 0.040. 2. The toner according to claim 1, wherein the toner is tetrahydrofuran (TH).
F) In the molecular weight distribution of the soluble component by gel permeation chromatography (GPC), the molecular weight of the polyester resin having a repeating unit in the structure of 10
2. The dry toner according to claim 1, wherein the content of the toner is equal to or less than 10.0% by weight based on the toner. 3. The dry toner according to claim 1, wherein the polyester resin does not contain an oxyethylene chain and an oxypropylene chain in a molecule. 4. The dry toner according to claim 1, wherein the polyester resin does not contain an aromatic ring. 5. The polyester resin having an acid value of 0.0
The dry toner according to any one of claims 1 to 4, wherein the amount is 1 to 20 mgKOH / g of resin. 6. The dry toner according to claim 1, wherein the polyester resin is contained in an amount of 0.1 to 30% by weight based on the total weight of the toner. 7. The content of the alicyclic skeleton contained in the polyester resin is from 0.1 to 0.1% based on the total weight of the toner.
The dry toner according to any one of claims 1 to 6, wherein the content is 10% by weight. 8. The polyester resin has a peak molecular weight of 1,000 to 50 in a molecular weight distribution by GPC.
The dry toner according to any one of claims 1 to 7, wherein the dry toner is within a range of 0000. 9. The polyester resin has a peak molecular weight of 2,000 to 10 in a molecular weight distribution by GPC.
The dry toner according to any one of claims 1 to 8, wherein the dry toner is in the range of 0000. 10. The dry toner according to claim 1, further comprising at least one charge control agent represented by the following general formula (I). Embedded image 11. The toner has an average circularity of 0.970 or more.
The dry toner according to any one of claims 1 to 10, wherein the circularity standard deviation is less than 0.035 at 0.995. 12. In a scattergram of circle-equivalent diameter-circularity based on the number of toners measured by the flow-type particle image measuring device, 15% by number or less of toner particles having a circularity less than 0.950 is less than 15%. The dry toner according to any one of claims 1 to 11, wherein: 13. A charging step of applying a voltage to a charging member from the outside to charge an electrostatic latent image carrier, and a latent image forming an electrostatic latent image on the charged electrostatic latent image carrier. A forming step, a developing step of developing the electrostatic image with toner to form a toner image on the electrostatic latent image carrier, and a transfer step of transferring the toner image on the electrostatic latent image carrier to a transfer material, A fixing step of heating and fixing the toner image on the transfer material, wherein the toner is a dry toner containing at least a binder resin, a colorant, a wax component, and a polyester resin; The system resin is composed of polyhydric carboxylic acids and polyhydric alcohols, and contains polyhydric carboxylic acids and / or
Alternatively, at least one of the polyhydric alcohols has an alicyclic structure, and the polyester resin is contained in the dry toner in an amount of 0.1 to 50% by weight based on the toner. In the scattergram of the circle equivalent diameter-circularity based on the number of toners measured by the apparatus, the circle equivalent number average diameter D1 (μm) of the dry toner is 2
And the average circularity of the toner is 0.1 to 10 μm.
An image forming method wherein the circularity standard deviation is 950 to 0.995 and is less than 0.040. 14. The toner according to claim 1, wherein the toner is tetrahydrofuran (T
HF) In the molecular weight distribution of soluble matter by gel permeation chromatography (GPC), the molecular weight of the polyester resin having a repeating unit in the structure is 1
14. The image forming method according to claim 13, wherein a component of not more than 000 is contained at 10.0% by weight or less based on the toner. 15. The image forming method according to claim 13, wherein the polyester resin does not contain an oxyethylene chain and an oxypropylene chain in a molecule. 16. The image forming method according to claim 13, wherein the polyester resin does not contain an aromatic ring. 17. The polyester resin having an acid value of 0.1.
17. The image forming method according to claim 13, wherein the amount is from 01 to 20 mgKOH / g of resin. 18. The image forming method according to claim 13, wherein the amount of the polyester resin is 0.1 to 30% by weight based on the total weight of the toner. 19. The content of the alicyclic skeleton contained in the polyester resin is 0.1 to the total weight of the toner.
3. The composition according to claim 1, wherein the content is 10 to 10% by weight.
9. The image forming method according to any one of items 8. 20. The polyester-based resin has a peak molecular weight of 1000 to 5 in a molecular weight distribution by GPC.
14. The range of 00000
20. The image forming method according to any one of claims 1 to 19. 21. The polyester resin has a peak molecular weight of 2,000 to 1 in a molecular weight distribution by GPC.
14. The range of 00000
21. The image forming method according to any one of the above items. 22. The image forming method according to claim 13, further comprising at least one charge control agent represented by the following general formula (I). Embedded image 23. The toner has an average circularity of 0.970 or more.
23. The image forming method according to claim 13, wherein the circularity standard deviation is less than 0.035 at 0.995. 24. In the scattergram of circle-based circularity-circularity based on the number of toners measured by the flow-type particle image measuring device, 15% by number or less of toner particles having a circularity less than 0.950 is less than 15%. The image forming method according to any one of claims 13 to 23, wherein: 25. In the developing step, the moving speed of the surface of the toner carrier in the developing area is 1.05 to 3.0 times the moving speed of the surface of the electrostatic latent image carrier. The image forming method according to any one of claims 13 to 24, wherein the surface roughness Ra (μm) is 1.5 or less. 26. The image forming method according to claim 13, wherein a ferromagnetic metal blade is arranged at a minute interval so as to face the toner carrier. 27. The image forming method according to claim 13, wherein a blade made of an elastic material is brought into contact with said toner carrier. 28. The image according to claim 13, wherein said electrostatic latent image carrier and said toner carrier have a certain gap, and are developed while applying an alternating electric field. Forming method. 29. The charging step includes: applying a voltage to the charging member from outside by bringing the charging member into contact with the electrostatic latent image carrier;
14. An electrostatic latent image carrier is charged.
29. The image forming method according to any one of the above items. 30. In a transfer step of electrostatically transferring the toner image on the electrostatic latent image carrier to a transfer material using a transfer device,
30. The image forming method according to claim 13, wherein the electrostatic latent image carrier and the transfer device are in contact with each other via the transfer material. 31. The heat fixing step, wherein a toner image is heat-fixed to a transfer material by a heat fixing device which does not supply an offset preventing liquid or does not have a fixing device cleaner. 31. The image forming method according to any one of the above items. 32. In the heat-fixing step, a toner image is transferred onto a transfer material by a fixedly supported heating element and a pressing member which is in pressure contact with the heating element and is in close contact with the heating element via a film. 13. The fixing method according to claim 13, wherein the fixing is performed by heating.
0. The image forming method according to any one of 0. 33. An untransferred residual toner on an electrostatic latent image carrier after transfer is collected by cleaning, and the collected toner is supplied to a developing unit and held again by the developing unit. 33. The image forming method according to claim 13, further comprising a toner reuse mechanism for developing an electrostatic latent image on the carrier. 34. At least a charging step of externally applying a voltage to a charging member to charge an electrostatic latent image carrier, and a latent image forming an electrostatic latent image on the charged electrostatic latent image carrier A forming step, a developing step of developing the electrostatic charge image with toner to form a toner image on the electrostatic latent image carrier, and a first step of transferring the toner image on the electrostatic latent image carrier to the intermediate transfer body A transfer step, and a second step of transferring the toner image on the intermediate transfer body to a transfer material.
And a fixing step of heating and fixing the toner image on the transfer material, wherein the toner is a dry toner containing at least a binder resin, a colorant, a wax component, and a polyester resin. The polyester resin is composed of polyhydric carboxylic acids and polyhydric alcohols, and contains polycarboxylic acids and / or
Alternatively, at least one of the polyhydric alcohols has an alicyclic structure, and the polyester resin is contained in the dry toner in an amount of 0.1 to 50% by weight based on the toner. In the circle equivalent diameter-circularity scattergram based on the number of toners measured by the apparatus, the circle equivalent number average diameter D1 (μm) of the dry toner is 2
And the average circularity of the toner is 0.1 to 10 μm.
An image forming method, wherein the circularity standard deviation is 950 to 0.995 and less than 0.040. 35. The toner comprises tetrahydrofuran (T
HF) In the molecular weight distribution of soluble matter by gel permeation chromatography (GPC), the molecular weight of the polyester resin having a repeating unit in the structure is 1
35. The image forming method according to claim 34, wherein a component of not more than 000 is contained at 10.0% by weight or less based on the toner. 36. The image forming method according to claim 34, wherein the polyester resin does not contain an oxyethylene chain and an oxypropylene chain in a molecule. 37. The image forming method according to claim 34, wherein the polyester resin does not contain an aromatic ring. 38. The polyester resin having an acid value of 0.1.
The image forming method according to any one of claims 34 to 37, wherein the amount is from 01 to 20 mgKOH / g of resin. 39. The image forming method according to claim 34, wherein the amount of the polyester resin is 0.1 to 30% by weight based on the total weight of the toner. 40. The content of the alicyclic skeleton contained in the polyester resin is 0.1 to the total weight of the toner.
34 to 3% by weight.
10. The image forming method according to any one of the above items 9. 41. The polyester resin has a peak molecular weight of 1000 to 5 in a molecular weight distribution by GPC.
35. The method according to claim 34, wherein the value is in the range of 00000.
40. The image forming method according to any one of the above items. 42. The polyester resin has a peak molecular weight of 2,000 to 1 in a molecular weight distribution by GPC.
35. The method according to claim 34, wherein the value is in the range of 00000.
40. The image forming method according to any one of the above items. 43. The image forming method according to claim 34, further comprising at least one charge control agent represented by the following general formula (I). Embedded image 44. The toner has an average circularity of 0.970 or more.
The image forming method according to any one of claims 34 to 43, wherein the circularity standard deviation is less than 0.035 at 0.995. 45. In the scattergram of the circle equivalent diameter-circularity based on the number of toners measured by the flow type particle image measuring device, 15% by number or less of toner particles having a circularity less than 0.950 are used. The image forming method according to any one of claims 34 to 44, wherein: 46. In the developing step, the moving speed of the surface of the toner carrier in the developing area is 1.05 to 3.0 times the moving speed of the surface of the electrostatic latent image carrier. The image forming method according to any one of claims 34 to 43, wherein the surface roughness Ra (μm) is 1.5 or less. 47. The image forming method according to claim 34, wherein a ferromagnetic metal blade is arranged at a minute interval so as to face the toner carrier. 48. The image forming method according to claim 34, wherein a blade made of an elastic material is brought into contact with said toner carrier. 49. An image according to claim 34, wherein said electrostatic latent image carrier and said toner carrier have a certain gap, and are developed while applying an alternating electric field. Forming method. 50. The charging step includes: bringing a charging member into contact with the electrostatic latent image carrier, applying a voltage to the charging member from the outside,
35. The electrostatic latent image carrier is charged.
50. The image forming method according to any one of the above items. 51. In a second transfer step of electrostatically transferring the toner image on the intermediate transfer member to a transfer material using a transfer device, the intermediate transfer member and the transfer device are interposed via the transfer material. The image forming method according to any one of claims 34 to 50, wherein the image forming apparatus is in contact with the image forming apparatus. 52. The heating and fixing step in which a toner image is heat-fixed to a recording material by a heating and fixing device which does not supply an offset preventing liquid or does not have a fixing device cleaner. 52. The image forming method according to any one of the above items. 53. In the heat fixing step, a toner image is formed on a recording material by a fixedly supported heating member and a pressing member which is in pressure contact with the heating member and closely adheres to the heating member via a film. The image forming method according to any one of claims 34 to 51, wherein heating and fixing are performed. 54. The untransferred residual toner on the electrostatic latent image carrier after transfer is collected by cleaning, and the collected toner is supplied to the developing unit and held again by the developing unit. The image forming method according to any one of claims 34 to 53, further comprising a toner reuse mechanism for developing the electrostatic latent image on the carrier.