JP2001013732A - Toner, its production and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which is excellent in environmental resistance, retains superior image characteristics even in an endurance test and suppresses image stain such as surface fog. SOLUTION: The toner contains a bonding resin, a colorant, a wax and an organometallic compound of the formula, wherein R1 and R4 are each an aromatic group, R2 and R3 are each H, alkyl or an aromatic group, M is an element selected from B, Ti, Fe, Co, Cr, Al and Ni and Xn+ is a cation. The shape factor SF-1 of the toner is >100 to 160 and the shape factor SF-2 is >100 to 140.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method utilizing an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet recording method and the like, and an image forming method. More specifically, the present invention relates to a toner used in a copying machine, a printer, a facsimile, which forms an image by forming a toner image on an electrostatic latent image carrier in advance, and then transferring the image onto a transfer material, and an image forming method.

[0002]

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

As a method for visualizing an electric 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 method, 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] In recent years, LED and LBP printers have become the mainstream in the market for printer devices, and the direction of technology has been increasing to higher resolutions, that is, from 300 and 600 dpi to 1200 and 2400 dpi. Accordingly, higher definition has been required for the developing system. Also, the functions of the copying machines have been advanced, and the digital copying machines have been 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. .

Therefore, in order to meet such a demand, a specific charge control agent is added for the purpose of imparting a desired triboelectric charging property to the toner particles. Charge control agents known in the art today include metal complexes of monoazo dyes, metal complexes of hydroxycarboxylic acids, dicarboxylic acids, aromatic diols, and the like, as resins with negative triboelectric charge, resins containing acid components, and the like. . Nigrosine dye, azine dye, triphenylmethane dye,
Quaternary ammonium salts and polymers having a quaternary ammonium salt in the side chain are known.

[0007] There have been proposals for toners containing a metal compound of oxycarboxylic acid. For example, JP-A-2-22167 discloses a toner containing a metal complex salt of an oxycarboxylic acid having an aromatic ring, and JP-A-5-61257 embeds a boron compound of an oxycarboxylic acid in a toner precursor. Japanese Patent Application Laid-Open Nos. 3-39973 and 5-728.
No. 12 discloses a toner containing a boron complex salt of benzylic acid, and JP-A-5-165257 discloses a color toner containing a boron complex salt of benzylic acid and an inorganic fine powder hydrophobized with silicone oil. JP-A-6-301240 discloses a toner containing a metal complex salt of benzylic acid having an amide as a counter ion. However, these toners have a drawback that although the charging speed is improved to some extent, the triboelectric charge amount of the toner is not sufficiently provided. In order to solve the above problem, Japanese Patent Application Laid-Open No. H10-90946 discloses a toner in which a charge control agent such as a boron complex salt of benzylic acid is added / fixed to toner particles without drying. Japanese Patent Application Laid-Open No. 10-312089 discloses a toner in which a boron complex salt of benzylic acid and a metal salt of a salicylic acid derivative are used in combination. According to the study of the present inventors, these toners can improve the triboelectric charge amount and the charging speed to some extent, but in the former case, the production process is complicated, and in the latter case, boron of benzyl acid is used. By using a complex salt and a metal salt of a salicylic acid derivative in combination, charge control agents exhibiting different charging sequences are mixed, so that there is still room for improvement in the triboelectric charge distribution of the toner. Further, the toner as described above requires further study on matching with the image forming apparatus.

[0008]

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

That is, an object of the present invention is to provide excellent transferability,
An object of the present invention is to provide a toner and an image forming method which have less transfer residual toner.

Another object of the present invention is to provide a toner and an image forming method which do not adversely affect a photoreceptor or an intermediate transfer member, have less image deterioration such as fog, and can be highly applied to an electrophotographic process. It is in.

It is a further object of the present invention to provide a toner and an image forming apparatus which are excellent in releasing property and slipperiness, have a small amount of photoreceptor shaving even after printing many sheets for a long period of time, and have a long service life. It is to provide a method.

Further, an object of the present invention is to provide excellent matching with an image forming apparatus in which no charging abnormality or image defect due to contamination of a member pressed against an electrostatic latent image carrier occurs or these phenomena are suppressed. An object of the present invention is to provide a toner and an image forming method.

It is a further object of the present invention to provide a toner and an image forming method which further enhance the uniform coatability of the toner on the toner carrier.

[0014]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by the following toner, and have completed the present invention.

That is, the present invention relates to a toner having toner particles containing at least a binder resin, a colorant, a wax and a compound represented by formula (A), wherein the toner has a shape factor of SF-1. Value is 100 <SF-1 ≦ 160
Wherein the value of SF-2 is 100 <SF-2 ≦ 140.

[0016]

[Outside 4] (Wherein, R ₁ and R ₄ represent a substituted or unsubstituted aromatic group (including a condensed ring), and R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic group (a condensed ring) , M represents an element selected from B, Ti, Fe, Co, Cr, Al, and Ni, and X ^{n +} represents a cation.)

Further, the present invention provides at least a polymerizable monomer,
Colorant, wax, polymerization initiator, and the above general formula <A>
A granulation step of dispersing a polymerizable monomer composition containing the compound represented by in an aqueous medium to produce particles of the polymerizable monomer composition, and A method for producing a toner having at least a polymerization step of polymerizing a polymerizable monomer in particles to form toner particles, wherein the polymerization reaction of the polymerizable monomer from the granulation step to the polymerization step is carried out by polymerization. The process is carried out while maintaining the pH of the aqueous medium at 4.5 to 8.5 until the polymerization conversion of the hydrophilic monomer becomes 10% or more. <S
F-1 ≦ 160, and SF-2 is 100 <SF-2 ≦
140 relates to a method for producing a toner.

Further, the present invention provides 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; a developing step of developing the electrostatic latent image with the toner carried on the toner carrier to form a toner image on the electrostatic latent image carrier; a toner image on the electrostatic latent image carrier Transferring the toner image onto a transfer material with or without an intermediate transfer member; and fixing the toner image of the transfer material by heating, wherein the toner comprises at least a binder resin and a colorant. , Wax and a compound containing the compound represented by the general formula <A>, and the shape factor of the toner is such that the value of SF-1 is 100 <SF-1 ≦ 16.
0, and the value of SF-2 is 100 <SF-2 ≦ 140.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by formula (A) will be described in detail below.

[0020]

[Outside 5]

In the formula, R ₁ and R ₄ represent a substituted or unsubstituted aromatic (including a condensed ring), and R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic (condensed ring) And M is B, Ti, Fe, Co, Cr, Al,
X represents an element selected from Ni, and X ^{n +} represents a cation.

Specifically, R ₁ , R ₂ , R ₃ and R ₄ include aromatics such as benzene and naphthalene, and the substituents of the aromatics include an alkyl group, an aralkyl group,
Examples include an alkoxy group, an alkenyl group, an aryl group, a halogen atom, a nitro group, a cyano group, an amino group, and a hydroxyl group, and R ₂ and R ₃ include a methyl group, an ethyl group, and an n-
Butyl group, t-butyl group, iso-propyl group, iso
-Alkyl groups such as amyl group, n-dodecyl group, n-octadecyl group and cyclohexyl group. Also,
M is a trivalent metal such as Cr, Al, Fe, C
o, Ti, and B. As X ^{n +} , various inorganic cations and organic cations are used. Examples of the inorganic cation include a hydrogen ion metal ion, and are monovalent or divalent.
Li ⁺ , Na ⁺ , K ⁺ , Mg
²⁺ , Ca ²⁺ , Zn ²⁺ , and Ba ²⁺ . Examples of the organic cation include an ammonium ion, an iminium ion, and a phosphonium ion.

Among the X ^{n +} exemplified above, inorganic cations are preferable from the viewpoint of the charging speed and charging stability of the toner.

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

[0025]

[Outside 6]

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

Examples of the alkyl group include a methyl group, an ethyl group, an n-butyl group, a t-butyl group, an iso-propyl group, an iso-amyl group, an n-dodecyl group, an n-octadecyl group and a cyclohexyl group. Examples of the aryl group include a phenyl group and an α-naphthyl group.The alkyl group or the aryl group is substituted with a substituent such as an alkyl group, an aralkyl group, a halogen group, an alkoxy group, a hydroxyl group, a cyano group, or an aryl group. It may be.
Examples of Z ₁ and Z ₂ include a group of nonmetallic atoms necessary for forming a heterocyclic ring such as a pyridine ring, an isoquinoline ring, a pyrrole ring, an imidazole ring, a piperidine ring and a pyrrolidine ring.

Tables 1 and 2 show specific examples of the compound represented by the general formula <A>. The compound No. Is commonly used in the embodiments.

[0029]

[Table 1]

[0030]

[Table 2]

The compound represented by the general formula <A> used as the charge control agent of the present invention can be prepared, for example, by adding an aqueous solution of boric acid and an amine to the following general formula <F> or <G> (wherein R ₁ , R
₂ , R ₃ and R ₄ can be easily obtained by adding and reacting a compound represented by the general formula <A>).

[0032]

[Outside 7]

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

When the toner is produced by a polymerization method, the compound represented by the formula (A) is used in an amount of 0.1 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the polymerizable monomer. 6 to 5 parts by weight are added.

When the amount of the compound represented by the general formula <A> is less than 0.1 part by weight, the effect of imparting charge to the toner particles is not generated, which is not preferable. On the other hand, when the amount of the compound represented by the general formula <A> exceeds 10 parts by weight, the cost is high and it is not economically preferable.

In the present invention, SF-1 and SF-2 indicating the shape factor of the toner are, for example, FE-S manufactured by Hitachi, Ltd.
Using EM (S-800), 2μ enlarged to 1000 times
100 toner particle images of m or more are sampled at random, and the image information is introduced into, for example, an image analyzer (Luzex III) manufactured by Nicole via an interface, analyzed, and a value obtained by the following equation is calculated. Is the shape factor SF
-1, SF-2.

[0037]

[Outside 8] (Where MXLNG is the absolute maximum length of the particle, PERIME
Is the perimeter of the grain, and AREA is the projected area of the grain. )

When the shape factor of the toner particles is measured by the above-mentioned method after the external additives are externally added to the toner particles, the external additives adhering to the surface of the toner particles are included in the image analysis data. Went so as not to be included.

The shape factor SF-1 indicates the degree of roundness of the particles, and the shape coefficient SF-2 indicates the degree of irregularities of the particles.

The ratio of the shape factor of the toner (SF-2) / (S
When the value of F-1) is more than 1.0, cleaning failure generally tends to occur, and the toner has a shape factor SF-1.
When it exceeds 160, it moves away from a sphere and approaches an irregular shape,
Since the toner is easily crushed in the developing device, the particle size distribution fluctuates, and the charge amount distribution becomes broad, the image density is reduced, and image fogging such as background fogging and reverse fogging is liable to occur. On the other hand, if SF-2 exceeds 140, the transfer efficiency of the toner image at the time of transfer from the electrostatic image holding member to the intermediate transfer member and the transfer material is lowered, and the transfer of characters and line images during transfer is not preferable.

In particular, the above tendency becomes obvious when a full-color copying machine that develops / transfers a plurality of toner images is used. That is, in the generation of a full-color image, it is difficult to uniformly transfer the toner images of four colors,
When an intermediate transfer member is used, problems tend to occur in terms of color unevenness and color balance, and it is difficult to stably output a high-quality full-color image.

Further, in the case where a normal amorphous toner is used, the space between the photosensitive member and the cleaning member, and / or
Due to slippage and rubbing force between the photoreceptor and the intermediate transfer member, toner fusion or filming occurs on the surface of the photoreceptor or the intermediate transfer member, which hinders matching with the image forming apparatus.

Therefore, in order to avoid these problems, the value of the toner shape factor SF-1 must be 100 <SF
−1 ≦ 160, and the value of the shape factor SF-2 is 100 <
SF-2 ≦ 140 is preferable, and the shape factor SF
More preferably, the value of -1 is 100 <SF-1 ≦ 150, and the value of the shape factor SF-2 is 100 <SF-2 ≦ 130, and the value of the shape factor SF-1 is 100 <SF−.
1 ≦ 140, and the value of the shape factor SF-2 is 100 <S
More preferably, F-2 ≦ 120. Also, (S
The value of (F-2) / (SF-1) is preferably 1.0 or less.

Further, the toner of the present invention can prevent toner fusion to a toner carrier due to an increase in transfer residual toner and a decrease in development efficiency by producing a toner having particularly good circularity distribution. It is possible.

In the toner of the present invention, in the circularity frequency distribution of the toner measured by the flow type particle image measuring apparatus, the average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0. By precisely controlling the particle shape of the toner so as to be less than 040, developability and transferability are improved in a well-balanced manner, and at the same time, matching with the image forming apparatus is significantly improved.

That is, the average circularity of the circularity frequency distribution of the toner is 0.920 to 0.995, preferably 0.950 to 0.950.
By setting the ratio to 0.995, more preferably 0.970 to 0.990, the transferability of a toner having a small particle diameter, which has been difficult in the past, is greatly improved, and the developing ability for a low potential latent image is also improved. Dramatically improved. In particular, the above tendency is very effective when developing a digital minute spot latent image or when forming a full-color image in which an intermediate transfer body is used to perform multiple transfers, and the matching with the image forming apparatus is also good. It becomes something.

Further, in the toner of the present invention, the circularity standard deviation of the circularity frequency distribution of the toner can be arbitrarily controlled, and the circularity standard deviation is less than 0.040, preferably less than 0.035. , More preferably 0.015 or more.
By setting it to be less than 035, the problem relating to the developability can be significantly improved.

The average circularity of the circularity frequency distribution is equal to 0.
By setting the toner content of less than 950 to 15% or less, the development efficiency in image formation becomes a sufficient level, and the image formation becomes good.

The above control of the average circularity, the circularity standard deviation and the number of toners having a circularity of less than 0.950 is based on the p of the water medium in the granulation step in the suspension polymerization method.
H is possible.

The circularity and the frequency distribution of the toner in the present invention are used as a simple method for quantitatively expressing the shape of the toner. In the present invention, the flow type particle image measuring apparatus FPIA-1000 is used. (Toa Medical Electronics Co., Ltd.)
Was measured using the following formula, and calculated using the following formula.

[0051]

[Outside 9]

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. The circularity is 1.000 when the toner is perfectly spherical, and the circularity becomes smaller as the surface shape becomes more complicated.

[0054] The average circularity c and circularity standard deviation SDc which means an average value of circularity frequency distribution, circularity at division point i of particle size distribution (central value) ci, when the frequency and f _ci Is calculated from the following equation.

[0055]

[Outside 10]

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. Then, 0.02 g of the measurement data is further added and uniformly dispersed. As a means for dispersing, an ultrasonic dispersing machine UH-50 type (manufactured by MMT 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.

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

Further, in order to faithfully develop minute latent image dots for high image quality, the toner has a weight average particle diameter (D
4) is 4 to 9 μm and the variation coefficient A in the number distribution is 3
It is preferably 0 or less, and more preferably the variation coefficient A is 25 or less. Also, 4. in the number distribution.
Amount of toner fine powder having a particle size of 00 μm or less is 25% by number
Or less, and the amount of toner fine powder is 20% by number.
It is more preferred that: By controlling the particle size distribution of the toner as described above, the powder characteristics exhibited by the toner particles are improved. Therefore, the compound represented by the general formula (A) according to the present invention is added to the toner for use. In this case, extremely excellent charging properties can be exhibited. When the weight average particle diameter of the toner is less than 4 μm or when the amount of the toner fine powder is more than 25% by number, it is difficult to uniformly receive triboelectric charge because the fluidity is reduced by filling the toner particles. This tends to cause unevenness in image density and image fogging and decrease in image density. In addition, the transfer efficiency is reduced, which causes not only uneven image density, but also undesirably increases the load on the image forming apparatus because the residual toner on the surface of the photoreceptor or the intermediate transfer member increases. On the other hand, when the weight average particle diameter of the toner exceeds 10 μm, it is not possible to faithfully reproduce minute latent image dots.

Conventionally, when toner particles having such a small particle size are used, problems often arise due to the chargeability of the toner. However, the compound represented by the general formula <A> according to the present invention is often used. Is added to the toner, the uniform chargeability and charge stability of the toner are further improved.

The particle size distribution of the toner can be measured by various methods. In the present invention, “Coulter Counter TA-II” or “Coulter Multisizer II” (both manufactured by Coulter Co., Ltd.) is used as a measuring device. Used. As the measuring electrolyte, an aqueous solution of primary-sodium chloride of 1% by weight in NaCl can be prepared or used, or a commercially available product, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersing agent to 100 to 150 ml of the electrolytic solution, and a sample to be measured is 2 to 20 ml.
Add mg. Next, the electrolyte solution to which the measurement sample was added was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the volume and number of toner particles were measured for each channel using a 100 μm aperture in the particle size distribution measurement device as described above. Each time, the volume distribution and the number distribution of the toner are calculated, and the weight average particle diameter (D
₄ ) and the number average particle diameter (D ₁ ) and standard deviation (S) are determined from the number distribution.

The measurement channels are 2.00 to 2.00.
2.52 μm; 2.52 to 3.17 μm; 3.17 to
4.00 μm; 4.00 to 5.04 μm; 5.04 to
6.35 μm; 6.35 to 8.00 μm; 8.01 to 1
0.08 μm; 10.08 to 12.70 μm; 12.7
0-16.00 μm; 16.0-20.20 μm; 2
0.20-25.40 μm; 25.40-32.00 μ
m; 13 channels of 32.00 to 40.30 μm were set, and the median value of each channel was used as a representative value for each channel in calculating the particle size distribution.

The variation coefficient A in the number distribution of the toner is calculated from the following equation.

Coefficient of variation A = [S / D ₁ ] × 100 [where S represents the standard deviation value in the number distribution of the toner, and D ₁ represents the number average particle diameter (μm) of the toner. ]

The binder resin used in the toner according to the present invention has a low molecular weight peak in the range of 3,000 to 15,000 in the GPC molecular weight distribution, which indicates that the shape of the toner produced by the pulverization method is thermomechanical. It is preferable for controlling by impact force.

When the peak of the low molecular weight exceeds 15,000, it is difficult to control the shape factors SF-1 and SF-2 within the range of the present invention, and the transfer efficiency is not sufficiently improved. Also, 3
If it is less than 000, fusion tends to occur during surface treatment.

The molecular weight is measured by GPC (gel permeation chromatography). As a specific method of measuring GPC, a toner was previously prepared using a Soxhlet extractor with a THF (tetrahydrofuran) solvent.
Using a sample extracted for 0 hours, the column configuration was A-801, 802, 803, 804, 805, manufactured by Showa Denko.
806 and 807 are connected, and the molecular weight distribution can be measured using a standard polystyrene resin calibration curve.

The weight average molecular weight (Mw) and the number average molecular weight (Mw) of the binder resin used in the toner according to the present invention are described below.
The ratio (Mw / Mn) of n) is preferably from 2 to 100.

The glass transition point Tg of the binder resin used in the toner is from 40 ° C. to 7 ° C. from the viewpoint of fixability and storage stability.
5 ° C (more preferably 52 ° C to 70 ° C) is preferred.

The glass transition point Tg of the toner according to the present invention is measured by, for example, a high-precision internal heating type input compensation type differential scanning calorimeter such as DSC-7 manufactured by PerkinElmer. The measuring method is performed according to ASTM D3418-82. In the present invention, the sample is heated once to obtain a pre-history, then rapidly cooled, and again at a temperature rate of 10 ° C./mi.
n, a DSC curve measured when the temperature is raised in the range of 0 to 200 ° C.

In general, the toner having the above-mentioned particle size distribution tends to have a uniform charge state as the shape becomes uniform, but the amount of triboelectric charge tends to decrease due to a decrease in specific surface area.

However, the toner of the present invention has the general formula <A>
Since the compound represented by the formula (1) is contained, the charge state of the toner can be preferably improved without reducing the triboelectric charge amount.

The binder resin used in the present invention is not particularly limited as long as it is used for producing a toner. Specific examples of the binder resin used in the present invention, a polymer of the following polymerizable monomer alone, or
A mixture of a single polymerizable monomer or a copolymer of two or more polymerizable monomers is used. More specifically, a styrene-acrylic acid copolymer or a styrene-methacrylic acid copolymer is preferred.

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

Examples of the acrylate-based polymerizable monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, and acrylic acid. Examples include acrylates such as 2-ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate. Examples of the methacrylate polymerizable monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, and methacrylic acid-2. Α such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate
-Methylene aliphatic monocarboxylic esters.

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

As the crosslinkable polymerizable monomer, a polymerizable monomer having two or more polymerizable double bonds is mainly used. Specific examples thereof include aromatic divinyl compounds such as divinylbenzene and divinylbenzene. Naphthalene; diacrylate compounds linked by an alkyl chain, for example, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate;
1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and compounds in which the acrylate of the above compounds is replaced with methacrylate; diacrylate compounds linked by an alkyl chain containing an ether bond, for example, diethylene glycol diacrylate, triethylene Ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol #
400 diacrylate, polyethylene glycol # 60
0 diacrylate, dipropylene glycol diacrylate, and compounds in which the acrylate of the above compound is replaced with methacrylate; diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, polyoxyethylene (2)- 2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and compounds in which the acrylate of the above compounds is replaced with methacrylate Further, polyester-type diacrylate compounds, for example, trade name MAN
DA (Nippon Kayaku). Examples of the multifunctional crosslinking agent include pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate,
Oligoester acrylates and compounds in which the acrylates of the above compounds are replaced with methacrylates; triallyl cyanurate and triallyl trimellitate.

When these crosslinkable polymerizable monomers are used in an amount of 1 part by weight or less based on 100 parts by weight of the other polymerizable monomer components, good low-temperature fixability and offset resistance can be obtained. Although satisfied, the storage stability of the toner is also improved.

Of these crosslinkable polymerizable monomers, those preferably used include aromatic divinyl compounds (particularly divinylbenzene) and diacrylate compounds linked by a chain containing an aromatic group and an ether bond. And 0.001 to 0.1 parts by weight based on 100 parts by weight of other polymerizable monomer components.
It is good to use in the range of 05 parts by weight. As a result, even when the particle diameter of the toner is reduced, the developing characteristics of the developer under each environment are stabilized, and the durability is improved.

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

Specifically, organic peroxides such as di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate and t-butyl peroxybenzoate , Azobisisobutyronitrile, diazoaminoazobenzene, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis (2-aminodinobutane) dihydrochloride, 2,2'-azobis (2 And azo and diazo compounds such as dimethyl 2,2'-azobis (2-methylpropylate) (dimethyl 2,2'-azobisisobutyrate).

These polymerization initiators may be used alone or in combination of two or more, and are used in an amount of 0.05 to 20 parts by weight, more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the polymerizable monomer. Used in 10 parts by weight.

In the present invention, a resin having polarity (hereinafter, referred to as a polar resin) such as a polyester resin or a polycarbonate resin can be used together with the above-mentioned binder resin. By adding a polar resin to the toner,
The state of the compound represented by the general formula <A> contained in the toner is good, and the charging characteristics can be improved.

For example, in the case where a toner is directly produced by a suspension polymerization method or the like described below, if the above-mentioned polar resin is added during the polymerization reaction from the dispersion step to the polymerization step, the polymerizable monomer which becomes the toner particles is formed. According to the balance between the polarity of the composition and the aqueous dispersion medium, the added polar resin is controlled to form a thin layer on the surface of the toner particles or to exist with a gradient from the toner particle surface toward the center. Can be done. At this time, by using a polar resin having an interaction with the compound represented by the general formula <A>,
It is possible to make the state of the compound present in the toner a desirable form. Particularly, the acid value is 1 to 20 mgKOH / g.
When a polar resin having the formula (1) is used, it is easy to control the state of the compound.

The amount of the polar resin added is 100
It is preferable to use 1 to 25 parts by weight with respect to parts by weight,
More preferably, it is 2 to 15 parts by weight. If the amount is less than 1 part by weight, the existence state of the polar resin in the toner particles becomes non-uniform. If the amount exceeds 25 parts by weight, the thin layer of the polar resin formed on the surface of the toner particles becomes thick. It becomes difficult to control the existing state of, and its function cannot be fully exhibited.

The composition of a typical polyester resin used as a polar resin is as follows.

As the alcohol component of the polyester resin, ethylene glycol, propylene glycol, 1,1,
3-butanediol, 1,4-butanediol, 2,3
-Butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A,
Examples thereof include bisphenol derivatives represented by the following formula (A) and diols represented by the following formula (A).

[0087]

[Outside 11]

The use of a reactive polyester resin or a polycarbonate resin as the polar resin is also a preferred embodiment of the present invention. When these polar resins are used, the charging characteristics of the toner are improved, image fogging and scattering are improved, and a commercial image having excellent dot reproducibility can be obtained. In addition, it is possible to impart appropriate mechanical strength to the toner particles, minimize the influence of toner deterioration received from the image forming apparatus, and improve durability against multiple-sheet printout and matching with an image forming apparatus described later. improves. Further, it is possible to minimize the influence of a toner manufacturing process such as a toner sphering process for achieving the toner shape distribution as described above or a drying process when directly manufacturing a toner by a polymerization method. In addition, two or more polar resins can be used in combination, and the chargeability of the polar resin itself can be used.

The reactive polyester resins used in the present invention include terephthalic acid, isophthalic acid, adipic acid, maleic acid, succinic acid, sebacic acid, thiodiglycolic acid, diglycolic acid, malonic acid, glitanic acid and pimelic acid. And polybasic acids such as suberic acid, azelaic acid, succinic acid, cyclohexanedicarboxylic acid, trimellitic acid; and ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (2-hydroxyethyl) benzene, 1,4-cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, bis Phenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, polycondensation with polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol. It has a reactive group in the main chain or side chain of the condensation polymer. The reactive group includes a carboxylic acid (or a salt thereof), a sulfonic acid (or a salt thereof), an ethyleneimino acid, an epoxy group, an isocyanate group, a double bond,
Acid anhydrides and halogen atoms can be exemplified. The reactive polyester resins are reacted with each other, or reacted with a polyfunctional crosslinking agent (for example, polyhydric alcohol, polybasic acid, etc.) to further react with the reactive polyester. The vinyl monomer can be reacted (eg, esterified, copolymerized, etc.) to obtain a THF-insoluble component. For example, when a toner is obtained by a polymerization method, an unsaturated polyester resin is used as a reactive polyester resin, and a vinyl monomer (including a crosslinking agent such as divinylbenzene as necessary) is copolymerized. In this case, the unsaturated polyester resin having polarity migrates to the vicinity of the toner surface with the progress of polymerization and forms a thin layer on the surface of the toner particles, so that a toner having particularly excellent blocking resistance and offset resistance is obtained. It is possible to get.

As the reactive polyester resin which can be used in the present invention, any resin may be used as long as it contains a reactive group as described above. However, if the molecular weight is too low, a polyester resin which does not participate in a crosslinking reaction may be used. It may be present on the toner surface, and the blocking resistance may be reduced. If the molecular weight is too high, for example, when a toner is obtained by a polymerization method, it becomes difficult to dissolve the reactive polyester resin in a vinyl-based monomer, so that production becomes difficult. Accordingly, the polymerization average molecular weight of the reactive polyester resin is preferably about 3,000 to 100,000 for obtaining a toner having particularly excellent performance.

On the other hand, as the polycarbonate resin according to the present invention, a polycarbonate resin having a repeating unit represented by the following general formula (I) in the molecular structure is preferably used.

[0092]

[Outside 12] [Wherein, R represents an organic group].

The general formula (I) has various structures. For example, any known polycarbonate produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method may be used. The following general formula (II) can be mentioned as an example.

[0094]

[Outside 13] [In the formula, R ² is a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic substituent. When a plurality of R ² are present, they may be the same or different, and m is , 0-4. Z is a single bond, an aliphatic hydrocarbon group, an aromatic substituent, -S -, - SO -, - SO 2 -, - O -, - CO
A bond represented by a bond). And a polymer having a repeating unit having a structure represented by the following formula:

Although various polycarbonate resins can be used, the polycarbonate resins generally have the general formula (III)
(V)

[0096]

[Outside 14] (Wherein, R ² , m and Z are the same as described above). Can be easily produced by reacting a dihydric phenol represented by the formula with a carbonate precursor such as phosgene or a carbonate compound. That is, for example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or a high molecular weight regulator, by the reaction of a dihydric phenol with a carbonate precursor such as phosgene, or a reaction between a dihydric phenol and diphenyl carbonate. It is produced by a transesterification reaction with such a carbonate precursor.

There are various dihydric phenols represented by the above general formulas (III) to (V), such as 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A). Bis (4-hydroxyphenyl) methane; bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane; bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; 5-dimethyl-4-hydroxyphenyl) methane; 1,1-bis (4
-Hydroxyphenyl) ethane; 1-naphthyl-1,1
-Bis (4-hydroxyphenyl) ethane; 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane;
1,2-bis (4-hydroxyphenyl) ethane; 2-
Methyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4
-Hydroxyphenyl) propane; 2,2-bis (3-
Methyl-4-hydroxyphenyl) propane; 1,1-
Bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) butane; 1,4-bis (4
-Hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) pentane: 4-methyl-2,2-bis (4-hydroxyphenyl) pentane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 2 , 2-
Bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane; 1-bis (4
Dihydroxyarylalkanes such as -hydroxyphenyl) cyclodecane; bis (4-hydroxyphenyl) sulfone; dihydroxyarylsulfones such as bis (3,5-dimethyl-4-hydroxyfel) sulfone; bis (4-hydroxyphenyl) ether Dihydroxyaryl ethers such as bis (3,5-dimethyl-4-hydroxyphenyl) ether, 4,4'-
Dihydroxybenzophenone; dihydroxyaryl ketones of 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide; bis (3-methyl-4-hydroxyphenyl sulfide) Bis (3,5-dimethyl-4-
Dihydroxyaryl sulfides such as (hydroxyphenyl) sulfide, bis (4-hydroxyphenyl)
Dihydroxyarylsulfoxides such as sulfoxide; dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl;hydroquinone;solcinol; dihydroxybenzenes such as methylhydroquinone;
Dihydroxynaphthalene; dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene; These dihydric phenols may be used alone or in combination of two or more.

Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The polycarbonate resin used in the present invention may be a homopolymer using one of these dihydric phenols, a copolymer using two or more of these dihydric phenols, or It may be a blend. Further, it may be a thermoplastic random branched polycarbonate resin obtained by reacting a polyfunctional aromatic compound with the above-mentioned dihydric phenol and / or carbonate precursor.

In order to adjust the glass transition temperature and the viscoelasticity of the polycarbonate resin, a part of the dihydric phenol is replaced with ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (2-hydroxyethyl) benzene, 1,4-cyclohexanedimethanol, Modification of polyethylene glycol, propylene glycol, hydrogenated bisphenol A and its derivatives, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, polyhydric alcohol such as glycerin, trimethylolpropane, pentaerythritol, etc. Polycarbonate resins are also preferably used. In this case, it is possible to produce the compound by the above-mentioned method by simply substituting a part of the dihydric phenol. However, as an example of another production method, dihydric phenol and an aliphatic or aromatic bischloroform A method of reacting a mate with a pyridine in a methylene chloride solvent using pyridine as a catalyst is exemplified. Of course, synthesis by other production methods is also possible.

Further, in the present invention, as the polycarbonate resin, the above-mentioned polycarbonate and polystyrene, styrene- (meth) acrylic copolymer, polyester, polyurethane, epoxy resin, polyolefin,
Block copolymers with polyamide, polysulfone, polycyanoaryl ether, polyarylene sulfide, alkyl (meth) acrylate, (meth) acrylic acid,
It is also possible to use a graft-modified copolymer in which maleic acid or a styrene-based monomer is grafted.

The molecular weight of the polycarbonate resin used in the present invention is not particularly limited, but preferably has a peak molecular weight measured by GPC in the range of 1,000 to 500,000, more preferably 2,000 to 50,000.
100,000. If the peak molecular weight is lower than 1000, adverse effects on charging characteristics may occur, and
If it is higher than this, the melt viscosity becomes too high, which may cause a problem in fixability. In producing the polycarbonate resin used in the present invention, a suitable molecular weight regulator, a branching agent for improving viscoelasticity, a catalyst for accelerating the reaction, and the like can be used as required.

The polar resins as described above are not limited to one kind of polymer, respectively. For example, two or more kinds of reactive polyester resins can be used simultaneously, and two or more kinds of vinyl polymers can be used. Yes, and completely different kinds of polymers such as non-reactive polyester resin, epoxy resin, polycarbonate resin, polyolefin, polyvinyl acetate, polyvinyl chloride, polyalkyl vinyl ether, polyalkyl vinyl ketone, polystyrene, poly (meth) acryl Acid ester, melamine formaldehyde resin, polyethylene terephthalate,
Polymers such as nylon and polyurethane can be added to the binder resin if necessary.

As the coloring agent used in the present invention, any conventionally known coloring agents can be used. Specifically, the following can be used. Further, as the black colorant, carbon black, aniline black, acetylene black, a magnetic substance, or a substance toned to black using a yellow / magenta / cyan colorant shown below can be used.

As the yellow colorant used in the present invention, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds are used. Specifically, for example, C.I. I. Pigment Yellow 12, 1
3, 14, 15, 16, 17, 62, 74, 83, 9
3, 94, 95, 97, 109, 110, 111, 12
0, 127, 128, 129, 147, 168, 17
4, 176, 180, 181, and 191 are preferably used.

The magenta colorant used in the present invention includes a condensed azo compound, a diketopyrrolopyrrole compound, anthraquinone, a quinacridone compound, a basic dye lake compound, a naphthol compound, a benzimidazolone compound,
Thioindigo compounds and perylene compounds are used. Specifically, for example, C.I. I. Pigment Red 1, 2,
3, 5, 6, 7, 23, 48: 2, 48: 3, 48:
4, 57: 1, 81: 1, 144, 146, 166, 1
69, 177, 184, 185, 202, 206, 22
It is particularly preferred to use 0, 221, 254.

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

These coloring agents can be used alone or as a mixture, and can also be used in the form of a solid solution. When a magnetic material is used as the colorant, it is preferable to add 40 to 150 parts by weight per 100 parts by weight of the binder resin. It is preferable to add 0.1 to 20 parts by weight, more preferably 2 to 10 parts by weight, per 100 parts by weight of the binder resin.

In the present invention, a magnetic toner can be obtained by incorporating a magnetic material. In this case, the magnetic material can also serve as a colorant. Magnetic materials that can be used in the present invention include magnetite, hematite,
Iron oxides such as ferrite; metals such as iron, cobalt, nickel, or these metals, and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium,
Examples include alloys with metals such as manganese, selenium, titanium, tungsten, and vanadium and mixtures thereof.

Furthermore, as these magnetic materials used in the present invention, more preferably, surface-modified magnetic materials are used. In particular, it is preferable to use one that has been subjected to a hydrophobic treatment with a surface modifier that does not inhibit polymerization. Examples of such a surface modifier include a silane coupling agent and a titanium coupling agent.

Further, as these magnetic materials, those having an average particle diameter of 1 μm or less, preferably 0.1 to 1 μm may be used. The magnetic material has a coercive force (H _C ) of 20 to 300 as a magnetic characteristic when a 10k sled is applied.
Oersted, saturation magnetization (σ _S ) 50-200 em
It is preferable to use those having a u / g and a residual magnetization (σ _r ) of 2 to 20 emu / g.

The wax according to the present invention is substantially spherical and / or spindle-shaped and island-shaped in a state in which the wax is not compatible with the binder resin, when observed on a tomographic plane using a transmission electron microscope (TEM). Preferably they are dispersed. FIG. 11 shows a typical example.

By dispersing the wax as described above and encapsulating it in the toner, the general formula <A> according to the present invention is obtained.
Since the compound represented by the formula (1) can be efficiently present in the vicinity of the surface of the toner particles, the charge control ability of the compound can be sufficiently exhibited. Further, since the deterioration of the toner and the matching with the image forming apparatus are also good, it is possible to maintain a good chargeability and to form a toner image excellent in dot reproduction for a long period of time. Further, since the wax works efficiently at the time of heat fixing, the low-temperature fixing property and the anti-offset property are satisfied.

In the present invention, the dispersion state of the wax as described above is defined as follows. That is, with respect to the weight average particle diameter D ₄ (μm) of the toner measured as described above, the tomographic surface of the toner having a major axis of D ₄ × 0.9 or more and D ₄ × 1.1 or less is determined. Select 20 places. And
The longest diameter R of the selected tomographic plane of each of the toners and the largest diameter r of the phase separation structure caused by the wax present in the tomographic plane of the toner having the longest diameter R are measured.
An arithmetic average (r / R) _st of / R is determined. The obtained r /
The arithmetic mean value of R (r / R) _st is 0.05 ≦ (r / R) _st
In a dispersion state satisfying ≦ 0.95, it is assumed that the wax has a substantially spherical and / or spindle-shaped island dispersion state without being compatible with the binder resin.

[0115] By dispersing wax as arithmetic mean of the above r / R (r / R) st satisfies _{0.05 ≦ (r / R) st} ≦ 0.95, formula <A> Can be efficiently localized on the surface of the toner, which can contribute to stabilization of the chargeability of the toner. In addition, since the wax is included in the toner particles, deterioration of the toner surface and contamination of the image forming apparatus can be prevented. Therefore, the effect of fixing the oxycarboxylic acid near the toner particle surface can be maintained. Can be done. Furthermore, the arithmetic mean value of r / R (r / R) _st is 0.25 ≦
(R / R) In a dispersion state satisfying _st ≦ 0.90,
It is preferable because good chargeability is maintained and a toner image excellent in dot reproducibility can be formed for a long period of time. In addition, since the wax acts efficiently at the time of heating, the low-temperature fixing property and the offset resistance are satisfactory.

As a method of observing the tomographic plane of the toner,
It is preferable to use an electron dyeing method in which the electron density of one component is increased by using a heavy metal by utilizing the difference in the fine structure of the crystal layer and the amorphous phase of the wax used and the resin constituting the outer shell to give a contrast between the materials. . Specifically, after sufficiently dispersing the toner particles in a cold-setting epoxy resin,
After curing for 2 days in an atmosphere temperature of 40 ° C., the obtained cured product is subjected to electronic staining using ruthenium tetroxide (RuO ₄ ) and, if necessary, osmium tetroxide (OsO ₄ ) in combination, and then to diamond. A flaky sample is cut out using an ultramicrotome equipped with a knife, and the sectional layer morphology of the toner is observed using a transmission electron microscope (TEM). By the above method, a thin layer of the polar resin existing on the surface of the toner particles can also be confirmed.

As the wax used in the present invention, known waxes usable for toner can be used, for example, paraffin wax and its derivatives, montan wax and its derivatives, microcrystal wax and its derivatives,
Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, polyester and its derivatives, ester wax and its derivatives, vegetable wax and its derivatives, animal wax and its derivatives, mineral wax and its derivatives. Includes oxides, alkylene oxide adducts, saponified compounds, and salts.

Of these, waxes preferably used are low molecular weight polyalkylenes, low molecular weight polyesters and ester waxes, and aliphatic derivatives.

From these waxes, the waxes were fractionated by molecular weight using a press sweating method, a solvent method, vacuum distillation, supercritical gas extraction, fractional crystallization (for example, liquid crystal precipitation and crystal filtration). Waxes are also preferably used in the present invention. After fractionation, oxidation, block copolymerization, or graft modification may be performed.

Further, the wax used in the present invention shows a maximum endothermic peak in the range of 50 to 100 ° C. at the time of temperature rise in a DSC curve measured by a differential scanning calorimeter, and the starting point of the endothermic peak including the maximum endothermic peak It is preferable to use those having an onset temperature of 40 ° C. or higher, and in particular, those having a temperature difference between the peak temperature of the maximum endothermic peak and the onset temperature in the range of 7 to 50 ° C. .

By using the wax exhibiting the above-mentioned thermal characteristics, not only the good fixability of the obtained toner but also the releasing effect by the wax is efficiently exhibited, and a sufficient fixing area is secured. Developability, blocking resistance and adverse effects on the image forming apparatus due to the wax known from the above can be eliminated, and the effects of the compound represented by the general formula <A> according to the present invention can be sufficiently obtained. . In particular, since the specific surface area of the toner decreases as the particle shape of the toner becomes spherical, it is very effective to control the thermal characteristics and the dispersion state of the wax component.

In the present invention, the thermal property of the wax is "AS
TM D3418-22 ", for example,
A differential scanning calorimeter "DSC-7" (manufactured by PerkinElmer) is used. The melting point of indium and zinc is used for the temperature correction of the device detection unit, and the heat of fusion of iridium is used for the correction of the calorie. At the time of measurement, a sample in which an aluminum pan was used as a measurement sample and a sample in which only an aluminum pan was used for control (empty pan) were set.
A DSC curve obtained when a sound is raised in a temperature range of 10 to 180 ° C. at a rate of 10 ° C./min is used. At this time, when only the wax component is measured, the temperature is increased and decreased in advance under the same conditions as the measurement, and the measurement is started after removing the previous history of the wax component. When the wax component contained in the toner is measured, the measurement is performed as it is without performing the operation of removing the previous history.

These waxes are preferably used in an amount of 3 to 40 parts by weight, more preferably 5 to 35 parts by weight, based on 100 parts by weight of the binder resin.

As the ester wax, an ester wax satisfying the following general formula is preferred.

R ₁ —COO—R ₂ [wherein R ₁ and R ₂ each represent a hydrocarbon group having 15 to 45 carbon atoms]

Further, the ester wax is an ester wax containing the ester compound represented by the above formula and containing 50 to 95% by weight of the ester compound having the same total carbon number. Is preferred.

In the present invention, the content of ester compounds having the same total number of carbon atoms was measured by a gas chromatography method (GC method) described below.

In the present invention, the gas chromatogram was measured using GC-17A (manufactured by Shimadzu Corporation). At this time, a solution previously dissolved at a concentration of 1% by weight in toluene is used as a measurement sample, and 1 microliter of the solution is injected into a GC apparatus equipped with an on-column injector. The column is
Ultra Alloy-1 with 0.5mm diameter x 10m length
(HT) was used. The column has an initial temperature of 40 ° C,
From there, 40 ° C / min. At a heating rate of 200 ° C., and further at 15 ° C./min. At 350 ° C., and then at 7 ° C./min. The temperature was raised up to 450 ° C. at the temperature raising speed. As a carrier gas, He gas was flowed under a pressure condition of 50 kPa. When identifying compound species, separately inject an alkane with a known carbon number, measure at the same effluent time as above, compare the obtained gas chromatograms, or mass spectrograph The structure was identified by methods such as introduction into The content of the ester compound having the same carbon number was calculated by calculating the ratio of each peak area to the total peak area of the chromatogram.

FIG. 1 shows an example of a chromatogram of the ester wax. From FIG. 1, it is found that the ester compound having a total carbon number of 38 as shown below is about 0.6% by weight.
Contained,

[0130]

[Outside 15] About 5.8% by weight of an ester compound having a total carbon number of 40 as described below is contained,

[0131]

[Outside 16] About 19.0% by weight of an ester compound having a total carbon number of 42 as described below is contained,

[0132]

[Outside 17] About 72.9% by weight of an ester compound having a total carbon number of 44 as described below is contained,

[0133]

[Outside 18] Further, it has been found that about 1.7% by weight of an ester compound having a total carbon number of 46 as described below is contained.

[0134]

[Outside 19] In addition, about the ester wax used for the said measurement,
It has been confirmed that an ester compound having a total carbon number of 44 and represented by the following formula is contained as a main component at about 72.6% by weight.

[0135]

[Outside 20] The ester wax particularly preferably used as the ester wax is generally synthesized from a higher carboxylic acid component, similarly to the higher alcohol component. These higher alcohol and higher carboxylic acid components are usually obtained from natural products in many cases, and are generally composed of a mixture having an even number of carbon atoms. When these mixtures are esterified as they are, by-products having various similar structures are produced as by-products in addition to the intended ester compound, so that each property of the toner is likely to be adversely affected. For this reason, in the present invention, it is preferable to use an ester wax obtained by purifying raw materials or products using a solvent extraction or vacuum distillation operation.

In the measurement by the gas chromatography method described above, when the content of the ester compound having the same total number of carbon atoms is less than 50% by weight, complicated crystal polymorphism and freezing point drop occur, so that the When it is contained in the toner, it tends to be one of the causes mainly having an adverse effect on the anti-blocking property and the developing property of the toner. Further, in the present invention, when the ester compound as described above is used, it is difficult to obtain a predetermined toner fluidity,
Since filming due to the ester wax easily occurs on the carrier particles and the surface of the photoreceptor, the frictional charge of the toner decreases, and it becomes difficult to continuously obtain a sufficient frictional charge.

The ester wax preferably contains 55 to 95% by weight, more preferably 60 to 9% by weight of an ester compound having the same total carbon number.
It is good to use what is contained in the range of 5% by weight.
Further, the ester compound having the same total number of carbon atoms contained in the ester wax and the ester compound including the ester compound having the total number of carbon atoms within a range of ± 2 with respect to the total number of carbon atoms are included. The total content is preferably 80 to 95% by weight, more preferably 90 to 95% by weight.
It is good to use what is.

The most preferred ester wax for constituting the toner of the present invention is an ester wax having a total carbon number of 44 as described above in the ester wax.
It contains about 0 to 95% by weight.

Specific examples of the ester compound represented by the general formula include the following ester compounds.

[0140]

[Outside 21]

As the ester wax, those having a maximum endothermic peak temperature of the DSC curve in the range of 40 to 90 ° C., more preferably 55 to 85 ° C., improve the low-temperature fixability and the offset resistance of the toner. It is preferable in aiming at.

That is, an ester wax having a peak temperature of less than 40 ° C. has a weak self-cohesive force of the ester wax, and as a result, tends to lower the high-temperature offset resistance of the toner. On the other hand, an ester wax having a high melting point having a peak temperature exceeding 90 ° C. performs good granulation and polymerization in an aqueous medium when toner particles are obtained by a direct polymerization method. Ester wax is precipitating, and there is a tendency that granulation with a sharp particle size distribution becomes difficult.

Further, the ester wax has a hardness of 0.5 to 0.5.
It is preferably one having 5.0. The hardness of this ester wax is a value obtained by preparing a cylindrical sample having a diameter of 20 mm and a thickness of 5 mm, and then measuring the Vickers hardness using a dynamic ultra-micro hardness tester (DUH-200) manufactured by Shimadzu Corporation. . As measurement conditions,
Under a load of 0.5 g and a load speed of 9.67 mm / sec, the plate was displaced by 10 μm and held for 15 seconds, and the resulting dent shape was measured to determine Vickers hardness. According to the study of the present inventors, when an ester wax having a hardness measured by the above method of less than 0.5 is used, the pressure dependency and the process speed dependency of the fixing device become large, and the hot offset resistance is increased. The effect tends to decrease. On the other hand, when the hardness exceeds 5.0, the storage stability of the toner is reduced, and the self-cohesive force of the ester wax itself is small, so that the high-temperature offset resistance tends to be reduced.

The ester wax has a weight average molecular weight (M
w) is 200 to 2,000 and the number average molecular weight (Mn) is 1
It is preferably 50 to 2,000, more preferably Mw is 300 to 1,000, and Mn is 250 to 1.0.
00 is preferred. That is, when an ester wax having an Mw of less than 200 and an Mn of less than 150 is used, the blocking resistance of the toner is reduced, and the low molecular weight component is easily present on the toner surface, and the fluidity of the toner is reduced. descend. On the other hand, when an ester wax having an Mw of more than 2,000 and an Mn of more than 2,000 is used, granulation is hindered in the production of a toner, and coalescence of the toner is likely to occur.

In the present invention, the molecular weight distribution of the wax was measured by GPC under the following conditions.

(GPC measurement conditions) • Apparatus: GPC-150C (Waters) • Column: GMH-HT 30 cm double (manufactured by Tosoh Corporation) • Temperature: 135 ° C. • Solvent: o-dichlorobenzene (0.1% ionol)・ Flow rate: 1.0 ml / min. -Sample: 0.4 ml of 0.15% sample is injected

The measurement was performed under the above conditions, and the molecular weight of the sample was calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. Furthermore, Mark-Hou
It was calculated by converting into polyethylene using a conversion formula derived from the win viscosity formula.

As the other additives to be added to the toner, for example, the following additives are used for the purpose of imparting various properties. As the lubricant, fluorine resin powders such as polyvinylidene fluoride and polytetrafluoroethylene, and fatty acid metal salts such as zinc stearate and calcium stearate are preferably used. As the charge control particles, metal oxides such as tin oxide, titanium oxide, zinc oxide, silicon oxide, and aluminum oxide, and carbon black are preferably used. These additives are used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin. These additives are used alone or as a mixture.

When the toner of the present invention is used as a developer, an inorganic fine powder having a specific surface area of preferably not less than 30 m ² / g by nitrogen adsorption measured by a BET method is preferably added to 100 parts by weight of toner particles. It is preferred that the toner be contained in the range of 0.5 to 5 parts by weight and that the degree of aggregation of the toner be in the range of 1 to 20%. As described above, by preparing the developer using the inorganic fine powder having a specific surface area controlled, the compound represented by the general formula <A> present near the toner surface interacts, This is because the control of the adsorption of moisture to the particles is more remarkably performed, so that the effect of suppressing a decrease in the triboelectric charge amount and the charging speed is increased. Further, the interaction between the compound and the inorganic fine powder increases the effect of preventing the compound from contaminating the toner carrier and the like. Further, by controlling the degree of aggregation of the toner, the contact state between the toner particles and the inorganic fine powder is controlled, and the above-described excellent effect is maintained even in continuous copying.

[0150] As described above, a preferable range of the specific surface area of the inorganic fine powder used in the present invention, but is 30 m ² / g or more, more preferably 50 to 400 m ² / g.
That is, in the case of an inorganic fine powder having a specific surface area of less than 30 m ² / g,
It is difficult to control the degree of aggregation of the toner, and when the compound represented by the general formula <A> is present on the surface of the toner particles, the site of interaction with the compound is saturated, The effect of preventing contamination of the toner carrier is reduced. If the specific surface area exceeds 400 m ² / g, the degree of aggregation of the toner may change with time because the inorganic fine powder is embedded in the surface of the toner particles during continuous copying. The specific surface area was determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device Autosoap 1 (manufactured by Yuasa Ionics) according to the BET method, and calculating the specific surface area using the BET multipoint method.

When the amount of the inorganic fine powder to be externally added is less than 0.5 part by weight, it is difficult to control the degree of aggregation of the toner. May pollute the body.

Further, the inorganic fine powder used in the present invention includes:
If necessary, silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, other organosilicon compounds, organic It is possible and preferable to use a treating agent such as a titanium compound or a combination of various treating agents. In particular, in order to maintain a high charge amount and achieve low consumption and high transfer rate, it is preferable that the inorganic fine powder be treated with at least silicone oil.

The toner of the present invention can be used as it is as a one-component developer, or can be used as a two-component developer using a carrier.

When used as a two-component developer, for example, magnetic carriers to be mixed with toner include iron,
It is composed of an element selected from copper, zinc, nickel, cobalt, manganese, and chromium, alone or in a composite ferrite state. The shape of the magnetic carrier used at this time includes a spherical shape, a flat shape, an irregular shape, and the like, and a shape in which the fine structure (for example, surface unevenness) of the surface state of the magnetic carrier is appropriately controlled may be used. it can. Also, a resin-coated carrier whose surface is coated with a resin can be suitably used. The average particle size of the carrier used is preferably 10 to
It is 100 μm, more preferably 20 to 50 μm. When the carrier and the toner are mixed to prepare a two-component developer, the toner concentration in the developer is preferably about 2 to 15% by weight.

As a method for producing the toner according to the present invention, a binder resin, a colorant, a wax and the like are melt-kneaded by a pressure kneader or the like, and then the cooled kneaded material is finely pulverized to a desired toner particle diameter. Further, a pulverization method of classifying the finely pulverized product to adjust the particle size distribution to obtain a toner;
A method of directly manufacturing a toner using a suspension polymerization method described in Japanese Patent No. 61842; a disk or a multi-fluid nozzle described in Japanese Patent Publication No. 56-13945, etc .; A method for producing a spherical toner by using;
And a known method such as an emulsion polymerization method represented by a soap-free polymerization method, but the suspension polymerization is performed while controlling the polymerization conversion of the polymerizable monomer and the pH in the aqueous medium. Thus, it is preferable to produce a toner whose shape is controlled.

That is, the compound represented by the general formula <A> added to the toner for the purpose of controlling the triboelectric charge amount and the charging speed has a large number of hydrophilic functional groups, and therefore, the aqueous dispersion When toner particles are formed by polymerizing granulated particles of the polymerizable monomer composition in a medium, the compound is eluted into an aqueous medium. When the compound is eluted, the obtained toner particles do not sufficiently exhibit the effect of improving the charge amount and the charge speed. Further, since the eluted compound takes a surfactant-like behavior, it becomes very difficult to maintain the shape of the toner particles in the polymerization step, and it is impossible to control the toner to a desired particle size distribution and shape. In particular, when the elution amount of the compound is large, particles having a fine particle diameter finer than the toner particles are produced as by-products, which hinders matching with the image forming apparatus.

On the other hand, by controlling the polymerization conversion rate of the polymerizable monomer and the pH in the aqueous medium, the elution of the compound is prevented, and the compound is fixed in a good state near the surface of the toner. Can be

More specifically, in the polymerization reaction of the polymerizable monomer composition, the polymerization of the polymerizable monomer is performed while maintaining the pH of the aqueous medium at 4.5 to 8.5, preferably 4.5 to 6.0. The first reaction step for increasing the conversion to 10% or more prevents the compound represented by the general formula <A> from being eluted into the aqueous medium, and is included in the toner particles. Further, after the first reaction step, the pH of the aqueous medium is readjusted to 9 to 13 to further increase the polymerization conversion. From the second reaction step, the toner capable of participating in the triboelectric charge of the compound encapsulated in the toner can be obtained. The compound present on the surface can be dissolved and removed under an alkaline atmosphere at the same time as the particles are pulled out to the vicinity of the surface of the particle.

This makes it possible to immobilize the compound represented by the general formula <A> in the vicinity of the surface of the toner particles in a good state, and to obtain a very good charging characteristic of the obtained toner. . Also, since the particle size distribution and shape of the toner particles can be controlled to a desired one without inducing by-products of minute particle size, the charging characteristics are synergistically improved and matching with the image forming apparatus is achieved. Can be made very good. In particular, by maintaining the pH of the aqueous medium in the first reaction step at 4.5 to 6.0, the encapsulating property of the compound is further increased, so that the above-mentioned improvement effect is further improved.

In the present invention, the “polymerization conversion” of the polymerizable monomer refers to the total weight (W ₁ ) of the polymerizable monomer used in the polymerizable monomer composition. It can be obtained from the following formula by quantifying the total weight (W ₂ ) of the unreacted polymerizable monomer.

[0161]

[Outside 22]

Further, immediately after sampling the unreacted polymerizable monomer from the reaction vessel, a polymerization terminator or cold methanol is added to the sample to stop the polymerization reaction.
It can be quantified by applying a known method such as a method using thermogravimetry (TG), which is measured as a weight loss amount upon heating with a thermobalance, or a method using gas chromatography (GC). Among these, the method using GC is a particularly effective method.

A specific example of the case where the polymerizable monomer in the toner is quantified using GC will be described below.

<GC measurement conditions> Apparatus: GC-14A (manufactured by Shimadzu Corporation) Column: fused silica capillary column (J & W SCI)
ENTIFC; Size: 30m x 0.249mm,
Liquid phase: DBWAX, film thickness: 0.25 μm) Sample: 2.55 mg of DMF as an internal standard, 100 m
Add 1 liter of acetone to make a solvent with internal standard. Next, 400 mg of the toner is made into a 10 ml solution with the above solvent. After 30 minutes on an ultrasonic shaker, leave for 1 hour. Next, the mixture is filtered with a 0.5 μm filter. The volume of the implanted sample is 4 μl. Detector: FID (split ratio: 1:20) Carrier gas: N ₂ gas Oven temperature: 70 ° C. → 220 ° C. (After waiting at 70 ° C. for 2 minutes, heating at a rate of 5 ° C./min.) Inlet temperature: 200 ° C. Detector temperature: 200 ° C Preparation of calibration curve: Gas chromatographic measurement of a standard sample in which the target polymerizable vinyl monomer was added to the same DMF and acetone solution as the sample solution, and the polymerizable vinyl monomer was used. The weight ratio / area ratio between the body and the internal standard DMF is determined.

In the present invention, when a toner is produced by a suspension polymerization method, known inorganic and organic dispersants can be used as a dispersant for preparing an aqueous dispersion medium. Specifically, as the inorganic dispersant, for example, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, Calcium metasilicate,
Examples include calcium sulfate, barium sulfate, bentonite, silica, and alumina. As the organic dispersant, for example, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose,
Ethyl cellulose, sodium salt of carboxymethyl cellulose and starch can be used.

It is also possible to use commercially available nonionic, anionic or cationic surfactants. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate can be used.

In the present invention, an inorganic hardly water-soluble dispersant is preferable, and a poorly water-soluble inorganic dispersant which is soluble in an acid is preferably used. Further, in the present invention, when using a poorly water-soluble inorganic dispersant to prepare an aqueous dispersion medium, these dispersants are used in an amount of 0.2 to 2.0 parts by weight based on 100 parts by weight of the polymerizable monomer. It is preferable to use them in such a ratio that they become parts. In the present invention, it is preferable to prepare an aqueous dispersion medium using 300 to 3,000 parts by weight of water with respect to 100 parts by weight of the polymerizable monomer composition.

In the present invention, when preparing an aqueous dispersion medium in which the above-mentioned poorly water-soluble inorganic dispersant is dispersed, a commercially available dispersant may be used as it is to disperse it. In order to obtain dispersant particles having the following formula (I), a poorly water-soluble inorganic dispersant as described above may be formed in a liquid medium such as water under high-speed stirring. For example, when using tricalcium phosphate as a dispersant,
By mixing the aqueous sodium phosphate solution and the aqueous calcium chloride solution under high-speed stirring to form tricalcium phosphate fine particles, a dispersant can be preferably obtained.

According to the method for producing a toner having the above-described structure, the amount of triboelectric charge at high humidity decreases and the friction at low humidity conventionally observed in toners containing a charge control agent. It is possible to easily obtain a toner capable of suppressing a decrease in the charging speed and effectively suppressing the occurrence of contamination of the toner carrier.

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.

In the apparatus system shown in FIG. 2, the developing units 4-1, 4-2, 4-3, and 4-4 have a developer containing a cyan toner and a developer containing a magenta toner, respectively.
A developer having a yellow toner and a developer having a black toner are introduced, and an electrostatic charge image formed on an electrostatic latent image carrier (for example, a photosensitive drum) 1 by a magnetic brush developing method or a non-magnetic one-component method is used. After development, toner images of each color are formed on the photosensitive drum 1.

The toner of the present invention can be mixed with a magnetic carrier and developed using, for example, a developing means as shown in FIG. Specifically, it is preferable to perform development in a state where the magnetic brush is in contact with the photosensitive drum 13 while applying an alternating electric field. Developer carrier (development sleeve) 1
The distance (distance between S-D) B between 1 and the photosensitive drum 13 is 10
A thickness of 0 to 1000 μm is favorable in preventing carrier adhesion and improving dot reproducibility. If it is smaller than 100 μm, the supply of the developer tends to be insufficient, and the image density becomes low. If it exceeds 1000 μm, the magnetic field lines from the magnetic pole S1 of the magnetic generation means 14 included in the developing sleeve are widened and the density of the magnetic brush is low. As a result, the dot reproducibility is inferior, the force for restraining the carrier is weakened, and the carrier is likely to adhere.

The voltage between the alternating electric field peaks (Vpp) is 5
00 to 5000 V is preferable, and the frequency (f) is 500 to
It is 10,000 Hz, preferably 500 to 3000 Hz, and each can be appropriately selected and used for the process. In this case, the waveforms are triangular, rectangular, sine,
Alternatively, various types of waveforms such as a waveform with a changed duty ratio can be used. If the applied voltage is lower than 500 V, it is difficult to obtain a sufficient image density, and it may not be possible to satisfactorily collect fog toner in the non-image area. 5000
When the voltage exceeds V, the electrostatic image is disturbed via the magnetic brush, and the image quality may be deteriorated.

By using a two-component developer having a well-charged toner, the fog removal voltage (Vback) can be reduced.
And the primary charge of the photoconductor can be reduced, so that the life of the photoconductor can be extended. Vbac
k is preferably 150 V or less, more preferably 100 V or less, depending on the developing system.

As the contrast potential, 200 V to 500 V is preferably used so that a sufficient image density can be obtained.

When the frequency is lower than 500 Hz, although it depends on the process speed, charge injection into the carrier may occur, and the image quality may be deteriorated by carrier adhesion or disturbing the latent image. If the frequency exceeds 10,000 Hz, the toner cannot follow the electric field, and the image quality is likely to deteriorate.

In order to obtain a sufficient image density, achieve excellent dot reproducibility, and perform development without carrier adhesion, the contact width (developing nip C) of the magnetic brush on the developing sleeve 11 with the photosensitive drum 13 is preferably set. 3 to 8 mm. If the developing nip C is narrower than 3 mm, it is difficult to sufficiently satisfy a sufficient image density and dot reproducibility.
When the width is larger than mm, packing of the developer occurs to stop the operation of the machine, and it is difficult to sufficiently suppress carrier adhesion. As a method of adjusting the development nip,
The nip width is appropriately adjusted by adjusting the distance A between the developer regulating member 18 and the developing sleeve 11 or adjusting the distance B between the developing sleeve 11 and the photosensitive drum 13.

In the output of a full-color image in which emphasis is placed on halftone, three or more developing units for magenta, cyan, and yellow are used, and the developer and the developing method of the present invention are used. By combining with a developing system that forms a latent image, it is possible to develop the dot latent image faithfully without being affected by the magnetic brush and disturbing the latent image. In the transfer step, a high transfer rate can be achieved by using the toner of the present invention, so that high image quality can be achieved in both the halftone portion and the solid portion.

Further, by using the toner of the present invention together with the initial improvement of the image quality, the effect of the present invention without deterioration in image quality can be sufficiently exhibited even when copying a large number of sheets.

The toner of the present invention can be suitably used for one-component development. An example of an apparatus for developing an electrostatic image formed on an electrostatic latent image carrier is shown, but the invention is not necessarily limited thereto.

In FIG. 4, reference numeral 20 denotes an electrostatic latent image carrier (photosensitive drum), and a latent image is formed by an electrophotographic process means or an electrostatic recording means. Reference numeral 24 denotes a toner carrier (developing sleeve), which is formed of a non-magnetic sleeve made of aluminum, stainless steel, or the like.

The substantially right half peripheral surface of the developing sleeve 24 is always in contact with the toner reservoir in the toner container 21, and the toner near the developing sleeve surface is brought into contact with the developing sleeve surface by the magnetic force of the magnetic generation means in the sleeve and / or Adhered and held by electrostatic force.

In the present invention, the surface roughness Ra of the toner carrier is
(Μm) is set to 1.5 or less. Preferably it is 1.0 or less. More preferably, it is 0.5 or less.

By adjusting the surface roughness Ra to 1.5 or less, the toner carrying ability of the toner carrier is suppressed, the toner layer on the toner carrier is made thinner, and the toner carrier is Since the number of times of contact of the toner is increased, the chargeability of the toner is also improved, so that the image quality is synergistically improved.

When the surface roughness of the toner carrier exceeds 1.5, not only is it difficult to reduce the thickness of the toner layer on the toner carrier, but also the chargeability of the toner is not improved. I can't hope.

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

[0187]

[Outside 23]

As the toner carrier used in the present invention, a cylindrical or belt-like member made of, for example, stainless steel, aluminum or the like is preferably used. If necessary, the surface may be coated with metal, resin, etc.
A resin in which fine particles such as a resin, metals, carbon black, and a charge control agent are dispersed may be coated.

According to the present invention, the surface moving speed of the toner carrier is set to be 1.05 to 3 times the surface moving speed of the electrostatic latent image carrier.
By setting the ratio to 0, 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.

If the surface moving speed of the toner carrier is less than 1.05 times the surface moving speed of the electrostatic latent image carrier, the stirring effect of the toner layer becomes insufficient, and good image formation is achieved. Can not hope. Further, when developing an image requiring a large amount of toner over a wide area, such as a solid black image, the amount of toner supplied to the electrostatic latent image is insufficient, and the image density is reduced. On the other hand, when it exceeds 3.0, in addition to the various problems caused by excessive charging of the toner as described above,
Deterioration of the toner due to mechanical stress and adhesion of the toner to the toner carrier occur and are accelerated, which is not preferable.

The toner T is stored in the toner container 21 and supplied by the supply member 22 onto the developing sleeve. As the supply member, a supply roller made of a porous material such as a foamed material such as a flexible polyurethane foam is preferably used. The supply roller is rotated with respect to the developing sleeve in a forward or reverse direction at a non-zero relative speed, so that the toner is supplied to the developing sleeve and the toner after development (undeveloped toner) on the sleeve is also removed. At this time, the contact width of the supply roller to the developing sleeve is preferably 2.0 to 10.0 mm in consideration of the balance between toner supply and stripping, and 4.0 to 6.0 mm.
mm is more preferable. On the other hand, excessive stress is inevitably applied to the toner, and the aggregation of the toner due to the deterioration of the toner is increased, or the fusion and fixation of the toner to the developing sleeve and the supply roller are easily caused. Is excellent in fluidity and releasability, and has durability stability. Therefore, is preferably used in a developing method having the supply member. Further, a brush member made of a resin fiber such as nylon or rayon may be used as the supply member. These supply members are extremely effective in a one-component developing method using a non-magnetic one-component toner that cannot utilize a magnetic binding force. It may be used in a one-component developing method using a magnetic one-component toner.

The toner supplied onto the developing sleeve is thinly and uniformly applied by the regulating member. The toner thinning regulating member 23 may be a doctor blade such as a metal blade or a magnetic blade disposed at a predetermined gap from the developing sleeve, or may be replaced with a doctor blade.
Rigid rollers or sleeves made of metal, resin, ceramic, or the like may be used, and a magnet generating means may be provided inside them. Further, an elastic body such as an elastic blade or an elastic roller for press-applying the toner may be used as a regulating member for thinning the toner. For example, in FIG. 4, the elastic blade 23 has a base on the upper side thereof in the toner container 2.
The developing sleeve 24 is bent in the forward or reverse direction against the elasticity of the blade, and the inner side of the developing sleeve 24 (in the case of the reverse direction, the outer side) is fixed to the lower side. The surface is brought into contact with moderate elastic pressure.
According to such a device, it is stable against environmental changes,
A dense toner layer is obtained. Although the reason is not clear, it is presumed that the elastic body is forcibly rubbed against the surface of the developing sleeve, so that charging is always performed in the same state regardless of a change in behavior due to a change in toner environment.

On the other hand, the toner is apt to be excessively charged and the toner is easily fused to the developing sleeve or the elastic blade. However, the toner used in the present invention is preferable because of its excellent releasability and stable triboelectric charging. Used.

For the elastic body, it is preferable to select a material of a triboelectric series suitable for charging the toner to a desired polarity. 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, steel, and phosphor bronze can be used. Further, a composite thereof may be used.

When durability is required for the elastic body and the toner carrier, it is preferable that the elastic body and the resin or rubber are bonded to the sleeve contact portion or applied by coating.

Further, an organic substance or an inorganic substance may be added to the elastic body, may be melted and 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 or the like. Particularly, 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 serving as the regulating member, the supply roller serving as the supplying member, and the brush member, a regulating portion on the developing sleeve is provided for the action of loosening the toner. According to the method, the uniform thin layer coating property and the uniform charging property are further improved, and the supply / stripping of the toner is more smoothly performed at the supply portion, so that a sufficient image density can be achieved and a high quality image can be obtained.

The contact pressure between the elastic body and the toner carrier is
The linear pressure in the generatrix direction of the toner carrier is 0.1 kg / m
Above, preferably 0.3 to 25 kg / m, more preferably 0.5 to 12 kg / m is effective. As a result, the aggregation of the toner can be effectively released, and the charge amount of the toner can be instantaneously increased. If the contact pressure is less than 0.1 kg / m, it becomes difficult to apply the toner uniformly, and the charge amount distribution of the toner becomes broad, causing fogging and scattering. On the other hand, when the contact pressure exceeds 25 kg / m, a large pressure is applied to the toner, and the toner is undesirably deteriorated and a toner aggregate is generated.
Further, a large torque is required to drive the toner carrier, which is not preferable.

Gap α between electrostatic latent image carrier and toner carrier
Is preferably set to 50 to 500 μm, and the gap between the doctor blade and the toner carrier is preferably set to 50 to 400 μm.

The layer thickness of the toner layer on the toner carrier is most preferably smaller than the gap α between the electrostatic latent image carrier and the toner carrier. Among them, the layer thickness of the toner layer may be restricted to such an extent that a part of the toner layer contacts the electrostatic latent image carrier.

On the other hand, a bias power source 2
By applying an alternating electric field between the toner carrying member and the electrostatic latent image carrying member, the transfer of the toner from the toner carrying member to the electrostatic latent image carrying member can be facilitated, and a higher quality image can be obtained.
Vpp of the alternating electric field is 100 V or more, preferably 200 to
3000V, more preferably 300-2000V. Further, f is 500 to 5000 Hz, preferably 1000 to 3000 Hz, and more preferably 1500
In this case, a waveform such as a rectangular wave, a sine wave, a sawtooth wave, and a triangular wave can be used as the waveform used in the range of 3000 Hz. Also, asymmetrical AC biases having different positive and reverse voltages and times can be used. It is also preferable to superimpose a DC bias.

In FIG. 2, the electrostatic latent image carrier 1 is aS
e, a photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as Cds, ZnO ₂ , OPC, and a-Si. The electrostatic latent image carrier 1 is rotated in the direction of the arrow by a driving device (not shown).

As the latent electrostatic image bearing member 1, a photosensitive member having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

As the organic photosensitive layer, the photosensitive layer contains a charge generating substance and a substance having a charge transporting property in the same layer.
It may be a single-layer type or a function-separated type photosensitive layer having a charge transport layer as a component of the charge transport layer. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated on a conductive substrate in this order is one of preferred examples.

The binder resin for the organic photosensitive layer is preferably a polycarbonate resin, a polyester resin, or an acrylic resin, particularly having good transferability and cleaning properties, and poor cleaning, fusion of the toner to the photoreceptor, and filming of external additives. Less likely.

In the charging step, there are a system in which the charging means and the electrostatic latent image carrier 1 are not in contact with each other, such as a corona charger, and a contact system, such as a charging roller. For efficient uniform charging, simplification, and low ozone generation, a contact type as shown in FIG. 2 is preferably used.

The charging roller 2 basically has a core 2b at the center and a conductive elastic layer 2a forming the outer periphery thereof. The charging roller 2 is pressed against the surface of the electrostatic latent image carrier 1 with a pressing force, and is driven to rotate as the electrostatic latent image carrier 1 rotates.

A preferable process condition when the charging roller is used is that the contact pressure of the roller is 5 to 500 g / cm.
When a DC voltage with an AC voltage superimposed is used, the AC voltage is 0.5 to 5 kVpp and the AC frequency is 50 kVpp.
Hz to 5 kHz, the DC voltage is ± 0.2 to ± 1.5 kV, and when only the DC voltage is used, the DC voltage is ± 0.2 to ± 0.5 kV.
2 to ± 5 kV.

Other charging means include a method using a charging blade and a method using a conductive brush. These contact charging means are effective in that high voltage is not required and generation of ozone is reduced.

The material of the charging roller and the charging blade as the contact charging means is preferably conductive rubber, and a release film may be formed on the surface thereof. As the release film, a nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride) or the like can be applied.

[0211] The toner image on the electrostatic latent image carrier is transferred to the intermediate transfer body 5 to which a voltage (for example, ± 0.1 to ± 5 kV) is applied. The surface of the electrostatic latent image carrier is cleaned by cleaning means 9 having a cleaning blade 8.

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

The medium resistance elastic layer 5a is made of silicone rubber, Teflon rubber, chloroprene rubber, urethane rubber,
EPDM (terpolymer of ethylene propylene diene)
A conductive material such as carbon black, zinc oxide, tin oxide, and silicon carbide is mixed and dispersed in an elastic material such as the above to adjust the electric resistance value (volume low efficiency) to a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm. It is a solid or foamed layer.

The intermediate transfer member 5 is provided so as to be supported in parallel with the electrostatic latent image carrier 1 and is in contact with the lower surface of the electrostatic latent image carrier 1. It rotates in the direction of the arrow at the same peripheral speed as.

The first color toner image formed and carried on the surface of the electrostatic latent image carrier 1 passes through a transfer nip where the electrostatic latent image carrier 1 and the intermediate transfer body 5 are in contact with each other. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer body 5 by the electric field formed in the transfer nip area by the transfer bias applied to the body 5.

If necessary, the surface of the intermediate transfer member 5 is cleaned by the detachable cleaning means 10 after the transfer of the toner image onto the transfer material. When there is a toner image on the intermediate transfer member, the cleaning unit 10 is separated from the surface of the intermediate transfer member so as not to disturb the toner image.

A transfer means for transferring a toner image from the intermediate transfer member to a transfer material by bearing in parallel with the intermediate transfer member 5 and contacting the lower surface of the intermediate transfer member 5 is provided.
The transfer unit 7 is, for example, a transfer roller or a transfer belt,
It rotates clockwise as indicated by an arrow at the same peripheral speed as the intermediate transfer member 5. The transfer unit 7 may be disposed so as to directly contact the intermediate transfer member 5, or a belt or the like may be disposed so as to contact between the intermediate transfer member 5 and the transfer unit 7.

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

For the intermediate transfer member and the transfer roller, general materials can be used. By setting the volume resistivity of the elastic layer of the transfer roller smaller than the volume resistivity of the elastic layer of the intermediate transfer body, the voltage applied to the transfer roller can be reduced, and a good toner image can be formed on the transfer material. In addition, it is possible to prevent the transfer material from winding around the intermediate transfer member. In particular, it is particularly preferable that the volume resistivity of the elastic layer of the intermediate transfer member is at least 10 times the volume resistivity of the elastic layer of the transfer roller.

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

Next, the toner image on the transfer material 6 is fixed by the heat and pressure fixing means H. As the heating and pressing fixing means, a heating roller having a built-in heating element such as a halogen heater and an elastic pressing roller pressed against the heating roller with a pressing force as a basic configuration, or a heating roller through a film. A method of heating and fixing (FIGS. 5 and 6) can be cited, but the toner of the present invention is excellent in fixability and anti-offset property, and thus shows good matching with the heat and pressure fixing means as described above.

The toner of the present invention has a high transfer efficiency in the transfer step, a small amount of untransferred toner, and an excellent cleaning property, so that filming hardly occurs on the electrostatic latent image carrier. Furthermore, even when a multi-sheet durability test is performed, the toner of the present invention has less embedding of the external additive in the surface of the toner particles than the conventional toner, so that good image quality can be maintained for a long time. In particular, it is preferably used in an image forming apparatus having a so-called reuse mechanism that removes transfer residual toner on an electrostatic latent image carrier or an intermediate transfer material by a cleaning unit such as a cleaning blade and reuses the collected transfer residual toner. .

The reuse mechanism will be described with reference to FIG.
After the transfer step, the transfer residual toner remaining on the photoconductor drum 120 is scraped off by the elastic blade 122 in contact with the photoconductor drum, and is collected inside the cleaner 121. The collected transfer residual toner is conveyed by a supply pipe 124 provided with a conveying screw via a cleaner screw 123, and returned to a developing device 126 via a hopper 125. The returned transfer residual toner is again
Provided for development.

Further, an elastic roller was used as a toner carrier, and the surface of the elastic roller was coated with toner.
It is also possible to use a one-component contact developing method in which a toner layer is formed and the toner layer is brought into contact with the surface of a photoreceptor as an image carrier to perform development.

In the one-component contact developing method, the toner is
It may be either magnetic or non-magnetic, and it is important that the toner layer and the surface of the photoreceptor are in contact. It is preferable that the toner carrier is substantially in contact with the surface of the photoconductor, but this means that the toner carrier is in contact with the surface of the photoconductor when the toner layer is removed from the toner carrier. means. At this time, in order to obtain an image having no edge effect by an electric field acting between the photosensitive member and the elastic roller facing the photosensitive member surface via the toner, the surface of the elastic roller or the vicinity of the surface has a potential, and the photosensitive member surface and An electric field needs to be formed between the surfaces of the toner carriers. For this reason, the elastic layer formed of the elastic rubber on the surface of the low-resistance core material of the elastic roller is resistance-controlled in the medium-resistance region to prevent conduction with the photoreceptor surface and maintain an electric field, or to provide a low-resistance conductive material. It is also possible to use a thin dielectric layer on the surface layer of the conductive roller.
Furthermore, a configuration in which the surface side facing the photoreceptor surface is coated with an insulating material on a conductive roller, or a configuration in which a conductive layer is provided on an inner surface side not facing the photoreceptor with an insulating sleeve is also possible.

When the one-component contact developing method is used, the surface of the developing roller and the surface of the photosensitive member as a toner carrier for carrying the toner may be rotated in the same direction, or may be rotated in the opposite direction. May be. When the rotation direction is the same, the peripheral speed of the surface of the developing roller is preferably greater than 100% in terms of the peripheral speed of the photosensitive member.
If it is less than 100%, there is a problem in image quality such as poor line breakage. The higher the peripheral speed ratio, the greater the amount of toner supplied to the development site, the more frequently the toner is attached to and detached from the latent image, and unnecessary portions are scraped off and added to necessary portions repeatedly. As a result, an image faithful to the latent image can be obtained.

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

FIG. 7 is a diagram schematically showing an image forming apparatus having a process cartridge as an example of the embodiment of the one-component contact developing method of the present invention.

The photosensitive member 56 is charged by a charging roller 51 as a contact charging means, and an image portion is exposed by a laser beam 60 to form an electrostatic latent image. The toner 50 accommodated in the developing device 52 is applied to the toner application roller 55 and the application blade 5.
3 is applied onto the toner carrier 54 and the toner carrier 5
The toner image on the photoconductor 56 is formed by bringing the toner layer on the photoconductor 4 into contact with the surface of the photoconductor 56 and developing the electrostatic latent image on the photoconductor 56 by the reversal development method. The toner carrier 54 includes
At least a DC bias is applied by the bias applying unit 61. The toner image on the photoreceptor 56 is transferred onto a recording material 58 as a transferred transfer material by a transfer roller 57 which is a transfer unit to which a bias is applied by a bias applying unit 62, and is transferred onto the recording material. The formed toner image is fixed by a heat and pressure fixing unit 63 having a heat roller and a pressure roller.

The image forming apparatus includes a photosensitive member 5 between a transfer portion by the transfer roller 57 and a charging portion by the charging roller 51.
Cleaning blade 59 in contact with the surface of blade 6
have. The transfer residual toner on the photoreceptor 56 after the transfer process is scraped off by the cleaning member 59 and collected by the cleaner. The photoreceptor 56 from which the transfer residual toner has been removed is again charged by the charging roller 51, and after charging, an electrostatic latent image is formed by exposure to the laser beam 60. The electrostatic latent image on the photoreceptor 56 is
4 is developed by the upper toner. Photoconductor 5 after development process
The toner image on 6 is transferred by the transfer roller 57 onto the conveyed recording material 58. Photoreceptor 5 after transfer process
After the toner remaining in the transfer is removed by the cleaning member 6, the toner 6 is charged again by the charging roller 51, and thereafter, the same process is repeatedly performed.

FIG. 8 shows another example of the image forming apparatus which can smoothly remove the toner contributed to the development from the developing sleeve in addition to supplying the toner to the developing sleeve as the toner carrier. Is shown.

In FIG. 9, reference numeral 71 denotes a photosensitive drum, around which a primary charging roller 72 as contact charging means, a developing device 78 as developing means, a transfer charging roller 91 as contact transferring means, and a register roller 89 are provided. ing. The photosensitive drum 71 is, for example, −
It is charged to 700V. The applied voltage by the bias applying means 75 is, for example, a DC voltage of -1350V. The photosensitive drum 71 is exposed by irradiating the photosensitive drum 71 with a laser beam 77 by a laser generator 76 to form a digital electrostatic latent image. The electrostatic latent image on the photosensitive drum 71 is developed with a non-magnetic one-component toner 85 by a developing device 78, and is transferred via a recording material 90 as a transfer material.
The image is transferred onto the recording material 90 by the transfer roller 91 to which a bias voltage is applied by the bias applying means 94 abutting on the recording material 90. The recording material 90 on which the toner image 96 is placed is heated and conveyed by a heating belt 98 and a pressing roller
And the toner image is fixed on the recording material 90. Reference numeral 102 denotes a cleaner having a cleaning member 101. The transfer residual toner on the photosensitive drum after the transfer process is removed by the cleaning member 101.
And is collected by the cleaner 102.

The charging roller 72 basically has a core metal 74 at the center and a conductive elastic layer 73 forming the outer periphery thereof.

As shown in FIG. 9, the developing device 78 includes the core metal 80 and the core metal 80 to which a bias is applied by the bias applying means 88 when the toner layer on the developing sleeve 79 as a toner carrier contacts the photosensitive drum 71. A developing sleeve as a toner carrier including an elastic roller 79 having an elastic layer 81 is provided. In the developing device 78, a core bar 83 to which a bias is applied by a bias applying unit 87 and an elastic layer 84 are provided.
Is provided. A toner regulating blade 86 is provided as a member that regulates the amount of toner adhered to and transported to the developing sleeve 79, and the amount of toner transported to the developing area by the contact pressure of the toner regulating blade 86 against the developing sleeve 79 ( Toner layer thickness)
Is controlled. In the developing area, at least a DC developing bias is applied to the developing sleeve 79, and the toner layer on the developing sleeve contacts the surface of the photosensitive drum 71, and is transferred onto the photosensitive drum 71 according to the electrostatic latent image to form a toner image. Form.

The light potential of the photosensitive drum 71 is 0 to 250 V
And when the dark portion potential is 300 to 1000 V,
It is preferable that the supply bias voltage applied by the bias applying unit 87 is 100 to 900 V, and the developing bias voltage applied by the bias applying unit 88 is 100 to 900 V.

Further, the supply bias voltage applied by the bias applying means 87 is 10 to 4 in absolute value from the developing bias voltage applied by the bias applying means 88.
The larger one by 00V is the developing sleeve 7 of the non-magnetic toner 85.
This is preferable because the supply of the non-magnetic toner to the developing sleeve 9 and the stripping of the non-magnetic toner from the developing sleeve 79 are performed smoothly.

With respect to the rotation direction of the developing sleeve 79, when the surfaces of the toner application rollers 82 move in the counter direction as indicated by the arrows (the rotation direction is the same direction), the supply of the nonmagnetic toner and the stripping are performed. It is preferred in that respect.

In FIGS. 7 and 8, the transfer residual toner which is not transferred in the transfer step and is present on the surface of the electrostatic latent image carrier is removed by bringing the cleaning member into contact with the surface of the electrostatic latent image carrier. Although it is removed, an image forming method using a “development / cleaning method” in which cleaning of the transfer residual toner is performed simultaneously with the developing step during development is also one of the preferable embodiments.

In this developing and cleaning system,
Between the transfer section and the charging section, and between the charging section and the developing section, for removing transfer residual toner present on the surface of the electrostatic latent image carrier by contacting the surface of the electrostatic latent image carrier; Does not have a cleaning member.

The charge of the transfer residual toner greatly changes depending on the transfer bias condition and the resistance of the transfer material. In general, a voltage having a polarity opposite to the charge polarity of the toner is applied to the transfer bias. However, when the development is a positive development (the charge polarity of the toner and the charge polarity of the photoreceptor are opposite), the transfer material may be a thick paper or an OHT film. If the resistance is high, the toner particles having a high charge will not be transferred due to a strong adhesive force to the photoreceptor, and will proceed to the cleaning process with the same charge polarity, so that it will be difficult to clean completely.

Therefore, as the toner, it is preferable that the charge amount of the developed toner on the photoconductor is appropriately controlled, and that the toner having the originally high charge amount is not developed on the photoconductor.

In order to prevent the toner having a high charge amount from being developed on the photoreceptor, it is necessary to suppress the chargeability of the toner in the area where the charge is applied to the toner. Further, adverse effects such as a decrease in transferability are likely to occur.

The toner according to the present invention contains the compound represented by the general formula <A> in the toner, thereby suppressing the generation of excessively high charged toner particles and providing the toner with an appropriate charge amount. It has become possible to let. Thereby, stable performance with excellent durability is exhibited also in the developing step.

On the other hand, in the case of reversal development (where the charge polarity of the toner and the charge polarity of the photoreceptor are the same), if the transfer material is easy to pass an electric field such as thin paper, it is strongly charged to the opposite polarity by the transfer bias. The toner particles, which are strongly charged to the opposite polarity, also have a strong adhesive force to the photoreceptor and cannot be easily cleaned.

On the other hand, in the present invention, the use of the toner containing the compound represented by the general formula <A> makes it possible to suppress the generation of excessively reversely charged toner particles. . Further, the control of the toner charge amount by the transfer bias becomes easy by using the toner containing the compound represented by the general formula <A> according to the present invention.

Although the reasons are not necessarily clear, according to the knowledge of the present inventors, the compound represented by the general formula <A> used in the present invention has a toner having an excessively high charge amount. This is considered to be due to the fact that the charge-up phenomenon is prevented and the toner particles do not easily retain excessive reverse charges even when a charge polarity and a reverse electric field are applied in the transfer step.

The principle of the developing / cleaning method is to control the charging polarity and the charging amount of the toner on the photoreceptor in each step of electrophotography and to use the reversal developing method.

For example, when a negatively charged photosensitive member and a negatively charged toner are used, an image visualized by a positively polarized transfer member is transferred to a transfer material in the transfer step. However, the charge polarity of the transfer residual toner varies from plus to minus depending on the relationship between the type of transfer material (difference in thickness, resistance, and dielectric constant) and the image area. However, due to the negative polarity charging member when charging the negatively charged photoreceptor, even the toner remaining on the transfer along with the photoreceptor surface is uniformly moved to the negative side even if the toner is swung to a positive polarity in the transfer process. The charging polarity can be made uniform. Therefore, even if toner particles uniformly negatively charged during development are present on the photoreceptor surface, when reversal development is used as a development method,
The transfer residual toner negatively charged remains in the light portion potential portion of the toner to be developed, and is attracted to the toner carrier due to the development electric field due to the dark portion potential of the toner not to be developed. , Does not remain.

However, when an image is to be formed at a higher process speed by using the developing and cleaning method, the photosensitive member is charged by the charging member in correlation with the reduction of the charging time per unit area of the photosensitive member. And it is difficult to make the charge polarity of the transfer residual toner uniform. For this reason, when reversal development is used as a developing method, it is also difficult to collect and transfer the residual toner on the dark potential, which should not be developed, to the toner carrier by the developing electric field. Furthermore, even if the toner remaining on the toner carrier is collected by a mechanical force such as rubbing, if the charge of the toner remaining after transfer is not uniform, the chargeability of the toner on the toner carrier is adversely affected, and the Deteriorate characteristics.

By controlling the charging polarity of the toner remaining after the transfer simultaneously with the charging of the photosensitive member, an image forming method using a developing and cleaning system is established. However, as described above, in forming an image at a higher process speed,
When the image forming method using the developing and cleaning method is applied, it is difficult to control the charging polarity of the residual toner in the transfer, and it is easy to cause a collection failure in the development, and the development itself is accelerated. There is a problem that the charging of the collected transfer residual toner greatly affects the developing characteristics, and the developing performance is likely to deteriorate.

Further, in the case of using a developing and cleaning system in forming an image at a high process speed, poor charging due to contamination of the charging member is likely to occur.

According to the study of the present inventors, the process speed of the developing roller is 120 mm / sec or more,
In image formation at a higher process speed of 50 mm / sec or more, in an image formation method using a developing and cleaning method, the charge polarity control is more quickly performed to improve the recoverability of transfer residual toner during development. It has been found that in order to maintain the developing performance, it is necessary to more reliably and uniformly control the charge polarity of the toner remaining after transfer when passing through the charging member.

In particular, in the so-called contact charging method in which the charging member is brought into contact with the photosensitive member to perform charging, if the discharging mechanism according to the so-called Passion's law is used as the charging mechanism, the charging member comes into contact with the photosensitive member. And the adhesion to the charging member is also deteriorated due to toner deterioration due to discharge energy.

In the cleaning method for removing the transfer residual toner from the photoreceptor by a cleaning member such as a blade or a fur brush, the toner existing on the photoreceptor is charged, the toner is collected by the developing device, and the toner is transferred to the developing device. No consideration has been given to the effects on the developing performance when the toner is collected and reused in the apparatus.

The inventors of the present invention have conducted intensive studies on various toners, and in the image forming method using the developing and cleaning method, the charge control characteristics of the toner when passing through the charging member are determined by these durability characteristics and image quality. It has been found that the toner has a close connection with quality characteristics, and in particular, it has been found that the inclusion of the compound represented by the general formula <A> in the toner improves the charge controllability of the toner when passing through the charging member. Was.

[0256]

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

Production Example of Toner (1) High-speed stirrer TK-Homomixer (manufactured by Tokushu Kika Kogyo KK)
710 parts of ion-exchanged water and 450 parts of a 0.1 mol / liter-Na ₃ PO ₄ aqueous solution are added to a two-liter four-necked flask equipped with
It was adjusted to 00 rpm and heated to 60 ° C. 68 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution is gradually added thereto, and fine minute hardly water-soluble dispersed Ca ₃ (PO ₄ ) _{2 is} added.
The aqueous dispersion medium containing was prepared.

On the other hand, styrene monomer 165 parts n-butyl acrylate monomer 35 parts divinylbenzene monomer 0.5 part Colorant (carbon black; bulk density 370 g / cm ³ ) 14 parts Saturation Polyester resin 10 parts (terephthalic acid-propylene oxide-modified bisphenol A, acid value 15 mgKOH / g) Charge control agent (compound No. 1) 2 parts Wax (ester compound; mp = 70 ° C.) 20 parts Attritor with above raw materials (Mitsui Metals Co., Ltd.) and dispersed for 3 hours, and then a polymerizable monomer composition obtained by adding 10 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator. The product was put into the aqueous dispersion medium, and granulation was performed while maintaining the rotation speed of the high-speed stirring device at 10,000 rpm. Thereafter, the mixture was reacted at 70 ° C. for 2 hours while stirring with a paddle stirring blade, and then polymerized at 90 ° C. for 10 hours.

After completion of the reaction, the suspension was cooled, diluted hydrochloric acid was added to dissolve the poorly water-soluble dispersant, and the mixture was filtered, washed with water, and dried. ) Got.

To 100 parts of the above colored particles (A), 1.5 parts of hydrophobic silica fine powder (BET: 250 m ^{2 /} g) was dry-mixed with a Henschel mixer (manufactured by Mitsui Kinzoku Co., Ltd.).
The toner (A) of the present invention was used.

The particle size of the toner (A) measured using a Coulter Counter Multisizer (manufactured by Coulter Inc.) was 6.8 μm for the weight average particle size (D4) and 5.4 μm for the number average particle size (D1). The coefficient of variation was 26, the amount of fine powder (the proportion of particles having a size of 4.00 μm or less in the number distribution) was 16% by number, the shape factor SF-1 was 120,
SF-2 is 115, (SF-2) / (SF-1) is 0.1.
96.

In addition, a flow type particle image measuring device FPIA-
The average circularity (c) measured using a Model 1000 (manufactured by Toa Medical Electronics Co., Ltd.) is 0.976, and the circularity standard deviation (SDc)
Is 0.031, and the ratio of particles having a circularity of less than 0.950 is 1
3 (% by number).

Further, when the triboelectric charge amount of the toner (A) was measured, it was -45 mC / kg.

In the present invention, the triboelectric charge of the toner was measured by a suction method. 8. First, 0.5 g of toner and a carrier (EFV-200 / 300, manufactured by Powder Tech)
5 g is weighed, placed in a 50 ml polyethylene container, and left under a measurement environment (23 ° C./60% Rh) for 2 days. Thereafter, the container is sealed and shaken 50 times to prepare a mixed sample of the toner and the carrier.

FIG. 12 shows the charge amount measuring apparatus used in the present invention.
Shown in 500 mesh conductive screen 4 having an opening diameter capable of capturing a carrier and sucking and removing only toner.
3 is weighed and placed in a metal measuring container 42 having a metal lid 4 at the bottom.
Do 4. Next, using a suction device connected to the measurement container 42 via an insulating portion, a vacuum gauge 45 is
Is suctioned from the suction port 47 for 1 minute so that the pressure becomes 250 mmH ₂ O. At this time, the voltage value V indicated by the electrometer 49
The value obtained by dividing the charge amount calculated from (V) and the capacitance C (μF) of the condenser 48 by the toner amount w (g) obtained by suction removal was defined as the triboelectric charge amount (mC / kg).

Amount of triboelectric charge (mC / kg) = CV / w

When the content of the wax in the toner (A) was observed by TEM, as shown in the schematic diagram of FIG. And the value of (r / R) _st was 0.62.

Further, 7 parts of the toner (A) and 93 parts of a resin-coated magnetic ferrite carrier (average particle size: 45 μm) were mixed to prepare a two-component developer (A).

Preparation Examples of Toners (2) to (4) Toners (B) to (D) and toners (B) to (D) in the same manner as in Production Example 1 of the toner except that the charge control agent and the colorant shown in Table 3 were used instead of the carbon black and No. 1 respectively. (D) was obtained.

Toner Production Example (5) 100 parts of styrene-butyl acrylate copolymer resin (glass transition temperature 70 ° C.) Colorant (carbon black used in toner production example (1); bulk density 370 g / cm ³ ) 5 parts-Charge control agent (Compound No. 1) 1 part-Wax component (low molecular weight polypropylene; mp = 125 ° C) 4 parts were mixed and melt-kneaded with a twin-screw extruder. After cooling, the kneaded material was coarsely pulverized by a hammer mill, finely pulverized by a jet mill, further heated and formed into a sphere, and then classified to obtain colored particles (E).

To 100 parts of the colored particles (E), 1.5 parts of a hydrophobic silica fine powder treated with hexamethyldisilazane (BET specific surface area: 200 m ^{2 /} g) was dry-mixed with a Henschel mixer. Thus, a toner (E) was obtained.

The wax in the toner (E) is finely dispersed, and (r / R) _st is 0.01 or less.

Further, 7 parts of the toner (E) and 93 parts of a resin-coated magnetic ferrite carrier (average particle diameter: 45 μm) were mixed to prepare a two-component developer (E).

Toner Production Examples (6), (7) Compound No. The toners (F) and (G), the two-component developers (F), and ( G) was prepared.

Comparative Production Example of Toner (1) A comparative toner (a) and a two-component developer for comparison were prepared in the same manner as in Production Example 5 of the toner except that the heating spheroidizing treatment was not performed. a) was obtained.

Comparative Production Example of Toner (2) Compound No. In place of 1, Fe complex of salicylic acid 2
Comparative toner (b) and a comparative two-component developer (b) in the same manner as in Production Example 1 of the toner, except that 4 parts of an acid-modified polypropylene wax (mp = 125 ° C.) were used as the wax. ) Got.

Table 3 shows the formulation of the toner and the properties of the obtained toner in each of the production examples.

[0278]

[Table 3]

Examples 1 to 7 and Comparative Examples 1 and 2 In the present Example and Comparative Example, an image forming apparatus as shown in FIG. 2 was used. The developing device shown in FIG. 3 was used.

The photosensitive drum 1 has a photosensitive layer 1b having an organic optical semiconductor on a substrate 1a, and rotates in the direction of the arrow to oppose and rotate in contact with the charging roller 2 (conductive elastic layer 2a,
The photosensitive drum 1 is charged to a surface potential of about -600 V by the cored bar 2b). The exposure 3 is turned on / off on the photoreceptor by a polygon mirror in accordance with digital image information, so that the exposed portion potential is -100V and the dark portion potential is -600V.
Is formed. Using the developing device 4-1, a toner image was obtained on the photoreceptor 1 using a reversal developing method. The toner image is transferred to the intermediate transfer member 5 (elastic layer 5a, core metal 5 as a support).
b) transferred onto The transfer material toner on the photoreceptor 1 is collected in a residual toner container 9 by a cleaner member 8.

The intermediate transfer member 5 was formed by coating a pipe-shaped core 5b with an elastic layer 5b in which a carbon black conductive member was sufficiently dispersed in nitrile-butadiene rubber (NBR). The hardness of the coat layer 5b is determined according to “JIS
And volume resistivity locations 30 degrees conforms to the K-6301 ", was 10 ⁹ Ω · cm. The transfer current required for the transfer from the photoreceptor 1 to the intermediate transfer member 5 was about 5 μA, which was obtained by applying +500 V from the power supply to the cored bar 5b.

The transfer roller 7 has an outer diameter of 20 mm and a diameter of 10 m.
An elastic layer 7a formed by coating a core material 7b having a carbon conductivity imparting member sufficiently dispersed in an ethylene-propylene-diene-based terpolymer (EPDM) foam on a metal core 7b having an elastic layer 7a. The elastic layer 7a has a volume resistivity of 10 ⁶ Ω · cm, which is described in “JIS K-630”.
The reference hardness of "1" used was a value showing a value of 35 degrees. A voltage was applied to the transfer roller, and a transfer current of 15 μA was passed.

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

At this time, both the upper roller and the lower roller having a surface layer of a fluororesin were used, and the diameter of the roller was 60 mm. The fixing temperature is 160 ° C.
The nip width was set to 7 mm.

Under the above conditions, at normal temperature and normal humidity (25 ° C., 60%
RH) In the environment, the two-component developers (A) to (G) and the two-component developers for comparison (a) and (b) are sequentially replenished at a printout speed of 12 sheets (A4 size) / min. A printout test was performed on 10,000 sheets in a single color intermittent mode (ie, a mode in which the developing unit was stopped for 10 seconds each time one sheet was printed out, and the deterioration of the toner was promoted by a preliminary operation at the time of restarting). The printout images obtained were evaluated for the items described below.

At the same time, the matching between the used image forming apparatus and the developer was also evaluated.

The transfer residual toner collected by the cleaning was conveyed to a developing device by a reuse mechanism and reused.

Table 4 shows the above evaluation results.

[0289]

[Table 4]

In Examples 1 to 4, matching with the image forming apparatus was particularly good. However, the present inventors have found that the reason is that in the present invention, the toner shape distribution and the internal structure of the toner are precisely controlled. Therefore, the charge control agent according to the present invention easily exerts the excellent charge-imparting ability, and the toner of the present invention suppresses the contamination of the image forming apparatus. It is considered that the points are the result of acting synergistically.

Embodiment 8 In this embodiment, a commercially available laser beam printer LBP-
EX (manufactured by Canon Inc.) was remodeled with a reuse mechanism attached to it and used again. Using a rubber roller (diameter 12 mm, contact pressure 50 g / cm) in which conductive carbon coated with nylon resin is dispersed as a primary charging roller,
Laser exposure (600 dpi) on the electrostatic latent image carrier causes dark portion potential V _D = −700 V and bright portion potential V _L = −200 V.
Was formed. A developing sleeve having a surface roughness Ra of 1.1 coated with a resin in which carbon black is dispersed as a toner carrier is set to be 1.1 times the moving speed of the photosensitive drum surface. The gap (between S and D) between the photosensitive drum and the developing sleeve is 270 μm,
A urethane rubber blade was used in contact with the toner regulating member. An AC bias component was superimposed on a DC bias component as a developing bias. The set temperature of the heat fixing device was 150 ° C.

Under the above set conditions, high temperature and high humidity (30 ° C., 8
0% RH) in an intermittent mode (that is, every time 100 sheets are printed out) at a printout speed of 12 sheets (A4 size) / min while sequentially replenishing toner (1).
The developing device was paused for 0 minutes, and the preparatory operation at the time of restarting accelerated the deterioration of the toner. 5000 sheets were printed out, and the obtained printout image was evaluated. The image density was good and stable. Good image output results with almost no image fog were obtained.

The matching between the image forming apparatus and the toner was also good.

Embodiment 9 The developing device of the image forming apparatus shown in FIG. 2 was replaced with the developing device shown in FIG. 4, and the moving speed of the surface of the toner carrying member was changed to the electrostatic latent temperature in a normal temperature and normal humidity (25 ° C., 60% RH) environment. The speed is set to be 3.0 times the moving speed of the surface of the image carrier, and the toner (A) is sequentially replenished, and the developing device is paused for one minute each time one sheet is printed out while the single-color intermittent mode is set. Then, the evaluation was performed in the same manner as in the above-described embodiment by using a mode in which the deterioration of the toner is promoted by the preliminary operation at the time of restart.

The surface roughness Ra of the toner carrier used here was 1.5, and the toner regulating blade adhered urethane rubber to the phosphor bronze base plate, and the contact surface with the toner carrier was made of nylon. The coated one was used. The fixing device shown in FIGS. 5 and 6 is used as the heat fixing device H, and a temperature detecting element of a heating element 31 (31a: heater substrate, 31b: heating element, 31c: surface protective layer, 31d: temperature detecting element). 31d has a surface temperature of 140 ° C., and the heating element 31 is a sponge pressure roller 3 having a silicone rubber foam as a lower layer.
3 is 8 kg, the nip between the pressure roller and the film is 6 mm, and the fixing film 32 has a low resistance separating member in which a conductive material is dispersed in PTFE (high molecular weight type) on the contact surface with the transfer material. A heat-resistant polyimide film having a mold layer and a thickness of 60 μm was used. Table 5 summarizes the above results.

[0296]

[Table 5]

Example 10 Using the image forming apparatus shown in FIG. 2, the two-component developers (A) to (D) were respectively
2,4-3,4-4, 25 ℃, 60% relative humidity
Under the environment, full-color image output was performed at a printout speed of 3 sheets (A4 vertical size) / minute, and image evaluation was performed. As a result, matching with the developing sleeve, photosensitive drum, intermediate transfer body, and fixing device was excellent, and As a result, a full-color image output with good image characteristics was obtained.

The evaluation items described in the examples of the present invention and the evaluation criteria will be described.

[Evaluation of Printout Image] <1> Image Density The image density was evaluated by maintaining the image density when a predetermined number of printouts were completed on ordinary paper for copying machines (75 g / m ² ). The image density was measured using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) with respect to a printout image of a white background portion of a document image of 0.00. A: 1.40 or more B: 1.35 or more and less than 1.40 C: 1.00 or more and less than 1.35 D: less than 1.00

<2> 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: less than 1.5% B: 1.5% or more, less than 2.5% C: 2.5% or more, less than 4.0% D: 4% or more

<3> Omission of Image The character pattern of “surprise” shown in FIG.
The printout at 8 g / m ² ) was visually evaluated for the void in the character portion (the state shown in FIG. 13B). A: Almost no occurrence B: Slight hollowing out C: Some hollowing out D: Remarkable hollowing out

[Evaluation of Image Forming Apparatus Matching] <1> Matching with Developing Sleeve After the printout test was completed, the state of fixation of the residual toner on the surface of the developing sleeve and the effect on the printout image were visually evaluated. A: Not generated B: Almost not generated C: There is sticking, but there is little effect on the image D: There is much sticking, and image unevenness occurs

<2> Matching with Photosensitive Drum After the end of the printout test, the occurrence of scratches on the surface of the photosensitive drum and sticking of residual toner and the effect on the printout image were visually evaluated. A: Not generated B: Slight scratches are seen, but there is no effect on the image C: There is sticking or scratching, but there is little effect on the image D: There are many sticking, and vertical streak-like image defects Arise

<3> Matching with Intermediate Transfer Body After the print-out test was completed, the surface of the intermediate transfer body and the state of fixation of residual toner were visually evaluated. A: Not generated B: Slight scratches are seen, but there is no effect on the image C: There is sticking or scratching, but there is little effect on the image D: There are many sticking and vertical streak-like image defects Arise

<4> Matching with Fixing Apparatus After the printout test, the flaws on the fixing roller and the fixing film surface and the state of fixation of the residual toner were visually evaluated. A: Not generated B: Almost not generated C: There is sticking or damage, but there is little effect on the image D: There is much sticking, and a vertical streak-like image defect occurs.

Production Example of Toner (8) 700 parts by weight of ion-exchanged water and 0.1 mol / L-Na ₃ PO were placed in a two-liter four-necked flask equipped with a high-speed stirrer CLEARMIX (manufactured by M-Technic).
₄ 800 parts by weight of the aqueous solution was charged, the rotation speed of the high-speed stirring device was set to 15000 rpm, and the mixture was heated to 65 ° C.
Here, 1.0 mol / l-CaCl ₂ aqueous solution 70
Parts by weight, and a fine hardly water-soluble dispersant Ca ₃ (PO
₄ ) An aqueous dispersion medium containing ₂ was prepared. Further, the aqueous dispersion medium was re-prepared with dilute hydrochloric acid so that the pH became 5.0.

On the other hand, as the dispersoids:-77 parts of styrene monomer-23 parts of 2-ethylhexyl acrylate monomer-0.2 part of divinylbenzene monomer-Colorant (carbon black; volatile matter: 1.0%) 5 parts ・ Polycarbonate resin (peak molecular weight = 7500) 5 parts ・ Charge control agent 2 parts ・ Ester wax A 7 parts

The above ester wax A and the ester wax B used in the later-described toner production example (12) were
It was prepared from the following long-chain alkyl carboxylic acid and long-chain alkyl alcohol. Table 6 shows the physical properties of the ester waxes A and B.
Shown in Long-chain alkyl carboxylic acid component Palmitic acid (C ₁₆ H ₃₂ O ₂ ) Stearic acid (C ₁₈ H ₃₆ O ₂ ) Arachidene acid (C ₂₀ H ₄₀ O ₂ ) Behenic acid (C ₂ H ₄₄ O ₂ ) · lignoceric acid (C ₂₄ H ₄₈ O ₂₎ long-chain alkyl alcohol component, palmityl alcohol (C ₁₆ H ₃₄ O) · stearyl alcohol (C ₁₈ H ₃₈ O) · arachidyl del alcohol (C ₂₀ H ₄₂ O) · behenyl (C ₂₂ H ₄₆ O)

[0309]

[Table 6]

After the above raw materials were dispersed for 3 hours using an attritor, 7 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 a high-speed stirring device was maintained at 15,000 rpm under an N ₂ atmosphere at an internal temperature of 70 ° C. while maintaining the rotation speed at 15,000 rpm.
The mixture was stirred for 5 minutes to granulate the polymerizable monomer composition. Then, replace the stirring device with a paddle stirring blade,
While maintaining the same temperature while stirring at 80 rpm, when the polymerization conversion of the polymerizable vinyl monomer reaches 93%,
The pH of the aqueous dispersion medium was changed to 12 by adding a 0.1 mol / liter aqueous solution of NaOH. Further, the reaction temperature was set at 8
The temperature was raised to 0 ° C., and when the polymerization conversion reached almost 100%, the polymerization reaction was completed.

After completion of the polymerization, the remaining monomers were distilled off under reduced pressure under heating, and then, after cooling, dilute hydrochloric acid was added to dissolve the poorly water-soluble dispersant. After repeating water washing several times,
Drying was performed using a conical ribbon dryer (manufactured by Okawara Seisakusho) to obtain colored particles (H).

100 parts by weight of the above colored particles (H) and hydrophobic oil-treated silica fine powder (BET specific surface area: 200 m ²⁾
/ G) 2 parts by weight of Henschel mixer (Mitsui Metals)
And dry-mixed to obtain the toner (H) of the present invention.

The particle size distribution of the toner (H) was such that the weight average particle size (D ₄ ) was 6.5 μm, the coefficient of variation was 21, and the amount of fine powder was 10
%, The shape factor SF-1 was 113, SF-2 was 111, and (SF-2) / (SF-1) was 0.98. The circularity frequency distribution has an average circularity of 0.985.
And the circularity standard deviation is 0.026, and the circularity is 0.9.
The ratio of particles having a particle size of less than 50 was 3% by number.

When the content of the wax in the toner (H) was observed by TEM, as shown in the schematic diagram of FIG. The value of (r / R) _st was 0.43.

Toner Production Examples (9) to (14) Toner production examples (8) except that the types and amounts of charge control agent, colorant and wax, and the pH of the aqueous dispersion medium during the polymerization reaction were changed. In the same manner as described above, the colored particles (I) to (N)
After the preparation, toners (I) to (N) of the present invention were prepared.

Comparative Production Examples of Toners (3) and (4) The same procedure as in Production Example (1) of Comparative Toner except that the types of the charge control agent, colorant and wax were changed, c) and (d) were obtained.

100 parts of each of the comparative colored particles (c) and (d) and 2 parts of a hydrophobic oil-treated silica fine powder (BET specific surface area: 200 m ² / g) were dry-mixed with a Henschel mixer and used for comparison. The toners were (c) and (d).

Comparative Production Example of Toner (5) 2 parts of salicylic acid boron complex as charge control agent and modified polyethylene wax as wax (mp = 115 ° C.)
After preparing comparative colored particles (e) in the same manner as in Production Example (8) of the toner except that the pH of the aqueous dispersion medium at the time of the polymerization reaction is kept constant using 4 parts, (E)
Was prepared.

[0320] Table 7 shows the toner formulation and production conditions in each production example, and Table 8 shows the properties of the obtained toner.

[0321]

[Table 7]

[0322]

[Table 8]

(Example of Production of Photosensitive Drum)
Using an aluminum cylinder with a length of 254 mm as a base,
The layers having the following structures were sequentially laminated by dip coating to produce a photoreceptor drum (1).

[0324] (1) Conductive coating layer: a powder of acid tin oxide and titanium as a main component which is dispersed in a phenol resin. The thickness is 15 μm.

(2) Subbing layer: Mainly composed of modified nylon and copolymerized nylon. The film thickness is 0.6 μm.

(3) Charge generation layer: mainly composed of an azo pigment having absorption in a long wavelength region dispersed in butyral resin. The film thickness is 0.6 μm.

(4) Charge transporting layer: mainly composed of a hole transporting triphenylamine compound dissolved in a polycarbonate resin (molecular weight 20,000 according to Ostwald viscosity method) at a weight ratio of 8:10, and further comprising polytetrafluoroethylene. Powder (particle size: 0.2 μm) was added at 10% by weight based on the total solid content, and dispersed uniformly. 25 μm thick.

The contact angle of the surface of the obtained photosensitive drum (1) with water was 95 degrees.

The contact angle was measured using pure water and a contact angle meter CA-DS (manufactured by Kyowa Interface Science Co., Ltd.).

Example 11 A 600 dpi laser beam printer (manufactured by Canon: LBP-8Mark IV) was prepared as an image forming apparatus. This device was modified to achieve a process speed of 80 mm /
s, 12 sheets were printed per minute on LTR size paper. As shown in FIG. 7, this device uniformly charges a photoconductor 56 (30φ) using a charging roller 51 to which DC and AC components are applied. At this time, the DC component is controlled to a constant voltage, and the AC component is controlled to a constant current. Following charging, a laser beam 60
The process has a process in which an electrostatic latent image is formed by exposing an image portion by using a toner image, a toner image is formed as a visible image by the toner 50, and the toner image is transferred to a transfer material 58 by a transfer roller 57 to which a voltage is applied.

Next, the developing container 52 in the process cartridge was modified. A medium resistance rubber roller (16φ) made of silicone rubber whose resistance is adjusted by dispersing carbon black instead of an aluminum sleeve containing a magnet serving as a toner supply body is used as the toner carrier 54.
It came into contact with the photoreceptor 56. The moving direction and the rotational peripheral speed of the surface of the toner carrier 54 are the same in the contact portion with the surface of the photosensitive drum, and the toner carrier 54 is driven to be 150% of the rotational peripheral speed of the photosensitive drum. That is, the peripheral speed of the toner carrier is 120 mm / s, and the relative speed with respect to the photoconductor surface is 40 mm / s.

As a means for applying the toner to the toner carrier, an application roller 55 was provided at the developing portion, and was brought into contact with the toner carrier. At the contact portion, the toner was applied onto the toner carrier by rotating the application roller 55 such that the moving direction of the surface of the applying roller 55 moved in the opposite direction to the moving direction of the toner carrier. Further, a stainless steel blade 53 coated with a resin was attached for controlling the coat layer of the toner on the toner carrier. As the cleaning member 59, a blade made of urethane rubber was used.

A photosensitive drum (1) was used as a photosensitive member.
The toner (H) was used as the toner.

Further, process conditions were set so as to satisfy the following developing conditions. Photoconductor dark area potential -700V Photoconductor light area potential -150V Development bias -450V (DC component only)

In a normal temperature and normal humidity environment (25 ° C., 60% RH), a continuous printout test of 2,000 sheets was performed while toner was supplied. Thereafter, the evaluation environment was changed to a high temperature and high humidity environment (30 ° C., 80% RH). ), And a further 3000 printout tests were performed. When the image was evaluated using the printout image, the image density, the image scattering suppression, the image dropout suppression, the image fog suppression, the dot reproducibility were good, and the cleaning failure did not occur. Got quality. After completion of the printout test, the developing roller, the photosensitive drum, and the fixing device were observed, but no replacement was necessary without fusing the toner. Table 9 shows the evaluation results.

Example 12 The same procedures as in Example 11 were carried out except for the following.

The toner was driven so that the direction of movement of the surface of the toner carrier was the same direction at the portion in contact with the surface of the photosensitive drum, and was 200% of the peripheral speed of the photosensitive drum. The peripheral speed of the toner carrier is 160 mm / s, and the relative speed with respect to the photosensitive member surface is 80 mm / s.

Further, process conditions were set so as to satisfy the following developing conditions.

Developing bias -500 V (DC component only)

A continuous print-out test was performed in the same manner as in Example 11. As a result, the conditions were more severe due to an increase in the process speed. The results were slightly inferior to Example 11, but were generally good, and poor cleaning occurred. Without this, the same image quality as the initial one was obtained. In addition, although the development roller, the photosensitive drum, and the fixing device were observed, there was no need for replacement without toner fusion or the like. Table 9 shows the evaluation results.

Examples 13 to 18 Except that toners (I) to (N) were used as toners, a printout test was performed and evaluated in the same manner as in Example 11. As shown in Table 9, generally good results were obtained.

Comparative Examples 3 to 5 A printout test was performed and evaluated in the same manner as in Example 11 except that comparative toners (c) to (e) were used as toners. Table 9 shows the evaluation results.

[0343]

[Table 9]

The evaluation items and the evaluation criteria in Examples 11 to 18 and Comparative Examples 3 to 5 will be described.

[Evaluation of Printout Image] <1> Image Density The evaluation standard of the image evaluation in Example 1 is used.

<2> Image Scattering This is an evaluation of scattering with delicate fine lines related to the image quality of a graphical image, and is a result of printing a 1-dot line image that is more easily scattered than a character image on plain paper (75 g / m ² ). The reproducibility of the line image and the scattering of the toner to the periphery were visually evaluated. A: Almost no occurrence, showing good line reproducibility. B: Slight scattering is observed. C: Slight scattering is observed, but little influence on line reproducibility. D: Remarkable scattering is observed, line reproduction. Inferior

<3> Omission in Image The evaluation standard for image evaluation in Example 1 is used.

<4> Image fogging The image fogging is based on the evaluation standard of the image evaluation in the first embodiment.

<5> Dot Reproducibility The electric field is easy to close due to the latent image electric field, making it difficult to reproduce.
An image of an isolated dot pattern having a small diameter (50 μm) as shown in FIG. 4 was printed out, and the dot reproducibility was evaluated. A: 2 or less defects in 100 B: 3 to 5 defects in 100 C: 6 to 10 defects in 100 D: 11 or more defects in 100

[Evaluation of Matching with Image Forming Apparatus] <1> Matching with Developing Roller After completion of the printout test, the state of adhesion of the toner to the developing roller and the effect on the printout image were visually evaluated. A: No sticking occurred B: Contamination occurred, but almost no sticking C: Sticking, but little effect on image D: Many sticking, causing image unevenness

<2> Matching with Photosensitive Drum The evaluation criterion for matching evaluation in Example 1 is used.

<3> Matching with Fixing Apparatus In accordance with the evaluation criterion for matching evaluation in the first embodiment.

Example 19 In the image forming apparatus used in Example 11, the developing container 5
Example 11 was the same as Example 11 except that a sponge roller having a single layer structure was used as the toner application roller 55 in No. 2 and a bias voltage was applied from a bias application unit (not shown) to the toner application roller 55. An image was formed and evaluated in the same manner as described above.

During development, only the DC component of -300 V was applied to the developing roller 54 as the developing bias voltage, and only -450 V of the DC component was applied to the toner application roller 55 as the application bias voltage.

The evaluation was performed in the same manner as in Example 11. As a result, both the image density and the image fogging suppression were stable and good, and no cleaning failure occurred, and excellent image quality was obtained. The matching with the image forming apparatus was also good.

Example 20 The developing device 4-4 of the image forming apparatus shown in FIG.
An image was formed by using the above method.

In the image forming apparatus, as shown in FIG.
After the transfer step, as a first cleaning means for removing the toner remaining on the surface of the photoconductor, a cleaner having a cleaning member in contact with the surface of the photoconductor includes a first transfer unit and a charging unit for charging the photoconductor. Further, as a second cleaning means for removing toner remaining on the surface of the intermediate transfer member after the second transfer step, a cleaner having a cleaning member in contact with the surface of the intermediate transfer member is provided. Downstream of the second transfer portion,
Is provided downstream of the transfer section.

As the developing device 4-4, the one having the structure of the developing device 78 shown in FIG. 9 was used.

A medium-resistance rubber roller (16) made of silicone rubber having carbon black dispersed and resistance adjusted.
(φ) was used as the toner carrier 79 and was in contact with the photoconductor. The moving direction and the rotational peripheral speed of the surface of the toner carrier 79 are the same in the contact portion with the surface of the photoconductor, and the toner carrier 79 is driven to be 150% of the peripheral speed of the photoconductor. That is, the peripheral speed of the toner carrier is 120 mm / s, and the relative speed with respect to the photoconductor surface is 80 mm / s.

As a means for applying toner to the toner carrier, a sponge roller having a single layer structure was provided as an application roller 82, and was brought into contact with the toner carrier. At the contact portion, the toner was applied onto the toner carrier by rotating the application roller so that the surface of the application roller moved in the direction opposite to the direction of movement of the toner carrier. Further, a stainless steel blade 86 coated with a resin was attached to control the coat layer of the toner on the toner carrier.

As the photosensitive member, the photosensitive drum (1) was used, and the following developing conditions and image forming conditions were set so as to satisfy the transfer member.

Photoconductor dark area potential: -700 V Photoconductor light area potential: -150 V Development bias applied to the developing roller: -450 V (only DC component) Bias applied to the toner application roller: -300 V
(Only DC component) Transfer bias applied to the intermediate transfer member in the first transfer step:
300V (DC component only) Transfer bias applied to the transfer roller in the second transfer step: 1000V (DC component only)

The toner image transferred onto the recording material under the above-described image forming conditions was heat-fixed to the recording material by the following heat fixing device.

The heating fixing device H used a fixing speed of a hot roll system without an oil application function. At this time, both the upper roller and the lower roller had a fluororesin surface layer, and the diameter of the roller was 60 mm. The fixing temperature was set at 150 ° C., and the nip width was set at 7 mm.

Using the image forming apparatus having the above configuration, 50
When a continuous printout test was performed on 00 sheets, a high-quality image with high density and no image contamination was obtained.

The matching with the image forming apparatus was also good.

Example 21 A 600 dpi laser beam printer (manufactured by Canon: LBP-860) was prepared as the image forming apparatus shown in FIG. 7, and the following points were changed, and the apparatus was modified to use a developing and cleaning system.

The cleaning rubber blade in the process cartridge is removed, the charging method of the apparatus is contact charging in which a rubber roller is brought into contact, the applied voltage is a DC component (-1400 V), and the process speed is 94 m.
m / s. As the process speed is increased, severe conditions are required for uniform charging of the photoconductor.

The photosensitive drum (1) was used as the photosensitive member.

Next, the developing portion of the process cartridge was modified. Medium resistance rubber roller (16φ, hardness ASKER C45 degrees, resistance 10 ⁵ Ω ·) made of urethane foam instead of stainless steel sleeve as toner carrier
cm) to make contact with the photoreceptor. The direction of movement of the surface of the toner carrier is the same as the direction of movement of the surface of the photoconductor, and the toner carrier is driven to be 130% of the peripheral speed of the photoconductor.

As means for applying the toner to the toner carrier, an application roller was provided at the developing portion in contact with the toner carrier. Further, a stainless steel blade coated with a resin for controlling the thickness of a toner coat layer was attached on the toner carrier. The developing bias voltage applied to the toner carrier at the time of development was only DC component (-450 V).

The remodeling of the image forming apparatus and the setting of process conditions were performed so as to be compatible with the remodeling of these process cartridges.

The charging potential of the photosensitive member was set to -800 V
And the bright portion potential was -150V. 7 for transfer material
5 g / m ² paper was used.

Using the toner (H), under normal temperature and normal humidity environment (2
(5 ° C., 60% RH), after continuously printing 100 sheets of a character image having a print area ratio of 4%, image evaluation and image contamination due to charging failure were evaluated.
The image stain suppression, transferability, image fog suppression and dot reproducibility were all good. Further, when the toner adhesion amount [mg] per unit surface area [cm ² ] of the charging roller was measured, it was very small as 0.01 mg / m ² . After the initial evaluation of 100 sheets, a continuous printout of 2000 sheets was further performed, and the image evaluation was performed again.
Image quality equivalent to the initial one was obtained. In addition, although both the photosensitive drum and the developing roller were observed, there was no need for replacement without toner fusion. There was no problem with the fixing property.

Example 22 Evaluation was made in the same manner as in Example 21 except that the process speed was increased to 120 mm / s. As shown in Table 10, as the process speed was increased, more severe conditions were obtained. Although the results were slightly inferior to those of the examples, the results were generally good.

Examples 23 to 25 A printout test was performed and evaluated in the same manner as in Example 21 except that toners (L) to (N) were used as toners. Table 10 shows the results.

Comparative Examples 6 to 8 Printout tests were performed and evaluated in the same manner as in Example 21 except that comparative toners (c) to (e) were used as toners. Table 10 shows the evaluation results.

In Comparative Examples 6 and 7, since the toner used did not satisfy the specific shape of the present invention, the adhesion of the toner to the surface of the charging roller became severe as the durability was increased. Since it was difficult to continue the continuous printout test, the test was stopped halfway.

[0379]

[Table 10]

The evaluation items and the evaluation criteria in Examples 21 to 25 and Comparative Examples 6 to 8 will be described.

[Evaluation of Printout Image] <1> Image Density The evaluation is based on the evaluation standard of the image evaluation in the first embodiment.

<2> Image Stain The image stain when a halftone image composed of one dot line and one dot space was printed out on plain paper (75 g / m ² ) was visually evaluated. A: Not generated B: Slight dirt is seen C: Fine black spot dirt is seen D: Periodic band dirt or vertical stripe dirt is seen

<3> Omission in Image The evaluation standard for image evaluation in Example 1 is used.

<4> Image Fogging The image fogging is based on the evaluation standard of the image evaluation in the first embodiment.

<5> Dot Reproducibility The evaluation is based on the evaluation criteria of the image evaluation in the eleventh embodiment.

[Amount of Toner Attached to Charging Roller] The weight of toner attached to the charging roller per unit area was measured.
The smaller the toner adhesion amount, the better. A: 0.20mg / cm ² less B: 0.20mg / cm ² or more, 0.35 mg / cm ²
Less than C: 0.35 mg / cm ² or more, 0.55 mg / cm ²
Less than D: 0.55 mg / cm ² or more

[Evaluation of Matching with Image Forming Apparatus] <1> Matching with Developing Roller The evaluation criterion for matching evaluation in Example 11 is used.

<2> Matching with Photosensitive Drum The evaluation criteria for matching evaluation in Example 1 are used.

<3> Matching with Fixing Device According to the evaluation criteria of the matching evaluation in the first embodiment.

[0390]

According to the present invention, the non-image area is free from image contamination such as background fog while maintaining high developability even when a large number of images are formed, and has excellent environmental resistance. Useful toner such that good matching with the toner can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a gas chromatogram of an ester wax.

FIG. 2 is a schematic explanatory view of an image forming apparatus suitable for the present invention.

FIG. 3 is an enlarged cross-sectional view of a main part of a developing device for two-component development used in an embodiment of the present invention.

FIG. 4 is an enlarged cross-sectional view of a main part of a developing device for one-component system development used in an embodiment of the present invention.

FIG. 5 is an exploded perspective view of a main part of the fixing device used in the embodiment of the present invention.

FIG. 6 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. 7 is a view schematically showing an image forming method using a contact one-component developing device, which is used as an example of an embodiment of the image forming method of the present invention.

FIG. 8 is a diagram schematically illustrating an image forming method using a contact one-component developing device, which is used as still another example of the image forming method of the present invention.

FIG. 9 is an enlarged view of a developing device of the image forming apparatus shown in FIGS. 7 and 8;

FIG. 10 is a schematic diagram illustrating an image forming apparatus that reuses untransferred toner.

FIG. 11 is a schematic diagram illustrating a cross section of toner particles containing wax.

FIG. 12 is a perspective view of an apparatus for measuring a triboelectric charge amount of a toner used in the present invention.

FIG. 13 is a schematic diagram showing a state of a hollow character image.

FIG. 14 is an explanatory diagram of an isolated dot pattern for evaluating dot reproducibility.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/08 507 G03G 9/08 2H078 15/16 365 15/24 371 21/10 374 384 384 15/08 507L 21/00 326 (72) Inventor Akira Hashimoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Keiji 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yasawa Ayaki 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H003 AA18 BB11 EE11 2H005 AA06 AA08 AA15 AA21 AB06 CA12 CA14 CA21 CA25 CB07 CB13 CB18 DA02 EA03 EA05 EA07 2H032 AA05 AA15 BA05 BA08 2H034 BF00 CB01 2H077 AA37 AD02 AD06 AD36 DB25 EA03 EA11 GA13 GA17 2H078 BB01 CC08 EE27

Claims (66)

[Claims] 1. A toner having toner particles containing at least a binder resin, a colorant, a wax and a compound represented by the general formula <A>, wherein the shape factor of the toner is such that the SF-1 value is 100 <. SF-
1 ≦ 160, and the value of SF-2 is 100 <SF−2 ≦
140. [Outside 1] (Wherein, R ₁ and R ₄ represent a substituted or unsubstituted aromatic group (including a condensed ring), and R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic group (a condensed ring) , M represents an element selected from B, Ti, Fe, Co, Cr, Al, and Ni, and X ^{n +} represents a cation.) 2. The shape factor SF-1 is 100 <SF-1 ≦
150, and the shape factor SF-2 is 100 <SF-2 ≦
The toner according to claim 1, wherein the number is 130. 3. The shape factor SF-1 is 100 <SF-1 ≦
140, and the shape factor SF-2 is 100 <SF-2 ≦
The toner according to claim 1, wherein the toner is 120. 4. The method according to claim 1, wherein the value of the ratio (SF-2) / (SF-1) of the shape factor SF-1 to the shape factor SF-2 is 1 or less. The toner according to 1. 5. In a circularity frequency distribution measured by a flow type particle image measuring apparatus, an average circularity is 0.920 to 0.5.
The toner according to any one of claims 1 to 4, wherein the circularity standard deviation is less than 0.040 at 995. 6. The circularity frequency distribution measured by a flow-type particle image measuring device has an average circularity of 0.950 to 0.5.
The toner according to any one of claims 1 to 4, wherein the circularity standard deviation is less than 0.040 at 995. 7. In a circularity frequency distribution measured by a flow type particle image measuring device, an average circularity is 0.970 to 0.5.
990, the circularity standard deviation is 0.015 or more to 0.03
The toner according to any one of claims 1 to 4, wherein the ratio is less than 5. 8. The toner according to claim 1, wherein the toner having an average circularity of less than 0.950 is 15% by number or less in a circularity frequency distribution measured by a flow-type particle image measuring apparatus. The toner according to any one of the above. 9. The toner according to claim 1, having a weight average particle size of 4 to 9 μm. 10. The toner according to claim 1, wherein a coefficient of variation in the number distribution is 30 or less. 11. The toner according to claim 1, wherein the fine powder content of the toner having a particle size of 4.00 μm or less is 25% by number or less. 12. The weight average particle diameter is 4 to 9 μm, the coefficient of variation in the number distribution is 30 or less, and 4.00 μm.
The toner according to any one of claims 1 to 8, wherein the amount of fine powder of the toner having a particle size of m or less is 25% by number or less. 13. The weight average particle size is 4 to 9 μm, the coefficient of variation in the number distribution is 25 or less, and 4.00 μm.
The toner according to any one of claims 1 to 8, wherein the amount of fine powder of the toner having a particle size of m or less is 20% by number or less. 14. Observation of a tomographic surface of a toner using a transmission electron microscope (TEM) shows that (1) the toner has a weight average particle diameter D ₄ (μm) of 0.1%;
Twenty tomographic planes of toner particles exhibiting a major diameter R (μm) satisfying the relationship of 9 ≦ R / D ₄ ≦ 1.1 are selected. When the longest diameter r of the largest of the separation structures was measured, the arithmetic mean value (r / R) _{st of the obtained} r / R was 0.05 ≦ (r / R) _st ≦ 0.95. The toner according to any one of claims 1 to 13, wherein the wax is dispersed in the binder resin in a substantially spherical or spindle-shaped island shape so as to be filled. 15. The (r / R) _st is, 0.25 ≦ (r / R) so as to satisfy the _st ≦ 0.90, island-like substantially spherical or spindle to the wax in the binder resin The toner according to claim 14, wherein the toner is dispersed in a toner. 16. The toner according to claim 1, wherein the wax has a maximum endothermic peak at 50 to 100 ° C. at a temperature rise in a DSC curve measured by a differential calorimeter. . 17. The toner according to claim 1, wherein the wax is an ester wax satisfying the following general formula. R ₁ —COO—R ₂ [wherein R ₁ and R ₂ each represent a hydrocarbon group having 15 to 45 carbon atoms. ] 18. The toner according to claim 17, wherein the ester wax contains 50 to 95% by weight of an ester compound having the same total number of carbon atoms. 19. The toner according to claim 1, comprising an inorganic fine powder. 20. The toner according to claim 19, wherein said inorganic fine powder is treated with silicone oil. 21. The toner according to claim 1, which is negatively chargeable. 22. A compound represented by the general formula <A>
22. The toner according to claim 1, wherein the toner is contained in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the binder resin. 23. A compound represented by the general formula <A>
22. The toner according to claim 1, wherein the toner is contained in an amount of 0.6 to 5 parts by weight per 100 parts by weight of the binder resin. 24. The toner particles are subjected to suspension polymerization of a polymerizable monomer composition containing at least a polymerizable monomer, a wax, and a compound represented by formula (A) in an aqueous medium. The toner according to any one of claims 1 to 23, wherein the toner is obtained by the above method. 25. A compound represented by the general formula <A>
25. The toner according to claim 24, wherein the toner is added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the polymerizable monomer. 26. A compound represented by the general formula <A>
25. The toner according to claim 24, wherein 0.6 to 5 parts by weight is added per 100 parts by weight of the polymerizable monomer. 27. A polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a wax, a polymerization initiator, and a compound represented by the general formula <A>, dispersed in an aqueous medium, A granulation step of forming particles of the polymerizable monomer composition, and a polymerization step of polymerizing a polymerizable monomer in the particles of the polymerizable monomer composition to form toner particles. A method for producing a toner, wherein the polymerization reaction of the polymerizable monomer from the granulation step to the polymerization step is carried out until the polymerization conversion of the polymerizable monomer reaches 10% or more. The shape factor of the obtained toner is such that the SF-1 value is 100 <
SF-1 ≦ 160, and the value of SF-2 is 100 <SF
A method for producing a toner, wherein -2 ≦ 140. [Outside 2] (Wherein, R ₁ and R ₄ represent a substituted or unsubstituted aromatic group (including a condensed ring), and R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic group (a condensed ring) , M represents an element selected from B, Ti, Fe, Co, Cr, Al, and Ni, and X ^{n +} represents a cation.) 28. A polymerization reaction of a polymerizable monomer from a granulation step to a polymerization step, wherein the polymerization conversion of the polymerizable monomer is 10%.
28. The method for producing a toner according to claim 27, wherein the step is performed while maintaining the pH of the aqueous medium at 4.5 to 6.0. 29. A polymerization reaction of a polymerizable monomer from a granulation step to a polymerization step, wherein the polymerization conversion of the polymerizable monomer is 1
The method for producing a toner according to claim 27, wherein after increasing by 0% or more, the pH of the aqueous medium is adjusted to 9 to 13 to further increase the polymerization conversion rate. 30. A charging step of applying an external voltage to a charging member to charge the electrostatic latent image carrier; and a latent image forming step of forming an electrostatic latent image on the charged electrostatic latent image carrier. A developing step of developing the electrostatic latent image with the toner carried on the toner carrier to form a toner image on the electrostatic latent image carrier; and A fixing step of heat-fixing a toner image on the transfer material via a transfer step with or without intermediary, wherein the toner comprises at least a binder resin, a colorant, a wax, It has toner particles containing a compound represented by the general formula <A>, and the shape factor of the toner is such that the value of SF-1 is 100 <SF−
1 ≦ 160, and the value of SF-2 is 100 <SF−2 ≦
140. An image forming method, comprising: [Outside 3] (Wherein, R ₁ and R ₄ represent a substituted or unsubstituted aromatic group (including a condensed ring), and R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic group (a condensed ring) , M represents an element selected from B, Ti, Fe, Co, Cr, Al, and Ni, and X ^{n +} represents a cation.) 31. 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 claim 30. 32. The surface roughness Ra (μ) of the toner carrier.
The image forming method according to claim 30 or 31, wherein m) is 1.5 or less. 33. 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. 31. The image forming method according to claim 30, wherein the surface roughness Ra (μm) of the body is 1.5 or less. 34. The image forming method according to claim 30, wherein a ferromagnetic metal blade is disposed with a minute gap facing the toner carrier. 35. The image forming method according to claim 30, wherein a blade made of an elastic body is brought into contact with the toner carrier. 36. The image forming apparatus according to claim 30, wherein in the charging step, the charging member is brought into contact with the electrostatic latent image carrier to charge the electrostatic latent image carrier. Method. 37. The image according to claim 30, wherein in the transfer step, the electrostatic latent image carrier or the intermediate transfer body is in contact with the transfer device via a transfer material. Forming method. 38. The fixing step, wherein the toner image is heat-fixed to the transfer material by a heat fixing device which does not supply an offset preventing liquid or does not have a fixing device cleaner. The image forming method according to any one of the above. 39. The transfer residual toner remaining on the electrostatic latent image carrier after the transfer step is cleaned and collected, and the collected toner is supplied to a developing unit and held by the developing unit again. 39. The image forming method according to claim 30, further comprising a toner reuse mechanism for developing an electrostatic latent image on the electrostatic latent image carrier. 40. In the developing step, the electrostatic latent image is developed by a toner layer formed by toner carried on the surface of the toner carrier coming into contact with the surface of the electrostatic latent image carrier. The image forming method according to any one of claims 30 to 39, wherein the method is performed. 41. The developing method according to claim 40, wherein in the developing step, the transfer residual toner remaining on the electrostatic latent image carrier after the transferring step is collected at the time of developing the electrostatic latent image. Image forming method. 42. The toner has a shape factor SF-1 of 10
0 <SF-1 ≦ 150, and the shape factor SF-2 is 10
4. The method according to claim 3, wherein 0 <SF-2 ≦ 130.
42. The image forming method according to any one of 0 to 41. 43. The toner having a shape factor SF-1 of 10
0 <SF-1 ≦ 140, and the shape factor SF-2 is 10
4. The device according to claim 3, wherein 0 <SF−2 ≦ 120.
42. The image forming method according to any one of 0 to 41. 44. The toner according to claim 30, wherein a value of a ratio (SF-2) / (SF-1) of a shape factor SF-1 to a shape factor SF-2 is 1 or less. 43. The image forming method according to any one of the items 43. 45. In the circularity frequency distribution measured by a flow type particle image measuring apparatus, the toner has an average circularity of 0.
920 to 0.995, and the circularity standard deviation is 0.04.
The image forming method according to any one of claims 30 to 44, wherein the value is less than 0. 46. In the circularity frequency distribution measured by a flow type particle image measuring apparatus, the toner has an average circularity of 0.950 to 0.995 and a circularity standard deviation of 0.
45. It is smaller than 040.
The image forming method according to any one of the above. 47. In the circularity frequency distribution measured by a flow type particle image measuring device, the toner has an average circularity of 0.970 to 0.990 and a circularity standard deviation of 0.
The image forming method according to any one of claims 30 to 46, wherein the number is from 015 to less than 0.035. 48. In the circularity frequency distribution measured by a flow-type particle image measuring apparatus, the toner contains 15% by number or less of toner having an average circularity of less than 0.950. The image forming method according to any one of claims 30 to 47. 49. The toner has a weight average particle size of 4 to 9 μm.
The image forming method according to any one of claims 30 to 48, wherein: 50. The toner according to claim 30, wherein the coefficient of variation in the number distribution of the toner is 30 or less.
The image forming method according to any one of the above. 51. The image forming method according to claim 30, wherein the toner contains toner fine powder having a particle diameter of 4.00 μm or less in an amount of 25% by number or less. . 52. The toner has a weight average particle diameter of 4 to 9 μm.
m, the coefficient of variation in the number distribution is 30 or less, and the fine powder of the toner having a particle size of 4.00 μm or less
4. The composition according to claim 3, wherein the content is 5% by number or less.
49. The image forming method according to any one of items 0 to 48. 53. The toner has a weight average particle diameter of 4 to 9 μm.
m, the coefficient of variation in the number distribution is 25 or less, and the fine powder of the toner having a particle size of 4.00 μm or less
4. The composition according to claim 3, wherein the content is 0% by number or less.
49. The image forming method according to any one of items 0 to 48. 54. A tomographic observation of the toner using a transmission electron microscope (TEM) shows that (1) the toner has a weight average particle diameter D ₄ (μm) of not more than 0.
Twenty tomographic planes of toner particles exhibiting a major diameter R (μm) satisfying the relationship of 9 ≦ R / D ₄ ≦ 1.1 are selected. When the major axis r of the largest of the separation structures is measured, the arithmetic mean value (r / R) _{st of the obtained} r / R is 0.05 ≦ (r / R) _st ≦ 0.95. The image forming method according to any one of claims 30 to 53, wherein the wax is dispersed in the binder resin in a substantially spherical or spindle-shaped island shape so as to satisfy the following. 55. The (r / R) _st is, 0.25 ≦ (r / R) so as to satisfy the _st ≦ 0.90, island-like substantially spherical or spindle to the wax in the binder resin 55. The image forming method according to claim 54, wherein the image is dispersed. 56. The image according to claim 30, wherein the wax has a maximum endothermic peak at 50 to 100 ° C. when the temperature is raised, in a DSC curve measured by a differential calorimeter. Forming method. 57. The image forming method according to claim 30, wherein the wax is an ester wax satisfying the following general formula. R ₁ —COO—R ₂ [wherein R ₁ and R ₂ each represent a hydrocarbon group having 15 to 45 carbon atoms. ] 58. The image forming method according to claim 57, wherein the ester wax contains 50 to 95% by weight of an ester compound having the same total number of carbon atoms. 59. The image forming method according to claim 30, wherein the toner has an inorganic fine powder. 60. The image forming method according to claim 59, wherein said inorganic fine powder is treated with silicone oil. 61. The image forming method according to claim 30, wherein the toner is negatively chargeable. 62. The toner according to claim 30, wherein the toner contains the compound represented by the general formula <A> in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the binder resin. 2. The image forming method according to 1., 63. The toner according to claim 30, wherein the toner contains the compound represented by the general formula <A> in an amount of 0.6 to 5 parts by weight per 100 parts by weight of the binder resin. 2. The image forming method according to 1., 64. A method in which the toner particles are subjected to suspension polymerization in a water-based medium of a polymerizable monomer composition containing a polymerizable monomer, a wax, and a compound represented by the above general formula <A>. 4. The method as claimed in claim 3, wherein:
64. The image forming method according to any one of 0 to 63. 65. A compound represented by the general formula <A>
The image forming method according to claim 64, wherein 0.1 to 10 parts by weight is added per 100 parts by weight of the polymerizable monomer. A compound represented by the general formula <A>
The image forming method according to claim 64, wherein 0.6 to 5 parts by weight is added per 100 parts by weight of the polymerizable monomer.