JPH10123764A - Toner for developing electrostatic images - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide excellent release properties, a wide fixing temperature range, excellent blocking resistance, excellent developability, stable image density in various environments, and no fog. Another object of the present invention is to provide an electrostatic image developing toner capable of forming a uniform toner layer on a toner carrier. SOLUTION: At least in a binder resin and a carbon number distribution obtained by gas chromatography, the abundance continuously changes for each carbon number, and the width of the carbon number in a region where the abundance continuously changes is Eight or more waxes,
A toner having a charge control agent, which is a specific imidazole derivative, and magnetism, which is hexahedral or polyhedral particles having ten or more faces.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image suitable for heat fixing used in electrophotography, electrostatic recording and magnetic recording.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Publication No. JP-A-Heisei, 43-24878 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. Forming and then developing the latent image with toner,
After transferring the toner image to a transfer material such as paper as necessary,
The process of fixing by heating, pressure, heating and pressurizing or solvent vapor to obtain a copy, and cleaning the toner remaining on the photoreceptor without being transferred by various methods is repeated.

In recent years, such copying apparatuses have begun to be used not only as office work copying machines for simply copying original documents, but also as printers as personal computer outputs or personal copying machines for individuals. .

[0004] For this reason, smaller, lighter, faster and more reliable devices have been strictly pursued, and machines have been constructed from simpler elements in various respects. As a result, the performance required of the toner has become higher, and a better machine cannot be realized unless the performance of the toner can be improved.

For example, various methods and apparatuses have been developed for the process of fixing a toner image to a sheet such as paper.
Specifically, there are a compression heating method using a heat roller, a heat fixing method in which a heating member is brought into close contact with a heating member via a film, and the like.

A heating method using a heating roller or a film is performed by passing a toner image surface of a sheet to be fixed onto a surface of a heat roller or a film formed of a material having a releasable property with respect to the toner while contacting the surface. The fixing is performed. In this method, since the surface of the heat roller or the film comes into contact with the toner image of the sheet to be fixed, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. It is very effective in electrophotographic copying machines. However, in the above method, a part of the toner image adheres and transfers to the fixing roller and the film surface because the heat roller and the film surface and the toner image melt, so that the toner image re-transfers to the next sheet to be fixed, a so-called offset phenomenon. May occur, and the sheet to be fixed may be stained. Preventing toner from adhering to the heat fixing roller or the film surface is one of the essential conditions of the heat fixing method.

Conventionally, for the purpose of preventing toner from adhering to the surface of the fixing roller, for example, the roller surface is formed of a material having excellent releasability with respect to the toner, such as silicone rubber or fluorine-based resin, and the surface of the roller is prevented from offsetting. In order to prevent the roller surface from being fatigued, the roller surface is coated with a thin film of a liquid having good releasability such as silicone oil. However, this method is extremely effective in preventing toner offset, but has a problem that a fixing device is complicated because a device for supplying an anti-offset liquid is required. .

[0008] This is in the opposite direction of miniaturization and weight reduction, and moreover, silicone oil and the like may evaporate due to heat and contaminate the inside of the machine. Therefore, instead of using a silicone oil supply device, a method of adding a release agent such as low-molecular-weight polyethylene or low-molecular-weight polypropylene to the toner has been proposed from the idea of supplying the anti-offset liquid during heating from the toner instead. Have been. If a large amount of such an additive is added in order to obtain a sufficient effect, filming on a photoreceptor or contamination of the surface of a toner carrier such as a carrier or a sleeve will cause deterioration of an image and pose a practical problem. Therefore, a small amount of release agent is added to the toner to the extent that the image is not deteriorated, and a small amount of release oil is supplied, or the offset toner is cleaned by a roll-up type device using a member such as a web. It has been used together.

However, in view of recent demands for miniaturization, weight reduction, and high reliability, it is preferable that these auxiliary devices are not required. Therefore, it cannot be coped with without further improvement in performance such as toner fixing property and anti-offset property, and it is difficult to realize without further improvement of toner binder resin and release agent.

As a means for improving the toner, a technique of containing a wax is disclosed in, for example, JP-A-52-3304.
It is disclosed in JP-A-52-3305, JP-A-57-52574 and the like.

Further, Japanese Patent Application Laid-Open Nos. Hei 3-50559 and 2
JP-A-79860, JP-A-1-109359, JP-A-62-14166, JP-A-61-273554, JP-A-61-94062, and JP-A-61-138259.
JP-A-60-252361, JP-A-60-252361
Japanese Patent Publication Nos. 360 and 60-217366 also disclose techniques for incorporating a wax into a toner.

[0012] Waxes are used for improving the offset resistance of the toner at low and high temperatures and for improving the fixing property at low temperatures. However, while these performances are improved, the developability deteriorates.

Particularly, in the case of a positively chargeable toner, since the waxes are negatively charged, the effect is large. For example, image defects such as low initial density, low endurance density, and fogging occur. It was easy.

In general, the toner must have a positive or negative charge according to the charging polarity of the electrostatic latent image to be developed. In order to impart the charging property to the toner, a dye, a pigment or a charge control is required. It is generally known to add agents.
Among these, positive charge control agents include denatured products such as nigrosine and fatty acid metal salts, quaternary ammonium salts and their lake pigments, triphenylmethane dyes and these lake pigments, tertiary amino groups or quaternary ammonium salts. Polymers having in the side chain are known. However, with these conventional positive charge control agents, the triboelectricity of the toner itself is easily affected by the wax contained as a fixing aid, and it is difficult to impart stable developability with little environmental dependency to the toner. . Specifically, for example, in a low-temperature and low-humidity environment, the charge amount of the toner becomes extremely excessive, and the toner coat becomes non-uniform on the toner carrier constituting the developing device, so-called blotch occurs, or ,
In a high-temperature and high-humidity environment, the amount of toner charge is insufficient to lower the image density, or the charge control agent selectively adheres to the surface of the toner carrier to cause contamination. There has been a problem that image defects such as fog tend to occur.

Further, the developing property of the toner greatly differs depending on the combination of the wax and the charge control agent.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems. That is, the object of the present invention is excellent in releasing property, a wide fixing temperature range, excellent in blocking resistance, and also excellent in developing property, high temperature and high humidity,
In order to provide a toner for developing an electrostatic charge image, which can provide stable image density in various environments such as low temperature and low humidity, has no fog, and has a stable uniformity of toner coat on a toner carrier in a developing device. is there.

Another object of the present invention is to provide a toner capable of imparting friction resistance to an image.

[0018]

According to the present invention, there is provided a toner for developing an electrostatic image containing at least a binder resin, a wax, a magnetic substance and a charge control agent, wherein the wax has a carbon number distribution obtained by gas chromatography. The abundance continuously changes for each number of carbon atoms, the width of the number of carbon atoms in the region where the abundance changes continuously is eight or more, and the charge control agent is represented by the following general formula (I). Imidazole derivatives

[0019]

Embedded image (Wherein, R _{1 to} R ₄ are a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, which may be the same or different), and the magnetic material is a hexahedral particle, or A toner for developing an electrostatic image, which is a polyhedral particle having ten or more faces or a mixture thereof.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In general, the distribution of carbon number of wax component and its abundance can be measured from a chromatogram obtained by gas chromatography, and the molecular weight distribution can be directly observed to determine the structure and component distribution of wax. You can know.

The gas chromatogram of waxes is shown in FIG.
As shown in FIG. 2, there is a difference in intensity between the peaks that are continuous without any regular intensity and the peaks of the odd-numbered carbon chain molecules or even-numbered carbon chain molecules or every several peaks as shown in FIG. Some have strong peaks every other to several,
The present invention is characterized by using a wax having the same chromatogram as the former.

For example, the wax shown in FIG. 2 is a synthetic wax having a compound having two or more carbon atoms having a carbon-carbon double bond as a monomer, and the wax shown in FIG. 1 is a natural wax or a compound having one carbon atom. Synthetic wax used as a monomer is exemplified.

Based on the gas chromatogram thus obtained, the carbon number of each peak molecule is determined by the detection time of the standard sample and the detection time of the analyte peak, and the abundance is determined from the peak area to obtain a carbon number distribution. be able to. For example, if the abscissa indicates the number of carbon atoms and the ordinate indicates the abundance (mass%), the distribution of the number of carbon atoms is as shown in FIGS.

According to the present invention, in the carbon number distribution obtained by gas chromatography, as shown in FIG. 3, the content continuously changes for each carbon number and the width of the carbon number in a region where the content continuously changes. , And particularly when applied to a positively chargeable toner, it is possible to provide not only excellent developability but also excellent slipperiness.

On the other hand, for example, as shown in FIG. 4, more molecules exist in even-numbered carbons, and the abundance of the molecules becomes discontinuous with respect to the number of carbons. If the number of odd-numbered carbon molecules is small and the abundance of molecules repeatedly increases and decreases according to the number of carbon atoms, and the abundance of molecules becomes intermittent every two carbon atoms, the developability and slip No effect on sex. The same applies to the case where the odd and even numbers are reversed.

It is assumed that the continuous region is continuous when it has 8 or more carbon atoms. When the continuous area is widened, it becomes easy to balance the fixing property and the offset resistance. It preferably has 10 or more carbon atoms, more preferably 20 or more carbon atoms, and particularly preferably 2 or more carbon atoms.
5 or more.

Here, assuming that the maximum peak carbon number is j, n is an arbitrary carbon number selected from a region of j−k carbon atoms to j + k carbon atoms. k is an integer of 3 or more and k
From the numerical value of, the number of carbon atoms in the continuous region is determined. When the abundance of carbon number n-1 is M _n-1 , the abundance of carbon number n is M _n , and the abundance of carbon number n + 1 is M _{n + 1} , the abundance ratio M between M and M _n-1 is M or abundance ratio M / M _{n + 1} of the _n-1 / M and M and M _{n + 1} is both 1 or less, or are both 1 or more, both 0.6 to 1.4 (preferably 0. 7-1.
3, more preferably 0.75 to 1.25) is defined as continuously changing.

These waxes having a continuous carbon number are hard due to their molecular weight distribution structure and are rich in slipperiness. Therefore, the toner using such a wax also exhibits characteristics such as being hard and slippery, and can be frictionally charged efficiently, and excellent charging stability can be obtained. This effect is particularly large when the toner is a positively chargeable toner. Generally, binder resin, wax, and the like used for toner are negatively charged, so that this frictional charging becomes more important. However, since triboelectric charging is performed efficiently, charging may be excessive depending on the charge control agent.

From the viewpoint of improving the releasability from the fixing member, the carbon distribution preferably has 20 or more carbon atoms.
More preferably, the main component is 25 or more, preferably 30 or more wax. From the viewpoint of improving the offset resistance, the largest peak is preferably a group having 30 carbon atoms.
Or more, more preferably 40 or more, desirably 50 to 1
A wax at 50 is preferred. These carbon number distributions can be arbitrarily selected depending on which characteristics are most required of the toner.

The waxes preferably used in the present invention include paraffin wax and derivatives thereof, microcrystalline wax and derivatives thereof, and synthetic waxes and derivatives thereof using a C1 compound (compound having one carbon atom) as a monomer. Is paraffin wax and C1 synthetic wax.

Some of the C1 synthetic waxes used in the present invention are those synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often two or more types). Specifically, hydrocarbons of up to about several hundred carbons obtained by the Zintall method, the hydrochol method (using a fluidized catalyst bed), or the Aage method (using a fixed catalyst bed), in which a large amount of waxy hydrocarbons are obtained, are used. is there. In addition, those obtained by adding hydrogen or those obtained by adding an antioxidant may be used. Particularly preferably used waxes are synthetic waxes obtained from the distillation residue of hydrocarbons obtained by the Age method from a synthesis gas consisting of carbon monoxide and hydrogen, such as Fischer-Tropsch wax, and those which are hydrogenated, distilled, A product obtained by extracting and separating a specific component using a fractionated crystal or the like may be used.

A wax obtained by subjecting the above-mentioned wax to a mother substance by a molecular weight based on a press sweating method, a solvent method, vacuum distillation, supercritical gas extraction method, fractional recrystallization, melt liquid crystal precipitation, crystal filtration and the like. Are also preferably used. Oxidized and graft-modified products can also be used.

From the viewpoint of improving blocking resistance,
The weight average molecular weight (Mw) / number average molecular weight (Mn) in the molecular weight distribution measured by GPC is preferably 3.0 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. In addition, Mn is 300 to 1500, and furthermore 350 to 1
Preferably it is 200. When Mw / Mn increases, the plasticizing effect increases and the blocking resistance may deteriorate.

For example, the molecular weight distribution by GPC is measured as follows.

(GPC measurement conditions) Apparatus: GPC-150C (manufactured by Waters) Column: GMH-HT 30 cm double column (manufactured by Tosoh Corporation) Temperature: 135 ° C Solvent: o-dichlorobenzene (added with 0.1% ionol) Flow rate: 1 0.0 ml / min sample: 0.4 ml of 0.15% sample is injected

Measurement is performed under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. Furthermore, Mark-Ho
It is calculated by converting to polyethylene using a conversion formula derived from the uwin viscosity formula.

The carbon number distribution of the wax is measured by gas chromatography (GC), for example, under the following conditions.

Apparatus: HP 5890 Series II (manufactured by Yokogawa Electric Corporation) Column: SGE HT-56 6 m × 0.53 mm ID ×
0.15 μm Carrier gas: He 20 ml / min Constant Flow Mode Oven temperature: 40 ° C. → 450 ° C. Inlet temperature: 40 ° C. → 450 ° C. Detector temperature: 450 ° C. Detector: FID Inlet: With pressure control

Under the above conditions, the injection port was pressure-controlled, and the measurement was performed while keeping the optimum flow rate constant, and n-paraffin was used as a standard sample.

The charge control agent contained in the toner of the present invention is an imidazole derivative represented by the following general formula (I).

[0041]

Embedded image (In the above formula, R _{1 to} R ₄ are a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group, and may be the same or different.)

In the present invention, when the imidazole derivative represented by the above general formula (1) is used in combination with the specific wax, high-temperature, high-humidity, low-temperature, low-humidity can be obtained without impairing the low-temperature fixability and offset resistance of the toner of the present invention. And a toner having a high charge level. In addition, the charge level is controlled to an appropriate value, and there is no occurrence of excessive charging and no occurrence of blotches or the like. Also, there is no sleeve contamination,
An image having a high density and little fog can be obtained, and a toner having excellent developability in which selective development is suppressed can be obtained.

The above imidazole derivative is synthesized as follows.

Using ethanol as a solvent, the following general formula (I)
Formaldehyde and potassium hydroxide as a catalyst are added to the imidazole compound represented by I), and the mixture is refluxed for several hours.

[0045]

Embedded image

After the precipitate was filtered and washed with water,
Recrystallize again with methanol. This synthesis method does not limit the imidazole derivative of the present invention at all. Hereinafter, specific examples of the imidazole derivative in consideration of ease of handling will be described.

[0047]

Embedded image

In the present invention, another charge control agent may be used in combination.

Generally, the above imidazole derivatives are
The weight average particle size (D4) is preferably 0.01 to 15 μm
m, preferably 1 to 8 μm.

The derivative is added in an amount of preferably 0.01 to 20.0 parts by weight, more preferably 0.1 to 10.0 parts by weight, and preferably 1 to 5 parts by weight, based on 100 parts by weight of the toner. Is good. As the addition method, there are a method of adding internally and a method of adding externally. If the addition amount is less than 0.01 parts by weight, the toner cannot have a sufficient charge amount, and the effect of adding the imidazole derivative does not appear. On the other hand, if it is more than 20 parts by weight, it is excessively added, and it is not preferable because it tends to be present in the form of agglomeration in the toner or uneven in the amount per toner.

The present inventors have found that the toner of the present invention
The imidazole derivative can take advantage of the positive charge stability imparted by the wax to obtain excellent developability and durability stability without impairing the low-temperature fixability and offset resistance of the specific wax. Was found. That is, the imidazole derivative can exert its positive charge controllability by the wax.

The imidazole derivative can be used in a component (such as a binder resin having a low molecular weight) which functions as a low-temperature fixing property of the toner, even if it is difficult to apply a load in production.
It has been found that a good dispersion state can be obtained.

Further, the imidazole derivative exhibits excellent developability in a toner. Since the imidazole derivative does not contaminate the surface of a toner triboelectric charging member such as a toner carrier or a carrier in a developing device, a high image density can be maintained. In addition, since the imidazole derivative is resistant to high temperature, high humidity, and low temperature and low humidity, the image density of the first sheet is not reduced in various environments without image density decrease at the beginning of the operation of the developing device due to insufficient toner charge, image density rise or fog. And that a good image can be obtained, and that the occurrence of blotches, which easily occur particularly under low humidity, can be suppressed.

Next, the magnetic material used in the toner of the present invention is a polyhedron having a particle shape of hexahedron or decahedron or more, and may be a mixture thereof. In the present invention, the polyhedron having a dodecahedron or more is preferably a polyhedron having a tetrahedron or more. By using a toner containing such a polyhedral magnetic material, a high image density can be obtained.

As the magnetic material used in the present invention, iron oxides such as magnetite, maghemite, and ferrite are used, and lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, calcium, scandium, titanium, vanadium, and chromium are used. , Manganese, cobalt, nickel, copper, zinc, germanium, arsenic, selenium, strontium, barium, zirconium, molybdenum, tungsten, palladium, silver, cadmium,
A magnetic metal oxide containing elements such as mercury, gallium, indium, tin, lead, antimony, and bismuth, and a magnetic iron oxide containing these elements are used. Preferably, magnetite is used, and one containing simultaneously the above-mentioned elements other than iron is also used.

The magnetic material used in the present invention will be described using magnetite as an example. A hexahedral or more polyhedral magnetite can be obtained by adjusting the pH during the neutralization reaction when magnetite is produced. During the reaction, octahedral particles are obtained in a high pH range, and spherical particles are obtained in a low pH range. In this intermediate pH range, hexahedral particles are mainly obtained in the high pH range, and decahedral or more polyhedral particles are mainly obtained in the low pH range, and a mixture thereof is obtained in the transition range between them. In addition, octahedral particles and spherical particles are mixed between the respective pHs. However, there is no problem if the content of these particles is 30% by number or less, preferably 20% by number or less, and more preferably 10% by number or less. It is.

Magnetite exhibits the following differences in properties when added to toner due to differences in particle shape. That is, when octahedral particles are used, fog suppression is good, but image density is low, and hexahedral particles or polyhedral particles of ten or more sides, and those using spherical particles have a high image density but tend to have poor fog suppression. . Further, the toner using the spherical particles may be excessively charged to easily cause blotting, or the spherical particles may fall off from the toner surface to contaminate the sleeve surface, resulting in a decrease in image density. On the other hand, in the case of polyhedral particles of hexahedron or more, since the particles are stably exposed on the toner surface, the charge is stabilized. In the present invention, fog suppression can be improved by using the imidazole derivative, and hexahedral particles capable of increasing image density or polyhedral particles having ten or more faces are used. Further, in the present invention, by using a specific wax, it is possible to make the toner hard and slippery. Therefore, it is possible to prevent the magnetic substance from falling off due to the stress applied to the toner particles, and it is possible to prevent the magnetic substance from falling off as compared with the octahedral particles. Hexahedral particles that can be easily formed, even in the case of polyhedral particles having ten or more faces, can be improved in detachment and can maintain good developability. In addition to good developability by the wax, very excellent developability can be obtained. Is obtained.

The magnetic material used in the present invention has a BET specific surface area of 1 to 40 m ² /
g, more preferably 3 to ²⁰ m ² / g,
Desirably, it is 5 to 15 m ² / g. The saturation magnetization of the magnetic material is 40 to 150 at a magnetic field of 795.8 kA / m.
Am ² / kg is preferred, and more preferably 50 to 12
0 Am ² / kg, desirably 60-100 Am ² / kg
It is. As the residual magnetization is preferably 2~50Am ² / kg at a magnetic field of 795.8 kA / m, more preferably 3~20Am ² / kg, preferably 4～10Am ²
/ Kg. Further, the coercive force of the magnetic material is 79
It is preferably from 40 to 200 kA / m at a magnetic field of 5.8 kA / m, more preferably from 60 to 150 kA / m, and more preferably from 80 to 120 kA / m. The average particle size of the magnetic material is preferably 0.05 to 0.5 μm, more preferably 0.1 to 0.3 μm.

The amount of the magnetic material contained in the toner is preferably 20 to 200 parts by weight, more preferably 30 to 150 parts by weight, based on 100 parts by weight of the binder resin.
Preferably, it is 40 to 120 parts by weight.

In the present invention, the shape and particle size of the magnetic material can be obtained by observation with a transmission electron microscope and a scanning electron microscope. The magnetic properties of the magnetic material can be measured by a vibration sample magnetometer VSM-3S-15 (manufactured by Toei Kogyo Co., Ltd.) or the like. Further, the specific surface area can be determined by measuring by nitrogen gas adsorption using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) according to the BET method and calculating by the BET multipoint method.

As the binder resin used in the present invention, the following binder resins can be used.

For example, homopolymers of styrene and its substituted substances such as polystyrene, poly-p-chlorostyrene and polyvinyl toluene; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-
Vinyl naphthalene copolymer, styrene-acrylic ester copolymer, styrene-methacrylic ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer -Based copolymer; furthermore, polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin , Epoxy resin, xylene resin, polyvinyl butyral, terpene resin, cumarone indene resin, and petroleum resin. Preferred binder resins include styrene copolymers and polyester resins.

Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.
Double such as dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide Monocarboxylic acid having a bond or a substituted product thereof; for example, dicarboxylic acid having a double bond such as maleic acid, butyl maleate, methyl maleate, or dimethyl maleate and a substituted product thereof; for example, vinyl chloride, vinyl acetate, benzoic acid Vinyl esters such as vinyl acid: ethylene olefins such as ethylene, propylene and butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl methyl ether and vinyl Chirueteru, vinyl ethers such as vinyl isobutyl ether; such vinyl monomers are used alone or two or more.

The styrene-based polymer or styrene-based copolymer may be crosslinked, or may be a mixed resin.

As a crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds can be mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; divinylaniline , Divinyl ether, divinyl sulfide, divinyl sulfone, and divinyl compounds; and compounds having three or more vinyl groups are used alone or as a mixture.

The method for synthesizing the binder resin may be any of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization.

In the bulk polymerization method, a polymer having a low molecular weight can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control.
In the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in chain transfer of radicals depending on the solvent, and by adjusting the amount of the initiator and the reaction temperature. It is preferable when a low molecular weight compound is obtained in the composition.

As the solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol, benzene and the like are used. In the case of a styrene monomer mixture, xylene, toluene or cumene is preferred. Each is appropriately selected depending on the polymer to be polymerized.

The reaction temperature varies depending on the solvent used, the initiator and the polymer to be polymerized.
It is better to carry out at 0 ° C. In solution polymerization, the solvent 100
It is preferable to use 30 parts by weight to 400 parts by weight of the monomer based on parts by weight.

Further, it is also preferable to mix another polymer in the solution at the end of the polymerization, and several types of polymers can be mixed well.

As a polymerization method for obtaining a high molecular weight component or a gel component, an emulsion polymerization method or a suspension polymerization method is preferable.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed in an aqueous phase as small particles with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, the reaction heat can be easily adjusted, and the phase in which the polymerization is performed (oil phase composed of a polymer and a monomer)
And the aqueous phase are separate, so that the termination reaction rate is low, resulting in a high polymerization rate and a high degree of polymerization. Furthermore, due to the relatively simple polymerization process and the fact that the polymerization product is fine particles, in the production of toner,
This method is advantageous as a method for producing a binder resin for a toner as compared with other methods because it is easy to mix with a colorant, a charge control agent and other additives.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to remove the polymer. Therefore, suspension polymerization is a simple method.

In the suspension polymerization, 100 parts by weight or less of the monomer (preferably 1 part by weight) is added to 100 parts by weight of the aqueous solvent.
(0 to 90 parts by weight). Usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like. There is an appropriate amount in terms of the amount of monomer relative to the aqueous solvent, and generally 0.05 to 100 parts by weight of the aqueous solvent. Used in an amount of 1 part by weight. Further, the polymerization temperature is suitably 50 to 95 ° C.,
It should be appropriately selected depending on the initiator used and the intended polymer. As the type of the initiator, any initiator that is insoluble or hardly soluble in water can be used.

Examples of the initiator used include t-butylperoxy-2-ethylhexanoate, cumin perpivalate, t-butylperoxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, -T-butyl peroxide, t
-Butylcumyl peroxide, dicumyl peroxide, 2,2′-azobisisobutyronitrile, 2,2 ′
-Azobis (2-methylbutyronitrile), 2,2'-
Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy)
3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxycarbonyl) cyclohexane, 2,2-bis (t-butylperoxy) Octane,
n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2, 5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane,
Di-t-butylperoxyisophthalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy-α-methylsuccinate, di-t-butyl Peroxydimethylglutarate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate,
2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate), di-t-butylperoxytrimethyl adipate, tris (t-butylperoxy) Triazine, vinyl tris (t-butylperoxy) silane and the like can be mentioned, and these can be used alone or in combination.

The amount used is 0.05 parts by weight or more (preferably 0.1 to 15 parts by weight) with respect to 100 parts by weight of the monomer.

The composition of the polyester resin used in the present invention is as follows.

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

[0079]

Embedded image (Wherein R is an ethylene or propylene group, x, y
Are each an integer of 0 or more, and the average value of x + y is 0 to 10.)

Diols represented by the following formula (B):

[0081]

Embedded image (Wherein R ′ is —CH ₂ CH ₂ — or

[0082]

Embedded image X 'and y' are integers of 0 or more, and x '
+ Y 'is from 0 to 10).

Examples of the divalent acid component include phthalic acid,
Benzenedicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides and lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides and lower alkyl esters; n- Alkenyl succinic acids or alkyl succinic acids such as dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides and lower alkyl esters thereof; fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acids such as itaconic acid or anhydrides, lower acids And dicarboxylic acids and derivatives thereof such as alkyl esters.

Further, it is preferable to use a trivalent or higher valent alcohol component and a trivalent or higher valent acid component which also function as a crosslinking component.

The trihydric or higher polyhydric alcohol component includes
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,
3,5-trihydroxybenzene and the like.

The polyvalent carboxylic acid component having three or more valences includes, for example, trimellitic acid, pyromellitic acid,
2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid,
2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8- Oxanetetracarboxylic acid, empol trimer acid, and anhydrides and lower alkyl esters thereof;

[0087]

Embedded image (Wherein X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having at least one side chain having 3 or more carbon atoms), such as tetracarboxylic acids, and anhydrides and lower alkyl esters thereof. And polyvalent carboxylic acids and derivatives thereof.

The alcohol component used in the binder resin of the present invention is 40 to 60 mol%, preferably 4 to 60 mol%.
5 to 55 mol%, 60 to 40 mol as the acid component
%, Preferably 55 to 45 mol%.

It is preferable that the content of the trivalent or higher polyvalent component is 1 to 60 mol% of all the components.

The binder resin used in the present invention is preferably a styrene-unsaturated carboxylic acid derivative copolymer, a polyester resin, a block copolymer thereof, a graft copolymer, And a mixture of a styrene-based copolymer and a polyester resin. T of the binder resin used in the toner of the present invention
g (glass transition point) is preferably from 50 to 70 ° C.

The binder resin used in the toner of the present invention has a molecular weight distribution of 10 as measured by GPC.
It is preferable to have a peak in ⁵ or more regions, and it is more preferable to have a peak in a region of 3 × 10 ^{3 to} 5 × 10 ^{4 from} the viewpoint of fixability and durability.

In the case of a positively chargeable toner, a styrene-acryl copolymer, a styrene-methacryl-acryl copolymer, a styrene-methacryl copolymer, a styrene-butadiene copolymer, a polyester resin, Block copolymers, grafted products, and blend resins are preferred. In the case of a negatively chargeable toner, styrene-
Acrylic copolymer, styrene-methacrylic-acrylic copolymer, styrene-methacrylic copolymer, copolymer of these constituent monomers and maleic acid monoester, polyester resin, block copolymer thereof, grafted product And a blend resin are preferred in terms of developability.

In the case of the heat fixing toner, when the styrene copolymer is used as the binder resin, the effect of the wax is sufficiently exhibited, and the deterioration of the blocking resistance and the developing property, which are adverse effects due to the plastic effect, are prevented. Therefore, the following toners are preferable.

The molecular weight distribution of the toner by GPC (gel permeation chromatography) is preferably in the range of 3 × 10 ^{3 to} 5 × 10 ⁴ , more preferably 3 × 10 ^{3 to} 5 × 10 ^4.
An area of × 10 ^{3 to} 3 × 10 ⁴ , preferably 5 × 10 ³ to
The presence of at least one peak (P ₁ ) in the region of 2 × 10 ⁴ makes it possible to obtain good fixability, developability and blocking resistance. The position of the peak is 3 × 10
^If it is less than ³ , good blocking resistance cannot be obtained and 5 × 1
0 ⁴ not obtained satisfactory fixability when exceeding. In addition, a region of 1 × 10 ⁵ or more, preferably 3 × 10 ^{5 to} 5 × 1
0 ⁶ least one peak in the region of (P ₂₎ is present, it is preferable that the maximum peak is present in the 1 × 10 ⁵ or more regions in the region of ^{3 × 10 5 ~2 × 10 6} ,
Good high-temperature offset resistance, blocking resistance, and developability are obtained. The larger the peak molecular weight, the stronger the high-temperature offset. However, when a peak exists in a region of 5 × 10 ⁶ or more, there is no problem with a hot roll to which pressure can be applied. In addition, the elasticity increases and the fixing property is affected. Therefore, in the heat fixing with a relatively low pressure used in a medium-to-low speed machine, a peak exists in a region of 3 × 10 ⁵ to 2 × 10 ⁶ , and this is a maximum peak in a region of 1 × 10 ⁵ or more. Is preferred.

The component in the region of 1 × 10 ⁵ or less is preferably 50% or more, more preferably 60 to 90%, particularly preferably 65 to 85%. By being within this range, the toner exhibits good fixability. 50% of the above ingredients
If it is less than 3, sufficient fixability cannot be obtained, and pulverizability also becomes poor. If it exceeds 90%,
It tends to be weak against the adverse effect of the plastic effect due to the addition of wax.

When a polyester resin is used as the binder resin in the present invention, the molecular weight distribution of the toner by GPC is preferably 3 × 10 ^{3 to} 1.5 × 1.
0 ⁴ in the region, more preferably 4 × 10 ³ ~1.2 × 1
0 ^4, particularly preferably it is preferred that the main peak is present in the region of ^{5 × 10 3 ~1 × 10 4} . Further, 1.
5 at least one peak or or 5 × 10 ⁴ or more regions shoulder is present in the × 10 ⁴ or more regions 5
% Is preferable. The weight average molecular weight (M
It is also preferable that w) / number average molecular weight (Mn) is 10 or more.

When the main peak is located at less than 3 × 10 ³ , the effect of the plasticity due to the addition of the wax tends to be adversely affected, and the blocking resistance and the developability are liable to be reduced. If the main peak is located in a region exceeding 1.5 × 10 ⁴ , good fixability cannot be obtained. On the other hand, 1.
When a peak or shoulder exists in a region of 5 × 10 ⁴ or more, or when a region of 5 × 10 ⁴ or more is 5% or more, M
When w / Mn is 10 or more, it is possible to suppress the adverse effect of the plastic effect due to the addition of wax.

In the present invention, the molecular weight distribution of the chromatogram of the toner by GPC is measured under the following conditions.

That is, the column is stabilized in a heat chamber at 40 ° C., THF (tetrahydrofuran) as a solvent is flown into the column at this temperature at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected for measurement. .
In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithm of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, Tosoh Corporation or Showa Denko Corporation has a molecular weight of 1 ×
It is appropriate to use a sample of about 10 ² to 10 ⁷ , and to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector. As the column, a combination of a plurality of commercially available polystyrene gel columns may be used. For example, a Shodex manufactured by Showa Denko KK
GPC KF-801,802,803,804,8
05, 806, 807, 800P, TSK Gel G1000H (H _XL ), G2000H manufactured by Tosoh Corporation.
(H _XL ), G3000H (H _XL ), G4000H
(H _XL ), G5000H (H _XL ), G6000H
(H _XL ), G7000H (H _XL ), TSKguardc
column, and combinations of the same.

A sample is prepared as follows.

After placing the sample in THF and leaving it to stand for several hours, it is shaken sufficiently, and the THF is mixed well (until the sample is no longer united), and left still for 12 hours or more. At this time T
The time of leaving in HF is set to 24 hours or more.
After that, the sample processing filter (pore size 0.45
μm to 0.5 μm, for example, Myshoridisk H-2
5-5 (manufactured by Tosoh Corporation, Exikurodisc 25CR, available from Germanic Science Japan) can be used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

In the toner of the present invention, in addition to the above-mentioned binder resin component, the following compounds may be contained at a ratio smaller than the content of the binder resin component. For example, silicone resin, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, and a copolymer of two or more kinds of α-olefins may be used.

In the toner of the present invention, charging stability,
In order to improve developability, fluidity and durability, it is preferable to add silica fine powder.

The fine silica powder used in the present invention is BE
The specific surface area by nitrogen adsorption measured by the T method is 20 m ² / g
Those within the above range (particularly 30 to 400 m ² / g) give good results. The silica fine powder is used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the toner.
It is better to use 5 parts by weight.

The silica fine powder used in the present invention may be used, if necessary, for the purpose of hydrophobization and charge control, silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, functional groups It is also preferable that the silane coupling agent is treated with a treating agent such as a silane coupling agent or another organosilicon compound, or by using various treating agents in combination.

It is also preferable to add the following inorganic powder in order to improve developability and durability. Magnesium, zinc, aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin,
Metal oxides such as antimony; composite metal oxides such as calcium titanate, magnesium titanate and strontium titanate; metal salts such as calcium carbonate, magnesium carbonate and aluminum carbonate; clay minerals such as kaolin;
Phosphate compounds such as apatite; silicon compounds such as silicon carbide and silicon nitride; and carbon powders such as carbon black and graphite. Among them, zinc oxide, aluminum oxide, cobalt oxide, manganese dioxide, strontium titanate, magnesium titanate and the like are preferable.

Further, the following lubricant powder can be added. Fluorine resins such as Teflon and polyvinylidene fluoride; fluorine compounds such as carbon fluoride; fatty acid metal salts such as zinc stearate; fatty acid derivatives such as fatty acids and fatty acid esters; molybdenum sulfide; amino acids; and amino acid derivatives.

The toner of the present invention can be used as a two-component developer in combination with a carrier. When the toner is used in the two-component developing method, any known carrier can be used. Specifically, particles having an average particle size of 20 to 300 μm, such as metals such as iron, nickel, cobalt, manganese, chromium, and rare earths, and their alloys and oxides whose surface is oxidized or not oxidized are used.

Further, those obtained by attaching or coating a substance such as a styrene resin, an acrylic resin, a silicone resin, a fluorine resin, or a polyester resin on the surface of the carrier particles are preferably used.

As the colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used. For example, pigments include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara,
Examples include phthalocyanine blue and indaslen blue.
These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and 0.1 to 20 parts by weight based on 100 parts by weight of the resin.
The addition amount is preferably from 0.2 to 10 parts by weight. A dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, based on 100 parts by weight of the resin.
0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight is good.

To prepare the toner of the present invention, a binder resin, a wax, a magnetic substance, a charge control agent, and a pigment or dye as a colorant and other additives are mixed by a mixer such as a Henschel mixer or a ball mill. After sufficient mixing, the mixture is melt-kneaded using a heat kneader such as a heating roll, kneader, extruder to make the resins compatible with each other, to disperse or dissolve the metal compound, pigment, dye, and magnetic substance, and to cool and solidify. The toner of the present invention can be obtained by pulverization and classification.

Further, if necessary, desired additives are sufficiently mixed with a mixer such as a Henschel mixer to obtain the toner of the present invention.

[0113]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.
Table 1 shows physical properties of the wax used in the present invention, and Table 2 shows physical properties of the magnetic substance.

[0114]

[Table 1]

[0115]

[Table 2]

Example 1 Styrene-butyl acrylate copolymer 100 parts by weight Magnetic substance 1 80 parts by weight Imidazole derivative (1) 2 parts by weight Wax 1 4 parts by weight
The mixture was melt-kneaded by a twin-screw kneading extruder set at a temperature of ° C.
After cooling the obtained kneaded material and coarsely pulverizing with a cutter mill, finely pulverizing it with a fine pulverizer using a jet stream, and classifying the obtained finely pulverized powder using a multi-part classifier utilizing the Coanda effect. Thus, a toner 1 having a weight average diameter of 7.6 μm was obtained. 100 parts by weight of this toner and 0.7 parts by weight of positively charged hydrophobic colloidal silica were externally added and mixed with a Henschel mixer to obtain a one-component developer 1.

Various evaluations were performed using a commercially available electrophotographic copying machine NP-4835 (manufactured by Canon Inc.). Table 3 shows the results in an environment of 23 ° C. and 5% RH at 32.5 ° C. and 90% RH.
Table 4 shows the environment of% RH. FIG. 3 shows the carbon number distribution of the wax 1.

(Fixing property test) Fixing property was evaluated by a first copy test. For evaluation of fixability, the image was made of silk paper,
Rubbing was performed 10 times, with a load of about 100 g, and the peeling of the image was evaluated by the reduction rate (%) of the reflection density.

(Offset Test) Transfer paper of B5
After continuous copying, copying was performed on A3 transfer paper, and the high-temperature offset due to the temperature rise at the edge was evaluated based on whether or not image contamination occurred.

(Durability Test) A durability test was performed on 10,000 sheets at A4 lengthwise feed to evaluate image density and fog.・ Evaluation of fog The evaluation was performed visually. ◎: Excellent Fog is not visually observed. ：: good No fog is observed if not carefully watched. Δ: Possible There is fog, but there is no practical problem. ×: Not possible Fog is noticeable.

(Blotch) The sleeve is visually observed at the 500th sheet from the start of image output.

(Sleeve contamination) A part of the sleeve is cleaned with silbon paper containing methyl ethyl ketone (solvent) every 1000 copies, and then one solid black copy is made. Then, the presence or absence of sleeve contamination is determined based on the density of the solid black density.

(Blocking Test) Approximately 20 g of the developer was put in a 100 cc plastic cup, left at 50 ° C. for 3 days, and evaluated visually. : Excellent No aggregates are observed. ：: Good Aggregates are seen but easily collapse. Δ: Yes Aggregates are observed, but collapse when shaken. ×: Not possible Aggregates can be grasped and do not collapse easily.

Example 2 Styrene-butyl acrylate copolymer 100 parts by weight Magnetic substance 1 80 parts by weight Imidazole derivative (1) 2 parts by weight Wax 2 4 parts by weight Component developer 2 was prepared and evaluated. The results are shown in Tables 3 and 4.

Example 3 100 parts by weight of a styrene-butyl acrylate copolymer 80 parts by weight of a magnetic substance 2 parts by weight of an imidazole derivative (1) 4 parts by weight of a wax 3 Component developer 3 was prepared and evaluated. The results are shown in Tables 3 and 4.

Example 4 100 parts by weight of styrene-butyl acrylate copolymer 80 parts by weight of magnetic substance 2 parts by weight of imidazole derivative (6) 4 parts by weight of wax 1 part by weight Component developer 4 was prepared and evaluated. The results are shown in Tables 3 and 4.

Example 5 100 parts by weight of a styrene-butyl acrylate copolymer 80 parts by weight of a magnetic substance 3 parts by weight of an imidazole derivative (9) 4 parts by weight of a wax 1 part by weight in the same manner as in Example 1 using the above materials Component developer 5 was prepared and evaluated. The results are shown in Tables 3 and 4.

Comparative Example 1 Styrene-butyl acrylate copolymer 100 parts by weight Magnetic iron oxide 80 parts by weight Nigrosine 2 parts by weight Wax 1 4 parts by weight One-component developer using the above materials and in the same manner as in Example 1. 6 was prepared and evaluated. The results are shown in Tables 3 and 4.

[Comparative Example 2] 100 parts by weight of styrene-butyl acrylate copolymer 80 parts by weight of magnetic iron oxide 2 parts by weight of quaternary ammonium salt 4 parts by weight of wax 1 component using the above materials and in the same manner as in Example 1 A system developer 7 was prepared and evaluated. The results are shown in Tables 3 and 4.

Comparative Example 3 Styrene-butyl acrylate copolymer 100 parts by weight Magnetic iron oxide 80 parts by weight Imidazole derivative (1) 2 parts by weight 4 parts by weight of wax 4 Component developer 8 was prepared and evaluated. The results are shown in Tables 3 and 4. FIG. 4 shows the carbon number distribution of the wax 4.

Comparative Example 4 Styrene-butyl acrylate copolymer 100 parts by weight Magnetic iron oxide 80 parts by weight Imidazole derivative (1) 2 parts by weight Wax 5 4 parts by weight Component developer 9 was prepared and evaluated. The results are shown in Tables 3 and 4. FIG. 5 shows the carbon number distribution of the wax 5.

Comparative Example 5 Styrene-butyl acrylate copolymer 100 parts by weight Magnetic substance 4 80 parts by weight Imidazole derivative (1) 2 parts by weight Wax 1 4 parts by weight Component developer 10 was prepared and evaluated. The results are shown in Tables 3 and 4.

[0133]

[Table 3]

[0134]

[Table 4]

[0135]

According to the toner of the present invention, by using the wax, the magnetic substance and the charge control agent as described above, it is possible to obtain a toner which satisfies the fixing property and the anti-offset property and is excellent in the developing property. Further, the present invention is a toner excellent in high image density, image density stability, and environmental stability, and has less fog and does not generate blotches and stains on a sleeve.

[Brief description of the drawings]

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

FIG. 2 is a view showing an example of a chromatogram of GC of wax.

FIG. 3 is a diagram showing an example of a carbon number distribution of wax.

FIG. 4 is a diagram showing an example of a carbon number distribution of wax.

FIG. 5 is a diagram showing an example of a carbon number distribution of wax.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masami Fujimoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Rika Haruba 3-30-2 Shimomaruko, Ota-ku, Tokyo Non Corporation

Claims (1)

[Claims] 1. An electrostatic image developing toner containing at least a binder resin, a wax, a magnetic substance and a charge controlling agent, wherein the wax is present in a carbon number distribution obtained by gas chromatography for each carbon number. Are continuously changing, and the width of the carbon number in the region where the abundance continuously changes is 8
Wherein the charge control agent is an imidazole derivative represented by the following general formula (I): (Wherein R _{1 to} R ₄ are a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and may be the same or different), and the magnetic material is a hexahedral particle, or A toner for developing an electrostatic image, comprising ten or more polyhedral particles or a mixture thereof.